TW202313713A - Sealing agent for liquid crystal display elements, and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, and liquid crystal display element Download PDFInfo
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- TW202313713A TW202313713A TW111123021A TW111123021A TW202313713A TW 202313713 A TW202313713 A TW 202313713A TW 111123021 A TW111123021 A TW 111123021A TW 111123021 A TW111123021 A TW 111123021A TW 202313713 A TW202313713 A TW 202313713A
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- Prior art keywords
- liquid crystal
- meth
- crystal display
- compound
- display elements
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 116
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 30
- 238000007789 sealing Methods 0.000 title abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 149
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- 239000004593 Epoxy Substances 0.000 claims abstract description 70
- -1 acrylic compound Chemical class 0.000 claims abstract description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 11
- 239000000565 sealant Substances 0.000 claims description 50
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000002265 prevention Effects 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 4
- 229930185605 Bisphenol Natural products 0.000 abstract 3
- 230000035699 permeability Effects 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- 239000010936 titanium Substances 0.000 description 19
- 229910052719 titanium Inorganic materials 0.000 description 19
- 239000000758 substrate Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000011859 microparticle Substances 0.000 description 9
- 239000000945 filler Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
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- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
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- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 2
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 2
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000004904 shortening Methods 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
- C09K2200/0647—Polyepoxides
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Liquid Crystal (AREA)
- Sealing Material Composition (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本發明係關於一種接著性、防透濕性及防止於注射器中掛壁之性能優異之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件用密封劑而成之液晶顯示元件。The present invention relates to a sealant for liquid crystal display elements which is excellent in adhesiveness, anti-moisture permeability and preventing wall hanging in a syringe. Moreover, this invention relates to the liquid crystal display element which used this sealing compound for liquid crystal display elements.
近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就縮短產距時間、優化液晶使用量等觀點而言，使用如專利文獻1、專利文獻2所揭示之使用密封劑之被稱為滴下工法之液晶滴下方式。 於滴下工法中，首先，於2片附電極之基板之一者上藉由點膠而形成框狀密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴下至基板之密封框內，於真空下重疊另一片基板，進行密封劑之硬化，製作液晶顯示元件。目前，該滴下工法為液晶顯示元件之主流製造方法。 In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoint of shortening the production lead time and optimizing the amount of liquid crystal usage, the method of using a sealant as disclosed in Patent Document 1 and Patent Document 2 is called dropping. Liquid crystal dropping method of construction method. In the drop method, first, a frame-shaped sealing pattern is formed by dispensing glue on one of the two substrates with electrodes. Then, in the uncured state of the sealant, liquid crystal droplets are dropped into the sealing frame of the substrate, and another substrate is stacked under vacuum to harden the sealant to produce a liquid crystal display element. At present, the dropping method is the mainstream manufacturing method of liquid crystal display elements.
且說，於行動電話、攜帶型遊戲機等各種附液晶面板之行動裝置逐漸普及之現代，裝置之小型化係最迫切之課題。作為小型化方法，可例舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下（以下，亦稱為「窄邊緣設計」）。 先前技術文獻 專利文獻 In addition, in the modern age when various mobile devices with liquid crystal panels such as mobile phones and portable game consoles are gradually popularized, the miniaturization of devices is the most urgent issue. As a miniaturization method, for example, narrowing the edge of the liquid crystal display part, such as arranging the position of the sealing part under the black matrix (hereinafter also referred to as "narrow edge design"). prior art literature patent documents
專利文獻1：日本特開2001-133794號公報 專利文獻2：國際公開第02/092718號 Patent Document 1: Japanese Patent Laid-Open No. 2001-133794 Patent Document 2: International Publication No. 02/092718
[發明所欲解決之課題][Problem to be Solved by the Invention]
伴隨著窄邊緣設計，於液晶顯示元件中，像素區域至密封劑之距離變近，容易因密封劑污染液晶而產生顯示不均。 又，伴隨著平板終端或移動終端之普及，對於液晶顯示元件越發要求於高溫高濕環境下驅動等時之耐濕可靠性，對於密封劑進一步要求防止水自外部滲入之性能。因此，需要提昇密封劑之防透濕性，但伴隨著窄邊緣設計，所塗布之密封劑之線寬變細，不易獲得即便於細線化之情形時防透濕性亦優異之密封劑。 本發明之目的在於：提供一種接著性、防透濕性及防止於注射器中掛壁之性能優異之液晶顯示元件用密封劑。又，本發明之目的在於：提供一種使用該液晶顯示元件用密封劑而成之液晶顯示元件。 [解決課題之技術手段] With the narrow edge design, in the liquid crystal display element, the distance from the pixel area to the sealant is shortened, and it is easy to produce uneven display due to the contamination of the liquid crystal by the sealant. In addition, with the popularization of tablet terminals and mobile terminals, the liquid crystal display element is required to be more reliable in moisture resistance when it is driven in a high-temperature and high-humidity environment, and the sealant is further required to prevent water penetration from the outside. Therefore, it is necessary to improve the moisture permeability resistance of the sealant, but with the narrow edge design, the line width of the applied sealant becomes thinner, and it is difficult to obtain a sealant with excellent moisture permeability resistance even when the lines are thinner. The object of the present invention is to provide a sealant for liquid crystal display elements with excellent adhesiveness, moisture-permeability prevention, and wall-hang prevention in syringes. Moreover, the object of this invention is to provide the liquid crystal display element which used this sealing compound for liquid crystal display elements. [Technical means to solve the problem]
本發明1係一種液晶顯示元件用密封劑，其係含有硬化性樹脂、自由基聚合起始劑及熱硬化劑者，且上述硬化性樹脂包含：（A）1個分子中具有3個以上芳香環之部分（甲基）丙烯酸改質環氧化合物；（B）選自由雙酚A型環氧（甲基）丙烯酸酯、雙酚F型環氧（甲基）丙烯酸酯、雙酚E型環氧（甲基）丙烯酸酯、部分（甲基）丙烯酸改質雙酚A型環氧化合物、部分（甲基）丙烯酸改質雙酚F型環氧化合物、及部分（甲基）丙烯酸改質雙酚E型環氧化合物所組成之群中之至少1種；以及（C）分子量為100以上300以下之（甲基）丙烯酸化合物。 本發明2係如本發明1之液晶顯示元件用密封劑，其中，上述分子量為100以上300以下之（甲基）丙烯酸化合物為1個分子中僅具有1個（甲基）丙烯醯基之單官能（甲基）丙烯酸化合物。 本發明3係如本發明1或2之液晶顯示元件用密封劑，其中，於上述硬化性樹脂整體100重量份中，上述分子量為100以上300以下之（甲基）丙烯酸化合物之含量為0.1重量份以上10重量份以下。 本發明4係一種液晶顯示元件，其包含本發明1、2或3之液晶顯示元件用密封劑之硬化物。 以下，對本發明進行詳述。 The present invention 1 is a sealant for liquid crystal display elements, which contains a curable resin, a radical polymerization initiator, and a thermosetting agent, and the curable resin includes: (A) having 3 or more aromatic compounds in one molecule Part of the ring (meth)acrylic modified epoxy compound; (B) selected from bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type ring Oxygen (meth)acrylate, part of (meth)acrylic modified bisphenol A epoxy compound, part of (meth)acrylic modified bisphenol F epoxy compound, and part of (meth)acrylic modified bisphenol At least one of the group consisting of phenolic E-type epoxy compounds; and (C) a (meth)acrylic compound having a molecular weight of 100 to 300. The present invention 2 is the sealant for liquid crystal display elements according to the present invention 1, wherein the above-mentioned (meth)acrylic compound having a molecular weight of 100 to 300 is a unit having only one (meth)acryl group in one molecule. Functional (meth)acrylic compound. Invention 3 is the sealant for liquid crystal display elements according to Invention 1 or 2, wherein the content of the (meth)acrylic compound having a molecular weight of 100 to 300 is 0.1 wt. More than 10 parts by weight. This invention 4 is a liquid crystal display element containing the hardened|cured material of the sealing compound for liquid crystal display elements of this invention 1, 2, or 3. Hereinafter, the present invention will be described in detail.
