TW201003257A

TW201003257A - Curable composition for liquid crystal sealant and liquid crystal display element

Info

Publication number: TW201003257A
Application number: TW98116092A
Authority: TW
Inventors: Yasunobu Suzuki; Hiroshi Miyao; Noriyasu Shinohara
Original assignee: Jsr Corp
Priority date: 2008-05-16
Filing date: 2009-05-15
Publication date: 2010-01-16
Also published as: JP5493422B2; JP2010170069A

Abstract

The object of the present invention is to provide a curable composition capable of corresponding to narrow edge which decreases contamination to liquid crystal and has sufficient hardness and adhesiveness even at the shaded region caused by wiring. The solution is to provide a curable composition comprising the following component (A) to (E), a liquid crystal sealant and a liquid crystal display element, (A) compound having ethylenic unsaturated group; (B) epoxy compound having 3 or more epoxy group in 1 molecule and having a molecular weight of 500 or less; (C) epoxy compound having 3 or more epoxy group in 1 molecule and having a molecular weight of 500 or more; (D) epoxy curable agent; (E) photo radical polymerizing initiator.

Description

201003257 % 六、發明說明：【發明所屬之技術領域】本發明係關於放射線硬化性組成物。更詳言之，係關於有效作爲液晶顯示元件用密封劑之放射線硬化性組成物及使用它之液晶顯示元件。【先前技術】液晶顯示胞等之液晶顯示元件係在隔著規定之間隔放置之相向的兩片附有電極之透明基板之間封入液晶而形成。以往，在製造液晶顯示胞時，首先在兩片附有電極之透明基板之一利用網版印刷、使用熱硬化性密封劑，在封入液晶之範圍的外周，形成設有液晶注入口之圖案。接著，使夾有間隔物之一邊的透明基板對向而進行定向，來貼合兩片基板，加熱以使密封劑硬化。接著從液晶注入口注入液晶後，以封口劑封止液晶注入口。此種方法一般係稱之爲液晶注入方式。液晶注入方式係有步驟數繁多、製造效率低、熱歪斜導致基板之位置偏移、間隙的偏差、密封劑與基板之密接性不足等問題。做爲解決液晶注入方式之問題點的手段’現在正硏究稱爲液晶滴下方式之技法，液晶密封劑之硬化係以光熱硬化倂用法爲主流。此種液晶滴下方式’首先係在兩片附有電極之透明基板之一利用網版印刷、以液晶密封劑’將封入液晶之範圍的周圍形成爲長方形的框架。此時’不設置液晶注入口。接著，在密封劑未硬化之狀態將液晶滴下塗布於該框架内全面，立刻重合另一透明基板並壓合’在液 201003257 晶密封劑部分照射紫外線進行暫時硬化。之後，在液晶退火時加熱，以進一步使密封劑硬化，來製造液晶胞。液晶滴下方式係可步驟數少且效率良好地製造液晶胞，亦適用於大型面板之製造。又，由於進行藉由紫外線之暫時硬化，亦可防止熱歪斜導致基板之位置偏移，亦提升密封劑與基板之密接性。然而，在液晶滴下方式具有使未硬化狀態之液晶密封劑與液晶接觸之階段，因此液晶密封劑的成分係溶解於液晶而污染液晶，而有產生使液晶的比電阻降低之不良的問題（專利文獻1 )。以未硬化之液晶密封劑成分導致對液晶之污染性的減低、硬化性的提升等做爲目的，已提議摻合各種成分而成的硬化性組成物（例如專利文獻2〜7 )。然而，近年來需求液晶顯示元件之邊緣狹窄化，由於邊緣狹窄化，液晶密封劑與黑色矩陣或配線重疊的情形變多。在該部分由於紫外線未照射液晶密封劑，因而在密封劑殘留未硬化之部分，其係與液晶接觸而溶出液晶密封劑 V... 成分，而產生污染液晶之問題。又，在近年設計變更要求對配向膜之黏著力，要求兼具對玻璃之黏著力與對配向膜之黏著力。〔專利文獻1〕特開2001-133794號公報〔專利文獻2〕特開2004-37937號公報〔專利文獻3〕特開2003-28004號公報〔專利文獻4〕特開200 5 -263 98 7號公報〔專利文獻5〕特開2005-60651號公報 201003257 〔專利文獻6〕特開2006-30481號公報〔專利文獻7〕特開2006-58466號公報【發明內容】發明所欲解決之課題本發明係有鑑於上述問題而完成者，目的爲提供一種減低對液晶之污染性、即使是因配線等而成爲陰影的部分，也可得充分之硬化性及黏著性、能夠對應邊緣狹窄化之硬化性組成物。解決課題之手段爲了達成上述目的，本發明人等進行鑽硏探討，發現藉由使用（甲基）丙烯酸酯單體、複數種在1分子中具有 3個以上之環氧基的環氧化合物、在潛在型環氧硬化劑具有肟酯構造之高感度光自由基起始劑，能夠得到作業性良好、對液晶之污染性低、且即使因配線等而成爲陰影的部分也能夠顯示良好硬化性及黏著性之硬化性組成物，而完成了本發明。即，本發明係提供下述硬化性組成物、其所構成之液晶密封劑、及使用它之液晶顯示元件。 1 . 一種液晶密封劑用硬化性組成物，其係含有下述成分（A) 〜（E): (A) 具有乙烯性不飽和基之化合物 (B) 芳香族環氧化合物 (C) 在1分子中具有3個以上之環氧基的脂肪族環氧化合物 (D) 環氧硬化劑 (E) 光自由基聚合引發劑 201003257 2 ·如前述第1項所記載之液晶密封劑用硬化性組成物，其中該（E)光自由基聚合引發劑係含有具肟構造之化合物。 3 _如前述第2項記載之液晶密封劑用硬化性組成物，該具肟構造之化合物係由下述通式（e-Ι)表示，〇201003257 % VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a radiation curable composition. More specifically, it relates to a radiation curable composition which is effective as a sealant for a liquid crystal display element, and a liquid crystal display element using the same. [Prior Art] A liquid crystal display element such as a liquid crystal display cell is formed by encapsulating a liquid crystal between two opposing transparent substrates with electrodes disposed at predetermined intervals. Conventionally, in the production of a liquid crystal display cell, first, a pattern in which a liquid crystal injection port is provided is formed by screen printing on one of two transparent substrates with electrodes and using a thermosetting sealant on the outer periphery of a range in which liquid crystal is sealed. Next, the transparent substrate on one side of the spacer is oriented to face each other, and the two substrates are bonded and heated to cure the sealant. Then, liquid crystal is injected from the liquid crystal injection port, and the liquid crystal injection port is sealed with a sealing agent. This method is generally referred to as a liquid crystal injection method. The liquid crystal injection method has many problems such as a large number of steps, low manufacturing efficiency, thermal skew, positional deviation of the substrate, variation in the gap, and insufficient adhesion between the sealant and the substrate. As a means to solve the problem of the liquid crystal injection method, the technique of liquid crystal dropping method is now being studied, and the curing of the liquid crystal sealing agent is mainly based on the use of photothermal hardening. Such a liquid crystal dropping method is first formed as a rectangular frame in which one of two transparent substrates with electrodes is screen-printed and a liquid crystal sealing agent is used to seal the liquid crystal. At this time, the liquid crystal injection port is not set. Next, the liquid crystal was dripped and coated in the frame in a state where the sealant was not hardened, and the other transparent substrate was immediately superposed and pressed. The liquid crystal sealant portion was irradiated with ultraviolet rays for temporary hardening. Thereafter, it is heated while the liquid crystal is annealed to further harden the sealant to produce a liquid crystal cell. The liquid crystal dropping method is capable of producing a liquid crystal cell with a small number of steps and efficiently, and is also suitable for the manufacture of a large panel. Further, since temporary curing by ultraviolet rays is performed, it is possible to prevent the positional deviation of the substrate due to thermal skew, and to improve the adhesion between the sealant and the substrate. However, since the liquid crystal sealing method has a step of bringing the liquid crystal sealing agent in an uncured state into contact with the liquid crystal, the liquid crystal sealing agent is dissolved in the liquid crystal to contaminate the liquid crystal, and there is a problem that the specific resistance of the liquid crystal is lowered (patent) Literature 1). In order to reduce the