TW201037029A - Photocurable composition for sealing liquid crystal display panel and liquid crystal display panel - Google Patents

Photocurable composition for sealing liquid crystal display panel and liquid crystal display panel Download PDF

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TW201037029A
TW201037029A TW099108446A TW99108446A TW201037029A TW 201037029 A TW201037029 A TW 201037029A TW 099108446 A TW099108446 A TW 099108446A TW 99108446 A TW99108446 A TW 99108446A TW 201037029 A TW201037029 A TW 201037029A
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liquid crystal
crystal display
display panel
manufactured
sealing
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TW099108446A
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Chinese (zh)
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TWI558754B (en
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Hiroyuki Takeda
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Dainippon Ink & Chemicals
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)

Abstract

The present invention provides a photocurable composition for sealing a liquid crystal display panel, wherein a nonionic surfactant comprising HLB value of more than 10 is 0.1 to 4 mass % relative to the total solid of photocurable composition. The nonionic surfactant is preferably alkylene oxide modified polydimethyl siloxane. The nonionic surfactant has excellent electrical properties and adherence (especially the material is plastic), as well as nonionic surfactant has excellent adherence relative to a substrate for liquid crystal cell comprising electrodes of SiOx, SiNx and ITO as a material of surface.

Description

201037029 六、發明說明： 【發明所屬之技術領域】 本發明係關於液晶顯示面板密封用光硬化性組成物’進 而詳言之，係關於光陽離子硬化性之液晶顯示面板密封用 光硬化性組成物。 【先前技術】 —般而言，液晶顯示面板之構成，係使具備薄膜電晶 體、像素電極、配向膜等的背面基板；及具備彩色濾光片' ^ 電極、配向膜等的前面基板相對向，封入液晶於兩基板間。 接著，以接著兩片基板爲目的，而使用密封劑。 近年來，目的在賦予液晶顯示面板之薄膜化或輕量化、 或可撓性，吾人有硏討將前面基板、或前背面基板雨者之 材質由以往的玻璃換成塑膠。但是，以往所使用的密封劑， 幾乎都是開發作爲玻璃用，欲照樣轉用則有困難。在使用 到以環氧系之熱硬化型樹脂爲主成分的熱硬化型密封劑之 q 情形，雖多是以150度硬化之情形，不過在上下基板之溫 度差，或者在貼合熱膨脹係數不同之基板彼此間之情形， 在冷卻面板至室溫爲止時，會有液晶顯示面板因而撓曲等 的問題。爲避免此問題之發生，吾人亦有嘗試在環氧樹脂， 添加二氧化矽等之無機固體酸或水楊酸等有機酸等的硬化 觸媒，在40°C以下低溫進行硬化反應的方法（參照例如專利 文獻1)，不過在硬化耗費過長時間，並非實用。 一方面，以丙烯酸酯等爲主成分之光硬化性密封劑（參 照例如專利文獻2)，雖在硬化熱並非必要，而由於短時間 201037029 可硬化，故適合於塑膠基板。但是丙烯酸酯，由於硬化收 縮大，故接著性弱，會因簡單的衝擊等而造成剝離，有實 用上的問題。又，周知有一種光熱硬化型密封劑，其係倂 用光硬化性成分與熱硬化成分，在最初以光硬化予以半硬 化後，藉由加熱（大體上是利用退火時之加熱）進行完全硬 化（例如專利文獻3至6)，但仍然相對於塑膠基板的接著性 弱，在實用上有問題。 一方面，有一種具有光二元硬化（binary curable)系的光 〇 硬化性密封劑，其係倂用：以環氧基等爲主成分之光陽離 子硬化性，與具有光自由基硬化性的丙烯酸酯等（參照例如 專利文獻7 )，其對硬化不需熱，不僅在短時間可進行硬化， 而且藉由利用光開環反應，而可大幅改善對有機保護層與 Si Ox之接著性。但是對SiNx或ITO電極基材表面之接著 性弱，會有限制可使用的基材之問題。 [先行技術文獻] Q 專利文獻 專利文獻1日本特開平1 1 - 1 5 3 8 0 0號公報 專利文獻2曰本特開2005 - 1 7 1 1 3 5號公報 專利文獻3日本特開平5-295087號公報 專利文獻4曰本特開2005-18022號公報 專利文獻5日本特開2〇〇6_23582號公報 專利文獻6曰本特開平3 _丨8 8丨8 6號公報 專利文獻7曰本特開2〇〇8_965 75號公報 201037029 【發明內容】 [發明欲解決課題] 本發明欲解決課題係提供一種液晶顯示面板密封用光 硬化性組成物，其具有優異電特性與接著性，尤其是以塑 膠爲材質’相對於液晶晶胞用基板，其具有使Si Ox、SiNx、 IT0電極成爲接著表面的基材，具有優異接著性者。 [解決課題之手段] 0 本發明人等’藉由少量添加非離子系界面活性劑於液晶 顯示面板密封用光硬化性組成物，則可解決上述課題。 界面活性劑因具有表面張力降低能，故主要在賦予或提 高濕潤性、滲透性、展延性（spreadability)、泡穩定性、流 動性、均平性、消泡性、乳化性、分散性、拒水拒油性之 目的下使用的添加劑。本發明人等，係首先發現特定的界 面活性劑，可增強液晶密封劑之接著性，而且不使電壓保 持率降低。 〇 亦即，本發明係提供一種液晶顯示面板密封用光硬化性 組成物，相對於光硬化性組成物固形物全量，含有HLB値 10以上的非離子系界面活性劑爲0.1〜4質量％。 又本發明係提供一種液晶顯示面板，其係使用前述記載 之液晶顯示面板密封用光硬化性組成物。 [發明效果] 藉由本發明，可獲得液晶顯示面板密封用光硬化性組成 物，其具有優異電特性與接著性，尤其是，以塑膠爲材質， 201037029 相對於液晶晶胞用基板，其具有使SiOx、SiNx、ITO電極 作爲接著表面的基材，本組成物具有優異接著性。 【實施方式】 (非離子系界面活性劑） 在本發明使用之非離子系界面活性劑方面，可使用例如 高級醇、高級胺、高級脂肪酸，或在聚矽氧主鏈加成環氧 烷之物。具體言之，較佳有例如聚氧乙烯烷醚、聚氧乙烯· 伸丙烷醚、聚氧乙烯烷苯醚、聚氧乙烯烷胺、聚氧乙烯脂 〇 肪酸醯胺、聚氧乙烯固醇、聚氧乙烯氫化固醇、聚氧乙烯 烷苯基甲醛縮合物、聚乙二醇脂肪酸乙醚、聚氧乙烯山梨 醇脂肪酸酯、聚氧乙烯山梨聚糖脂肪酸酯、聚甘油脂肪酸 酯、聚氧乙烯甘油脂肪酸酯、聚氧乙烯烷乙醚乙酸酯等， 更佳爲環氧烷改性聚二甲矽氧烷等環氧烷改性聚矽氧系界 面活性劑，因接著性增強作用優異且不致降低電壓保持率 故佳。[Technical Field] The present invention relates to a photocurable composition for sealing a liquid crystal display panel, and further relates to a photocurable composition for sealing a photocationic curable liquid crystal display panel. . [Prior Art] In general, a liquid crystal display panel is configured such that a rear substrate including a thin film transistor, a pixel electrode, an alignment film, and the like, and a front substrate having a color filter '^ electrode, an alignment film, and the like are opposed to each other The liquid crystal is enclosed between the two substrates. Next, a sealing agent is used for the purpose of following two substrates. In recent years, in order to provide thinning, weight reduction, or flexibility to a liquid crystal display panel, it has been suggested that the material of the front substrate or the front and back substrate rains be changed from conventional glass to plastic. However, almost all of the sealants used in the past have been developed as glass, and it is difficult to switch them to use. In the case of using a thermosetting sealant containing an epoxy-based thermosetting resin as a main component, it is often cured at 150 degrees, but the temperature difference between the upper and lower substrates is different, or the thermal expansion coefficient is different. In the case of the substrates, when the panel is cooled to room temperature, there is a problem that the liquid crystal display panel is deflected. In order to avoid this problem, we have tried to apply a hardening catalyst such as an inorganic solid acid such as cerium oxide or an organic acid such as salicylic acid to an epoxy resin at a low temperature of 40 ° C or lower ( For example, Patent Document 1) is used, but it takes a long time to harden, and it is not practical. On the other hand, a photocurable sealant containing acrylate or the like as a main component (see, for example, Patent Document 2) is not necessary for heat of hardening, and is hardenable in a short time 201037029, so it is suitable for a plastic substrate. However, since the acrylate has a large hardening shrinkage, the adhesiveness is weak, and peeling is caused by a simple impact or the like, which has a practical problem. Further, it is known that a photocurable sealant is a photocurable component and a thermosetting component which are semi-cured by photohardening at first, and then completely hardened by heating (generally by heating at the time of annealing). (for example, Patent Documents 3 to 6), but the adhesion to the plastic substrate is still weak, and there is a problem in practical use. On the other hand, there is a photocurable sealant having a binary curable system, which is used for photocationic hardening property mainly composed of an epoxy group or the like, and acrylic acid having photo-hardening property. Ester or the like (see, for example, Patent Document 7), which does not require heat for curing, can be hardened not only in a short period of time, but also can be greatly improved in adhesion to the organic protective layer and Si Ox by utilizing a photo-opening reaction. However, the adhesion to the surface of the SiNx or ITO electrode substrate is weak, and there is a problem that the substrate which can be used is limited. [PRIOR ART DOCUMENT] Patent Document 1 Patent Publication No. 1 1 - 1 5 3 8 0 0 Patent Document 2 曰本特开 2005 - 1 7 1 1 3 5 No. 5 Patent Document 3 Japanese Special Kaiping 5- Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a photocurable composition for sealing a liquid crystal display panel, which has excellent electrical characteristics and adhesion, particularly The plastic material is a substrate for a liquid crystal cell, and has a substrate having Si Ox, SiNx, and IT0 electrodes as a bonding surface, and has excellent adhesion. [Means for Solving the Problem] The inventors of the present invention have solved the above problems by adding a nonionic surfactant in a small amount to a photocurable composition for sealing a liquid crystal display panel. Since the surfactant has a surface tension reducing ability, it mainly imparts or improves wettability, permeability, spreadability, bubble stability, fluidity, leveling, defoaming, emulsifying, dispersing, and rejection. An additive used for the purpose of water repellency. The present inventors first discovered a specific surfactant which can enhance the adhesion of the liquid crystal sealing agent without lowering the voltage holding ratio. In other words, the present invention provides a photocurable composition for sealing a liquid crystal display panel, and the nonionic surfactant containing HLB 10 or more is 0.1 to 4% by mass based on the total amount of the solid of the photocurable composition. Further, the present invention provides a liquid crystal display panel using the photocurable composition for sealing a liquid crystal display panel described above. Advantageous Effects of Invention According to the present invention, it is possible to obtain a photocurable composition for sealing a liquid crystal display panel, which has excellent electrical properties and adhesion, and in particular, a plastic material, 201037029, with respect to a liquid crystal cell substrate, has The SiOx, SiNx, and ITO electrodes are used as the substrate on the surface, and the composition has excellent adhesion. [Embodiment] (Nonionic Surfactant) In terms of the nonionic surfactant used in the present invention, for example, a higher alcohol, a higher amine, a higher fatty acid, or an alkylene oxide-added alkylene oxide may be used. Things. Specifically, for example, polyoxyethylene alkyl ether, polyoxyethylene propane ether, polyoxyethylene alkyl ether, polyoxyethylene alkylamine, polyoxyethylene fatty acid decylamine, polyoxyethylene sterol are preferred. , polyoxyethylene hydrogen sterol, polyoxyethylene alkyl phenyl formaldehyde condensate, polyethylene glycol fatty acid ethyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyglycerin fatty acid ester, Polyoxyethylene glycerin fatty acid ester, polyoxyethylene alkyl ether acetate, etc., more preferably an alkylene oxide-modified polyoxonane surfactant such as an alkylene oxide-modified polydimethyloxane, which is enhanced by adhesion It is excellent in function and does not lower the voltage holding ratio.