本發明人等進行了以下研究：藉由使用1個分子中具有3個以上芳香環之部分（甲基）丙烯酸改質環氧化合物作為硬化性樹脂，而提昇液晶顯示元件用密封劑之防透濕性。又，進行了以下研究：為了確保接著性，進而使用雙酚A型環氧（甲基）丙烯酸酯等作為硬化性樹脂。然而，在將所獲得之液晶顯示元件用密封劑填充於點膠用注射器中繼續使用時，有液晶顯示元件用密封劑容易於注射器中產生掛壁之問題。因此，本發明人等進行了努力研究，結果發現：藉由進而使用分子量為100以上300以下之（甲基）丙烯酸化合物，可獲得接著性、防透濕性及防止於注射器中掛壁之性能優異之液晶顯示元件用密封劑，從而完成本發明。The inventors of the present invention have conducted research on improving the anti-permeability of a sealant for liquid crystal display elements by using a partially (meth)acrylic acid-modified epoxy compound having three or more aromatic rings in one molecule as a curable resin. wetness. In addition, in order to ensure adhesiveness, studies have been made to further use bisphenol A epoxy (meth)acrylate or the like as a curable resin. However, when the obtained sealant for liquid crystal display elements is filled in a dispensing syringe and continues to be used, there is a problem that the sealant for liquid crystal display elements tends to hang on the syringe. Therefore, the inventors of the present invention conducted diligent research and found that by further using a (meth)acrylic compound with a molecular weight of 100 to 300, adhesiveness, moisture permeability prevention, and performance of preventing wall hanging in the syringe can be obtained. An excellent sealant for liquid crystal display elements, thus completing the present invention.
本發明之液晶顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂包含（A）1個分子中具有3個以上芳香環之部分（甲基）丙烯酸改質環氧化合物（以下，亦稱為「本發明之硬化性樹脂A」）。藉由含有本發明之硬化性樹脂A，本發明之液晶顯示元件用密封劑之防透濕性優異。 再者，於本說明書中，上述「（甲基）丙烯酸」意指丙烯酸或甲基丙烯酸。又，上述「部分（甲基）丙烯酸改質環氧化合物」意指1個分子中具有環氧基及（甲基）丙烯醯基各1個以上之化合物，該化合物係使1個分子中具有2個以上環氧基之環氧化合物之一部分環氧基與（甲基）丙烯酸進行反應而獲得。進而，上述「（甲基）丙烯醯基」意指丙烯醯基或甲基丙烯醯基。 The sealing compound for liquid crystal display elements of this invention contains curable resin. The curable resin includes (A) a partially (meth)acrylic modified epoxy compound having three or more aromatic rings in one molecule (hereinafter, also referred to as "curable resin A of the present invention"). By containing curable resin A of this invention, the sealing compound for liquid crystal display elements of this invention is excellent in moisture permeability prevention. In addition, in this specification, said "(meth)acrylic acid" means acrylic acid or methacrylic acid. In addition, the above-mentioned "partially (meth)acrylic modified epoxy compound" means a compound having one or more epoxy groups and (meth)acryl groups in one molecule. It is obtained by reacting a part of epoxy groups with (meth)acrylic acid in the epoxy compound having two or more epoxy groups. Furthermore, the above-mentioned "(meth)acryl" means acryl or methacryl.
本發明之硬化性樹脂A於1個分子中具有3個以上之芳香環。藉由使用1個分子中具有3個以上芳香環之本發明之硬化性樹脂A，本發明之液晶顯示元件用密封劑即便於細線化塗布之情形時，防透濕性亦優異。藉由增多本發明之硬化性樹脂A所具有之芳香環數，可實現兼顧所獲得之液晶顯示元件用密封劑之硬化物之防透濕性及接著力。 又，就塗布性等觀點而言，本發明之硬化性樹脂A較佳為於1個分子中具有5個以下之芳香環。 The curable resin A of the present invention has three or more aromatic rings in one molecule. By using curable resin A of this invention which has 3 or more aromatic rings in 1 molecule, the sealant for liquid crystal display elements of this invention is excellent in moisture-permeability prevention even when it applies for thinning lines. By increasing the number of aromatic rings that the curable resin A of the present invention has, both moisture permeability prevention and adhesive force of the cured product of the obtained sealant for liquid crystal display elements can be achieved. Moreover, it is preferable that curable resin A of this invention has 5 or less aromatic rings in 1 molecule from viewpoints, such as coatability.
本發明之硬化性樹脂A所具有之芳香環可為芳香族烴環，亦可為芳香族雜環。 作為本發明之硬化性樹脂A所具有之芳香環，具體而言，例如可例舉：苯環、萘環、蒽環、呋喃環等。其中，較佳為苯環。 The aromatic ring contained in the curable resin A of the present invention may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. As an aromatic ring which curable resin A of this invention has, a benzene ring, a naphthalene ring, an anthracene ring, a furan ring etc. are mentioned specifically,, for example. Among them, a benzene ring is preferred.
本發明之硬化性樹脂A之分子量之較佳之下限為300，較佳之上限為600。藉由使本發明之硬化性樹脂A之分子量為300以上，本發明之液晶顯示元件用密封劑之低液晶污染性更加優異。藉由使本發明之硬化性樹脂A之分子量為600以下，本發明之液晶顯示元件用密封劑之塗布性更加優異。本發明之硬化性樹脂A之分子量之更佳之下限為400，更佳之上限為500。 再者，於本說明書中，上述「分子量」係對於分子結構特定之化合物，根據結構式所求出之分子量，但對於聚合度分布較廣之化合物及改質部位不特定之化合物，有時使用重量平均分子量來表示。 又，於本說明書中，上述「重量平均分子量」係利用凝膠滲透層析法（GPC）並使用四氫呋喃作為溶劑進行測定，藉由聚苯乙烯換算所求出之值。作為藉由GPC測定基於聚苯乙烯換算之重量平均分子量時所使用之管柱，例如可例舉Shodex LF-804（昭和電工公司製造）等。 The preferred lower limit of the molecular weight of curable resin A of the present invention is 300, and the preferred upper limit is 600. By making the molecular weight of curable resin A of this invention 300 or more, the low liquid crystal contamination property of the sealing compound for liquid crystal display elements of this invention is more excellent. By making the molecular weight of the curable resin A of this invention 600 or less, the coating property of the sealing compound for liquid crystal display elements of this invention becomes more excellent. The more preferable lower limit of the molecular weight of curable resin A of the present invention is 400, and the more preferable upper limit is 500. Furthermore, in this specification, the above-mentioned "molecular weight" refers to the molecular weight obtained from the structural formula for a compound with a specific molecular structure, but for a compound with a wide distribution of polymerization degree and a compound with an unspecified modified site, it is sometimes used Expressed by weight average molecular weight. In addition, in this specification, the said "weight average molecular weight" is the value calculated|required by polystyrene conversion by the gel permeation chromatography (GPC) measuring using tetrahydrofuran as a solvent. As a column used when measuring the weight average molecular weight based on polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.
作為本發明之硬化性樹脂A，具體而言，較佳為下述式（1-1）～（1-6）所表示之化合物，更佳為下述式（1-5）所表示之化合物。Specifically, the curable resin A of the present invention is preferably a compound represented by the following formulas (1-1) to (1-6), more preferably a compound represented by the following formula (1-5) .
式（1-1）～（1-6）中，R表示氫原子或甲基。In formulas (1-1) to (1-6), R represents a hydrogen atom or a methyl group.