contamination of the liquid crystal and the improvement of the hardenability, the uncured liquid crystal sealant component has been proposed to contain various components (for example, Patent Documents 2 to 7). However, in recent years, it has been demanded that the edge of the liquid crystal display element is narrowed, and the liquid crystal encapsulant overlaps with the black matrix or the wiring due to the narrowing of the edge. In this portion, since the liquid crystal sealing agent is not irradiated with the ultraviolet ray, the portion which is not hardened by the sealant is in contact with the liquid crystal to elute the liquid crystal sealing agent V... component, which causes a problem of contamination of the liquid crystal. Further, in recent years, the design change requires adhesion to the alignment film, and it is required to have adhesion to the glass and adhesion to the alignment film. [Patent Document 1] JP-A-2004-13737 (Patent Document 3) JP-A-2003-37937 (Patent Document 3) JP-A-2003-28004 (Patent Document 4) JP-A-200-263-98 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. 2006-58466 (Patent Document No. 2006-58466). In view of the above-mentioned problems, the object of the present invention is to provide a portion which is less likely to be contaminated by liquid crystals and which is shaded by wiring or the like, and which has sufficient curability and adhesiveness and can be hardened in accordance with narrowing of the edge. Composition. Means for Solving the Problem In order to achieve the above object, the inventors of the present invention have found that by using a (meth) acrylate monomer, a plurality of epoxy compounds having three or more epoxy groups in one molecule, A high-sensitivity photoradical initiator having an oxime ester structure in a latent epoxy curing agent, which is excellent in workability, low in contamination to liquid crystal, and exhibits good curability even in a portion which is shaded by wiring or the like. And the adhesive hardening composition, and completed the present invention. That is, the present invention provides the following curable composition, a liquid crystal sealing agent comprising the same, and a liquid crystal display element using the same. 1 . A curable composition for a liquid crystal sealing agent comprising the following components (A) to (E): (A) a compound having an ethylenically unsaturated group (B) an aromatic epoxy compound (C) in 1 An aliphatic epoxy compound having three or more epoxy groups in the molecule (D) Epoxy curing agent (E) Photoradical polymerization initiator 201003257 2 The hardening composition of the liquid crystal sealing agent according to the above item 1 The (E) photoradical polymerization initiator contains a compound having a ruthenium structure. (3) The curable composition for a liquid crystal sealing agent according to the above item 2, wherein the compound having the fluorene structure is represented by the following formula (e-Ι), 〇

NN

(式中，R1表示氫原子、苯基、碳數1〜10之烷基、R2表示氫原子、苯基、碳數1〜10之烷基、R3表示取代或非取代之咔唑基、或Ph-S-Phe-CO-基（Ph表示苯基、Phe表示伸苯基）。 4 如前述第1至3項中任一項所記載之液晶密封劑用硬化性組成物，其中該（B)成分及該（C)成分係在常溫、常壓下爲液體。 5 .如前述第1至4項中任一項所記載之液晶密封劑用硬化性組成物，其中該（B)成分及該（C)成分之環氧基當量係在 50〜2000之範圍内。 6.如前述第1至5項中任一項所記載之液晶密封劑用硬化性組成物，該（A)具有乙烯性不飽和基之化合物係具有1個以上之（甲基）丙烯醯基之化合物。 7 ·如前述第1至6項中任一項記載之液晶密封劑用硬化性組成物，其係進一步含有（F)無機微粒子。 201003257 8. 一種液晶顯示元件，其係使用如前述第7項記載之液晶密封劑而製造。發明效果根據本發明，可提供一種對液晶之污染性低、且即使是因配線等而成爲陰影的部分也能夠顯示良好之硬化性及黏著性的硬化性組成物。根據本發明，可提供一種在藉由液晶滴下技法製造液晶顯示元件時，特別有用之液晶密封劑。根據本發明，可提供一種降低未硬化之液晶密封劑導致之液晶污染性、長期安定性優良的液晶顯示元件。【實施方式】實施發明之最佳形態 I.硬化性組成物本發明之硬化性組成物（以下稱爲本發明之組成物）係可含下述成分（A)〜（I)。下述成分之中，（A)〜（E)爲必須成分、（F)〜（H)爲視需要可摻合之任意成分。 (A) 具有乙烯性不飽和基之化合物（以下稱爲成分（A)。） (B) 芳香族環氧化合物（以下稱爲成分（B)。） (C) 在1分子中具有3個以上之環氧基的脂肪族環氧化合物 (以下稱爲成分（C)。） (D) 環氧硬化劑（以下稱爲成分（D)。） (E) 光自由基聚合引發劑（以下稱爲成分（E)。） (F) 無機微粒子（以下稱爲成分（F)。） (G) 矽烷偶合劑（以下稱爲成分（〇)。） (H) 添加劑（以下稱爲成分（H)。） 201003257(wherein R1 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, R2 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, and R3 represents a substituted or unsubstituted carbazolyl group, or The sclerosing composition for a liquid crystal sealing agent according to any one of the above items 1 to 3, wherein the (B) is a phenyl group, and the phenyl group is a phenyl group. The component (C) is a curable composition for a liquid crystal sealing agent according to any one of the above items 1 to 4, wherein the component (B) and the component (B) are in a liquid state. The epoxy group equivalent of the (C) component is in the range of 50 to 2,000. The hardening composition for a liquid crystal sealing agent according to any one of the above items 1 to 5, wherein the (A) has ethylene The compound of the unsaturation group is a compound which has one or more (meth) propylene oxime groups, and the curable composition for liquid crystal sealing agents of any one of the above-mentioned items 1 to 6 further contains (F) Inorganic fine particles 201003257 8. A liquid crystal display element produced by using the liquid crystal sealing agent according to item 7 above. According to the present invention, it is possible to provide a curable composition which is low in contamination property to liquid crystal and which exhibits good curability and adhesion even in a portion which is shaded by wiring or the like. According to the present invention, it is possible to provide a A liquid crystal sealing agent which is particularly useful when a liquid crystal display element is produced by a liquid crystal dropping technique. According to the present invention, it is possible to provide a liquid crystal display element which is excellent in liquid crystal contamination by uncured liquid crystal sealing agent and excellent in long-term stability. BEST MODE FOR CARRYING OUT THE INVENTION I. Curable composition The curable composition of the present invention (hereinafter referred to as the composition of the present invention) may contain the following components (A) to (I). Among the following components, A) to (E) are essential components, and (F) to (H) are optional components which can be blended as necessary. (A) A compound having an ethylenically unsaturated group (hereinafter referred to as component (A).) (B) An aromatic epoxy compound (hereinafter referred to as a component (B).) (C) An aliphatic epoxy compound having three or more epoxy groups in one molecule (hereinafter referred to as component (C).) (D) Epoxy hardener (below It is component (D).) (E) Photoradical polymerization initiator (hereinafter referred to as component (E).) (F) Inorganic fine particles (hereinafter referred to as component (F).) (G) Decane coupling agent (hereinafter referred to as It is a component (〇).) (H) Additive (hereinafter referred to as ingredient (H).) 201003257