具體言之，由即使少量添加由在聚矽氧主鏈加成環氧烷 的一般式（1)所示聚矽氧系界面活性劑，亦可賦予特優的接 著性之點觀之，更佳。 ⑴Specifically, even if a small amount of a polyoxynoxy surfactant represented by the general formula (1) added to the polyalkylene oxide main chain is added, a superior adhesion can be imparted, and good. (1)

201037029 該一般式（1)中，R表示氫原子、丁基或乙醯基；χ、y、 z、a及b表示重複單位之整數；X爲0SxS50; y爲l$y $10; z 爲 OSzSIO; a 爲 l$a$200; b 爲 OSbSlOO。 其中以該一般式（1)中環氧乙烷鏈之重複單位數a’更宜 爲aS 100 »藉由100，則由於在該一般式（1)所示之非離 子界面活性劑中，使得疏水性部分與親水性部分適度地混 在其中，故有密接性易於顯現的傾向。 該非離子性界面活性劑亦可具有環氧基。藉由具有環氧 〇 基，則因光陽離子硬化而被擷取於硬化性組成物之構造， 且因對密接性有利地作用，故佳。 該非離子系界面活性劑可使用市售品，可使用例如日光 化學品公司製之「BT」系列、三洋化成公司製之「Nonipol」 系列、竹本油脂公司製之「D-」 「P-」系列、Air products 公司製之「Sarfinol」系列、日信化學公司製之「〇mne」 系列、日本乳液公司製之「EM ALEX D APE」系列、Tor ay Dow Q Corning公司製或信越化學公司製等聚醚改性聚矽氧等。 在本發明中，該非離子系界面活性劑之H L B値爲1 〇以 上。最宜爲11至14。HLB値低於10時，易於失去對Si0x、 ITO、SiNx表面之密接性，一方面，HLB値超過15時，易 於產生對電特性之不良影響，故不佳。 此外，HLB値係以界面活性劑之親水性、親油性表示的 指標使用’有一些計算方法的提案，例如非離子系界面活 性劑HLB値可以下述式定義來求出。 201037029 HLB= [{(環氧乙烷鏈之分子量）/(界面活性劑之分子量）} xl00]+5 該非離子系界面活性劑藉由極少量添加本發明之液晶 顯示面板密封用光硬化性組成物（以下稱爲密封用光硬化 性組成物），則可發揮相對於以SiOx、SiNx或ITO電極作 爲接著表面之基材，可良好的接著具備該等構件的塑膠液 晶晶胞用基板。爲更提高接著力，相對於本發明密封用光 硬化性組成物之固形物全量，添加量宜爲0.1至4.0質量％ 〇 之範圍，最宜爲0.1至2.0質量％。添加量過多時，則產生 對液晶之溶離，產生招致電壓保持率之降低等電特性的影 響，故不佳。 (液晶顯示面板密封用光硬化性組成物） 本發明之液晶顯示面板密封用光硬化性組成物之硬化 形態，在自由基光硬化系、陽離子光硬化系、或倂用該等 之物之任一種均無妨，不過以倂用陽離子光硬化系或自由 Q 基光硬化系與陽離子光硬化系之物，由於光速硬化性，與 相對於表面具有SiOx、SiNx或IT0的基板之密接性的均衡 性優異，可更加發揮本發明之效果，故佳。 (陽離子光硬化系之組成物） 陽離子光硬化系之組成物（以下稱爲陽離子光硬化性組 成物），係含有陽離子聚合性化合物與陽離子光聚合引發劑 的組成物。陽離子聚合性化合物方面，只要是在UV硬化 之領域一般所使用的具有環氧基、氧雜環丁烷基、乙烯醚 201037029 基的周知慣用之化合物，則並無特別限定。但是，具有氧 雜環丁烷基的化合物，由於因聚合而產生的羥基量少，與 玻璃基板比較，因與變形大的塑膠基板之接著性有不利之 處，宜爲事先限制於少量之使用。 一分子中具有1個以上環氧基的陽離子聚合性化合物方 面，有例如雙酚A型環氧樹脂（DIC公司製之商品名「Epiclon 850CRP」、「Epiclon 850S」、「Ep i c 1 ο η 1 0 5 0」、「Epiclon 1 055」、雙酚F型環氧樹脂（DIC公司製之商品名「Epiclon 〇 830CRP」、「Epiclon 830」、雙酚S型谓氧樹脂（DIC公司 製之商品名「Epiclon EXA 1514」、氫化雙酚型環氧樹脂（DIC 公司製之商品名「Epiclon EXA7015」、環氧丙烷加成雙酚 A型環氧樹脂（旭電化公司製之商品名「EP-4000S」、間苯 二酹型環氧樹脂（Nagase Chemtex 公司製之商品名 ^ EX-201」）、聯苯基型環氧樹脂（日本環氧樹脂公司製之 商品名「Epikote YX-4000H」、二環戊二烯型環氧樹脂（旭 Q 電化公司製，商品名「EP_408 8S」、萘型環氧樹脂（DIC公 司製，商品名「Epiclon HP4032」、「Epiclon EXA-4700」 酚系酚醛清漆型環氧樹脂（DIC公司製，商品名^ Epiclon N-770」、原甲酚酚醛清漆型環氧樹脂（DIC公司製，商品名 「Epiclon N-67 0-EXP-S」'NC-3000P(日本化藥公司製）等聯 苯基酚醛清漆型環氧樹脂、ESN-165S(東都化成公司製）等 萘酚系酚醛清漆型環氧樹脂、Epikote 630(日本環氧樹脂公 司製）、橡膠改性型環氧樹脂（Daicel化學公司製，商品名 201037029 「1^3600」、雙酚A型環氧硫化物樹脂（日本環氧樹脂公司 製，商品.名「Epikote YL-7000」等。脂環式環氧樹脂（Daicel 化學公司，製商品名「Celloside 2021」、「Celloside2080」、 「Celloside 3000」、「ΕΗΡΕ」等。 在具有上述1個以上乙烯醚基的陽離子聚合性化合物之 市售品方面，可例舉4-乙烯氧丁醇（BASF公司製，商品名 「乙烯-4-羥丁醚」、三乙二醇二乙烯醚（ISP公司製，商品 ^ 名「Rapi-Cure DVE-3」、1,4-環己烷二甲醇二乙烯醚（日本 〇201037029 In the general formula (1), R represents a hydrogen atom, a butyl group or an ethyl fluorenyl group; χ, y, z, a and b represent an integer of a repeating unit; X is 0SxS50; y is l$y $10; z is OSzSIO ; a is l$a$200; b is OSbSlOO. Wherein the repeating unit number a' of the ethylene oxide chain in the general formula (1) is more preferably aS 100 » by 100, because in the nonionic surfactant represented by the general formula (1), Since the hydrophobic portion and the hydrophilic portion are moderately mixed therein, the adhesion tends to be easily exhibited. The nonionic surfactant may also have an epoxy group. When the epoxy ruthenium group is provided, the photocationic cation is hardened and the structure is extracted from the curable composition, and it is preferable because it acts favorably on the adhesion. For the non-ionic surfactant, a "BT" series manufactured by Nippon Chemical Co., Ltd., "Nonipol" series manufactured by Sanyo Chemical Co., Ltd., and "D-" "P-" series manufactured by Takeshi Oil Co., Ltd. can be used. "Sarfinol" series manufactured by Air Products Co., Ltd., "〇mne" series manufactured by Nissin Chemical Co., Ltd., "EM ALEX D APE" series manufactured by Nippon Emulsion Co., Ltd., or manufactured by Tor ay Dow Q Corning Co., Ltd. or Shin-Etsu Chemical Co., Ltd. Ether-modified polyfluorene and the like. In the present invention, the nonionic surfactant has a H L B値 of 1 Å or more. The most suitable is 11 to 14. When the HLB 値 is less than 10, the adhesion to the surfaces of Si0x, ITO, and SiNx tends to be lost. On the other hand, when the HLB 値 exceeds 15, it is liable to cause adverse effects on electrical characteristics, which is not preferable. Further, the HLB oxime is used as an index indicating the hydrophilicity and lipophilicity of the surfactant. There are proposals for some calculation methods. For example, the nonionic surfactant HLB 値 can be obtained by the following formula. 201037029 HLB=[{(molecular weight of ethylene oxide chain)/(molecular weight of surfactant)} xl00]+5 The nonionic surfactant is composed of a light curable composition for sealing a liquid crystal display panel of the present invention by a small amount. In the case of the substrate (hereinafter referred to as a photocurable composition for sealing), a substrate for a plastic liquid crystal cell which can be satisfactorily provided with the SiOx, SiNx or ITO electrode as a substrate. In order to further increase the adhesion, the total amount of the solid matter of the photocurable composition for sealing of the present invention is preferably in the range of 0.1 to 4.0% by mass, and most preferably 0.1 to 2.0% by mass. When the amount of addition is too large, the dissolution of the liquid crystal occurs, and the influence of the electrical characteristics such as a decrease in the voltage holding ratio is caused, which is not preferable. (Photocurable composition for sealing a liquid crystal display panel) The cured form of the photocurable composition for sealing a liquid crystal display panel of the present invention is used in a radical photocuring system, a cationic photocuring system, or the like. Any one of them may be used, but a cationic photohardening system, a free Q-based photocuring system, and a cationic photocuring system have a balance of adhesion to a substrate having SiOx, SiNx or IT0 with respect to the surface due to the light-speed hardening property. It is excellent, and the effect of the present invention can be further exerted, so it is preferable. (Composition of cationic photocuring system) The composition of the cationic photocuring system (hereinafter referred to as a cationic photocurable composition) is a composition containing a cationically polymerizable compound and a cationic photopolymerization initiator. The cationically polymerizable compound is not particularly limited as long as it is a conventionally known compound having an epoxy group, an oxetanyl group or a vinyl ether 201037029 group which is generally used in the field of UV curing. However, the compound having an oxetane group has a small amount of hydroxyl groups due to polymerization, and is disadvantageous in adhesion to a plastic substrate having a large deformation as compared with a glass substrate, and is preferably limited to a small amount in advance. . For the cationically polymerizable compound having one or more epoxy groups in one molecule, for example, a bisphenol A type epoxy resin (trade name "Epiclon 850CRP", "Epiclon 850S", "Ep ic 1 ο η 1" manufactured by DIC Corporation 0 5 0", "Epiclon 1 055", bisphenol F type epoxy resin (trade name "Epiclon 〇 830CRP" manufactured by DIC Corporation, "Epiclon 830", bisphenol S type oxygen resin (trade name of DIC company) "Epiclon EXA 1514", hydrogenated bisphenol type epoxy resin (trade name "Epiclon EXA7015" manufactured by DIC Corporation, propylene oxide addition bisphenol A type epoxy resin (trade name "EP-4000S" manufactured by Asahi Kasei Corporation" , benzophenone type epoxy resin (product name: EX-201 manufactured by Nagase Chemtex Co., Ltd.), biphenyl type epoxy resin (product name "Epikote YX-4000H" manufactured by Nippon Epoxy Co., Ltd., second ring Pentadiene type epoxy resin (product name "EP_408 8S", manufactured by Asahi Denki Co., Ltd., naphthalene type epoxy resin (trade name "Epiclon HP4032", "Epiclon EXA-4700" phenolic novolak type ring made by DIC Corporation) Oxygen resin (made by DIC company, trade name ^ Epiclon N-77 0", a cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name "Epiclon N-67 0-EXP-S" 'NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) Naphthol novolac type epoxy resin such as resin, ESN-165S (manufactured by Tohto Kasei Co., Ltd.), Epikote 630 (manufactured by Nippon Epoxy Co., Ltd.), and rubber-modified epoxy resin (manufactured by Daicel Chemical Co., Ltd., trade name 201037029 " 1^3600", bisphenol A type epoxy epoxide resin (manufactured by Nippon Epoxy Co., Ltd., product name "Epikote YL-7000", etc. alicyclic epoxy resin (Daicel Chemical Co., Ltd., trade name "Celloside 2021" "Celloside 2080", "Celloside 3000", "ΕΗΡΕ", etc. The commercially available product of the cationically polymerizable compound having one or more vinyl ether groups may, for example, be 4-vinyloxybutanol (manufactured by BASF Corporation). Trade name "ethylene-4-hydroxybutyl ether", triethylene glycol divinyl ether (manufactured by ISP, product name "Rapi-Cure DVE-3", 1,4-cyclohexane dimethanol divinyl ether (Japan 〇