本發明之硬化性樹脂A例如可藉由以下方式製造：使1個分子中具有3個以上芳香環之二環氧化合物之一部分環氧基按照常規方法於鹼性觸媒之存在下與（甲基）丙烯酸進行反應。 作為上述1個分子中具有3個以上芳香環之二環氧化合物，例如可例舉1個分子中具有3個以上芳香環之二環氧丙醚等，較佳為下述式（2-1）～（2-6）所表示之化合物，更佳為下述式（2-5）所表示之化合物。 The curable resin A of the present invention can be produced, for example, by making a part of the epoxy group of a diepoxy compound having three or more aromatic rings in one molecule react with (methanol) in the presence of an alkaline catalyst according to a conventional method. base) acrylic acid to react. As the diepoxy compound having 3 or more aromatic rings in the above-mentioned 1 molecule, for example, diglycidyl ether having 3 or more aromatic rings in 1 molecule, etc., is preferably the following formula (2-1 ) to (2-6), more preferably a compound represented by the following formula (2-5).
於上述硬化性樹脂100重量份中，本發明之硬化性樹脂A之含量之較佳之下限為15重量份，較佳之上限為60重量份。藉由使本發明之硬化性樹脂A之含量為15重量份以上，所獲得之液晶顯示元件用密封劑之防透濕性更加優異。藉由使本發明之硬化性樹脂A之含量為60重量份以下，所獲得之液晶顯示元件用密封劑之接著性及防止於注射器中掛壁之性能更加優異。本發明之硬化性樹脂A之含量之更佳之下限為30重量份，更佳之上限為50重量份。In 100 parts by weight of the above-mentioned curable resin, the lower limit of the content of the curable resin A of the present invention is preferably 15 parts by weight, and the upper limit is preferably 60 parts by weight. By making content of curable resin A of this invention 15 weight part or more, the moisture permeability prevention property of the sealing compound for liquid crystal display elements obtained is more excellent. By making content of curable resin A of this invention 60 weight part or less, the adhesiveness of the sealant for liquid crystal display elements obtained, and the performance of preventing wall hanging in a syringe are more excellent. The more preferable lower limit of the content of curable resin A of the present invention is 30 parts by weight, and the more preferable upper limit is 50 parts by weight.
上述硬化性樹脂包含（B）選自由雙酚A型環氧（甲基）丙烯酸酯、雙酚F型環氧（甲基）丙烯酸酯、雙酚E型環氧（甲基）丙烯酸酯、部分（甲基）丙烯酸改質雙酚A型環氧化合物、部分（甲基）丙烯酸改質雙酚F型環氧化合物、及部分（甲基）丙烯酸改質雙酚E型環氧化合物所組成之群中之至少1種（以下，亦稱為「本發明之硬化性樹脂B」）。藉由含有本發明之硬化性樹脂B，本發明之液晶顯示元件用密封劑之接著性等優異。其中，作為本發明之硬化性樹脂B，較佳為雙酚A型環氧（甲基）丙烯酸酯。 再者，於本說明書中，上述「（甲基）丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，上述「環氧（甲基）丙烯酸酯」表示使環氧化合物中所有環氧基與（甲基）丙烯酸進行反應而成之化合物。 又，即便為部分（甲基）丙烯酸改質雙酚A型環氧化合物、部分（甲基）丙烯酸改質雙酚F型環氧化合物、及部分（甲基）丙烯酸改質雙酚E型環氧化合物，1個分子中具有3個以上芳香環者亦視作本發明之硬化性樹脂A，而非本發明之硬化性樹脂B。 The curable resin includes (B) selected from bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, part (meth)acrylic acid modified bisphenol A type epoxy compound, part of (meth)acrylic acid modified bisphenol F type epoxy compound, and part of (meth)acrylic acid modified bisphenol E type epoxy compound At least one of the group (hereinafter also referred to as "curable resin B of the present invention"). By containing curable resin B of this invention, the adhesiveness etc. of the sealing compound for liquid crystal display elements of this invention are excellent. Among them, as curable resin B of the present invention, bisphenol A type epoxy (meth)acrylate is preferable. Furthermore, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound are combined with ( A compound formed by the reaction of meth)acrylic acid. Also, even for partially (meth)acrylic modified bisphenol A epoxy compounds, partially (meth)acrylic modified bisphenol F epoxy compounds, and partially (meth)acrylic modified bisphenol E epoxy compounds Oxygen compounds having three or more aromatic rings in one molecule are also regarded as the curable resin A of the present invention, not the curable resin B of the present invention.
本發明之硬化性樹脂B之分子量之較佳之下限為200，較佳之上限為1600。藉由使本發明之硬化性樹脂B之分子量為200以上，本發明之液晶顯示元件用密封劑之低液晶污染性更加優異。藉由使本發明之硬化性樹脂B之分子量為1600以下，本發明之液晶顯示元件用密封劑之塗布性更加優異。本發明之硬化性樹脂B之分子量之更佳之下限為300，更佳之上限為500。The preferred lower limit of the molecular weight of curable resin B of the present invention is 200, and the preferred upper limit is 1600. By making the molecular weight of curable resin B of this invention 200 or more, the low liquid-crystal contamination property of the sealing compound for liquid crystal display elements of this invention is more excellent. By making the molecular weight of the curable resin B of this invention 1600 or less, the coating property of the sealing compound for liquid crystal display elements of this invention becomes more excellent. The more preferable lower limit of the molecular weight of the curable resin B of the present invention is 300, and the more preferable upper limit is 500.
於上述硬化性樹脂100重量份中，本發明之硬化性樹脂B之含量之較佳之下限為40重量份，較佳之上限為75重量份。藉由使本發明之硬化性樹脂B之含量為40重量份以上，所獲得之液晶顯示元件用密封劑之接著性更加優異。藉由使本發明之硬化性樹脂B之含量為75重量份以下，所獲得之液晶顯示元件用密封劑之防透濕性更加優異。本發明之硬化性樹脂B之含量之更佳之下限為45重量份，更佳之上限為65重量份。In 100 parts by weight of the above curable resin, the lower limit of the curable resin B content of the present invention is preferably 40 parts by weight, and the upper limit is 75 parts by weight. By making content of curable resin B of this invention 40 weight part or more, the adhesiveness of the sealing compound for liquid crystal display elements obtained becomes more excellent. By making content of the curable resin B of this invention 75 weight part or less, the moisture permeability prevention property of the sealing compound for liquid crystal display elements obtained is more excellent. The more preferable lower limit of the content of curable resin B in the present invention is 45 parts by weight, and the more preferable upper limit is 65 parts by weight.
上述硬化性樹脂包含（C）分子量為100以上300以下之（甲基）丙烯酸化合物（以下，亦稱為「本發明之硬化性樹脂C」）。藉由含有本發明之硬化性樹脂C，本發明之液晶顯示元件用密封劑之防止於注射器中掛壁之性能優異。 再者，於本說明書中，上述「（甲基）丙烯酸化合物」意指具有（甲基）丙烯醯基之化合物。 又，即便分子量為100以上300以下，1個分子中具有3個以上芳香環之部分（甲基）丙烯酸改質環氧化合物亦視作本發明之硬化性樹脂A，而非本發明之硬化性樹脂C。 進而，即便分子量為100以上300以下，選自由雙酚A型環氧（甲基）丙烯酸酯、雙酚F型環氧（甲基）丙烯酸酯、雙酚E型環氧（甲基）丙烯酸酯、部分（甲基）丙烯酸改質雙酚A型環氧化合物、部分（甲基）丙烯酸改質雙酚F型環氧化合物、及部分（甲基）丙烯酸改質雙酚E型環氧化合物所組成之群中之至少1種亦視作本發明之硬化性樹脂B，而非本發明之硬化性樹脂C。 The curable resin includes (C) a (meth)acrylic compound having a molecular weight of 100 to 300 (hereinafter also referred to as "curable resin C of the present invention"). By containing curable resin C of this invention, the sealing compound for liquid crystal display elements of this invention is excellent in the performance which prevents wall hanging in a syringe. In addition, in this specification, the said "(meth)acryl compound" means the compound which has a (meth)acryl group. Also, even if the molecular weight is 100 to 300, a partially (meth)acrylic-modified epoxy compound having 3 or more aromatic rings in one molecule is regarded as the curable resin A of the present invention, not the curable resin A of the present invention. Resin C. Furthermore, even if the molecular weight is 100 to 300, it is selected from bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate , some (meth)acrylic acid modified bisphenol A type epoxy compounds, some (meth)acrylic acid modified bisphenol F type epoxy compounds, and some (meth)acrylic acid modified bisphenol E type epoxy compounds At least one of the formed groups is also regarded as the curable resin B of the present invention, not the curable resin C of the present invention.