V 本發明之硬化性組成物係藉由使用2種類以上的環氧化合物，而顯現先前難以兼具之對玻璃基板與配向膜的高黏著力，且提高液晶顯示面板之設計自由度。 1.以下針對各成分加以說明。 (A)具有乙烯性不飽和基之化合物具有乙烯性不飽和基之化合物係進行自由基聚合之成分，使顯現提升強度、低線膨脹係數化、提升位置安定性等效果。作爲乙烯性不飽和基，沒有特別限定，可舉出例如（甲基）丙烯醯基、伸乙基等，較佳爲（甲基）丙烯醯基。作爲具有（甲基）丙烯醯基之化合物，可舉出例如丙烯酸2-羥基乙酯、（甲基）丙烯酸3-羥基丙酯、（甲基）丙烯酸2-羥基丙酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸 t-丁酯、（甲基）丙烯酸異辛酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂酯、（甲基）丙烯酸異冰片酯、（甲基）丙 % : 烯酸環己酯、（甲基）丙烯酸2 -甲氧基乙酯、（甲基）丙烯酸甲氧基乙二醇酯、（甲基）丙烯酸2-乙氧基乙酯、（甲基）丙烯酸四氫呋喃酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸乙基卡必醇酯、（甲基）丙烯酸苯氧基乙酯、苯氧基二乙二醇（甲基）丙烯酸酯、苯氧基聚乙二醇（甲基）丙烯酸酯、甲氧基聚乙二醇（甲基）丙烯酸酯、（甲基）丙烯酸2，2,2,-三氟乙酯、（甲基）丙烯酸2,2,3,3,-四氟丙酯、（甲基）丙烯酸1H，1H,5H，-八氟戊酯、（甲基）丙烯酸醯亞胺酯、（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸η- 201003257 丁酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸η-丁酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸η-辛酯、（甲基）丙烯酸異壬酯、（甲基）丙烯酸異十四烷酯、（甲基）丙烯酸2-丁氧基乙酯、（甲基）丙烯酸2-苯氧基乙酯、（甲基）丙烯酸雙環戊烯酯、（甲基）丙烯酸異癸酯、（甲基）丙烯酸二乙基胺基乙酯、（甲基）丙烯酸二甲基胺基乙酯、2-(甲基）丙烯醯氧基乙基琥珀酸、2-(甲基）丙烯醯氧基乙基六氫酞酸、酞酸2-(甲基）丙烯醯氧基乙基2-羥基丙酯、（甲基）丙烯酸縮水甘油酯、磷酸2-(甲基）丙烯醯氧基乙酯、二（甲基）丙烯酸1，4-丁二醇酯、二（甲基）丙烯酸1，3_丁二醇酯、二（甲基）丙烯酸 1，6-己二醇酯、二（甲基）丙烯酸1，9-壬二醇酯、二（甲基）丙烯酸1，1〇_癸二醇酯、2-η-丁基-2-乙基-1，3-丙二醇二（甲基）丙烯酸酯、二丙二醇二（甲基）丙烯酸酯、三丙二醇二（甲基）丙烯酸酯、聚二醇（甲基）丙烯酸酯、乙二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯 '環氧丙烷加成雙酚Α二（甲基）丙烯酸酯、環氧乙院加成雙酚A二（甲基）丙烯酸酯、環氧乙烷加成雙酌ρ二 (甲基）丙烯酸酯、二羥甲基二環戊二烯二（甲基）丙稀酸酯、1，3-丁二醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙嫌酸酯、環氧乙院改性異氰脲酸二（甲基）丙稀酸醋、2 -經基-3-(甲基）丙烯酿氧基丙基（甲基）丙稀酸酯、碳酸酯二醇二（甲基）丙烯酸酯、聚醚二醇二（甲基）丙烯酸酯、聚酯二醇二（甲基）丙烯酸酯、聚己内酯二醇二 -10- 201003257 (甲基）丙烯酸酯、聚丁二烯二醇二（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、環氧丙烷加成三羥甲基丙烷三（甲基）丙烯酸酯、環氧乙烷加成三羥甲基丙烷三（甲基）丙烯酸酯、己内酯改性三羥甲基丙烷三（甲基）丙烯酸酯、環氧乙烷加成異氰脲酸三（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、二三羥甲基丙烷四（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、甘油三（甲基）丙烯酸酯、環氧丙烷加成甘油三（甲基）丙烯酸酯、參（甲基）丙烯醯基氧基乙基磷酸酯等。作爲此種具有（甲基）丙烯醯基之化合物的市售品，可舉出例如VR-77LC (昭和高分子（股）公司製）、EB3 700 (Daicel Cytec(股）公司製）等。以組成物整體爲1 00質量％時，本發明之組成物中成分（A)之摻合量爲0.1〜90質量％、較佳爲1〜80質量％、更佳爲5〜70質量％。成分（A)之摻合量脫離上述〇.1〜90 質量％之範圍時，於照射紫外線實無法得到適度的硬度，有容易因熱引起位置偏移的可能性。關於（B)芳香族環氧化合物、（C)在1分子中具有3個以上之環氧基的脂肪族環氧化合物成分（B)係芳香族環氧化合物，成分（〇係在1分子中具有3個以上之環氧基的環氧化合物，較佳爲在常溫、常壓下爲液體。在此，「在常溫、常壓下爲液體」係指在常溫、常壓下的黏度爲5,000Pa’s以下、較佳爲uoopa.s以下、更佳爲100Pa，s以下。在此，「常溫」具體而言爲15。〇〜30 -11 - 201003257 °C，「常壓」具體而言爲大氣壓（O.IMPa)。上述黏度係在 25 °C用B型黏度計進行測定的値。藉由使成分（B)、成分（C) 在常溫、常壓下爲液體，將其當作原料使用之液晶密封劑係低黏度且作業性優良。成分（B)及成分（C)之環氧化合物的環氧基當量較佳爲在50〜2,000之範圍内、更佳爲在60〜1000之範圍内。在此，「環氧基當量」係指每1個環氧基之環氧化合物的分子量。環氧基當量小於5 0時，對液晶之耐污染性恐有不良影響，大於2000時，可能無法得到充分之硬化強度。成分（B)爲芳香族環氧化合物，特佳爲一分子中之環氧基係3官能以上，可抑制對液晶之污染、且可得黏著強度更加提升之效果。作爲成分（B)，可舉出例如、二胺基二苯基甲烷型環氧化合物、m-甲酚型環氧化合物、雙酚F型環氧化合物、苯酚酚醛型環氧化合物等。此等之中，在可抑制對液晶之污染、且更加提升黏著強度之點，特佳爲二胺基二苯基甲烷型環氧化合物之Ν,Ν,Ν’，Ν’-四縮水甘油基 -4,4’-二胺基二苯基甲烷。作爲此等（Β)成分之市售品的實例，可舉出Araldite MY721、同 DY203 (亨斯邁先進材料股份有限公司 (Huntsman advanced materials corporation)製多官肯g 環氧化合物）' Epikote 806、同806L、同807、同152(日本環氧樹脂公司製）等。成分（B)之環氧化合物係可1種單獨使用、亦可組合2種以上而使用。作爲成分（C)之環氧化合物係在1分子中具有3個以上之環氧基的化合物，若在常溫、常壓下爲液體則沒有特別 -12- 201003257 限定，可舉出例如山梨糖醇聚縮水甘油基醚、聚甘油聚縮水甘油基醚、新戊四醇聚縮水甘油基醚、二甘油聚縮水甘油基醚、三羥甲基丙烷聚縮水甘油基酸等。在本發明所使用之成分（C)的環氧化合物較佳爲化合物本身的液晶污染性低及黏度低的山梨糖醇聚縮水甘油基醚、三經甲基丙院聚縮水甘油基醚等。由於此等環氧化合物爲低黏度’因此將此等作爲原料而成之液晶密封劑係低黏度且作業性優良。作爲此種環氧化合物之市售品的實例’可舉出 EX-314、EX-4U、EX-614B、EX-610U-P、EX-1610-P( Nagase ChemteX(股）製多官能環氧化合物）、GT401 ( Daicel化學工業（股）製4官能環氧化合物）、SR-SEP(阪本藥品工業（股）製多官能環氧化合物等成分（C)之環氧化合物係可1種單獨使用、亦可組合2 種以上而使用。以組成物整體爲1 0 0質量％時’本發明之組成物中成分（B)及成分（C)之摻合量爲〇_1〜90質量％、較佳爲1〜80 質量％、更佳爲5〜60質量％。成分（B)之摻合量脫離上述 0 . 1〜9 0質量％之範圍時，無法得到充分之黏著強度、或照射紫外線時無法得到適度之硬度，有容易因熱引起位置偏移的可能性。又，成分（B)與成分（C)之摻合比較佳係在成分（B):成分（C) = 10: 90〜90: 10之範圍、更佳爲20: 80 〜80 : 20之範圍。 (D)環氧硬化劑環氧硬化劑係爲了使含環氧基之化合物交聯、且顯現黏著性、硬度之效果而予以摻合。作爲環氧硬化劑，可舉 -13- 201003257 出酸性化合物、酸產生劑、鹼性化合物或鹼產生劑等。又，作爲環氧硬化劑，較佳爲使用硬化劑本身係與環氧基進行交聯反應、而倂入已交聯的聚合物中之「潛在型環氧硬化劑」。潛在性環氧硬化劑可使用眾所周知之物，惟從使用一液型可得黏度安定性良好之摻合物的點而言，較佳係有機酸二醯肼化合物、咪唑及其衍生物、二氰二醯胺、芳香族胺等。此等係可單獨使用亦可組合使用。此等之中，作爲潛在型環氧硬化劑，以胺系潛在型硬化劑、且其融點或環球法（根據JISK2207 )之軟化點溫度爲100〜25 0°C爲更佳。使用胺系潛在型硬化劑時，由於胺的活性氫係對本發明之組成物中具有（甲基）丙烯醯基的其他成分之（甲基）丙烯醯基引起熱親核加成反應，而提升本發明之組成物的硬化性。即’由於胺系潛在型硬化劑係對成分（A)之具有乙烯性不飽和基之化合物及/或成分（B)、成分（C)之環氧化合物雙 % 方顯示熱反應特性，因此作爲兩成分之相溶化成分的功肯g ’而使液晶表示面板的顯示特性、黏著信賴性等之面板信賴性變得良好而較佳。作爲係胺系潛在型硬化劑且其融點或環球法之軟化點溫度爲100〜250 °c之潛在型環氧硬化劑的具體例，可舉出例如二氰二醯胺（融點209°C )等之二氰二醯胺類；己二酸二醯肼（融點181 °C)、1，3 -雙（肼基羧乙基）-5-異丙基乙內醯脲（融點120 °C)等之有機酸二醯肼；2,4-二胺基 -14- 201003257 -6-[2’-乙基咪唑基-(1’）]-乙基三阱（融點215°(：〜225°〇)、 2 -苯基咪唑（融點 137〜147 °C)、2 -苯基-4 -甲基咪唑（融點174〜184 °C )、2 -苯基-4-甲基-5-羥基甲基咪唑（融點191 〜195°C )等之咪唑衍生物、水楊基醯肼（融點140°C )等。又，在本發明所使用之潛在性環氧硬化劑較佳係使用藉由水洗法、再結晶法等進行高純度化處理者。作爲上述胺系潛在型硬化劑之市售品的實例，可舉出例如 Ajicure VDH、VDH-J、UDH、UDH-J ( AJIMOTO FINETECHNO(股）製）、7j<楊基醯肼（大塚化學（股）製）等。潛在型環氧硬化劑係可1種單獨使用、亦可組合2種以上而使用。以組成物整體爲1 00質量％時，本發明之組成物中成分（D)之慘合量爲0.1〜60重量％、較佳爲1〜50質量％、更佳爲3〜30質量％。成分（D)之摻合量若比0.1質量％少時，與環氧基之硬化性不足，無法得到充分之硬度、黏著性，同時液晶污染可能性變高。又，比6 0質量％多時，沒有與環氧基反應之過剩硬化劑污染液晶之可能性變高。 (E)光自由基聚合引發劑本發明所用之光自由基聚合引發劑係藉由紫外線照射生成自由基用以使（A)成分聚合而添加。（E)成分雖可使用眾所周知化合物’但從高感度、即使是成爲配線或黑色矩陣等之陰影而紫外線不直接照射的部位，也可藉由反射光、散射光、繞射光以使本發明之組成物硬化之點而論，較佳爲含有具肟酯構造之化合物。 -15- 201003257 具有肟酯構造之化合物較佳爲下述通式（e-1)所示之化合物。〇V The curable composition of the present invention exhibits high adhesion to a glass substrate and an alignment film which have been difficult to achieve by using two or more types of epoxy compounds, and improves the degree of freedom in designing the liquid crystal display panel. 