Carbide工業公司製，商品名「CHDVE」等。 一分子中具有1個以上氧雜環丁烷基的陽離子聚合性化 合物方面，有例如3-乙基-3-(苯氧甲基）氧雜環丁烷（東亞合 成公司製，商品名「0XT-211」、3-乙基-3-(環己基）甲基氧 雜環丁烷（東亞合成公司製，商品名「CH0X」等。具有氧 雜環丁烷環2個以上的化合物方面，可例舉1，4-雙[{(3-乙 基氧雜環丁烷-1基）甲氧基}甲基]苯（東亞合成公司製，商 〇 品名「0XT-121」）、1,3-雙[(3-乙基氧雜環丁烷-3基）甲氧 基]苯（東亞合成公司製之商品名「OXT-223」、雙[1-乙基（3-氧雜環丁烷）]甲醚（東亞合成公司製，商品名「OXT-221」、 酚系酚醛清漆氧雜環丁烷（東亞合成公司製，商品名 「PNOX- 1 009」）、4,4’ -雙[{(3-乙基氧雜環丁烷-1基）甲氧 基}甲基]聯苯基（宇部興產公司製，商品名「0XBP」）。 上述陽離子聚合性化合物之中，藉由芳香環彼此間相互 作用的利用而可獲得凝聚力，因對接著有利，故特佳爲具 -10- 201037029 有具芳香環之環氧基的聚合性化合物。具體言之，可例舉 雙酚A型環氧樹脂（DIC公司製，商品名「Epiclon 850CRP」、 「Epiclon 850S j 、「Epiclon 1 050」、「Epiclon 1 055」、 雙酚F型環氧樹脂（DIC公司製，商品名「Epiclon 830CRP」、 「Epiclon 830」等。 由於黏度特低，與一般式（1)所示化合物之稀釋效果亦 高，故特佳爲雙酚A型環氧樹脂（DIC公司製，商品名 「Epiclon 8 5 0CRP」）、雙酚F型環氧樹脂（DIC公司製，商 〇 品名「Epiclon 830CRP」）。 又，在陽離子光聚合引發劑方面，可例舉例如芳香族重 氮鹽、芳香族碘鐵鹽、芳香族鎏鹽等鎗鹽。在使用該陽離 子光聚合引發劑之情形，照射之光的波長區域之較佳下限 爲300nm，較佳上限爲420nm。 在該等鎗鹽中，市售方面，有例如 Optomer SP-150、 Optomer SP-151、Optomer SP-170、Optomer SP-171(均爲旭 Q 電化工業公司製）、UVE-1014(通用電子公司製）、Irgacure 261(Ciba Geigy 公司製）、Sunaid SI-60L、Sunaid SI-80L、 UVI-6990(Union Carbide 公司製）、BBI-103、MPI-103、 TPS-103、MDS-103、DTS-103、NAT-103、NDS-103(均爲綠 化學公司製）、Sunaid SI-100L(均爲三新化學工業公司製）、 CI-2064、CI-2639、CI-2624、CI-248 1 (均爲日本曹達公司 製）' 光起始劑 2074(Rhone Poulenc 公司製）、 CD-1012(Sartomer 公司製）等。其中，以 Optomer SP-150， 201037029 因難以引起鑰鹽所致電極腐蝕，且易於獲得實效上的硬化 性，故更佳。 該陽離子光聚合引發劑可單獨使用，亦可倂用二種以 上。又，可因應需要倂用蒽系、噁烷9-氧硫岫嗶系等增感 劑。又該陽離子光聚合引發劑之混合比率方面並無特別限 定，通常相對於陽離子聚合性化合物全量，可在0.1至10 質量％之範圍內使用。小於0.1質量％時，會有本發明密封 劑之硬化性不充分之可能性。超過10質量％時則會有不能 〇 充分反應的陽離子光聚合引發劑殘存，而有溶出於液晶的 可能性。其中宜爲0.3至3質量％。 (自由基光硬化系之組成物） 自由基光硬化系之組成物（以下稱爲自由基光硬化性組 成物）係指，含有自由基聚合性化合物與自由基光聚合引發 劑的組成物。在自由基聚合性化合物方面，只要是在UV 硬化之領域一般所使用的具有（甲基）丙烯醯基的周知慣用 Q 之化合物，則並無特別限定，在使用作爲液晶顯示面板密 封用之情形，則以難與液晶作緊密混合之物可更適當的使 用。但，爲了避免過度之硬化收縮，則較佳係使硬化收縮 變大之五及六丙烯酸二新戊四醇酯、四丙烯酸新戊四醇酯 等的（甲基）丙烯酸酯事先限制於少量之使用。又，具有羧 酸基的自由基聚合性化合物，由於在保存中與環氧基反 應，會有使組成物黏度急遽上升之虞，故事先限於少量之 使用則佳。 -12- 201037029 在UV硬化之領域中，稱爲「光聚合性寡聚物」，在主 鏈構造具有酯鍵，具有至少二個以上（甲基）丙烯醯基的聚 酯（甲基）丙烯酸酯；以環氧氯丙烷改性而得的環氧（甲基） 丙烯酸醋；乙醚（ethyl oxide);以環氧丙烷、環狀內酯等改 性的（甲基）丙烯酸酯等亦可適當的使用。但，具有胺基甲 酸酯基的丙烯酸酯，在與陽離子硬化系組合之情形，因會 引起胺基甲酸酯基所致硬化阻礙，故宜爲事先限制於少量 使用。 ❹ 本發明所使用（甲基）丙烯酸酯之具體例方面，有例如單 甲基丙烯酸甘油酯（日本油脂公司製，商品名「Bremmer GLM」）、鄰苯二酸丙烯醯氧乙酯（共榮公司化學公司製，商 品名「H0A-MPE」）、（甲基）丙烯酸苄酯（大阪有機化學公司 製，商品名「bisuko-to#160」）、壬基苯氧基聚丙烯酸乙二 醇酯（東亞合成公司製，商品名「人^11。5厘111」）、「六1'01148 M113」、「AronicsM117」）、ECH改性丙烯酸苯氧酯（東亞 Q 合成公司製，商品名「Aronics M5700」）、E0改性琥珀酸 丙烯酸酯（共榮社化學公司製，商品名^ H0A-MS」）、E0 改性磷酸甲基丙烯酸酯（共榮社化學公司製，商品名 「P-1M」）、松香改性丙烯酸環氧酯（荒川化學公司製，商 品名「beam set 101」）等，具有1個（甲基）丙烯醯基的（甲 基）丙烯酸酯；異三聚氰酸雙（丙烯醯乙基）羥乙酯（東亞合成 公司製，商品名「Aronics M2 15」）、E◦改性雙酚A二丙烯 酸酯（日本油脂公司製，商品名「ADPE-150」）、P0改性雙 -13- 201037029 酚A二丙烯酸酯（日本油脂公司製，商品名「ADBP-200」）、 ECH改性雙酚A型丙烯酸酯（DIC化學公司製，商品名 「DICLITE UE8200」）、ECH改性酞酸二丙烯酸酯（Nagase 化成公司製，商品名「DA-721」）、ECH改性六氫酞酸二丙 烯酸酯（Nagase化成公司製，商品名「DA-722」）、二丙烯 酸三環癸烷二甲醇酯（Daicel UCB公司製，商品名 ^ IRR214」）、松香改性酯丙烯酸酯（荒川化學公司製，商 品名「beam set 1 15B」）、EO改性磷酸二甲基丙烯酸酯（共 〇 _ 榮社化學公司製，商品名「P-2M」）、參（丙烯醯氧乙基）異 三聚氰酸酯（東亞合成公司製，商品名「AronicsM315」）、 四丙烯酸二羥甲丙酯（東亞合成公司製，商品名「Aronics M408」）、六丙烯酸二新戊四醇酯（日本化藥公司製，商品 名「Kayarad DPHA」）、己內酯改性六丙烯酸二新戊四醇酯 (日本化藥公司製，商品名「Kayarad DPCA-30」、「Kayarad DPCA-120」）等’具有2個以上（甲基）丙烯醯基的（甲基）丙 Q 烯酸酯等。 尤其是，在上述自由基聚合性化合物中，特佳係以內酯 改性的（甲基）丙烯酸酯、以松香改性的（甲基）丙烯酸酯，因 可使硬化性組成物具有柔軟性，且使密接性更有利。具體 言之’可例舉內酯改性二丙烯酸羥三甲基乙酸新戊二醇酯 (日本化藥公司製’商品名「HX620」）、內酯改性BPA環氧 酞酸酯二丙烯酸酯（Daicel cytec公司製，商品名「Ebecryl -14- 201037029 37 08」）、松香改性丙烯酸環氧酯（荒川化學公司製，商品名 「beam set 101」等。 該（甲基）丙烯酸酯之使用量，只要不損及本發明之範 圍，則並無特別限定。具體言之，相對於本發明密封用光 硬化性組成物之固形物全量宜爲20至70質量％之範圍。 又，在自由基光聚合引發劑方面，可使用例如二苯酮、 2,2-二乙氧乙醯苯、苄基、苯甲醯基異丙醚、苄二甲縮酮、 1-羥環己苯酮、噁烷9-氧硫卩III喔等。該等自由基光聚合引 〇 發劑可單獨使用，亦可倂用二種以上。 又，亦可使用具有光開始能的順丁烯二醯亞胺化合物。 在具有光開始能的順丁烯二醯亞胺化合物之具體例方面， 可例舉例如日本特開 2000-19868號公報、日本特開 2004-070297號公報記載之順丁烯二醯亞胺化合物。 該自由基光聚合引發劑可單獨使用，亦可倂用二種以 上。又該自由基光聚合引發劑之混合比率方面雖無特別限 〇 定，不過相對於自由基聚合性化合物全量，宜在0.1至20 質量％之範圍內使用。小於0.1質量％時，會有本發明密封 劑之硬化性不充分的可能性，在超過1 0質量％時，則會有 不能充分反應的陽離子光聚合引發劑殘留，而有溶出於液 晶的可能性。其中宜爲0.3至10質量％❶ 又，在倂用自由基光硬化系與陽離子光硬化系之情形， 亦可使用具有自由基聚合性基與陽離子聚合性基兩者之基 的化合物。在具有自由基聚合性基與陽離子聚合性基兩者 -15- 201037029 之基的聚合性化合物方面’有例如，市售之BPF環氧半丙 烯酸酯或BPA環氧半丙烯酸酯（Daicel cytec公司製’商品 名「UVal561」），或使一分子中具有複數環氧基的化合物 之環氧基一部分與（甲基）丙烯酸反應’成爲（甲基）丙烯醯基 化的化合物。 其中BPA環氧半丙烯酸酯、BPF環氧半丙烯酸酯與一般 式（1)所示化合物之稀釋效果高’更佳。 本發明中，若係與自由基光硬化系與陽離子光硬化系倂 〇 用之物，具體言之，在該組成物中，若作爲自由基光硬化 系的（甲基）丙烯醯基，與作爲陽離子光硬化系的環氧基爲 共存的組成物時，則因光照射，而使環氧基進行陽離子聚 合，（甲基）丙烯醯基進行自由基聚合而硬化，因相對於基 板而堅固地接著，故更佳。在該情形，爲了使硬化更有效 率的進行聚合，宜爲在該光硬化性組成物中，倂用：使環 氧基進行陽離子聚合的陽離子光聚合引發劑；使（甲基）丙 〇 烯醯基進行自由基聚合的自由基光聚合引發劑。 (其它成分 矽烷偶合劑） 又，在本發明之液晶顯示面板密封用光硬化性組成物， 爲了提高接著性，亦可混合周知慣用之矽烷偶合劑。即使 在此種矽烷偶合劑之中，具有（甲基）丙烯醯基或環氧基等 聚合性基的矽烷偶合劑，在光硬化時，則與該一般式（1)戶斤 示化合物等共聚，由於可獲得高度接著性，故佳。 -16- 201037029 在具有聚合性基的矽烷偶合劑方面，可例舉例如3-(甲 基）丙烯醯氧丙基三甲氧矽烷、3-環氧基氧丙基三甲氧矽烷 等。在具有此種聚合性基的矽烷偶合劑之市售品方面，有 例如信越化學公司製，商品名「KBM5 03」、「KBE503」、 「KBM502」、「KBE502」、「KBM5102j、「KBM5103」、 「KBM403」等。 相對於全硬化性組成物量，倂用該矽烷偶合劑情形之使 用量，宜爲在0.1至10質量％之範圍使用，特宜爲在1至5 〇 質量％之範圍。矽烷偶合劑之比率小於0.1質量％時，會無 法獲得充分接著效果，在超過10質量％之量，有引起相分 離之可能性。更佳的下限爲0.5質量份，更佳的上限爲5 質量份。 (其它成分其它） 在本發明之密封用光硬化性組成物，因應黏度調整或保 存穩定性等目的，亦可添加周知慣用之添加劑、塡充劑。 Q 例如塡充劑係因應力分散效果所致本發明密封用光硬 化性組成物之接著性改善，及線膨脹率改善等目的而添加 的。有例如：滑石、石綿、二氧化砂、砍藻土（diatomaceous)、 膨潤石（smectite)、島土（Bentonite)、碳酸釣、碳酸鎂、氧 化鋁、蒙脫石、矽藻土、氧化鎂、氧化鈦、氫氧化鎂、氫 氧化鋁、玻璃珠、硫酸鋇、石膏、矽酸鈣、滑石、玻璃珠、 絹雲母活性石膏粉（sericite terra abla)、皂土（Bentonite)等 -17- 201037029 無機充塡劑或聚酯微粒子、聚胺基甲酸酯微粒子、乙烯聚 合體微粒子、丙烯酸聚合體微粒子等有機充塡劑等。 上述塡充劑之混合比率方面並無特別限定，相對於上述 硬化性組成物量，宜爲1至1 00質量％。在1質量％以下， 則幾乎無法得到添加塡充劑的效果，在超過100質量％之 量，則有降低本發明密封用光硬化性組成物之繪圖性等操 作性之虞。更佳的下限爲5質量份，更佳的上限爲50質量 份。 〇 (黏度） 本發明之液晶顯示面板密封用光硬化性組成物，若使用 E型黏度計，在25°C測定的黏度爲lOOPa · s以上時，作爲 後述滴下法（dropping method)所致液晶顯示元件之製造用 液晶密封劑可更佳的使用。 在小於lOOPa · s時，藉由滴下法來製造液晶顯示面板 時，則無法保持形成於透明基板上的密封圖型之形狀，會 Q 在液晶中使密封劑成分溶離而造成液晶污染。更佳的下限 爲100Pa*s，更佳的上限爲500Pa*s。在超過500Pa*s時， 則本發明密封劑之繪圖性不夠充分，會使滴下法所致液晶 顯示面板之製造變得困難。此時，在測定黏度的E型黏度 計方面並無特別限定，可使用例如 Brookfield公司製 「DV-III」等。 (液晶顯示面板用密封劑） -18- 201037029 本發明之液晶顯示面板密封用光硬化性組成物，可在製 成液晶顯示面板時作爲密封劑，又，在液晶顯示面板注入 液晶材料後，可使用作爲封閉注入口的封閉劑。 液晶顯示面板係例如，具備薄膜電晶體、像素電極、配 向膜、彩色濾光片、電極等的前面，或背面基板之任一者 的基板面上，塗布本發明之液晶顯示面板密封用光硬化性 組成物後，貼合另一方之基板，自該基板之基板面側，或 自該基板之側面照射光，將本發明液晶顯示面板密封用光 Ο 硬化性組成物硬化。接著，在所得之液晶晶胞注入液晶後， 藉由以封閉劑封閉注入口，而製成液晶顯示面板。 又，液晶顯示面板係在該任意一方之基板面之外緣部， 塗布本發明液晶顯示面板密封用光硬化性組成物成爲畫框 狀，在使液晶滴下於其中後，在真空下，在貼合另一方之 基板之後，可藉由光硬化之方法而製成。 要塗布本發明液晶顯示面板密封用光硬化性組成物於 Q 基板面，就得使用分配器（dispenser)，或使用網版印刷法。 在此情形，一般是塗布成線寬0.08至0.1mm，線高度5至 50 u m。 爲了硬化本發明液晶顯示面板密封用光硬化性組成物 而使用之光宜爲紫外線或可視光線，其中宜爲300nm至 4OOnm波長之光。在光源方面，可使用例如高壓汞燈、金 屬鹵素燈等。該光源之照度爲5 00 W/m2以上時，硬化快較 佳。照射之光量，換算成累計光量只要爲2000(H/m2以上， -19- 201037029 則可良好地硬化。又，本發明之液晶顯示面板密封用光硬 化性組成物，即使在空氣環境下亦可顯示良好的光硬化 性，不過若在氮等惰性氣體環境下予以光硬化時，因可以 少量的累計光量使之硬化，故更佳。 實施例 茲依照實施例及比較例具體說明本發明如下。在實施 例、比較例中之「份」在無特別說明下，則表示「質量份」。 此外，關於接著性、電壓保持率之評價則以下列方式進行。 Ο <使用於接著劑試驗的基材> (全面附（SiN)x玻璃） 在厚度0.7mm之無驗玻璃板（Corning公司製，製品名 「cornig 1 7 37」）表面全面，以濺鍍形成厚度約50nm之（SiN)x 層，成爲附（SiN)x無鹼玻璃板。 (全面附IT0塑膠薄膜） 使用遍及全面形成有IT0膜的聚醚楓薄膜（住友Bakelite Q 公司製，商品名「FS-5 300」。 (全面丙烯酸塗布玻璃） 在厚度 0.7mm之無鹼玻璃板（Corning公司製製品名 「cornig 1 7 37」表面全面，依照日本專利第3321858號公報 記載之實施例1，塗布丙烯酸，成爲全面附丙烯酸塗布無 鹼玻璃板。 (全面附（SiN)x塑膠薄膜） -20- 201037029 在厚度0.125mm之聚碳酸酯薄膜（帝人化成之商品名 「Panlite」）之全面依照日本特開2006_57121號公報之實施 例3的實施例C ’形成厚度50nm之（SiN)x層，製成附 (SiN)xPC薄膜基板。 (全面附（SiO)x塑膠薄膜） 使用到將SiOx層濺鍍形成的附（SiO)xPES薄膜基板（住 友 Bakelite 商品名「FST1 300」。 (全面附ITO玻璃） 〇 在厚度 0.7mm之無鹼玻璃板（Corning公司製製品名 「cornig 1737」表面全面，濺鍍形成IT◦層，以成爲表面 電阻100Ω，並製成附IT0無鹼玻璃板。 <使用接著劑試驗的基材之組合> 該基板之組合係如下述。 組合A :全面附IT0塑膠薄膜/全面附（SiN)x玻璃 組合B :全面附IT0塑膠薄膜/全面丙烯酸塗布玻璃 Q 組合C :全面附（SiN)x塑膠薄膜/全面附（SiN)x玻璃 組合D :全面附（SiN)x塑膠薄膜/全面丙烯酸塗布玻璃 組合E :全面附（SiO)x塑膠薄膜/全面附（SiN)x玻璃 組合F :全面附（SiO)x塑膠薄膜/全面附ITO玻璃 <接著性試驗組合A之例> 在後述之密封用光硬化性組成物，添加平均粒徑約5.5 # m球狀間隔件「Hayabeads L-11S」1質量％，使用攪拌脫 -21- 201037029 泡機（Thinky公司製，商品名「脫泡錬太郎AR250」）進行 攪拌•脫泡，做成試料。 自裝備了 〇.2mm徑之精密噴嘴的注射器前端排出該試 料，使用桌上型塗布機器人（武藏工程公司製，商品名「SH〇T MINI」）’在預先切去I50mmxl5mm的「全面附IT0塑膠薄 膜」上’跨越9cm長度而塗布成直線狀，以與該基板之長 軸方向平行，在其上’使「全面附（SiN)x玻璃（大小95x15mm) q 予以重疊，以使該面與該塑膠薄膜之面平行。 接著使用EHC公司之附石英窗加壓硬化裝置，在經 0.1 MPa、2分鐘加壓後，在原力日壓之狀態下，自該「全面 附（SiN)x玻璃」側，使用高壓金屬鹵素燈，照射500W/m2 之紫外線40秒。此時之照射，係通過該附石英窗加壓硬化 裝置之石英窗，在空氣環境下進行。藉此，而獲得接著寬 1mm，接著層厚度爲5.5//m之評價樣本。 將已貼合的該評價樣本，進行JIS K 6854-1記載的浮動 Ο 輥（floating roller)法剝離試驗（以100mm/分速度經90度剝 離），同樣地藉由以JIS K 6854- 1記載之最適直線法所求得 之剝離負荷（mN)除以接著寬度，而求得接著強度（mN/mm)。 <電壓保持率試驗用液晶顯示面板之製成> 1.液晶顯示面板製作1(注入方式） 在EHC公司製之附IT0玻璃基板「RZ-B107N1N」1片上， 噴霧早川橡膠公司製間隔件「LH1 1S」之5%乙醇分散液。 接著在另1片之附IT0玻璃基板上，各自使用分配器，以 -22- 201037029 約1 mm寬塗布密封用光硬化性組成物，用以設置2處液晶 注入口於基板外緣部，其後，使2片玻璃基板相對向並貼 合，在氮氣環境下，使用高壓金屬鹵素燈，使500W/m2之 紫外線照射於該密封劑部分40秒，來製作2孔晶格。在真 空下，將TFT(薄膜電晶體）驅動用液晶組成物（組成如後述） 注入2孔晶格，使該液晶組成物製成光罩以不直接曝露於 紫外線，其後，以密封用光硬化性組成物封閉2孔，在氮 氣環境下，使用高壓金屬鹵素燈，再照射500W/ m2之紫外 0 線40秒，來製作液晶顯示面板。 2.液晶顯示面板製作2(滴下法方式） 準備EHC公司製玻璃基板RS-B107M1N(硏磨完成之附定 向膜、附ITO)2片，其一片噴霧早川橡膠公司製之間隔件 「LH11S」之5%乙醇分散液。接著，在另一片玻璃基板， 使用分配器，將實施例6製作的密封材，在基板外緣部以 密封寬約1mm塗布成矩形。接著，在該基板上之矩形上密 封劑之內側，在真空下，滴下適當量TFT(薄膜電晶體）驅動 q 用液晶組成物（組成如後述），使2片玻璃基板之硏磨方向 呈正交並貼合，以製作晶格。使該晶格回至大氣壓下，使 基板間之間隔成爲間隔件之尺寸後，使用高壓金屬鹵素 燈，對該密封劑部分照射500W/m2之紫外線40秒，來製作 TN型之液晶顯示面板。 將該液晶顯示面板在2片呈正交之偏光板間，調 整光學軸並予以夾住（pinch)，製成液晶顯示元件。 在不外加電壓時，觀看呈透明，成爲明亮顯示，若 -23- 201037029 外加電壓時，晶格之電極部分並不通過光而成爲暗黑顯 示，顯示良好的顯示狀態。 3.使用於液晶顯示面板作成的TFT(薄膜電晶體）驅動用 液晶組成物 本實施例使用之TFT(薄膜電晶體）驅動用液晶組成物方 面，係使用以下三種。Carbide Industrial Co., Ltd., trade name "CHDVE", etc. In the case of a cationically polymerizable compound having one or more oxetanyl groups in one molecule, for example, 3-ethyl-3-(phenoxymethyl)oxetane (manufactured by Toagosei Co., Ltd., trade name "0XT" -211", 3-ethyl-3-(cyclohexyl)methyloxetane (manufactured by Toagosei Co., Ltd., trade name "CH0X", etc., which has two or more compounds of oxetane ring, Illustratively, 1,4-bis[{(3-ethyloxetane-1yl)methoxy}methyl]benzene (manufactured by Toagosei Co., Ltd., trade name "0XT-121"), 1,3 - bis[(3-ethyloxetane-3-yl)methoxy]benzene (trade name "OXT-223", manufactured by Toagosei Co., Ltd., bis [1-ethyl (3-oxetane) )] Methyl ether (trade name "OXT-221", phenolic novolac oxetane (manufactured by Toagosei Co., Ltd., trade name "PNOX-1 009"), 4,4'-double {(3-Ethyloxetane-1yl)methoxy}methyl]biphenyl (manufactured by Ube Industries, Ltd., trade name "0XBP"). Among the above cationically polymerizable compounds, by aromatic Coagulation can be obtained by utilizing the interaction of the rings with each other The force is advantageous for the subsequent ones, and it is particularly preferably a polymerizable compound having an epoxy group having an aromatic ring of -10-201037029. Specifically, a bisphenol A type epoxy resin (trade name, manufactured by DIC Corporation) can be exemplified. "Epiclon 850CRP", "Epiclon 850S j", "Epiclon 1 050", "Epiclon 1 055", bisphenol F-type epoxy resin (made by DIC, trade name "Epiclon 830CRP", "Epiclon 830", etc. Low, and the dilution effect of the compound represented by the general formula (1) is also high, so it is particularly preferred to be a bisphenol A type epoxy resin (trade name "Epiclon 8 5 0 CRP", manufactured by DIC Corporation), and a bisphenol F type epoxy resin. (The product name "Epiclon 830CRP", manufactured by DIC Corporation). The cationic photopolymerization initiator may, for example, be a gun salt such as an aromatic diazonium salt, an aromatic iodine salt or an aromatic sulfonium salt. In the case of the cationic photopolymerization initiator, a preferred lower limit of the wavelength region of the irradiated light is 300 nm, and a preferred upper limit is 420 nm. Among the gun salts, commercially available, for example, Optomer SP-150, Optomer SP-151 , Optomer SP-170, Optomer SP-171 (both Asahi Electric Industrial Co., Ltd.), UVE-1014 (manufactured by General Electric Co., Ltd.), Irgacure 261 (manufactured by Ciba Geigy Co., Ltd.), Sunaid SI-60L, Sunaid SI-80L, UVI-6990 (manufactured by Union Carbide Co., Ltd.), BBI-103 , MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (all manufactured by Green Chemical Co., Ltd.), Sunaid SI-100L (all manufactured by Sanxin Chemical Industry Co., Ltd.), CI- 2064, CI-2639, CI-2624, CI-248 1 (all manufactured by Nippon Soda Co., Ltd.) 