本發明之硬化性樹脂C之分子量之下限為100，上限為300。藉由使本發明之硬化性樹脂C之分子量處於該範圍，本發明之液晶顯示元件用密封劑之防止於注射器中掛壁之性能優異。本發明之硬化性樹脂C之分子量之較佳之下限為120，更佳之下限為140，且較佳之上限為250，更佳之上限為220。The lower limit of the molecular weight of curable resin C of the present invention is 100, and the upper limit is 300. By making the molecular weight of the curable resin C of this invention into this range, the performance of the sealing agent for liquid crystal display elements of this invention is excellent in the performance which prevents wall hanging in a syringe. The preferred lower limit of the molecular weight of the curable resin C of the present invention is 120, the more preferred lower limit is 140, and the preferred upper limit is 250, and the more preferred upper limit is 220.
就防止於注射器中掛壁之性能更加優異之方面而言，本發明之硬化性樹脂C較佳為1個分子中僅具有1個（甲基）丙烯醯基之單官能（甲基）丙烯酸化合物。In terms of better performance in preventing wall hanging in the syringe, the curable resin C of the present invention is preferably a monofunctional (meth)acrylic compound having only one (meth)acryl group in one molecule .
作為本發明之硬化性樹脂C，具體而言，例如可例舉：（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸-2-羥基丁酯、（甲基）丙烯酸-2-羥基-3-苯氧基丙酯、（甲基）丙烯酸異莰酯、（甲基）丙烯酸-2-羥基-3-（甲基）丙烯醯氧基丙酯等。As curable resin C of the present invention, specifically, for example, phenoxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, -3-phenoxypropyl, isocamphoryl (meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, etc.
於上述硬化性樹脂100重量份中，本發明之硬化性樹脂C之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由使本發明之硬化性樹脂C之含量為0.1重量份以上，所獲得之液晶顯示元件用密封劑之防止於注射器中掛壁之性能更加優異。藉由使本發明之硬化性樹脂C之含量為10重量份以下，所獲得之液晶顯示元件用密封劑之接著性及低液晶污染性更加優異。本發明之硬化性樹脂C之含量之更佳之下限為1重量份，進而較佳之下限為2重量份，且更佳之上限為5重量份。In 100 parts by weight of the above curable resin, the lower limit of the content of the curable resin C of the present invention is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making content of curable resin C of this invention 0.1 weight part or more, the performance of preventing the wall hanging in the syringe of the obtained sealing compound for liquid crystal display elements is more excellent. By making content of curable resin C of this invention 10 weight part or less, the adhesiveness and low liquid-crystal contamination property of the sealing compound for liquid crystal display elements obtained are more excellent. The more preferable lower limit of the content of curable resin C of the present invention is 1 weight part, and the more preferable lower limit is 2 weight parts, and the more preferable upper limit is 5 weight parts.
上述硬化性樹脂除含有本發明之硬化性樹脂A～C以外，還可於不阻礙本發明之目的之範圍含有其他硬化性樹脂。 作為上述其他硬化性樹脂，可例舉：環氧化合物、或除本發明之硬化性樹脂A及本發明之硬化性樹脂B中所含之部分（甲基）丙烯酸改質環氧化合物以外之部分（甲基）丙烯酸改質環氧化合物、或除本發明之硬化性樹脂B中所含之環氧（甲基）丙烯酸酯以外之環氧（甲基）丙烯酸酯等。 The above curable resin may contain other curable resins in addition to the curable resins A to C of the present invention within the range that does not hinder the object of the present invention. Examples of the above-mentioned other curable resins include epoxy compounds, or parts other than the part of the (meth)acrylic-modified epoxy compound contained in the curable resin A of the present invention and the curable resin B of the present invention. (Meth)acryl-modified epoxy compound, epoxy (meth)acrylate other than the epoxy (meth)acrylate contained in curable resin B of this invention, etc.
作為上述環氧化合物，例如可例舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚E型環氧化合物、雙酚S型環氧化合物、間苯二酚型環氧化合物、聯苯型環氧化合物、硫醚型環氧化合物、二苯醚型環氧化合物、二環戊二烯型環氧化合物、萘型環氧化合物、苯酚酚醛清漆型環氧化合物、鄰甲酚酚醛清漆型環氧化合物、二環戊二烯酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物、萘酚酚醛清漆型環氧化合物、縮水甘油胺型環氧化合物、烷基多元醇型環氧化合物、橡膠改質型環氧化合物、環氧丙酯化合物等。Examples of the above-mentioned epoxy compounds include bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol E epoxy compounds, bisphenol S epoxy compounds, and resorcinol epoxy compounds. compound, biphenyl type epoxy compound, thioether type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, o-formaldehyde Phenol novolak type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy compound, naphthol novolac type epoxy compound, glycidylamine type epoxy compound, alkyl polyol Epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, etc.
本發明之液晶顯示元件用密封劑含有自由基聚合起始劑。 作為上述自由基聚合起始劑，可例舉：藉由光照射而產生自由基之光自由基聚合起始劑、藉由加熱而產生自由基之熱自由基聚合起始劑等。 The sealing compound for liquid crystal display elements of this invention contains a radical polymerization initiator. As said radical polymerization initiator, the photoradical polymerization initiator which generate|occur|produces a radical by light irradiation, the thermal radical polymerization initiator which generates a radical by heating, etc. are mentioned.
作為上述光自由基聚合起始劑，例如可例舉：二苯甲酮系化合物、苯乙酮系化合物、醯基氧化膦系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、9-氧硫𠮿
作為上述熱自由基聚合起始劑，例如可例舉由偶氮化合物或有機過氧化物等所構成者。其中，就抑制液晶污染之觀點而言，較佳為由偶氮化合物所構成之起始劑（以下，亦稱為「偶氮起始劑」），更佳為由高分子偶氮化合物所構成之起始劑（以下，亦稱為「高分子偶氮起始劑」）。 上述熱自由基聚合起始劑可單獨使用，亦可組合2種以上使用。 再者，於本說明書中，上述「高分子偶氮化合物」意指具有偶氮基，會藉由熱而生成可使（甲基）丙烯醯基硬化之自由基的數量平均分子量為300以上之化合物。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter, also referred to as an "azo initiator") is preferred, and an initiator composed of a high-molecular azo compound is more preferred. Initiator (hereinafter also referred to as "polymeric azo initiator"). The said thermal radical polymerization initiator may be used individually or in combination of 2 or more types. In addition, in this specification, the above-mentioned "polymeric azo compound" means a compound having an azo group, which generates free radicals capable of hardening (meth)acryl groups by heat, and has a number-average molecular weight of 300 or more. compound.