1. The following describes each component. (A) Compound having an ethylenically unsaturated group The compound having an ethylenically unsaturated group is a component which undergoes radical polymerization, and exhibits effects such as improvement in strength, low linear expansion coefficient, and improvement in position stability. The ethylenically unsaturated group is not particularly limited, and examples thereof include a (meth)acryl fluorenyl group and an exoethyl group, and a (meth) acryl fluorenyl group is preferred. Examples of the compound having a (meth)acryl fluorenyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 4-hydroxybutyl ester, 2-hydroxybutyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylic acid Lauryl ester, stearyl (meth) acrylate, isobornyl (meth) acrylate, (meth) propyl %: cyclohexyl enoate, 2-methoxyethyl (meth) acrylate, (methyl) ) methoxyethylene glycol acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofuran (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate , phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (methyl Acrylate, 2,2,2,-trifluoroethyl (meth)acrylate, 2,2,3,3,-tetrafluoropropene (meth)acrylate , (meth)acrylic acid 1H, 1H, 5H,-octafluoropentyl ester, yttrium (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate - 201003257 Butyl ester, propyl (meth) acrylate, η-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, η (meth) acrylate -octyl ester, isodecyl (meth)acrylate, isotetradecyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(methyl) Ethyl ethoxyethyl succinic acid, 2-(methyl) propylene oxiranyl ethyl hexahydro phthalic acid, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, (methyl) ) glycidyl acrylate, 2-(meth) propylene methoxyethyl phosphate, 1,4-butylene glycol di(meth) acrylate, 1,3 butyl di(meth) acrylate Ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,1〇-nonanediol di(meth)acrylate, 2- Η-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyglycol (methyl) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Propylene oxide addition bisphenol quinone di(meth) acrylate, epoxy bisphenol addition bisphenol A di(meth) acrylate, ethylene oxide addition bis bis(meth) acrylate, Dimethylol dicyclopentadienyl di(meth) acrylate, 1,3-butanediol di(meth) acrylate, neopentyl glycol di(methyl) propyl acrylate, epoxy B-modified isocyanuric acid di(meth)acrylic acid vinegar, 2-carbyl-3-(methyl)acryloxypropyl (meth) acrylate, carbonate diol di Methyl) acrylate, polyether Alcohol di(meth)acrylate, polyester diol di(meth) acrylate, polycaprolactone diol di-10-201003257 (meth) acrylate, polybutadiene diol di(methyl) Acrylate, neopentyl alcohol tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, propylene oxide addition trimethylolpropane tri(meth) acrylate, ethylene oxide Addition of trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid tri(meth)acrylate , dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl alcohol tetra (methyl) Acrylate, glycerol tri(meth) acrylate, propylene oxide addition glycerol tri(meth) acrylate, gin(meth) propylene decyl oxyethyl phosphate, and the like. For example, VR-77LC (manufactured by Showa Polymer Co., Ltd.), EB3 700 (manufactured by Daicel Cytec Co., Ltd.), and the like can be mentioned as a commercial product of the compound having a (meth) acrylonitrile group. When the total amount of the composition is 100% by mass, the blending amount of the component (A) in the composition of the present invention is 0.1 to 90% by mass, preferably 1 to 80% by mass, more preferably 5 to 70% by mass. When the blending amount of the component (A) is out of the above range of from 0.1 to 90% by mass, an appropriate hardness cannot be obtained by irradiation with ultraviolet rays, and there is a possibility that positional displacement is likely to occur due to heat. (B) an aromatic epoxy compound, (C) an aliphatic epoxy compound component (B) having three or more epoxy groups in one molecule, an aromatic epoxy compound, and a component (in a molecule) The epoxy compound having three or more epoxy groups is preferably a liquid at normal temperature and normal pressure. Here, "liquid at normal temperature and normal pressure" means that the viscosity at normal temperature and normal pressure is 5,000. Below Pa's, it is preferably uoopa.s or less, more preferably 100 Pa or less. Here, "normal temperature" is specifically 15. 〇~30 -11 - 201003257 °C, "normal pressure" is specifically atmospheric pressure (O.IMPa) The above-mentioned viscosity is measured by a B-type viscometer at 25 ° C. The component (B) and the component (C) are used as a raw material by using a liquid at normal temperature and normal pressure. The liquid crystal sealing agent is low in viscosity and excellent in workability. The epoxy equivalent of the epoxy compound of the component (B) and the component (C) is preferably in the range of 50 to 2,000, more preferably in the range of 60 to 1,000. Here, "epoxy equivalent" means the molecular weight of the epoxy compound per one epoxy group. At 50°, there is a possibility of adversely affecting the stain resistance of liquid crystal. When it is more than 2000, sufficient hardening strength may not be obtained. Component (B) is an aromatic epoxy compound, and particularly preferably an epoxy group in one molecule. When it is a trifunctional or more, it can suppress the contamination of a liquid crystal, and can improve the adhesive strength further. As a component (B), a diamino diphenylmethane type epoxy compound and m- cresol type ring are mentioned, for example. Oxygen compound, bisphenol F-type epoxy compound, phenol novolac type epoxy compound, etc. Among these, in the point of suppressing contamination of liquid crystal and further improving adhesion strength, it is particularly preferred to be diaminodiphenylmethane. An epoxy compound of the type, Ν, Ν', Ν'-tetraglycidyl-4,4'-diaminodiphenylmethane. Examples of commercially available products of such (Β) components include Araldite MY721, same as DY203 (Huntsman advanced materials corporation), Epikote 806, 806L, 807, 152 (made by Nippon Epoxy Co., Ltd.), etc. The epoxy compound of the component (B) can be one kind It is used alone or in combination of two or more. The epoxy compound as the component (C) is a compound having three or more epoxy groups in one molecule, and is not particularly liquid when it is liquid at normal temperature and normal pressure. 