'Photoinitiator 2074 (manufactured by Rhone Poulenc Co., Ltd.), CD-1012 (manufactured by Sartomer Co., Ltd.), and the like. Among them, Optomer SP-150, 201037029 is more preferable because it is difficult to cause corrosion of the electrode due to the key salt, and it is easy to obtain practical hardenability. The cationic photopolymerization initiator may be used singly or in combination of two or more. Further, a sensitizer such as a lanthanide or an oxane 9-oxothiolane may be used as needed. Further, the mixing ratio of the cationic photopolymerization initiator is not particularly limited, and it is usually from 0.1 to 10% by mass based on the total amount of the cationically polymerizable compound. When the amount is less than 0.1% by mass, the curing agent of the present invention may have insufficient curability. When the amount is more than 10% by mass, the cationic photopolymerization initiator which does not sufficiently react may remain, and there is a possibility that it dissolves in the liquid crystal. Among them, it is preferably from 0.3 to 3% by mass. (Composition of a radical photocuring system) The composition of the radical photocuring system (hereinafter referred to as a radical photocurable composition) is a composition containing a radical polymerizable compound and a radical photopolymerization initiator. The radically polymerizable compound is not particularly limited as long as it is a compound of conventionally known Q having a (meth) acrylonitrile group which is generally used in the field of UV curing, and is used as a liquid crystal display panel for sealing. , it is more suitable to use in an intimate mixing with the liquid crystal. However, in order to avoid excessive hardening shrinkage, the (meth) acrylate such as pentaerythritol hexaacrylate or pentaerythritol tetraacrylate is preferably limited to a small amount in advance. use. Further, since the radically polymerizable compound having a carboxylic acid group reacts with the epoxy group during storage, the viscosity of the composition is rapidly increased, and the case is preferably limited to a small amount. -12- 201037029 In the field of UV hardening, it is called "photopolymerizable oligomer", polyester (meth)acrylic acid having an ester bond in a main chain structure and having at least two (meth)acryl fluorenyl groups. Ester; epoxy (meth) acrylate vinegar modified with epichlorohydrin; ethyl ether; (meth) acrylate modified with propylene oxide, cyclic lactone, etc. usage of. However, the acrylate having an urethane group is preferably limited to a small amount in advance when it is combined with a cationic curing system because it causes hardening inhibition by the urethane group.具体 Specific examples of the (meth) acrylate used in the present invention include, for example, glyceryl monomethacrylate (manufactured by Nippon Oil Co., Ltd., trade name "Bremmer GLM"), and propylene oxyethyl phthalate (co-prosperous) Manufactured by the company's chemical company, trade name "H0A-MPE"), benzyl (meth)acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name "bisuko-to#160"), nonylphenoxy poly(ethylene acrylate) (made by East Asia Synthetic Co., Ltd., trade name "man ^11. 5 PCT 111"), "six 1'01148 M113", "Aronics M117"), ECH modified phenoxy acrylate (manufactured by East Asia Q Synthetic Co., Ltd., trade name "Aronics" M5700"), E0 modified succinic acid acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: H0A-MS), E0 modified phosphate methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "P-1M" "), rosin-modified acrylate epoxy ester (manufactured by Arakawa Chemical Co., Ltd., trade name "beam set 101"), etc., having one (meth) acrylonitrile-based (meth) acrylate; iso-cyanuric acid (Acrylhydrazine ethyl) hydroxyethyl ester (manufactured by Toagos Corporation) Product name "Aronics M2 15"), E◦ modified bisphenol A diacrylate (manufactured by Nippon Oil Co., Ltd., trade name "ADPE-150"), P0 modified double-13- 201037029 Phenol A diacrylate (Japanese fat Co., Ltd., product name "ADBP-200"), ECH modified bisphenol A type acrylate (trade name "DICLITE UE8200", manufactured by DIC Chemical Co., Ltd.), ECH modified phthalic acid diacrylate (manufactured by Nagase Chemical Co., Ltd., product "DA-721"), ECH modified hexahydrophthalic acid diacrylate (manufactured by Nagase Chemical Co., Ltd., trade name "DA-722"), tricyclodecane dimethanol diacrylate (Daicel UCB company, trade name ^ IRR214"), rosin-modified ester acrylate (manufactured by Arakawa Chemical Co., Ltd., trade name "beam set 1 15B"), EO-modified phosphate dimethacrylate (common product, manufactured by Ryosho Chemical Co., Ltd., trade name "P -2M"), ginseng (propylene oxyethyl) isomeric cyanurate (manufactured by Toagosei Co., Ltd., trade name "Aronics M315"), and dimethylglycol tetraacrylate (manufactured by Toagosei Co., Ltd., trade name "Aronics M408" "), dipentaerythritol hexaacrylate (Day Manufactured by Kosei Pharmaceutical Co., Ltd. under the trade name "Kayarad DPHA", caprolactone modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayarad DPCA-30", "Kayarad DPCA-120") And the like (meth) propylene enoate having two or more (meth) acrylonitrile groups. In particular, among the above-mentioned radically polymerizable compounds, a lactone-modified (meth) acrylate or a rosin-modified (meth) acrylate is particularly preferable because the curable composition can be made soft. And make the adhesion more favorable. Specifically, a lactone-modified hydroxytrimethylacetic acid neopentyl glycol diacrylate (trade name "HX620" manufactured by Nippon Kayaku Co., Ltd.) and a lactone-modified BPA epoxy phthalate diacrylate can be exemplified. (Daicel cytec company, trade name "Ebecryl -14- 201037029 37 08"), rosin-modified acrylic epoxy ester (manufactured by Arakawa Chemical Co., Ltd., trade name "beam set 101", etc. Use of this (meth) acrylate The amount of the solid content of the photocurable composition for sealing of the present invention is preferably in the range of 20 to 70% by mass, in particular, in the range of 20 to 70% by mass. As the base photopolymerization initiator, for example, benzophenone, 2,2-diethoxyethyl benzene, benzyl, benzhydryl isopropyl ether, benzyl ketal, 1-hydroxycyclohexanone, Oxane 9-oxosulfonium III, etc. These radical photopolymerization primers may be used singly or in combination of two or more. In addition, a maleimide having a light-starting energy may also be used. a compound. In a specific example of a maleimide compound having a light-starting energy, For example, the maleimide compound described in JP-A-2000-19868 and JP-A-2004-070297 may be used. The radical photopolymerization initiator may be used singly or in combination of two or more. Further, although the mixing ratio of the radical photopolymerization initiator is not particularly limited, it is preferably used in the range of 0.1 to 20% by mass based on the total amount of the radically polymerizable compound. When it is less than 0.1% by mass, there may be When the curing agent of the present invention is insufficient in curability, when it exceeds 10% by mass, the cationic photopolymerization initiator which does not sufficiently react may remain, and may be dissolved in liquid crystal. Among them, it is preferably 0.3 to 10%. In the case of the radical photocuring system and the cationic photocuring system, a compound having a radical polymerizable group and a cationic polymerizable group may be used. For example, a commercially available BPF epoxy semi-acrylate or BPA epoxy semi-acrylate (manufactured by Daicel cytec Co., Ltd.) is a polymerizable compound based on both of the cationically polymerizable groups -15 to 201037029. 'Product name "UVal561"), or a part of an epoxy group of a compound having a plurality of epoxy groups in one molecule reacted with (meth)acrylic acid to form a (meth)acrylonitrile-based compound. The acrylate, BPF epoxy semi-acrylate and the compound of the general formula (1) have a higher dilution effect. In the present invention, if it is used for a radical photocuring system or a cationic photocuring system, In this case, when a (meth)acryl fluorenyl group which is a radical photocuring type and a composition which is a cationic photocuring epoxy group coexist, the ring is formed by light irradiation. The oxy group is subjected to cationic polymerization, and the (meth) acrylonitrile group is hardened by radical polymerization, and is more preferably adhered to the substrate. In this case, in order to carry out the polymerization more efficiently, it is preferred to use a cationic photopolymerization initiator for cationically polymerizing an epoxy group in the photocurable composition; and (meth)propene A radical photopolymerization initiator in which a mercapto group is subjected to radical polymerization. (Other components: decane coupling agent) Further, in order to improve the adhesion, the photocurable composition for sealing a liquid crystal display panel of the present invention may be mixed with a conventionally used decane coupling agent. In the decane coupling agent, a decane coupling agent having a polymerizable group such as a (meth) acryl fluorenyl group or an epoxy group is copolymerized with the general formula (1), and the like. Because it is highly adhesive, it is good. -16-201037029 The decane coupling agent having a polymerizable group may, for example, be 3-(methyl)propenyloxypropyltrimethoxydecane or 3-epoxyoxypropyltrimethoxydecane. For the commercial product of the decane coupling agent having such a polymerizable group, for example, the company name "KBM5 03", "KBE503", "KBM502", "KBE502", "KBM5102j, "KBM5103", "KBM403" and so on. The amount of use of the decane coupling agent is preferably from 0.1 to 10% by mass, particularly preferably from 1 to 5% by mass, based on the total amount of the sclerosing composition. When the ratio of the decane coupling agent is less than 0.1% by mass, a sufficient adhesion effect cannot be obtained, and if it exceeds 10% by mass, there is a possibility of causing phase separation. A more preferred lower limit is 0.5 parts by mass, and a more preferred upper limit is 5 parts by mass. (Other components) In the photocurable composition for sealing of the present invention, a conventionally used additive or a chelating agent may be added for the purpose of viscosity adjustment or storage stability. For example, the squeezing agent is added for the purpose of improving the adhesion of the photohardenable composition for sealing of the present invention and improving the coefficient of linear expansion due to the stress dispersion effect. For example: talc, asbestos, silica sand, diatomaceous, bentonite (smectite), island soil (Bentonite), carbonated fishing, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, Titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium citrate, talc, glass beads, sericite terra abla, bentonite, etc.-17- 201037029 Inorganic An organic filling agent such as a sulphate or a polyester fine particle, a polyurethane fine particle, an ethylene polymer fine particle, or an acrylic polymer fine particle. The mixing ratio of the above-mentioned chelating agent is not particularly limited, and is preferably from 1 to 100% by mass based on the amount of the curable composition. When the amount is more than 1% by mass, the effect of adding the chelating agent is hardly obtained. When the amount is more than 100% by mass, the workability such as the patterning property of the photocurable composition for sealing of the present invention is lowered. A more preferred lower limit is 5 parts by mass, and a more preferred upper limit is 50 parts by mass. 