上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由使上述高分子偶氮化合物之數量平均分子量處於該範圍，可防止對液晶之不良影響，且容易混合至硬化性樹脂中。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 再者，於本說明書中，上述數量平均分子量係利用凝膠滲透層析法（GPC）並使用四氫呋喃作為溶劑進行測定，藉由聚苯乙烯換算所求出之值。作為藉由GPC測定基於聚苯乙烯換算之數量平均分子量時之管柱，例如可例舉Shodex LF-804（昭和電工公司製造）等。 The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferable upper limit is 300,000. When the number average molecular weight of the above-mentioned high molecular weight azo compound is within this range, adverse effects on liquid crystals can be prevented, and it can be easily mixed into a curable resin. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is preferably 5000, the upper limit is 100,000, the lower limit is 10,000, and the upper limit is 90,000. In addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) and the like may be mentioned.
作為上述高分子偶氮化合物，例如可例舉具有經由偶氮基鍵結有複數個聚環氧烷或聚二甲基矽氧烷等單元之結構者。 作為具有上述經由偶氮基鍵結有複數個聚環氧烷等單元之結構的高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 作為上述高分子偶氮化合物，具體而言，例如可例舉：4,4’-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4’-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之縮聚物等。 作為上述高分子偶氮起始劑中之市售者，例如可例舉：VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001（均為富士膠片和光純藥公司製造）等。 又，作為並非高分子之偶氮起始劑，例如可例舉：V-65、V-501（均為富士膠片和光純藥公司製造）等。 As said polymeric azo compound, the thing which has the structure which unites, such as a polyalkylene oxide or polydimethylsiloxane, couple|bonded via an azo group, is mentioned, for example. As the polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferable. As the above-mentioned polymeric azo compound, specifically, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Polycondensate of azobis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amino group, etc. Examples of commercially available polymeric azo initiators include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) wait. Moreover, as an azo initiator which is not a polymer, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), etc. are mentioned, for example.
作為上述有機過氧化物，例如可例舉：過氧化酮、過氧化縮酮、過氧化氫、二烷基過氧化物、過氧化酯、二乙醯過氧化物、過氧化二碳酸酯等。As said organic peroxide, a ketone peroxide, a peroxyketal, a hydrogen peroxide, a dialkyl peroxide, a peroxyester, a diacetyl peroxide, a peroxydicarbonate etc. are mentioned, for example.
相對於上述硬化性樹脂100重量份，上述自由基聚合起始劑之含量之較佳之下限為0.01重量份，較佳之上限為10重量份。藉由使上述自由基聚合起始劑之含量處於該範圍，所獲得之液晶顯示元件用密封劑抑制液晶污染，並且保存穩定性或硬化性更加優異。上述自由基聚合起始劑之含量之更佳之下限為0.1重量份，更佳之上限為5重量份。The preferable lower limit of content of the said radical polymerization initiator is 0.01 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 10 weight part. By making content of the said radical polymerization initiator into this range, the obtained sealing compound for liquid crystal display elements suppresses contamination of a liquid crystal, and is more excellent in storage stability or curability. The more preferable lower limit of the content of the above-mentioned radical polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑含有熱硬化劑。 作為上述熱硬化劑，例如可例舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，可較佳地使用有機酸醯肼。 上述熱硬化劑可單獨使用，亦可組合2種以上使用。 The sealing compound for liquid crystal display elements of this invention contains a thermosetting agent. As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, a polyphenol type compound, an acid anhydride, etc. are mentioned, for example. Among them, organic acid hydrazine can be preferably used. The above thermosetting agents may be used alone or in combination of two or more.
作為上述有機酸醯肼，例如可例舉：癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二醯肼等。 作為上述有機酸醯肼中之市售者，例如可例舉：大塚化學公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 作為上述大塚化學公司製造之有機酸醯肼，例如可例舉：SDH、ADH、MDH等。 作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可例舉：Ajicure VDH、Ajicure VDH-J、Ajicure UDH、Ajicure UDH-J等。 Examples of the organic acid hydrazide include dihydrazide sebacate, dihydrazide isophthalate, dihydrazide adipate, and malonylhydrazine. As what is marketed among the said organic acid hydrazides, the organic acid hydrazide by Otsuka Chemical Co., Ltd., the organic acid hydrazide by Ajinomoto Fine-Techno company, etc. are mentioned, for example. Examples of the organic acid hydrazide produced by the aforementioned Otsuka Chemical Co., Ltd. include SDH, ADH, and MDH. As the organic acid hydrazide manufactured by the said Ajinomoto Fine-Techno Co., Ltd., Ajicure VDH, Ajicure VDH-J, Ajicure UDH, Ajicure UDH-J etc. are mentioned, for example.
相對於上述硬化性樹脂100重量份，上述熱硬化劑之含量之較佳之下限為1重量份，較佳之上限為50重量份。藉由使上述熱硬化劑之含量處於該範圍，可不使所獲得之液晶顯示元件用密封劑之塗布性或保存穩定性等變差而使熱硬化性更加優異。上述熱硬化劑之含量之更佳之上限為30重量份。The preferable lower limit of the content of the said thermosetting agent is 1 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 50 weight parts. By making content of the said thermosetting agent into this range, it becomes possible to make thermosetting property more excellent, without deteriorating applicability, storage stability, etc. of the sealing compound for liquid crystal display elements obtained. The more preferable upper limit of the content of the said thermosetting agent is 30 weight part.
出於提昇黏度、進一步提昇由應力分散效應帶來之接著性、改善線膨脹率、提昇硬化物之耐濕性等目的，本發明之液晶顯示元件用密封劑較佳為含有填充劑。For the purposes of increasing viscosity, further improving adhesiveness due to stress dispersion effect, improving linear expansion rate, and improving moisture resistance of hardened products, the sealant for liquid crystal display elements of the present invention preferably contains a filler.
上述填充劑可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可例舉：二氧化矽（silica）、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可例舉：聚酯微粒子、聚胺酯微粒子、乙烯系聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨使用，亦可組合2種以上使用。 As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica (silica), talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, Zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc. As said organic filler, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. are mentioned, for example. These fillers may be used alone or in combination of two or more.
於本發明之液晶顯示元件用密封劑100重量份中，上述填充劑之含量之較佳之下限為10重量份，較佳之上限為70重量份。藉由使上述填充劑之含量處於該範圍，不使塗布性等變差而使改善接著性等效果更加優異。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。In 100 parts by weight of the sealant for liquid crystal display elements of the present invention, the preferable lower limit of the content of the filler is 10 parts by weight, and the upper limit is preferably 70 parts by weight. By making content of the said filler into this range, the effect of improving adhesiveness etc. will become more excellent, without deteriorating applicability etc. The more preferable lower limit of the content of the above filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑還可含有矽烷偶合劑。上述矽烷偶合劑主要具有作為接著助劑之作用，該接著助劑用於將密封劑與基板等良好地接著。The sealing compound for liquid crystal display elements of this invention may contain a silane coupling agent further. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for good adhesion of the sealant, the substrate, and the like.
作為上述矽烷偶合劑，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等提高與基板等之接著性之效果優異，可藉由與硬化性樹脂化學鍵結而抑制硬化性樹脂流出至液晶中。 上述矽烷偶合劑可單獨使用，亦可組合2種以上使用。 As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isopropyltrimethoxysilane, Cyanatopropyltrimethoxysilane, etc. These are excellent in the effect of improving the adhesiveness with a board|substrate etc., and can suppress curable resin from flowing out into liquid crystal by chemically bonding with curable resin. The above-mentioned silane coupling agents may be used alone or in combination of two or more.