12-201003257 Qualified, for example, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, neopentyl alcohol polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane poly Glycidyl acid, etc. The epoxy compound of the component (C) used in the present invention is preferably a sorbitol polyglycidyl ether having a low liquid crystal pollution property and a low viscosity of the compound itself, and a trimethoprim. Glycidyl ether and the like. Since these epoxy compounds have a low viscosity, the liquid crystal sealing agent which is made of these materials is low in viscosity and excellent in workability. Examples of the commercial product of such an epoxy compound include EX-314, EX-4U, EX-614B, EX-610U-P, and EX-1610-P (a multifunctional epoxy resin manufactured by Nagase ChemteX). Compounds), GT401 (a tetrafunctional epoxy compound manufactured by Daicel Chemical Co., Ltd.), and an epoxy compound of a component (C) such as a SR-SEP (a polyfunctional epoxy compound manufactured by Sakamoto Pharmaceutical Co., Ltd.) can be used alone. When the total amount of the composition is 100% by mass, the blending amount of the component (B) and the component (C) in the composition of the present invention is 〇_1 to 90% by mass. It is preferably 1 to 80% by mass, more preferably 5 to 60% by mass. When the blending amount of the component (B) is out of the above range of 0.1 to 90% by mass, sufficient adhesive strength or ultraviolet irradiation cannot be obtained. When the hardness is not moderate, there is a possibility that the position is likely to be displaced due to heat. Moreover, the blending of the component (B) and the component (C) is better in the component (B): the component (C) = 10: 90 The range of ~90:10, more preferably 20:80~80:20. (D) Epoxy hardener epoxy hardener is used to make epoxy-containing compounds The epoxy curing agent can be blended with an effect of adhesion and hardness. As an epoxy curing agent, an acidic compound, an acid generator, a basic compound, an alkali generating agent, etc. can be mentioned as an epoxy curing agent. The agent is preferably a "potential epoxy hardener" which is a crosslinking agent which is crosslinked with an epoxy group and is incorporated into a crosslinked polymer. A latent epoxy hardener can be used as a known epoxy hardener. However, from the viewpoint of using a one-liquid type blend having a good viscosity stability, an organic acid diterpenoid compound, imidazole and a derivative thereof, dicyanodiamide, an aromatic amine, etc. are preferable. These may be used singly or in combination. Among these, as a latent epoxy hardener, an amine-based latent curing agent, and its melting point or ring and ball method (according to JIS K2207) has a softening point temperature of 100 to 25 It is more preferable to use 0 ° C. When an amine-based latent type hardener is used, the active hydrogen of the amine causes heat to the (meth) acrylonitrile group having other components of the (meth) acryl fluorenyl group in the composition of the present invention. Nuclear addition reaction The hardenability of the composition of the composition. That is, the amine-based latent curing agent is a compound of the component (A) having an ethylenically unsaturated group and/or the compound (B) and the epoxy compound of the component (C). Since the thermal reaction characteristics are exhibited, the reliability of the panel such as the display characteristics and the adhesion reliability of the liquid crystal display panel is improved as the function of the two components of the melt-dissolving component, and it is preferable as a urethane-based latent curing agent. Specific examples of the latent epoxy curing agent having a melting point or a ringing point temperature of 100 to 250 ° C in the melting point or the ring method include dicyandiamide such as dicyandiamide (melting point 209 ° C). Organic acids such as amines; diterpene adipate (melting point 181 ° C), 1,3 - bis(decyl carboxyethyl)-5-isopropylhydantoin (melting point 120 ° C) Dioxane; 2,4-diamino-14-201003257 -6-[2'-ethylimidazolyl-(1')]-ethyl tri-trap (melting point 215° (:~225°〇), 2-phenylimidazole (melting point 137~147 °C), 2-phenyl-4-methylimidazole (melting point 174~184 °C), 2-phenyl-4-methyl-5-hydroxymethyl Imidazole such as imidazole (melting point 191 ~ 195 ° C) Biology, salicyl acyl hydrazide (melting point 140 ° C) and the like. Further, the latent epoxy curing agent used in the present invention is preferably a one which is highly purified by a water washing method, a recrystallization method or the like. Examples of the commercial product of the above-described amine-based latent curing agent include Ajicure VDH, VDH-J, UDH, UDH-J (made by AJIMOTO FINETECHNO), and 7j<Yang Jiyu (Dayu Chemical ( Stock system) and so on. The latent epoxy curing agent may be used singly or in combination of two or more. When the total amount of the composition is 100% by mass, the amount of the component (D) in the composition of the present invention is 0.1 to 60% by weight, preferably 1 to 50% by mass, more preferably 3 to 30% by mass. When the blending amount of the component (D) is less than 0.1% by mass, the curing property with the epoxy group is insufficient, and sufficient hardness and adhesiveness cannot be obtained, and the possibility of liquid crystal contamination becomes high. Further, when the amount is more than 60% by mass, the possibility that the excessive hardener which does not react with the epoxy group contaminates the liquid crystal becomes high. (E) Photoradical polymerization initiator The photoradical polymerization initiator used in the present invention is obtained by polymerizing a component (A) by generating a radical by ultraviolet irradiation. Although the (E) component can use a well-known compound', the present invention can be reflected by light, scattered light, or diffracted light from a high sensitivity, even if it is a portion where ultraviolet rays are not directly irradiated by a shadow such as a wiring or a black matrix. In the case where the composition is hardened, it is preferred to contain a compound having an oxime ester structure. -15-201003257 The compound having an oxime ester structure is preferably a compound represented by the following formula (e-1). 〇