〇 (Viscosity) When the viscosity measured at 25 ° C is 100 Pa·s or more, the liquid curable composition for sealing a liquid crystal display panel of the present invention is used as a liquid crystal by a dropping method described later. A liquid crystal sealing agent for manufacturing a display element can be more preferably used. When the liquid crystal display panel is manufactured by the dropping method at less than 100 Pa·s, the shape of the seal pattern formed on the transparent substrate cannot be maintained, and the sealant component is dissolved in the liquid crystal to cause liquid crystal contamination. A more preferred lower limit is 100 Pa*s, and a more preferred upper limit is 500 Pa*s. When it exceeds 500 Pa*s, the moldability of the sealant of the present invention is insufficient, and the production of the liquid crystal display panel by the dropping method becomes difficult. In this case, the E-type viscosity meter for measuring the viscosity is not particularly limited, and for example, "DV-III" manufactured by Brookfield Co., Ltd., or the like can be used. (Sealing Agent for Liquid Crystal Display Panel) -18- 201037029 The photocurable composition for sealing a liquid crystal display panel of the present invention can be used as a sealant when a liquid crystal display panel is formed, and can be used as a liquid crystal material in a liquid crystal display panel. A blocking agent is used as a closed injection port. The liquid crystal display panel is provided with, for example, a front surface of a thin film transistor, a pixel electrode, an alignment film, a color filter, an electrode, or the like, or a substrate surface of any of the back substrates, and the photocuring of the liquid crystal display panel of the present invention is applied. After the composition, the other substrate is bonded, and light is irradiated from the substrate surface side of the substrate or from the side surface of the substrate to cure the optically-curable composition for sealing the liquid crystal display panel of the present invention. Next, after the obtained liquid crystal cell is injected into the liquid crystal, the liquid crystal display panel is formed by closing the injection port with a blocking agent. Further, the liquid crystal display panel is applied to the outer edge portion of the substrate surface of any one of the substrates, and the photocurable composition for sealing the liquid crystal display panel of the present invention is applied in a frame shape, and after the liquid crystal is dropped therein, the film is applied under vacuum. After the other substrate is bonded, it can be formed by photohardening. To apply the photocurable composition for sealing a liquid crystal display panel of the present invention to the surface of the Q substrate, it is necessary to use a dispenser or use a screen printing method. In this case, it is generally applied to have a line width of 0.08 to 0.1 mm and a line height of 5 to 50 μm. The light to be used for hardening the photocurable composition for sealing a liquid crystal display panel of the present invention is preferably ultraviolet light or visible light, and preferably light having a wavelength of from 300 nm to 400 nm. As the light source, for example, a high pressure mercury lamp, a metal halogen lamp or the like can be used. When the illuminance of the light source is 500 00 W/m2 or more, the hardening is faster. The amount of light to be irradiated can be satisfactorily cured as long as it is 2000 (H/m2 or more, -19-201037029. Further, the photocurable composition for sealing a liquid crystal display panel of the present invention can be used even in an air atmosphere. Although it is excellent in photocurability, it is more preferable to cure by light hardening in an inert gas atmosphere such as nitrogen. Embodiments The present invention will be specifically described below based on examples and comparative examples. In the examples and the comparative examples, "parts" means "parts by mass" unless otherwise specified. In addition, the evaluation of the adhesion and the voltage holding ratio is carried out in the following manner: Ο < used in the adhesive test Substrate> (Completely attached (SiN) x glass) The surface of the non-glass plate (manufactured by Corning Co., Ltd., product name "cornig 1 7 37") having a thickness of 0.7 mm is comprehensively formed by sputtering to form a thickness of about 50 nm (SiN). The x-layer is made of a (SiN)x alkali-free glass plate. (Comprehensively attached to the IT0 plastic film) Polyether maple film (made by Sumitomo Bakelite Q Co., Ltd., trade name "FS-5 300") is used throughout. comprehensive The olefinic coated glass is coated on the surface of a non-alkali glass plate having a thickness of 0.7 mm (the product name "cornig 1 7 37" manufactured by Corning Co., Ltd., and coated with acrylic acid according to Example 1 described in Japanese Patent No. 3321858. (Iron-free (SiN)x plastic film) -20- 201037029 A polycarbonate film having a thickness of 0.125 mm (trade name "Panlite" by Teijin Chemical Co., Ltd.) is fully in accordance with the example of JP-A-2006-57121. Example C of 3 'Formed a (SiN)x layer having a thickness of 50 nm to form a (SiN)xPC film substrate. (Full-attached (SiO)x plastic film) Attached (SiO)xPES formed by sputtering a SiOx layer Film substrate (Sumitomo Bakelite trade name "FST1 300". (Full-attached ITO glass) 无In the alkali-free glass plate with a thickness of 0.7mm (Corning's product name "cornig 1737" has a comprehensive surface and is sputtered to form an IT layer to become The surface resistance was 100 Ω, and it was made into an IT0 alkali-free glass plate. <Combination of substrate using adhesive test> The combination of the substrates was as follows. Combination A: Fully attached to IT0 plastic film/full attachment (S iN)x Glass Combination B: Fully attached to IT0 plastic film / full acrylic coated glass Q Combination C: Fully attached (SiN) x plastic film / fully attached (SiN) x glass combination D: fully attached (SiN) x plastic film / comprehensive Acrylic coated glass combination E: Fully attached (SiO)x plastic film/Full-attached (SiN)x glass combination F: Fully attached (SiO)x plastic film/Full-attached ITO glass<Example of adhesion test combination A> In the photocurable composition for sealing, a spherical spacer (Hayabeads L-11S) having an average particle diameter of about 5.5 # m is added in an amount of 1% by mass, and a stirring machine is used to remove the 21-201037029 foaming machine (manufactured by Thinky Co., Ltd. Soaking Taro AR250") is stirred and defoamed to make a sample. The sample was discharged from the front end of the syringe equipped with a precision nozzle of 2 mm diameter, and the I50mmxl5mm "full I0 plastic" was cut in advance using a desktop coating robot (manufactured by Musashi Engineering Co., Ltd., trade name "SH〇T MINI"). The film "on" is applied in a straight line across a length of 9 cm so as to be parallel to the long axis direction of the substrate, on which the "full-size (SiN) x glass (size 95x15 mm) q is overlapped so that the surface The surface of the plastic film is parallel. Then use the quartz window pressure hardening device of EHC Company, after pressing at 0.1 MPa for 2 minutes, under the condition of the original force and daily pressure, from the side of the "SiN) x glass Use a high-pressure metal halide lamp to illuminate 500W/m2 of ultraviolet light for 40 seconds. The irradiation at this time was carried out in an air atmosphere through the quartz window of the quartz window press-hardening device. Thereby, an evaluation sample having a width of 1 mm and then a layer thickness of 5.5 / / m was obtained. The evaluation sample to be bonded was subjected to a floating roller peeling test described in JIS K 6854-1 (separated by 90 degrees at a speed of 100 mm/min), and is similarly described by JIS K 6854-1. The peeling load (mN) obtained by the optimum straight line method was divided by the subsequent width to obtain the joint strength (mN/mm). <Production of Liquid Crystal Display Panel for Voltage Retention Rate Test> 1. Liquid Crystal Display Panel Production 1 (Injection Method) On a piece of IT0 glass substrate "RZ-B107N1N" manufactured by EHC Co., Ltd., sprayed a spacer made by Hayakawa Rubber Co., Ltd. 5% ethanol dispersion of "LH1 1S". Then, on the other attached IT0 glass substrate, each of the dispensers is used to apply a photocurable composition of about 1 mm wide to -22-201037029 to provide two liquid crystal injection ports on the outer edge of the substrate. Thereafter, two glass substrates were opposed to each other and bonded together, and a high-pressure metal halide lamp was used to irradiate ultraviolet rays of 500 W/m 2 to the sealant portion for 40 seconds in a nitrogen atmosphere to prepare a 2-hole crystal lattice. The liquid crystal composition for driving a TFT (thin film transistor) (the composition is described later) is injected into a 2-hole lattice under vacuum, so that the liquid crystal composition is made into a mask so as not to be directly exposed to ultraviolet rays, and thereafter, the light for sealing is used. The curable composition was sealed in 2 wells, and a liquid crystal display panel was produced by using a high-pressure metal halide lamp under a nitrogen atmosphere and irradiating an ultraviolet 0 line of 500 W/m 2 for 40 seconds. 2. Liquid crystal display panel production 2 (Drip method) Two sheets of the glass substrate RS-B107M1N (with directional film and ITO attached) prepared by EHC Co., Ltd., and a piece of the spacer "LH11S" manufactured by Hayakawa Rubber Co., Ltd. 5% ethanol dispersion. Next, on the other glass substrate, the sealing material produced in Example 6 was applied in a rectangular shape with a seal width of about 1 mm on the outer edge portion of the substrate. Next, on the inside of the rectangular upper sealant on the substrate, an appropriate amount of TFT (thin film transistor) is driven under vacuum to drive the liquid crystal composition for q (the composition will be described later), and the honing directions of the two glass substrates are positive. Make and fit to make a lattice. After the lattice was returned to atmospheric pressure so that the interval between the substrates became the size of the spacer, a high-pressure metal halide lamp was used, and the sealing agent portion was irradiated with ultraviolet rays of 500 W/m2 for 40 seconds to fabricate a TN-type liquid crystal display panel. The liquid crystal display panel was placed between two orthogonal polarizing plates, and the optical axis was adjusted and pinched to form a liquid crystal display element. When no voltage is applied, the viewing is transparent and becomes a bright display. If a voltage is applied to -23-201037029, the electrode portion of the crystal lattice does not pass through the light and becomes a dark display, showing a good display state. 3. Liquid crystal composition for driving TFT (thin film transistor) which is formed by a liquid crystal display panel The following three types are used for the liquid crystal composition for driving a TFT (thin film transistor) used in the present embodiment.