於本發明之液晶顯示元件用密封劑100重量份中，上述矽烷偶合劑之含量之較佳之下限為0.1重量份，較佳之上限為10重量份。藉由使上述矽烷偶合劑之含量處於該範圍，抑制液晶污染之產生，並且提昇接著性之效果更加優異。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為5重量份。In 100 parts by weight of the sealant for liquid crystal display elements of the present invention, the lower limit of the content of the above-mentioned silane coupling agent is preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making the content of the above-mentioned silane coupling agent within this range, the occurrence of liquid crystal contamination is suppressed, and the effect of improving adhesion is more excellent. The more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
本發明之液晶顯示元件用密封劑還可含有遮光劑。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent further. By containing the said light-shielding agent, the sealing compound for liquid crystal display elements of this invention can be used preferably as a light-shielding sealing compound.
作為上述遮光劑，例如可例舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. are mentioned, for example. Among them, titanium black is preferred.
上述鈦黑係對於紫外線區域附近、尤其是波長370 nm以上450 nm以下之光之穿透率高於波長300 nm以上800 nm以下之光之平均穿透率的物質。即，上述鈦黑係具有以下性質之遮光劑：藉由充分地遮蔽可見光區域之波長之光而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面，使紫外線區域附近之波長之光穿透。因此，作為上述光自由基聚合起始劑，使用藉由上述鈦黑之穿透率提高之波長（370 nm以上450 nm以下）之光能夠使反應開始者，藉此可進一步增大本發明之液晶顯示元件用密封劑之光硬化性。又，另一方面，作為本發明之液晶顯示元件用密封劑中所含有之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，鈦黑亦較佳。 上述鈦黑較佳為每1 μm之光學密度（OD值）為3以上，更佳為4以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值並無特佳之上限，通常為5以下。 The above-mentioned titanium black is a material whose transmittance is higher than the average transmittance of light with a wavelength of 300 nm to 800 nm near the ultraviolet region, especially with a wavelength of 370 nm to 450 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of imparting light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, shielding light of wavelengths near the ultraviolet region penetrate. Therefore, as the above-mentioned photoradical polymerization initiator, use the light of the wavelength (below 370 nm to 450 nm) that the transmittance of the above-mentioned titanium black improves can make the reaction start, thereby further increasing the scope of the present invention. Photohardenability of sealants for liquid crystal display elements. On the other hand, as the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a substance with high insulating property is preferable, and titanium black is also preferable as the light-shielding agent with high insulating property. The above-mentioned titanium black preferably has an optical density (OD value) per 1 μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the above-mentioned titanium black, the better. There is no particularly good upper limit for the OD value of the above-mentioned titanium black, and it is usually 5 or less.
上述鈦黑即便未經表面處理亦發揮充分之效果，但亦可使用表面經偶合劑等有機成分處理者或被氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分覆蓋者等經表面處理之鈦黑。其中，於可進一步提高絕緣性之方面而言，經有機成分處理者較佳。 又，使用摻合有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑而製造之液晶顯示元件具有充分之遮光性，因此可實現不漏光且具有較高之對比度，具有優異之圖像顯示品質之液晶顯示元件。 The above-mentioned titanium black has sufficient effect even without surface treatment, but it can also be used if the surface is treated with organic components such as coupling agent or covered with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Those who have been surface-treated titanium black. Among them, those treated with an organic component are preferable in that the insulation properties can be further improved. Also, the liquid crystal display element manufactured by using the sealant for liquid crystal display element of the present invention blended with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so it can realize no light leakage and high contrast, and has excellent image quality. Liquid crystal display elements with image display quality.
作為上述鈦黑中之市售者，例如可例舉：三菱綜合材料公司製造之鈦黑、赤穗化成公司製造之鈦黑等。 作為上述三菱綜合材料公司製造之鈦黑，例如可例舉：12S、13M、13M-C、13R-N、14M-C等。 作為上述赤穗化成公司製造之鈦黑，例如可例舉Tilack D等。 As what is marketed among the said titanium blacks, the titanium black by Mitsubishi Materials Corporation, the titanium black by Ako Kasei Corporation, etc. are mentioned, for example. Examples of titanium black manufactured by Mitsubishi Materials Corp. include 12S, 13M, 13M-C, 13R-N, and 14M-C. As titanium black manufactured by the said Ako Kasei Co., Ltd., Tilack D etc. are mentioned, for example.
上述鈦黑之比表面積之較佳之下限為13 m 2/g，較佳之上限為30 m 2/g，更佳之下限為15 m 2/g，更佳之上限為25 m 2/g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω・cm，較佳之上限為3 Ω・cm，更佳之下限為1 Ω・cm，更佳之上限為2.5 Ω・cm。 The lower limit of the specific surface area of the titanium black is preferably 13 m 2 /g, the upper limit is 30 m 2 /g, the lower limit is 15 m 2 /g, and the upper limit is 25 m 2 /g. In addition, the lower limit of the volume resistance of the titanium black is preferably 0.5 Ω·cm, the upper limit is 3 Ω·cm, the lower limit is 1 Ω·cm, and the upper limit is 2.5 Ω·cm.
上述遮光劑之一次粒徑為液晶顯示元件之基板間之距離以下即可，並無特別限定，較佳之下限為1 nm，較佳之上限為5000 nm。藉由使上述遮光劑之一次粒徑處於該範圍，可不使所獲得之液晶顯示元件用密封劑之塗布性等變差而使遮光性更加優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造），使上述遮光劑分散於溶劑（水、有機溶劑等）中來進行測定。 The primary particle size of the above-mentioned light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element. The lower limit is preferably 1 nm, and the upper limit is 5000 nm. By making the primary particle diameter of the said light-shielding agent into this range, it becomes possible to make light-shielding property more excellent, without deteriorating coatability, etc. of the sealing compound for liquid crystal display elements obtained. The more preferable lower limit of the primary particle size of the above-mentioned sunscreen agent is 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm. In addition, the primary particle diameter of the said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS).
於本發明之液晶顯示元件用密封劑100重量份中，上述遮光劑之含量之較佳之下限為5重量份，較佳之上限為80重量份。藉由使上述遮光劑之含量處於該範圍，可不大幅度降低所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度及描繪性而發揮更加優異之遮光性。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。In 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention, the preferable lower limit of the content of the above-mentioned light-shielding agent is 5 parts by weight, and the upper limit is preferably 80 parts by weight. By making content of the said light-shielding agent into this range, the adhesiveness of the sealing compound for liquid crystal display elements obtained, the intensity|strength after hardening, and drawing property can be exhibited more excellent light-shielding property without reducing significantly. The lower limit of the content of the sunscreen agent is more preferably 10 parts by weight, the upper limit is 70 parts by weight, the lower limit is 30 parts by weight, and the upper limit is 60 parts by weight.
本發明之液晶顯示元件用密封劑進而視需要可含有應力緩和劑、反應性稀釋劑、觸變劑、間隔劑（spacer）、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relieving agents, reactive diluents, thixotropic agents, spacers, hardening accelerators, defoamers, leveling agents, polymerization inhibitors, etc., if necessary .
作為製造本發明之液晶顯示元件用密封劑之方法，例如可例舉：使用勻相分散機、均質攪拌機、萬能混合機、行星式混合機、捏合機、三輥研磨機等混合機，將硬化性樹脂、自由基聚合起始劑、熱硬化劑及視需要添加之矽烷偶合劑等添加劑加以混合之方法等。As a method of manufacturing the sealant for liquid crystal display elements of the present invention, for example, using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill, to harden The method of mixing additives such as permanent resin, radical polymerization initiator, thermosetting agent and if necessary, silane coupling agent, etc.
藉由向本發明之液晶顯示元件用密封劑摻合導電性微粒子，可製造上下導通材料。A vertical conduction material can be manufactured by mixing electroconductive microparticles|fine-particles with the sealing compound for liquid crystal display elements of this invention.
作為上述導電性微粒子，可使用金屬球、於樹脂微粒子之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者因樹脂微粒子之優異彈性，能夠不損傷透明基板等而實現導電連接，故而較佳。As said electroconductive microparticles|fine-particles, what formed the electroconductive metal layer on the surface of a metal ball, the resin microparticles, etc. can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferable because resin fine particles have excellent elasticity and can realize conductive connection without damaging a transparent substrate or the like.