在式（e-ι)中，R1較佳爲氫原子、苯基、碳數1〜10之烷基等。 R2較佳爲氫原子、苯基、碳數1〜10之烷基等。 R3較佳爲取代或非取代之含咔唑基的1價有機基、 Ph-S-Phe-CO -基（Ph表示苯基、Phe表示伸苯基）等。又，成分（E)較佳爲具有肟酯構造之化合物，可舉出〇-醯基肟系化合物。作爲〇-醯基肟系化合物，較佳爲9. Η -咔唑系之0-醯基肟型聚合引發劑。可舉出例如1.2-辛二醇，1-〔4-(苯硫基）-，2-(0-苄基肟）〕、1-〔9-乙基-6-苄基- 9.H.-咔唑-3-基〕-壬烷-1，2-壬烷-2-肟-0-苯甲酸酯、 1-〔 9 -乙基-6-苄基- 9.H.-咔唑-3-基〕-壬烷-1，2-壬烷-2-肟- 0-乙酸酯、1-〔 9-乙基-6-苄基- 9.H.-咔唑-3-基〕-戊烷-1,2-戊烷-2-肟-0-乙酸酯、1-〔9-乙基-6-苄基- 咔唑-3-基〕 -辛烷-1-酮肟-〇-乙酸酯、1-〔 9-乙基- 6-( 2-甲基苄基）-9·Η·-咔唑-3-基〕-乙烷-1-酮肟-0-苯甲酸酯、1-〔 9-乙基- 6-( 2-甲基苄基）-9.H.-咔唑-3-基〕-乙烷-1-酮肟-0-乙酸酯、1-〔9-乙基-6- (1,3,5-三甲基苄基）-9.H.-咔唑-3-基〕-乙烷 -16 - 201003257 -1-酮肟- Ο-苯甲酸酯、l-〔 9-丁基- 6-(2-乙；咔唑-3-基〕-乙烷-1-酮肟-〇-苯甲酸酯、i_〔甲基-4-四氫吡喃甲氧基苄基）-9.Η. -咔唑-2 酮肟-〇-乙酸酯、1-〔 9-乙基- 6-( 2 -甲基-4-匹基苄基）咔唑-3-基〕-乙烷-1-酮肟- : 1-〔 9 -乙基-6-〔 2 -甲基-4- ( 2,2-二甲基-1，3 甲氧基苄基〕-9.H.-咔唑-3-基〕-、1-(〇-乙此等〇-醯基肟化合物之中，特佳爲1-〔甲基苄基）咔唑-3-基〕-乙烷-1-酮肟. 酮、1-〔 9-乙基-6-〔2-甲基- 4-(2，2-二甲基基）甲氧基苄基〕-9.H.-咔唑-3-基〕-、1-( 1.2-辛二醇，1-〔 4-(苯硫基）-，2- ( Ο-苄基作爲具有肟酯構造的化合物之市售品實如 Irgacure 0X01、OXE02 ( Ciba Specialty 公司製）、N-1919(Adeca(股）公司製）等。成分（E)之光自由基聚合引發劑係可1卷可組合2種以上而使用。又’亦可組合適當移劑。亦可使用光自由基起始劑本身賦予交成分（E)之光自由基聚合引發劑較佳係通式（e-2)所示構造之化合物。基苄基） 9-乙基-6- ( 2-!-基〕-乙烷-1-丨氫呋喃基甲氧乙酸酯、乙酮、 -二氧戊環基），醯基肟）等。 9-乙基-6- ( 2--0-乙酸酯、乙 -1，3-二氧戊環〇 -乙醯基肟）、肟）〕。例，可舉出例 Chemicals(股） I單獨使用、亦 '增感劑或鏈轉聯性基者。摻合具有下述 -17- 201003257 R27In the formula (e-), R1 is preferably a hydrogen atom, a phenyl group or an alkyl group having 1 to 10 carbon atoms. R2 is preferably a hydrogen atom, a phenyl group or an alkyl group having 1 to 10 carbon atoms. R3 is preferably a substituted or unsubstituted oxazolyl-containing monovalent organic group or a Ph-S-Phe-CO- group (Ph represents a phenyl group, Phe represents a phenylene group). Further, the component (E) is preferably a compound having an oxime ester structure, and examples thereof include an anthracene-fluorenyl compound. As the fluorene-fluorenyl fluorene-based compound, a quinone-carbazole-based 0-fluorenyl hydrazine type polymerization initiator is preferred. For example, 1.2-octanediol, 1-[4-(phenylthio)-, 2-(0-benzylhydrazine), 1-[9-ethyl-6-benzyl- 9.H. -oxazol-3-yl]-decane-1,2-decane-2-indole-0-benzoate, 1-[9-ethyl-6-benzyl- 9.H.-carbazole 3-yl]-decane-1,2-decane-2-indole- 0-acetate, 1-[9-ethyl-6-benzyl- 9.H.-carbazol-3-yl ]-Pentane-1,2-pentane-2-indole-0-acetate, 1-[9-ethyl-6-benzyl-oxazol-3-yl]-octane-1-one oxime -〇-acetate, 1-[9-ethyl-6-(2-methylbenzyl)-9.indole-oxazol-3-yl]-ethane-1-one oxime-0-benzene Formate, 1-[9-ethyl-6-(2-methylbenzyl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-0-acetate, 1-[9-ethyl-6-(1,3,5-trimethylbenzyl)-9.H.-oxazol-3-yl]-ethane-16 - 201003257 -1-one oxime - Ο -benzoic acid ester, 1-[9-butyl-6-(2-ethane; oxazol-3-yl)-ethane-1-one oxime-indole-benzoate, i_[methyl-4 -tetrahydropyranylmethoxybenzyl)-9.Η.-carbazole-2 ketooxime-oxime-acetate, 1-[9-ethyl-6-(2-methyl-4-pilyl) Benzyl)oxazol-3-yl]-ethane-1-one oxime- : 1-[ 9 -ethyl-6-[ 2 -methyl-4- ( 2,2 - dimethyl-1,3 methoxybenzyl]-9.H.-carbazol-3-yl]-, 1-(〇-B, etc. among the 〇-mercaptopurine compounds, particularly preferably 1 -[Methylbenzyl)oxazol-3-yl]-ethane-1-one oxime. Ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl) Methoxybenzyl]-9.H.-carbazol-3-yl]-, 1-(1.2-octanediol, 1-[4-(phenylthio)-,2-( Ο- A commercially available product of a benzyl group as a compound having an oxime ester structure is, for example, Irgacure 0X01, OXE02 (manufactured by Ciba Specialty Co., Ltd.), N-1919 (manufactured by Adeca Co., Ltd.), etc. Photopolymerization initiator of component (E) It is also possible to use two or more types in combination, and it is also possible to combine an appropriate transfer agent. It is also possible to use a photoradical initiator which imparts a photo-radical polymerization initiator to the component (E). E-2) a compound of the structure shown. benzyl) 9-ethyl-6-(2-!-yl)-ethane-1-indolehydrofuranylmethoxyacetate, ethyl ketone, dioxane Pentocyclo), fluorenyl), etc. 9-ethyl-6-(2--0-acetate, ethyl-1,3-dioxolane-ethenyl), ruthenium). For example, Chemicals (shares) I can be used alone, and also as a sensitizer or a chain-transfer group. Blending has the following -17- 201003257 R27

=0 R24--R25 R26 (e-2) 式中，R24、R25係各自獨立地表示碳數1〜4之烷基， R26表示羥基或碳數1〜4之烷基、R2 7表示氫原子或甲基。再者，（e-2)亦可爲複數相連之構造’此時之分子量較佳爲350〜10,000之範圍。 (e-2)所示之化合物藉由倂用上述具有肟酯構造之光自由基聚合引發劑，可更有效地降低對液晶之污染性。具有肟酯構造之光自由基聚合引發劑與（e-2)所示之光自由基起始劑的摻合比例（重量比）較佳爲3 5 : 65〜65 : 3 5之範圍内、特佳爲50: 50。具有肟酯構造之光自由基聚合引發劑太少時，暗處硬化性降低’相反地過多時’對液晶之耐污染性降低。若在上述範圍内，可得黏著性、對液晶之耐污染性及暗處硬化性任一性能均爲優良之硬化性組成物。本發明所用的（e_2)所示之光自由基聚合引發劑之具體例，可舉出下述式（e-2’）所示之低（2 -羥基-2-甲基- l- [4-( 1-甲基乙嫌基）苯基]丙酮’市售品可舉出例如=0 R24--R25 R26 (e-2) wherein R24 and R25 each independently represent an alkyl group having 1 to 4 carbon atoms, R26 represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R2 7 represents a hydrogen atom. Or methyl. Further, (e-2) may also be a structure in which plural numbers are connected, and the molecular weight at this time is preferably in the range of 350 to 10,000. The compound represented by the formula (e-2) can more effectively reduce the contamination to the liquid crystal by using the above-mentioned photopolymerizable polymerization initiator having an oxime ester structure. The blending ratio (weight ratio) of the photoradical polymerization initiator having an oxime ester structure to the photoradical initiator represented by (e-2) is preferably in the range of 3 5 : 65 to 65 : 3 5 , Very good for 50: 50. When the photoradical polymerization initiator having an oxime ester structure is too small, the hardenability in the dark portion is lowered. When the amount is too large, the stain resistance to the liquid crystal is lowered. When it is in the above range, it is possible to obtain a curable composition which is excellent in adhesion, liquid stain resistance, and darkness hardening property. Specific examples of the photoradical polymerization initiator represented by (e_2) used in the present invention include low (2-hydroxy-2-methyl-l-[4] represented by the following formula (e-2'). -(1-Methylethyl phenyl) phenyl]acetone's commercially available product can be exemplified by