c2h5- -C,HC2h5- -C,H

OCH 3 C 2 H5~C H2 C Hjf 2 0質量％ 2 5質量％ 2 0質量％ 2 0質量％. 7質量％ 8質量％OCH 3 C 2 H5~C H2 C Hjf 2 0% by mass 2 5 mass% 2 0 mass% 2 0 mass%. 7 mass% 8 mass%

液晶組成物（1) 液晶組成物（1)之物性 介電率之異方向性（△ ε ) : 5.30 電阻率値：5.2χ1014Ω · m 24- 201037029 0C2H5 14% n-C^H Π·〇5Η”_Liquid crystal composition (1) Physical properties of liquid crystal composition (1) Dielectric directionality (Δ ε ) : 5.30 Resistivity 値: 5.2 χ 1014 Ω · m 24- 201037029 0C2H5 14% n-C^H Π·〇5Η”_

°2ΗΚΙ)·0·^-°2ΗΚΙ)·0·^-

4.5%4.5%

n-CgH^n-CgH^

OCH3 10% och3 9%OCH3 10% och3 9%

n-CsHu 鄕 Π-Ο3Η'n-CsHu 鄕 Π-Ο3Η'

rvC^Hg 2% 液晶組成物（2) 液晶組成物（2)之物性 介電率之異方向性（△ ε ): -3.1 複折射（△ η) : 0.07 電阻率値：5.6χ1014Ω · m 25- 201037029rvC^Hg 2% Liquid crystal composition (2) The liquid crystal composition (2) The dielectric property of the dielectric property (△ ε ): -3.1 Complex refraction (Δ η) : 0.07 Resistivity 値: 5.6 χ 1014 Ω · m 25 - 201037029

C3Hr〇-〇<：K：--Q-CN c^ig-^y-c^c—^y-ψC3Hr〇-〇<:K:--Q-CN c^ig-^y-c^c-^y-ψ

10重量% 10重獻 15重獻 15重齡 10重獻 10重獻 5重獻 15重獻 10重獻 液晶組成物（3)10% by weight 10 rewards 15 rewards 15 years old 10 rewards 10 rewards 5 rewards 15 rewards 10 rewards Liquid crystal composition (3)