又，包含本發明之液晶顯示元件用密封劑之硬化物之液晶顯示元件亦為本發明之一。Moreover, the liquid crystal display element containing the hardened|cured material of the sealing compound for liquid crystal display elements of this invention is also one of this invention.
又，作為本發明之液晶顯示元件，較佳為窄邊緣設計之液晶顯示元件。具體而言，較佳為液晶顯示部周圍之框部分之寬度為2 mm以下。 進而，製造本發明之液晶顯示元件時，本發明之液晶顯示元件用密封劑之塗布寬度較佳為1 mm以下。 Also, as the liquid crystal display element of the present invention, a liquid crystal display element with a narrow edge design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display portion is 2 mm or less. Furthermore, when manufacturing the liquid crystal display element of this invention, it is preferable that the coating width of the sealing compound for liquid crystal display elements of this invention is 1 mm or less.
本發明之液晶顯示元件用密封劑可較佳地用於藉由液晶滴下工法製造液晶顯示元件。作為藉由液晶滴下工法製造本發明之液晶顯示元件之方法，例如可例舉以下方法等。 可藉由以下方法獲得液晶顯示元件：首先，進行以下步驟：藉由網版印刷、點膠機（dispenser）塗布等將本發明之液晶顯示元件用密封劑於基板上形成為框狀密封圖案。繼而，進行以下步驟：於本發明之液晶顯示元件用密封劑等未硬化之狀態下，將液晶之微小液滴滴下塗布於密封圖案之框內整面，立即重疊其他基板。其後，進行以下步驟：對密封圖案部分照射紫外線等光而使密封劑暫時硬化；及對暫時硬化之密封劑進行加熱而使其正式硬化。 [發明之效果] The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacturing a liquid crystal display element by the liquid crystal dropping method. As a method of manufacturing the liquid crystal display element of this invention by the liquid crystal dropping method, the following method etc. are mentioned, for example. The liquid crystal display element can be obtained by the following method: First, the following steps are performed: forming the sealant for liquid crystal display element of the present invention into a frame-shaped sealing pattern on the substrate by screen printing, dispenser coating, or the like. Next, in the uncured state of the sealant for liquid crystal display elements of the present invention, droplet-coating tiny droplets of liquid crystal on the entire surface of the frame of the seal pattern, and immediately overlapping other substrates. Thereafter, the steps of temporarily hardening the sealant by irradiating light such as ultraviolet rays to the seal pattern portion, and heating the temporarily hardened sealant are finally cured. [Effect of Invention]
根據本發明，可提供一種接著性、防透濕性及防止於注射器中掛壁之性能優異之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之液晶顯示元件。According to the present invention, it is possible to provide a sealant for a liquid crystal display element that is excellent in adhesiveness, moisture permeability prevention, and wall hanging prevention in a syringe. Moreover, according to this invention, the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.
以下，例舉實施例進一步對本發明進行詳細說明，但本發明並不僅限於該等實施例。Hereinafter, the present invention will be further described in detail with reference to examples, but the present invention is not limited to these examples.
（式（1-1）所表示之化合物之製作） 送入空氣，並同時將37.4重量份之上述式（2-1）所表示之化合物、0.1重量份之作為聚合抑制劑之對甲氧基苯酚、0.1重量份之作為反應觸媒之三乙胺及7.2重量份之丙烯酸於90℃回流攪拌5小時而使其等反應。為了吸附反應物中之離子性雜質，利用填充有10重量份之石英與高嶺土之天然結合物（霍夫曼礦物公司製造之「Silicin V85」）的管柱對100重量份之所獲得之反應產物進行過濾，獲得上述式（1-1）所表示之化合物（R為氫原子）。 上述式（1-1）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-1)) Air is fed, and at the same time, 37.4 parts by weight of the compound represented by the above formula (2-1), 0.1 parts by weight of p-methoxyl as a polymerization inhibitor Phenol, 0.1 parts by weight of triethylamine as a reaction catalyst, and 7.2 parts by weight of acrylic acid were refluxed and stirred at 90° C. for 5 hours to react them. In order to adsorb ionic impurities in the reactant, 100 parts by weight of the obtained reaction product Filtration is carried out to obtain the compound represented by the above formula (1-1) (R is a hydrogen atom). The structure of the compound represented by the above formula (1-1) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（1-2）所表示之化合物之製作） 除使用40.2重量份之上述式（2-2）所表示之化合物來代替37.4重量份之上述式（2-1）所表示之化合物以外，以與上述「（式（1-1）所表示之化合物之製作）」相同之方式，獲得上述式（1-2）所表示之化合物（R為氫原子）。 上述式（1-2）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-2)) In addition to using 40.2 parts by weight of the compound represented by the above formula (2-2) instead of 37.4 parts by weight of the compound represented by the above formula (2-1), The compound represented by the above formula (1-2) (R is a hydrogen atom) was obtained in the same manner as in the above "(Preparation of the compound represented by the formula (1-1))". The structure of the compound represented by the above formula (1-2) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（1-3）所表示之化合物之製作） 除使用46.4重量份之上述式（2-3）所表示之化合物來代替37.4重量份之上述式（2-1）所表示之化合物以外，以與上述「（式（1-1）所表示之化合物之製作）」相同之方式，獲得上述式（1-3）所表示之化合物（R為氫原子）。 上述式（1-3）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-3)) In addition to using 46.4 parts by weight of the compound represented by the above formula (2-3) instead of 37.4 parts by weight of the compound represented by the above formula (2-1), In the same manner as in the above "(Preparation of compound represented by formula (1-1))", the compound represented by the above formula (1-3) (R is a hydrogen atom) was obtained. The structure of the compound represented by the above formula (1-3) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（1-4）所表示之化合物之製作） 除使用43.4重量份之上述式（2-4）所表示之化合物來代替37.4重量份之上述式（2-1）所表示之化合物以外，以與上述「（式（1-1）所表示之化合物之製作）」相同之方式，獲得上述式（1-4）所表示之化合物（R為氫原子）。 上述式（1-4）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-4)) In addition to using 43.4 parts by weight of the compound represented by the above formula (2-4) instead of 37.4 parts by weight of the compound represented by the above formula (2-1), In the same manner as in the above "(Preparation of compound represented by formula (1-1))", the compound represented by the above formula (1-4) (R is a hydrogen atom) was obtained. The structure of the compound represented by the above formula (1-4) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（1-5）所表示之化合物之製作） 除使用46.4重量份之上述式（2-5）所表示之化合物來代替37.4重量份之上述式（2-1）所表示之化合物以外，以與上述「（式（1-1）所表示之化合物之製作）」相同之方式，獲得上述式（1-5）所表示之化合物（R為氫原子）。 上述式（1-5）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-5)) In addition to using 46.4 parts by weight of the compound represented by the above formula (2-5) instead of 37.4 parts by weight of the compound represented by the above formula (2-1), In the same manner as in the above "(Preparation of compound represented by formula (1-1))", the compound represented by the above formula (1-5) (R is a hydrogen atom) was obtained. The structure of the compound represented by the above formula (1-5) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（式（1-6）所表示之化合物之製作） 除使用55.4重量份之上述式（2-6）所表示之化合物來代替37.4重量份之上述式（2-1）所表示之化合物以外，以與上述「（式（1-1）所表示之化合物之製作）」相同之方式，獲得上述式（1-6）所表示之化合物（R為氫原子）。 上述式（1-6）所表示之化合物之結構藉由 1H-NMR、 13C-NMR及FT-IR來確認。 (Preparation of the compound represented by the formula (1-6)) In addition to using 55.4 parts by weight of the compound represented by the above formula (2-6) instead of 37.4 parts by weight of the compound represented by the above formula (2-1), In the same manner as in the above "(Preparation of compound represented by formula (1-1))", the compound represented by the above formula (1-6) (R is a hydrogen atom) was obtained. The structure of the compound represented by the above formula (1-6) was confirmed by 1 H-NMR, 13 C-NMR and FT-IR.
（實施例1～14、比較例1～9） 按照表1、2中所記載之摻合比，利用行星式攪拌裝置（Thinky公司製造之「去泡攪拌太郎」）對各材料進行攪拌後，利用陶瓷三輥研磨機混合均勻，從而獲得實施例1～14、比較例1～9之液晶顯示元件用密封劑。 (Examples 1-14, Comparative Examples 1-9) According to the blending ratios recorded in Tables 1 and 2, each material was stirred using a planetary stirring device ("Defoaming Stirring Taro" manufactured by Thinky Company), and then mixed uniformly using a ceramic three-roller mill to obtain the examples. 1-14. The sealing compound for liquid crystal display elements of Comparative Examples 1-9.
＜評價＞ 對實施例及比較例所獲得之各液晶顯示元件用密封劑進行以下評價。將結果示於表1、2。 ＜Evaluation＞ The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
（接著性） 藉由行星式攪拌裝置使1重量份之平均粒徑5 μm之間隔粒子（積水化學工業公司製造之「Micropearl SP-2050」）均勻分散於100重量份之實施例及比較例所獲得之各液晶顯示元件用密封劑中。取極微量之分散有間隔粒子之密封劑置於玻璃基板（20 mm×50 mm×厚度0.7mm）之中央部，將同形之玻璃基板重疊於其上。攤開液晶顯示元件用密封劑，使用金屬鹵素燈照射3000 mJ/cm 2之紫外線後，於120℃加熱1小時而使密封劑硬化，獲得接著試驗片。 對於所獲得之接著試驗片，使用張力計測定接著強度。將接著強度為2.5 kg/cm 2以上之情況設為「○」，將接著強度未達2.5 kg/cm 2之情況設為「×」，而對接著性進行評價。 (Adhesion) 1 part by weight of spacer particles with an average particle diameter of 5 μm ("Micropearl SP-2050" manufactured by Sekisui Chemical Co., Ltd.) was uniformly dispersed in 100 parts by weight of the samples of Examples and Comparative Examples by a planetary stirring device. In the sealing compound for each liquid crystal display element obtained. Take a very small amount of sealant dispersed with spacer particles and place it on the central part of the glass substrate (20 mm x 50 mm x thickness 0.7mm), and overlap the glass substrate of the same shape on it. The sealant for liquid crystal display elements was spread out, irradiated with ultraviolet rays of 3000 mJ/cm 2 using a metal halide lamp, and then heated at 120° C. for 1 hour to harden the sealant to obtain an adhesive test piece. The bonding strength of the obtained bonding test piece was measured using a tensiometer. The adhesion strength was evaluated as "○" when the adhesion strength was 2.5 kg/cm 2 or more, and "×" when the adhesion strength was less than 2.5 kg/cm 2 .
（防透濕性） 使用塗布機將實施例及比較例所獲得之各液晶顯示元件用密封劑以厚度成為200～300 μm之方式塗布於平滑之脫模膜上。繼而，使用金屬鹵素燈照射3000 mJ/cm 2之紫外線後，於120℃加熱1小時而使密封劑硬化，獲得透濕度測定用膜。利用依據JIS Z 0208之防濕包裝材料之透濕度試驗方法（杯式法）之方法製作透濕度試驗用杯，安裝所獲得之透濕度測定用膜，投入至80℃、90%RH之恆溫恆濕烘箱中，測定透濕度。將所獲得之透濕度之值未達60 g/m 2・24小時之情況設為「○」，將所獲得之透濕度之值為60 g/m 2・24小時以上且未達80 g/m 2・24小時之情況設為「△」，將所獲得之透濕度之值為80 g/m 2・24小時以上之情況設為「×」，而對防透濕性進行評價。 (Moisture permeability prevention) Each sealing compound for liquid crystal display elements obtained in the Example and the comparative example was coated on the smooth release film so that thickness may become 200-300 micrometers using the coater. Next, after irradiating 3000 mJ/cm 2 of ultraviolet rays using a metal halide lamp, the sealant was cured by heating at 120° C. for 1 hour, and a film for moisture permeability measurement was obtained. Make a cup for moisture permeability test according to the moisture permeability test method (cup method) of moisture-proof packaging materials according to JIS Z 0208, install the obtained film for moisture permeability measurement, and put it into a constant temperature of 80°C and 90%RH. In a humid oven, the moisture permeability was measured. If the obtained moisture permeability value is less than 60 g/m 2 · 24 hours, set it as "○", and if the obtained moisture permeability value is 60 g/m 2 · 24 hours or more, it is less than 80 g/ The case of m 2 ·24 hours was rated as "△", and the obtained value of moisture permeability was 80 g/m 2 ·24 hours or more was rated as "×" to evaluate the moisture permeability prevention.
（注射器殘留防止性） 將10 g之實施例及比較例所獲得之各液晶顯示元件用密封劑封入至注射器（武藏高科技公司製造之「PSY-10EU-OR」）中，安裝0.4 mmΦ之噴嘴。其後，使用桌上型塗布裝置（武藏高科技公司製造之「SHOTMASTER 300」）及空氣脈衝式點膠機（武藏高科技公司製造之「ML-808EX」），以100～400 kPa之壓力噴出密封劑，於15 cm×15 cm之玻璃基板上描繪出9個3.5 cm×3.5 cm之框狀密封圖案。繼而，向各密封圖案之框內滴下6 μL之液晶後，藉由真空壓接將基板貼合而製作單元，重複進行上述作業。此時，所有單元產生液晶洩漏時結束單元之製作，測量注射器內殘留之密封劑。 將注射器內殘留之密封劑未達3 g之情況設為「◎」，將注射器內殘留之密封劑為3 g以上且未達5 g之情況設為「○」，將注射器內殘留之密封劑為5 g以上之情況設為「×」，而對注射器殘留防止性進行評價。 (Syringe residue prevention) 10 g of each sealant for liquid crystal display elements obtained in Examples and Comparative Examples was sealed in a syringe ("PSY-10EU-OR" manufactured by Musashi High-Tech Co., Ltd.), and a nozzle of 0.4 mmΦ was attached. Then, use a desktop coating device ("SHOTMASTER 300" manufactured by Musashi High-Tech Co., Ltd.) and an air pulse dispenser ("ML-808EX" manufactured by Musashi High-Tech Co., Ltd.) to spray at a pressure of 100 to 400 kPa Sealant, draw nine frame-shaped sealing patterns of 3.5 cm x 3.5 cm on a glass substrate of 15 cm x 15 cm. Next, after dropping 6 μL of liquid crystal into the frame of each seal pattern, the substrates were bonded together by vacuum pressure bonding to produce a unit, and the above operation was repeated. At this time, when liquid crystal leakage occurred in all the cells, the production of the cells was terminated, and the sealant remaining in the syringe was measured. The case where the sealant remaining in the syringe is less than 3 g is marked as "◎", the case where the sealant remaining in the syringe is more than 3 g and less than 5 g is marked as "○", and the sealant remaining in the syringe is marked as "○". The case where it was 5 g or more was regarded as "x", and the syringe residue prevention property was evaluated.
[表1]
[表2]
根據本發明，可提供一種接著性、防透濕性及防止於注射器中掛壁之性能優異之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之液晶顯示元件。According to the present invention, it is possible to provide a sealant for a liquid crystal display element that is excellent in adhesiveness, moisture permeability prevention, and wall hanging prevention in a syringe. Moreover, according to this invention, the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.
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