液晶組成物（3)之物性 介電率之異方向性（△ ε ): 4.7 複折射（△ η) : 0·29 電阻率値：1.6χ1014Ω . m <電壓保持率試驗> 將以該任一方法所製成的液晶顯示面板’進行60°c、 90%RH濕熱暴露試驗，測定120小時後電壓保持率。電壓 保持率，在241，外加交流5V之初期電壓’ 64微秒於液 -26- 201037029 晶顯示面板，計算在167微秒之框時間（frame time)前後之 電壓比乘以100之値。 [實施例 1](HLB = 12) 將具有雙酚A骨架的二環氧化合物（DIC化學工業公司 製，商品名「EPICRON 850CRP」）25份；具有雙酚A骨架 的環氧化合物（DIC化學工業公司製，商品名「EPICRON 1050」）10份；相對於具有雙酚A骨架的環氧基與酞酸酐反 應所得之反應中間體，使己內酯、羥乙基丙烯酸乙酯依 〇 順序反應所得之環氧酯丙烯酸酯（Daicel cytec公司製，商 品名「Ebecryl 3 708」）20份；雙酚A型環氧半丙烯酸酯（Daicel cytec公司製，商品名「UVal561」）10份，在140度溶解。 其後，在120度一邊攪拌，一邊添加己內酯改性二丙烯酸 羥三甲基乙酸新戊二醇酯（日本化藥公司製，商品名 「KAYARAD HX620」）25份、松香改性丙烯酸環氧酯（荒川 化學公司製，商品名「beam set 101」）10份，予以攪拌。 ❹ 使混合物在室溫，添加爲非離子性界面活性劑之環氧乙烷 及環氧丙烷改性聚二甲基矽氧烷化合物（以下稱爲化合物 A)(信越化學公司製，商品名「KF6011」，HLB = 12)1份， 予以良好的攪拌。 添加鎏鹽系光陽離子引發劑（旭電化公司製之商品名 「SP150」）2.5份、矽烷系偶合劑（信越化學工業股份有限 公司，商品名「KBM5103」）5.0份、及爲自由基光聚合引 發劑之2,2-二甲氧基-2-苯基乙醯苯（Ciba特用化學品之商 -27- .201037029 品名「IRGACURE651」），可因應需要一邊加熱、溶解，— 邊攪拌後.’添加日本Aerosil公司製，商品名「ry_2〇〇s」5 份’以3輥捏合，獲得液晶顯示面板密封用光硬化性組成 物A。 關於液晶顯示面板密封用光硬化性組成物A，以該液晶 顯示面板製作1之方法，製作液晶顯示面板，同時，依照 該評價方法進行評價，其結果如表1所示。 [實施例 2](HLB = 14) 〇 在實施例1中’除了使用以聚環氧乙烷改性的聚二甲矽 氧院化合物（B)(TorayDow Corning公司製，商品名 「TSF-4440」，HLB = 14)1份’以替代化合物（a)i份以外， 其它則依照與實施例1記載相同的方法，獲得液晶顯示面 板密封用光硬化性組成物。關於該組成物，以該液晶顯示 面板製作1之方法製作液晶顯示面板，同時，依照該評價 方法予以評價，結果如表1所示。 〇 [實施例 3](HLB = 10) 在實施例1中，除了使用以聚環氧乙烷所改性的聚二甲 矽氧烷化合物（C)(信越化學工業公司製之商品名 「KF-353」，HLB=10，430mPas)l 份，以替代化合物（A)l 份以外，其它則依照與實施例1記載相同之方法，獲得液 晶顯示面板密封用光硬化性組成物。關於該組成物，以該 液晶顯示面板製作1之方法製作液晶顯示面板，同時依照 該評價方法予以評價，其結果如表1所示。 -28- .201037029 [實施例 4](HLB = 13) 在實施例1中’除了使用聚環氧乙院、聚環氧丙院、及 環氧丙醚基所改性的聚二甲矽氧烷化合物（D)(信越化學公 司製，商品名「X22-4741」，HLB = 13」0.75份，以替代化 合物（A) 1份以外，其它則依照與實施例1記載相同方法， 獲得液晶顯示面板密封用光硬化性組成物。關於該組成 物，以該液晶顯示面板製作1之方法製作液晶顯示面板， 同時依照該評價方法，其結果如表1所示。 〇 [實施例 5](HLB = 13 ’ 0.3 份） 在實施例1中，除了使用聚環氧乙烷、聚環氧丙烷、及 環氧丙醚基所改性的聚二甲基矽氧烷化合物（D)(信越化學 公司製，商品名「X22-474 1」，HLB = 13)0.3份，以替代化 合物（A) 1份以外，其它則依照與實施例1記載相同之方 法，而獲得液晶顯示面板密封用光硬化性組成物。關於該 組成物，以該液晶顯示面板製作1之方法製作液晶顯示面 Q 板，同時依照該評價方法予以評價其結果如表1所示。 [實施例 6](HLB = 13 ’ 1.5 份） 在實施例1中’除了使用聚環氧乙烷、聚環氧丙烷、環 氧丙醚基所改性的聚二甲矽氧烷化合物（D)(信越化學公司 製，商品名「X22-474 1」，HLB = 13)0.3份，以替代化合物 (A) 1份以外，其它則依照與實施例1記載相同之方法而獲 得液晶顯示面板密封用光硬化性組成物。關於該組成物， -29- '201037029 以該液晶顯示面板製作1之方法製作液晶顯示面板，同時 依照該評價方法予以評價，其結果如表1所示。 [實施例7](氧雜環丁烷使用） 在實施例4中，除了使用聯苯酚型氧雜環丁烷化合物（宇 份興產公司製，商品名「OXBP」）1〇份，以替代具有雙酚A 骨架的環氧化合物（DIC公司製，商品名「EPICRON 1050」）10 份以外，其它則依照與實施例1記載相同之方法而獲得液 0 晶顯示面板密封用光硬化性組成物。關於該組成物，以該 液晶顯示面板製作1之方法製作液晶顯示面板，同時依照 該評價方法予以評價，其結果如表1所示。 [實施例8](HLB = 13，與引用文獻7之比較） 在實施例1中，除了使用聚環氧乙烷、聚環氧丙烷、及 環氧丙醚基所改性的聚二甲矽氧烷化合物（D)(信越化學公 司製，商品名「X22-4741」，HLB = 13)1.0份以替代化合物 (A)l份，並使用引用文獻7記載之下述一般式所示化合物 Ο (EP)10份，以替代具有雙酚A骨架的環氧化合物（DIC公司 製，商品名「EPICRON 1 050」）10份以外，其它則依照與實 施例1記載相同之方法而獲得液晶顯示面板密封用光硬化 性組成物。關於該組成物，以該液晶顯示面板製作1之方 法製作液晶顯示面板，同時依照該評價方法予以評價，其 結果如表1所示。 -30- 201037029The directionality (Δ ε ) of the physical dielectric constant of the liquid crystal composition (3): 4.7 birefringence (Δ η) : 0·29 resistivity 値: 1.6 χ 1014 Ω . m < voltage retention test > The liquid crystal display panel manufactured by either method was subjected to a 60 ° C, 90% RH wet heat exposure test, and the voltage holding ratio was measured after 120 hours. The voltage holding ratio, at 241, plus the initial voltage of AC 5V '64 microseconds to liquid -26-201037029 crystal display panel, calculates the voltage ratio before and after the frame time of 167 microseconds multiplied by 100. [Example 1] (HLB = 12) 25 parts of a diepoxy compound (trade name "EPICRON 850CRP", manufactured by DIC Chemical Co., Ltd.) having a bisphenol A skeleton; an epoxy compound having a bisphenol A skeleton (DIC chemistry) 10 parts by the industrial company, trade name "EPICRON 1050"); the reaction intermediates obtained by reacting an epoxy group having a bisphenol A skeleton with phthalic anhydride, and reacting caprolactone and ethyl hydroxyethyl acrylate in a sequential manner 20 parts of the obtained epoxy ester acrylate (trade name "Ebecryl 3 708", manufactured by Daicel cytec Co., Ltd.), and 10 parts of bisphenol A type epoxy semi-acrylate (product name "UVal561" manufactured by Daicel cytec Co., Ltd.) at 140 Degree dissolved. Then, while stirring at 120 degrees, 25 parts of caprolactone-modified hydroxytrimethylacetate neopentyl glycol diester (trade name "KAYARAD HX620" manufactured by Nippon Kayaku Co., Ltd.) and rosin-modified acrylic ring were added. 10 parts of oxyester (manufactured by Arakawa Chemical Co., Ltd., trade name "beam set 101") was stirred.环氧 Ethylene oxide and propylene oxide-modified polydimethyl siloxane compound (hereinafter referred to as compound A) which is added as a nonionic surfactant at room temperature (manufactured by Shin-Etsu Chemical Co., Ltd., trade name " KF6011", HLB = 12) 1 part, with good agitation. 2.5 parts of a sulfonium-based photocationic initiator (trade name "SP150" manufactured by Asahi Kasei Co., Ltd.), 5.0 parts of a decane-based coupling agent (Shin-Etsu Chemical Co., Ltd., trade name "KBM5103"), and radical photopolymerization Initiator 2,2-dimethoxy-2-phenylethyl benzene (Ciba special chemical -27-.201037029 product name "IRGACURE651"), can be heated and dissolved as needed - while stirring 'The product name "ry_2〇〇s", 5 parts by the Japanese company Aerosil Co., Ltd. was kneaded by a three-roller, and the photocurable composition A for liquid crystal display panel sealing was obtained. With respect to the photocurable composition A for sealing a liquid crystal display panel, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1, and the evaluation was carried out in accordance with the evaluation method. The results are shown in Table 1. [Example 2] (HLB = 14) In Example 1, 'In addition to the use of polyethylene oxide modified polydimethylene oxide compound (B) (manufactured by Toray Dow Corning Co., Ltd., trade name "TSF-4440" In the same manner as described in Example 1, a photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in Example 1 except that the compound (a) was used in the same manner as in Example 1. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1. The evaluation was carried out in accordance with the evaluation method, and the results are shown in Table 1.实施 [Example 3] (HLB = 10) In Example 1, except that polydimethyl siloxane compound (C) modified with polyethylene oxide (trade name "KF manufactured by Shin-Etsu Chemical Co., Ltd." was used. -353", HLB = 10, 430 mPas), and a photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in Example 1 except that the compound (A) was replaced by one part. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. -28-.201037029 [Example 4] (HLB = 13) In Example 1, 'except for the use of poly(ethylene oxide), polyepoxypropylene, and propylene oxide based polydimethyl oxime The alkyl compound (D) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X22-4741", HLB = 13" 0.75 parts, and the liquid crystal display was obtained in the same manner as in Example 1 except that one part of the compound (A) was used instead of the compound (A). A photocurable composition for panel sealing. A liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 according to the composition, and the results are shown in Table 1. [Example 5] (HLB) = 13 '0.3 parts) In Example 1, except for polydimethyl siloxane compound (D) modified with polyethylene oxide, polypropylene oxide, and epipylation group (Shin-Etsu Chemical Co., Ltd.) The product name "X22-474 1", HLB = 13) 0.3 parts, and the photocurability of the liquid crystal display panel sealing was obtained by the same method as that described in Example 1 except that the compound (A) was replaced by 1 part. The composition is produced by the method of producing the liquid crystal display panel 1 The crystal display surface Q plate was evaluated in accordance with the evaluation method, and the results are shown in Table 1. [Example 6] (HLB = 13 '1.5 parts) In Example 1, 'except for using polyethylene oxide, poly ring Polydimethyloxane compound (D) modified by oxypropane or epoxidized ether group (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X22-474 1", HLB = 13) 0.3 parts instead of compound (A) In the same manner as described in Example 1, a photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in Example 1. For the composition, -29-'201037029 was used to produce a liquid crystal display by the method of producing the liquid crystal display panel 1. The panel was evaluated in accordance with the evaluation method, and the results are shown in Table 1. [Example 7] (Use of oxetane) In Example 4, except that a biphenol type oxetane compound was used. In addition to the epoxy compound having a bisphenol A skeleton (trade name "EPICRON 1050", manufactured by DIC Corporation), it is used in the same manner as in the first embodiment. The same method is described to obtain a liquid crystal display panel The photocurable composition was sealed. A liquid crystal display panel was produced by the method of the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Example 8] (HLB) = 13, compared with the reference 7) In Example 1, except for the polydimethyl siloxane compound (D) modified with polyethylene oxide, polypropylene oxide, and epoxidized ether group ( Shin-Etsu Chemical Co., Ltd., trade name "X22-4741", HLB = 13) 1.0 part to replace compound (A), and use 10 parts of the compound Ο (EP) shown in the following general formula cited in Reference 7 A photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in Example 1 except that 10 parts of an epoxy compound having a bisphenol A skeleton (trade name "EPICRON 1 050", manufactured by DIC Corporation) was used. . With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. -30- 201037029

(EP) [實施例 9](HLB = 13_6，1.0 份） 在實施例1中，除了使用聚氧乙烯月桂醚化合物（花王股 份有限公司製，商品名「Emalgenl09P」，HLB = 13)l.〇份， 0 以替代化合物（A) 1份以外，其它則依照與實施例1記載相 同之方法而獲得液晶顯示面板密封用光硬化性組成物。關 於該組成物，以該液晶顯示面板製作1之方法製作液晶顯 示面板，同時依照該評價方法予以評價，其結果如表1所 示。 [實施例 10](HLB=15.5，1.0 份） 在實施例1中，除了使用單月桂酸十甘油醋化合物（日光 化學品股份有限公司製，商品名「DECAGLYN-l-L」，HLB 〇 = 15.5)1.0份，以替代化合物（A)l份以外，其它則依照與 實施例1記載相同之方法而獲得液晶顯示面板密封用光硬 化性組成物。關於該組成物，以該液晶顯示面板製作1之 方法製作液晶顯示面板，同時依照該評價方法予以評價， 其結果如表1所示。 [實施例 1 1](HLB=15.0，1.0 份） 在實施例1中，除了使用聚氧乙烯山梨聚糖單油酸酯化 合物（日光化學品股份有限公司製，商品名「TO-10V」， -31 -(EP) [Example 9] (HLB = 13_6, 1.0 part) In Example 1, except that a polyoxyethylene lauryl ether compound (manufactured by Kao Co., Ltd., trade name "Emalgenl 09P", HLB = 13) was used. In the same manner as in the first embodiment, a photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in the first embodiment. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Example 10] (HLB = 15.5, 1.0 part) In Example 1, except that a monolauric acid glycerin compound (manufactured by Nikko Chemical Co., Ltd., trade name "DECAGLYN-lL", HLB 〇 = 15.5) was used. In the same manner as described in Example 1, a photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as in Example 1 except that the compound (A) was replaced by one part. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Example 1 1] (HLB = 15.0, 1.0 part) In Example 1, except that a polyoxyethylene sorbitan monooleate compound (manufactured by Nikko Chemicals Co., Ltd., trade name "TO-10V", -31 -

201037029 H L B = 1 5.0) 1.0份，以替代化合物（a ) 1份以外，其它 與實施例1記載相同之方法而獲得液晶顯示面板密 硬化性組成物。關於該組成物，以該液晶顯示面板 之方法製作液晶顯示面板’同時依照該評價方法予 價，其結果如表1所示。 [實施例 12](HLB=16.3，1_0 份） 在實施例1中，除了使用將1-(烯丙氧基）-2,3 -環| 以碳數11-14之醇與環氧乙烷改性的下述一般式所$ 物（ERHADEKA 公司製，商品名「ER-30」，HLB = 16.3 水溶液），利用凍結乾燥經脫水處理之物1 . 〇份，以| 合物（A) 1份以外，其它則依照與實施例1記載相同力 而獲得液晶顯示面板密封用光硬化性組成物。關於雲 物，以該液晶顯示面板製作1之方法製作液晶顯示B 同時依照該評價方法予以評價，其結果如表1所示。 依照 用光 作1 以評 ，丙烷 :化合 ，65% ;代化 .方法 :組成 ί板，201037029 H L B = 1 5.0) 1.0 part, and the liquid crystal display panel thermosetting composition was obtained by the same method as that described in Example 1 except that the compound (a) was replaced by 1 part. With respect to this composition, a liquid crystal display panel was produced by the method of the liquid crystal display panel, and the evaluation was carried out in accordance with the evaluation method. The results are shown in Table 1. [Example 12] (HLB = 16.3, 1_0 parts) In Example 1, except that 1-(allyloxy)-2,3- ring was used as the alcohol having 11 to 14 carbon atoms and ethylene oxide. Modified the following general formula (manufactured by ERHADEKA, trade name "ER-30", HLB = 16.3 aqueous solution), using freeze-dried dehydrated material 1. 〇份, |合合(A) 1 Other than the parts, the photocurable composition for sealing a liquid crystal display panel was obtained in the same manner as described in Example 1. Regarding the cloud, the liquid crystal display B was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. According to the use of light for evaluation, propane: compound, 65%; generation. Method: composition ί plate,

ch2-o-rCHg—CH —CH2~0*~CH2^CH -〇-〇H 2~C H2 OH n (ER) 該一般式中，R爲碳數10至14的烷基，n表示 位之整數，n = 30。 [比較例1](無添加劑） 在實施例1中，除了無添加化合物（A) 1份以外， 依照與實施例1記載相同之方法，而獲得液晶顯示 複單 它則 板密 -32- 201037029 封用光硬化性組成物。關於該組成物，以該液晶顯示面板 製作1之方法製作液晶顯示面板，同時依照該評價方法予 以評價，其結果如表1所示。 [比較例 2](HLB = 5) 在實施例1中，除了聚環氧乙烷、聚環氧丙烷所改性的 聚二甲矽氧烷化合物（E)(信越化學公司製，商品名 「KF-6015」，HLB = 5)以替代化合物（A)l份以外，其它則依 照與實施例1記載相同之方法，而獲得液晶顯示面板密封 〇 用光硬化性組成物。關於該組成物，係以該液晶顯示面板 製作1之方法製作液晶顯示面板，同時依照該評價方法予 以評價，其結果如表1所示。 [比較例 3](HLB = 7) 在實施例1中，除了聚環氧乙烷、聚環氧丙烷所改性的 聚二甲基矽氧烷化合物（E)(信越化學公司製之商品名 「KF-6012」’ HLB = 7)，以替代化合物（A)l份以外，其它則 Q 依照與實施例1記載相同之方法而獲得液晶顯示面板密封 用光硬化性組成物。關於該組成物，以該液晶顯示面板製 作1之方法製作液晶顯示面板，同時依照該評價方法予以 評價，其結果如表1所示。 [比較例4](添加HLB = 12，5份） 在實施例1中，除了使化合物（A) 1份改爲5份以外，其 它則依照與實施例1記載相同之方法而獲得液晶顯示面板 密封用光硬化性組成物。關於該組成物，以該液晶顯示面 -33- 201037029 板製作1之方法製作液晶顯示面板，同時依照該評價方法 予以評價’其結果如表1所示。 [比較例5](無添加劑，與引用文獻7比較） 在實施例9中，除了不添加聚環氧乙烷、聚環氧丙烷、 環氧丙酸基所改性的聚二甲矽氧烷化合物（D)(信越化學公 司製，商品名「X22-474 1」，；HLB = 13)以外，其它則依照與 實施例7記載相同之方法’而獲得液晶顯示面板密封用光 硬化性組成物。關於該組成物’以該液晶顯示面板製作1 〇 、 、 之方法製作液晶顯示面板，同時依照該評價方法予以評 價，其結果如表1所示。 [比較例 6](HLB = 9.6，1 .〇 份） 在實施例1中，除了使用聚氧乙烯山梨聚糖單硬脂酸酯 化合物（日光化學品公司製，商品名「TS-106」，HLB = 9.6)1.0 份’以替代化合物（A) 1份以外，其它則依照與實施例1記 載相同之方法，獲得密封用光硬化性組成物。關於該組成 〇 物’以該液晶顯示面板製作1之方法製作液晶顯示面板， 同時依照該評價方法予以評價，其結果如表1所示。 [比較例7](氟系界面活性劑1.0份） 在實施例1中，除了使用全氟烷環氧乙烷化合物（DIC股 份有限公司製，商品名「megafuck F-444」1.0份，以替代 化合物（A) 1份以外，其它則依照與實施例1記載相同之方 法，獲得密封用光硬化性組成物。關於該組成物，以該液 -34- 201037029 晶顯示面板製作1之方法製作液晶顯示面板，同時依照該 評價方法予以評價，其結果如表1所示。 表1 表1 接著強度(mN/mm) 電1 g保持率(％) 組合A 組合B 組合C 組合D 組合E 組合F 液晶組 成物1 液晶組 成物2 液晶組 成物3 實施例1 250 240 260 240 270 250 94 96 93 實施例2 240 220 240 210 240 240 94 93 91 實施例3 200 200 220 210 240 210 96 97 93 實施例4 250 250 260 200 270 260 95 96 93 實施例5 200 200 240 200 240 200 96 97 93 實施例6 270 250 270 250 270 270 95 96 93 實施例7 170 180 200 190 210 170 95 96 93 實施例8 200 210 230 200 240 200 96 97 93 實施例9 180 160 200 160 210 190 92 94 90 實施例10 170 170 210 170 220 180 96 97 93 實施例11 200 190 220 190 220 200 92 94 91 實施例12 200 210 230 220 240 220 91 93 90 比較例1 120 120 130 110 130 130 96 97 93 比較例2 X X X X X X — — 一 比較例3 X X X X X X — — — 比較例4 250 240 260 240 270 250 90 92 87 比較例5 100 90 110 90 110 110 96 97 93 比較例6 X X X X X X — — — 比較例7 90 100 90 90 100 110 91 93 90 -35- 201037029 表1中，χ表不「容易剝離，無法測定」。 結果，使用到實施例1至1 2所得之密封用光硬化性組 成物的液晶顯示面板，電壓保持率顯示90%以上，接著強 度亦良好》比較例1、5係無添加非離子性界面活性劑之 例。又，比較例2 ' 3、6係添加了 HLB小於1 〇之非離子性 界面活性劑之例，比較例7係添加了氟系界面活性劑之 例。全部接著性不良。又’比較例4雖係添加量超過4質 量％之例，不過電壓保持率卻降低° ❹ 【圖式簡單說明】 無。 【主要元件符號說明】 無。ch2-o-rCHg-CH-CH2~0*~CH2^CH-〇-〇H 2~C H2 OH n (ER) In the general formula, R is an alkyl group having 10 to 14 carbon atoms, and n represents a position Integer, n = 30. [Comparative Example 1] (No Additive) In Example 1, except that 1 part of the compound (A) was not added, a liquid crystal display was obtained in the same manner as in Example 1, and the plate was dense-32-201037029 The photocurable composition is sealed. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Comparative Example 2] (HLB = 5) In the first embodiment, a polydimethyl siloxane compound (E) modified by polyethylene oxide or polypropylene oxide (manufactured by Shin-Etsu Chemical Co., Ltd., trade name " KF-6015", HLB = 5) A photocurable composition for liquid crystal display panel sealing was obtained in the same manner as in Example 1 except that the compound (A) was replaced by one part. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Comparative Example 3] (HLB = 7) In the first embodiment, a polydimethyl siloxane compound (E) modified with polyethylene oxide or polypropylene oxide (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) "KF-6012" 'HLB = 7), and the photocurable composition for sealing a liquid crystal display panel was obtained by the same method as that described in Example 1 except that the compound (A) was replaced by one part. With respect to this composition, a liquid crystal display panel was produced by the method of the liquid crystal display panel 1 described above, and evaluated according to the evaluation method. The results are shown in Table 1. [Comparative Example 4] (Addition of HLB = 12, 5 parts) In Example 1, a liquid crystal display panel was obtained in the same manner as described in Example 1 except that 1 part of the compound (A) was changed to 5 parts. A photocurable composition for sealing. With respect to this composition, a liquid crystal display panel was produced by the method of producing the liquid crystal display surface -33 - 201037029, and the evaluation was carried out in accordance with the evaluation method. The results are shown in Table 1. [Comparative Example 5] (No additive, compared with Reference 7) In Example 9, except that polydimethyl siloxane was modified without adding polyethylene oxide, polypropylene oxide, or glycidyl group. The compound (D) (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X22-474 1"; HLB = 13) was obtained in the same manner as described in Example 7 to obtain a photocurable composition for sealing a liquid crystal display panel. . With respect to this composition, a liquid crystal display panel was produced by the method of producing a liquid crystal display panel, and the evaluation was carried out in accordance with the evaluation method. The results are shown in Table 1. [Comparative Example 6] (HLB = 9.6, 1. 〇) In Example 1, except that a polyoxyethylene sorbitan monostearate compound (manufactured by Nikko Chemical Co., Ltd., trade name "TS-106", HLB = 9.6) 1.0 part of the photocurable composition for sealing was obtained in the same manner as described in Example 1 except that one part of the compound (A) was replaced. The composition of the liquid crystal display panel was produced by the method of producing the liquid crystal display panel 1 and evaluated according to the evaluation method. The results are shown in Table 1. [Comparative Example 7] (Fluorine-based surfactant 1.0 part) In Example 1, a perfluoroalkane oxirane compound (manufactured by DIC Corporation, trade name "megafuck F-444" 1.0 part) was used instead. A photocurable composition for sealing was obtained in the same manner as in Example 1 except that the compound (A) was used in the same manner as in Example 1. With respect to the composition, the liquid crystal was produced by the method of producing the liquid-34-201037029 crystal panel. The display panel was evaluated according to the evaluation method, and the results are shown in Table 1. Table 1 Table 1 Next strength (mN/mm) Electric 1 g retention rate (%) Combination A Combination B Combination C Combination D Combination E Combination F Liquid crystal composition 1 Liquid crystal composition 2 Liquid crystal composition 3 Example 1 250 240 260 240 270 250 94 96 93 Example 2 240 220 240 210 240 240 94 93 91 Example 3 200 200 220 210 240 210 96 97 93 Example 4 250 250 260 200 270 260 95 96 93 Example 5 200 200 240 200 240 200 96 97 93 Example 6 270 250 270 250 270 270 95 96 93 Example 7 170 180 200 190 210 170 95 96 93 Example 8 200 210 230 200 240 200 96 97 93 Implementation 9 180 160 200 160 210 190 92 94 90 Example 10 170 170 210 170 220 180 96 97 93 Example 11 200 190 220 190 220 200 92 94 91 Example 12 200 210 230 220 240 220 91 93 90 Comparative Example 1 120 120 130 110 130 130 96 97 93 Comparative Example 2 XXXXXX — — A Comparative Example 3 XXXXXX — — — Comparative Example 4 250 240 260 240 270 250 90 92 87 Comparative Example 5 100 90 110 90 110 110 96 97 93 Comparative Example 6 XXXXXX — — — Comparative Example 7 90 100 90 90 100 110 91 93 90 -35- 201037029 In Table 1, the χ table is not “easy to peel and cannot be measured”. As a result, in the liquid crystal display panel using the photocurable composition for sealing obtained in Examples 1 to 2, the voltage holding ratio was 90% or more, and the strength was also good. Comparative Examples 1 and 5 had no added nonionic interfacial activity. An example of a dose. Further, in Comparative Example 2 '3, 6, an example of a nonionic surfactant having an HLB of less than 1 Å was added, and Comparative Example 7 was an example in which a fluorine-based surfactant was added. All of the adhesions are poor. Further, in Comparative Example 4, the amount of addition exceeds 4% by mass, but the voltage holding ratio is lowered by ❹ [Simple description of the drawing] None. [Main component symbol description] None.

-36--36-

Claims (1)

201037029 七、申請專利範圍： 1. 一種液晶顯示面板密封用光硬化性組试 硬化性組成物固形物全量，含有HLB値 子系界面活性劑爲0.1至4質量％。 2. 如申請專利範圍第1項記載之液晶顯月 化性組成物，其中該非離子系界面活哲 聚二甲砍氧院。 3 .如申請專利範圍第1或2項記載之液| 〇 光硬化性組成物’其含有陽離子聚合伯 離子聚合引發劑。 4 _如申請專利範圍第3項記載之液晶顯3 化性組成物，其含有自由基聚合性化合 5.—種液晶顯示面板，其特徵爲：使用如 至4項中任一項所記載之液晶顯示面丰j 組成物。 〇 :物，其相對於光 爲1 〇以上的非離 ^面板密封用光硬 :劑係環氧烷改性 ^顯示面板密封用 :化合物，及光陽 >面板密封用光硬 物。 ΐ請專利範圍第1 ΐ密封用光硬化性 -37 - 201037029 四、指定代表圖： (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明: Μ 〇 j\w 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式：201037029 VII. Patent application scope: 1. Photocuring group test for sealing liquid crystal display panel The solid content of the curable composition is full, and the HLB scorpion surfactant is 0.1 to 4% by mass. 2. The liquid crystal display composition according to the first aspect of the patent application, wherein the non-ionic interface is a polymethyl sulphide. 3. The liquid according to claim 1 or 2, wherein the photocurable composition contains a cationic polymerization primary polymerization initiator. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The liquid crystal display surface is a composition of j. 〇 : Object, which is used for sealing of non-ionizing panel seals with a light of 1 〇 or more: Agent-based alkylene oxide modification ^ Display panel sealing: Compound, and Gwangyang > Light-resistant hardener for panel sealing.专利 专利 范围 第 第 第 ΐ - - - - - - - -37 - 201037029 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 j\w 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention:
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CN102822731A (en) * 2010-12-13 2012-12-12 Dic株式会社 Cationic curing liquid crystal sealant and liquid crystal display element

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