EsacureKIP150、150P (以上 Satomer 公司製）。 -18- 201003257EsacureKIP150, 150P (manufactured by Satomer Corporation). -18- 201003257

(e-2，） (式中，k表示2〜50之數。）以組成物整體爲1 00質量％時’本發明之組成物中成分（E)之摻合量爲〇.〇1〜20質量％、較佳爲0.1〜15質量％、更佳爲0.2〜10質量％。成分（E)之摻合量比0.01質量％少時，液晶污染性有惡化之可能性。又，比20質量％多時，液晶污染性及黏著強度降低。 (F)無機微粒子藉由摻合無機微粒子，可成爲高玻璃轉移溫度、低線膨脹係數、顯現尺寸安定性提升的效果（改善、改良），因而較佳使用。作爲無機微粒子，可舉出以矽石、氧化鋁、氧化锆、氧化鎂、碳酸鈣、碳酸鎂、硫酸鋇、滑石、蒙脫石等爲主成分之粒子，較佳爲以矽石及氧化鋁爲主成分之粒子。無機微粒子之形狀可爲球狀、棒狀、板狀、繊維狀、不定形狀之任一者，又，此等亦可爲實心狀、中空狀、多孔質狀。無機微粒子的數平均粒徑通常爲0.001〜10 μιη、較佳爲0.0 1〜5 μχη之範圍。若超過1 0 μιη，液晶胞製作時玻璃基 -19- 201003257 板貼合的間隙形成會有出錯的可能。在此，無機微粒子之數平均粒徑係藉由雷射光繞射法加以測定。無機微粒子係可將粉體狀直接添加·混合於其他成分、亦可做成溶媒分散液再添加·混合於其他成分並餾去溶劑。作爲無機微粒子之市售品的實例，可舉出例如 ADMAFINESO-E 1 、 SO-E2、 SO-E3 、 SO-E4、 SO-E5、 SE3200-SEJ( Admatechs(股）公司製）、SS01、SS03、SS15、 SS35 (大阪化成（股）公司製）等。無機微粒子係可1種單獨使用、亦可組合2種以上而使用。無機微粒子亦可藉由矽烷偶合劑等加以表面處理。藉由進行表面處理，可提升與其他成分之相溶性，能夠提升在組成物中之分散性、機械強度。以組成物整體爲1 00質量％時，本發明之組成物中成分（F)之摻合量爲1〜50質量％、較佳爲5〜40質量％、更佳爲10〜30質量％。成分（F)之摻合量比1質量％少時，尺寸安定性有惡化的可能。又，比5 0質量％多時，液晶胞製作時玻璃基板貼合的間隙形成會有出錯的可能。 (G)矽烷偶合劑藉由摻合矽烷偶合劑，可顯現黏著強度之耐久性提升的效果（改善、改良），因而較佳使用。矽烷偶合劑較佳爲具有環氧基者、及具有（甲基）丙烯醯基者。矽烷偶合劑係可1種單獨使用、亦可組合2種以上而 -20- 201003257 使用。作爲具有環氧基之矽烷偶合劑的實例，可舉出例如r _ 環氧丙氧基丙基三甲氧基砂垸等。此等砂院偶合劑之市售品的實例，可舉出例如、SH6040(東麗道康寧（股）公司製）、 KBM-403 (信越聚矽氧（股）公司製）等。作爲具有（甲基）丙烯醯基之矽烷偶合劑的實例，可舉出例如、r-甲基丙烯醯氧基丙基三甲氧基矽烷等。作爲此等矽烷偶合劑之市售品的實例，可舉出例如SZ6030(東麗道康寧（股）公司製）、KBM-503、KBM-5103 (信越聚矽氧 (股）公司製）。以組成物整體爲1 〇〇質量％時，本發明之組成物中成分（G)之摻合量爲0.001〜15質量％、較佳爲0.01〜10質量 %、更佳爲0.05〜5質量％。成分（G)之摻合量比0.001質量 %少時，可能無法得到充分黏著耐久性。又，比1 5質量％多時，液晶污染可能性變高。 (H)其他添加劑在本發明之組成物中，於不損及本發明之效果的範圍 V.- 內，可摻合其他添加物。作爲此種添加劑，可舉出例如成分（E)以外之光自由基起始劑、增感劑、鏈轉移劑、消泡劑、離子捕捉劑、吸水劑、有機微粒子、均平劑、間隔物、有機溶劑等。 2.硬化性組成物之製造法本發明之組成物係可藉由將成分（A)〜（E)、及視需要的成分（F)〜（H)投入容器中，使用行星式攪拌機等之攪拌機充分地混合後，在真空下進行脫泡，來加以製造。 -21 - 201003257 3 ·硬化性組成物之硬化方法·硬化條件本發明之組成物係可藉由紫外線照射、或加熱來使其硬化。將本發明之組成物作爲液晶密封劑使用且採用液晶滴下技法時’通常係利用紫外線照射使暫時硬化後，進一步藉由加熱使完全硬化。用以使本發明之組成物硬化所用的光之波長係沒有特別限定，惟考慮對配向膜及對液晶之損害，較佳爲35〇〜 700nm。照射線量較佳爲500〜l〇〇〇〇mj/cm2、更佳爲1〇〇〇〜3000mJ/cm2 ° 熱硬化的溫度係沒有特別限定，惟，較佳爲硬化溫度係7 0°C以上小於200°C、更佳爲100°C以上小於150°C。又，硬化時間較佳爲20分以上小於3小時、更佳爲30分以上小於2小時。 II. 液晶密封劑液晶密封劑係用於使液晶顯示元件的兩片玻璃基板黏 ^ 著、保護内部，同時防止液晶流出。本發明之液晶密封劑的特徵係由上述本發明之硬化性組成物構成。因此，本發明之液晶密封劑係有用於具備耐液晶污染性、暗處硬化性、拉伸黏著強度等，並藉由液晶滴下技法的液晶顯示元件（液晶顯示胞）之製造。本發明之液晶密封劑的黏度係沒有特別限定，惟從分配性、形狀保存性的觀點來看，較佳爲10〜1 000 Pa. S、更佳爲 100〜500Pa，s。 III. 液晶顯示元件 -22- 201003257 本發明之液晶顯示元件的特徵係用上述本發明之液晶密封劑所製造。因此，根據本發明，可得耐液晶污染性、拉伸黏著強度優良、長期安定性、信賴性優異之液晶顯示元件。邊參照第1圖所示本發明之液晶顯示元件之一實施形態的模式圖，邊針對本發明之液晶顯示元件的構造加以說明。液晶顯示元件1係如第1圖所示，具有在兩片玻璃基板1 〇之間設有透明電極1 4、配向膜1 2 '彩色濾光片1 6，夾著間隔物1 8，藉由液晶密封劑來保持液晶22的構造。藉由液晶密封劑20黏著兩片玻璃基板1 〇，同時將液晶22封入·保持於玻璃基板1 0與液晶密封劑20所圍著的空間。由第1圖可知，由於液晶密封劑20係與液晶22直接接觸，未硬化之液晶密封劑20中的成分會溶解於液晶 22中，而使液晶22的比電阻降低，結果損及液晶顯示元件1的長期安定性、信賴性。由於本發明之液晶顯示元件係使用上述本發明之液晶密封劑，因此可防止未硬化之液晶密封劑成分溶解於液晶，故長期安定性、信賴性優異。本發明之液晶顯示元件較佳係藉由液晶滴下方式加以製造。參照第2圖同時針對藉由液晶滴下方式之液晶顯示元件之製造步驟的槪要加以說明。在一邊的玻璃基板上使用分配器圍住封入液晶的範圍，以形成液晶密封劑的框架。液晶密封劑的線寬、膜厚通常分別爲 0.1〜5 mm、0.1〜20 μιη左右、較佳爲〇.5〜 -23- 201003257 3mm、1〜1〇μιη。此時所用之液晶密封劑的分配器可舉出 SHOTminiSL (武藏工程（股）製）等。不使液晶密封劑硬化，在液晶密封劑的框架中滴下液晶、除去氣泡等之後，貼合另一玻璃基板，將2片玻璃基板壓合而封止液晶。接著，照射紫外線使液晶密封劑暫時硬化。此時所用之紫外線較佳爲使用波長200〜700nm者，若考慮對配向膜及液晶之損害，更佳爲使用波長350〜700nm者。紫外線之光源較佳爲使用高壓水銀燈、金屬鹵素燈、LED等。之後，將該基板以7 0〜2 0 0 °C、較佳爲9 0〜1 5 0 °C加熱 10分〜5小時、較佳爲30分〜2小時進行液晶退火，同時使液晶密封劑完全硬化而得液晶顯示元件。 [實施例] 以下列舉實施例及比較例進一步具體說明本發明，惟本發明係不因此等實施例而受任何限定。製造例1 胺甲酸酯丙烯酸酯（（A)成分；甘油-AOI )之合成對附有攪拌機的容器内之2-異氰酸酯基乙基丙烯酸酯 (昭和電工（股）製Karenz AOI) 75.4份與二丁基錫二月桂酸酯0.1份所構成的溶液，以1 〇 °c、1小時之條件滴下甘油（阪本藥品工業（股）製精製甘油）24.6份後’以60°c、4 小時之條件攪拌而做成反應液。以FT-IR測定該反應液中生成物的殘存異氰酸酯量爲〇· 1質量％以下，確認反應係大致上定量地進行。又’確認分子内含有胺甲酸酯鍵、及丙烯醯基（聚合性不飽和基）。 -24- 201003257 藉由以上操作，得到100份之甘油-AOI。實施例1 量取下述表1之實施例1所示成分至容器中，使用行星式攪拌機（THINK Y Mixer、Thinky公司製）充分地混合。之後在真空下進行脫泡，製得硬化性組成物。實施例2〜4及比較例1〜2 除了變更爲下述表1所示組成以外，與實施例1同樣地製造各硬化性組成物。 <硬化物之特性評價> 評價將上述實施例及比較例所得之硬化性組成物硬化時的下述特性。所得之結果示於表1。 1 ·拉伸黏著強度[玻璃] 使相對於硬化性組成物1 00質量份而言爲1質量份之間隔物粒子分散，取其置於載玻片的中央部份，將另一片載玻片以成爲十字的方式重合，壓合使其成爲均勻厚度。對其照射紫外線（500mW/cm2、3000mJ/cm2 )後，在 120 t放置1小時，做成拉伸黏著強度測定用之樣品。藉由拉伸試驗機測定該樣品之黏著強度（N/mm2 )。若爲4N/mm2 以上則拉伸黏著強度爲良好。 2.拉伸黏著強度[配向膜] 於載玻片上塗布OPTMERAL60101 ( JSR (股）製配向膜用組成物）作爲配向膜’在8 0 °C預烘烤2分鐘後在2 0 0 °C 之烘箱加熱60分鐘。除了使用附有配向膜之載玻片以外’ 進行與1 .同樣的操作。 3 .液晶相轉移溫度變化 -25- 201003257 在樣品瓶（内徑1 〇mm )投入硬化性組成物0 · 02 5 g後，投入液晶（Merck公司製MLC-6608) 0.075g。從該樣品瓶的底面照射紫外線（3000mJ/cm2 )後，在12(TC放置1小時。放置冷卻到25°C後，取出液晶的上部澄清物，進行DSC 測定（昇溫速度2 °C /分）。由所測得之相轉移溫度與未處理的液晶（空白試樣（blank))之相轉移溫度的差求出變化量，依照下述評價基準進行評價。 A : 對空白試樣而言差（變化量）爲小於〇 . 5 °C : B ：對空白試樣而言差（變化量）爲0 · 51以上小於 1.0 C: 對空白試樣而言差（變化量）爲1.0 °c以上 4. 環氧基反應率分別對硬化前之硬化性組成物、與照射紫外線（光量： 500mW/cm2、照射量：3000mJ/cm2)且在 120°C 放置 1 小時之硬化性組成物進行IR測定。將1 720(:1^1之波峰強度作爲基準，由環氧基之波峰（910cm·1)強度減少率求得環氧 ^ , 基之反應率。將硬化前之環氧基反應率當作〇%，將硬化後環氧基之波峰強度爲0時當作100%進行計算。環氧基反應率越高，硬化性組成物之硬化性越好。 5. 儲存安定性測定在23 °C靜置2日的硬化性組成物之黏度（E型黏度計使用），與初期的硬化性組成物之黏度相比求得黏度上升率。〇：相對於初期黏度而言上升率小於1 〇%。 X :相對於初期黏度而言上升率爲1 〇 %以上。 -26- 201003257 6.暗處硬化性準備將載玻片全面進行遮光處理而成之物（丨）、及將一半部分進行遮光處理而成之物（2)。在（D之中央部分點狀塗布樹脂組成物’並貼合（2 )(此時’（2 )之遮蔽部分與非遮蔽部分的交界成爲密封劑的中心）。充分壓合後’ 照射紫外線（3000mJ/cm2 )之後在120°C放置1小時。剝開2片載玻片，對從非遮蔽部份及遮蔽部份的末端開始 0.5mm内側部分進行IR測定，由下式算出丙烯酸基反應率算出，並依照下述評價基準進行評價。丙烯酸基反應率={1-(硬化後之丙烯酸基波峰面積/硬化後之基準波峰面積）/(硬化前之丙烯酸基波峰面積/硬化前之基準波峰面積）}χ 100 A :從遮蔽部份末端開始0.5mm部分之丙烯酸基反應率爲 5 0 %以上 B :從遮蔽部份末端開始0.5mm部分之丙烯酸基反應率爲 3 0 %以上小於5 0 % ， C :從遮蔽部份末端開始0.5mm部分之丙烯酸基反應率爲小於3 0 % -27- 201003257 比較例5 35.80 26.60 10.00 1 1 5.40 1.00 1.00 20.00 0.20 100.0 因凝膠化而無法測定比較例4 35.80 26.60 10.00 1 5.40 1 1.00 1.00 20.00 0.20 100.0 00 ίη rn 〇 g X 〇比較例3 35.80 26.60 10.00 5.40 I I 1.00 1.00 20.00 0.20 100.0 Ο) — CN 〇 kT) 〇〇比較例2 32.0 20.8 15.0 1 9.63 0.37 ο ο 20.0 <Ν Ο 100.0 〇 — 00 〇 00 (Ν 〇〇比較例1 35.0 20.2 1 15.0 7.32 0.28 ο ο 20.0 CN Ο 100.0 Ο) rn 〇〇〇實施例4 34.0 20.3 10.0 ο 8.23 0.32 ρ ρ 20.0 <Ν Ο 100.0 ΓΛ — 〇 S 〇〇實施例3 35.0 20.4 〇 10.0 7.15 0.30 ο Ο 20.0 CN Ο 100.0 00 un m … 〇 ON Ό 〇〇實施例2 1- 32.0 22.8 m 7.70 0.30 ο ο 20.0 (Ν Ο 100.0 Os kn Os 〇 cn 〇〇實施例1 35.8 26.6 Ο ο 5.20 0.20 ο ο Η 20.0 (Ν Ο 100.0 VO 寸* 〇 JO 〇〇組成（質量％ ) ΕΒ3700 甘油-ΑΟΙ Araldite ΜΥ721 ΕΧ-1610-Ρ Ajicure UDH-J Ajicure VDH-J 水楊基醯肼 Ν-1919 ΚΙΡ150 ADMAFINE SE3200-SEJ SH6040 合計〈硬化物之特性〉拉伸黏著強度（N/mm2)[玻璃] 拉伸黏著強度（N/mm2)[配向膜] 液晶相轉移溫度變化環氧基反應率（％) 儲存安定性暗處硬化性 g O'" g g ϋ -8Z, 201003257 表1中之市售品係表示下述之物。 (A)成分(e-2,) (wherein k represents a number of 2 to 50.) When the composition as a whole is 100% by mass, the blending amount of the component (E) in the composition of the present invention is 〇.〇1~ 20% by mass, preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass. When the blending amount of the component (E) is less than 0.01% by mass, the liquid crystal contamination property may be deteriorated. Moreover, when it is more than 20 mass%, liquid crystal contamination and adhesive strength fall. (F) Inorganic fine particles The inorganic fine particles can be preferably used because they have a high glass transition temperature, a low linear expansion coefficient, and an improved dimensional stability (improvement and improvement). Examples of the inorganic fine particles include particles mainly composed of vermiculite, alumina, zirconia, magnesia, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite, etc., preferably vermiculite and alumina. The particles of the main component. The shape of the inorganic fine particles may be any of a spherical shape, a rod shape, a plate shape, a 繊 shape, and an indefinite shape, and these may be solid, hollow, or porous. The number average particle diameter of the inorganic fine particles is usually in the range of 0.001 to 10 μηη, preferably 0.01 to 5 μχη. If it exceeds 10 μιη, there is a possibility of error in the formation of the gap between the glass substrate -19-201003257 when the liquid crystal cell is fabricated. Here, the number average particle diameter of the inorganic fine particles is measured by a laser light diffraction method. The inorganic fine particle system can be directly added to and mixed with the powder in the form of a powder, or can be added as a solvent dispersion, added to and mixed with other components, and the solvent can be distilled off. Examples of the commercial product of the inorganic fine particles include ADMAFINESO-E 1 , SO-E 2 , SO-E 3 , SO-E 4 , SO-E 5 , SE 3 200-SEJ (manufactured by Admatechs Co., Ltd.), SS01, SS03. , SS15, SS35 (Osaka Chemicals Co., Ltd.) and so on. The inorganic fine particle system may be used singly or in combination of two or more. The inorganic fine particles may also be surface-treated by a decane coupling agent or the like. By surface treatment, compatibility with other components can be improved, and the dispersibility and mechanical strength in the composition can be improved. When the total amount of the composition is 100% by mass, the blending amount of the component (F) in the composition of the present invention is 1 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the blending amount of the component (F) is less than 1% by mass, the dimensional stability may be deteriorated. Further, when the amount is more than 50% by mass, there is a possibility that an error may occur in the gap formed by bonding the glass substrate during the production of the liquid crystal cell. (G) decane coupling agent It is preferred to use a decane coupling agent to exhibit an effect of improving the durability of the adhesive strength (improvement and improvement). The decane coupling agent is preferably one having an epoxy group and having a (meth) acrylonitrile group. The decane coupling agent may be used singly or in combination of two or more kinds -20-201003257. Examples of the decane coupling agent having an epoxy group include, for example, r _ glycidoxypropyltrimethoxysilylene. Examples of such a commercial product of the sand compound coupling agent include, for example, SH6040 (manufactured by Toray Dow Corning Co., Ltd.), KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Examples of the decane coupling agent having a (meth) acrylonitrile group include, for example, r-methacryloxypropyltrimethoxydecane. As an example of the commercial product of such a decane coupling agent, for example, SZ6030 (manufactured by Toray Dow Corning Co., Ltd.), KBM-503, and KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited. When the total amount of the composition is 1% by mass, the blending amount of the component (G) in the composition of the present invention is 0.001 to 15% by mass, preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass. . When the blending amount of the component (G) is less than 0.001% by mass, sufficient adhesion durability may not be obtained. Moreover, when it is more than 15 mass%, the possibility of liquid crystal contamination becomes high. (H) Other additives In the composition of the present invention, other additives may be blended in the range of V.- which does not impair the effects of the present invention. Examples of such an additive include a photoradical initiator other than the component (E), a sensitizer, a chain transfer agent, an antifoaming agent, an ion scavenger, a water absorbing agent, organic fine particles, a leveling agent, and a spacer. , organic solvents, etc. 2. Method for Producing Curable Composition The composition of the present invention can be put into a container by using the components (A) to (E) and optionally components (F) to (H), and a planetary mixer or the like can be used. After the mixer was sufficiently mixed, defoaming was carried out under vacuum to produce. -21 - 201003257 3 - Hardening method of hardening composition · Hardening condition The composition of the present invention can be cured by ultraviolet irradiation or heating. When the composition of the present invention is used as a liquid crystal sealing agent and a liquid crystal dropping technique is employed, it is usually temporarily cured by ultraviolet irradiation, and further cured by heating. The wavelength of light used to harden the composition of the present invention is not particularly limited, but is preferably 35 Å to 700 nm in consideration of damage to the alignment film and the liquid crystal. The irradiation line amount is preferably 500 to 1 〇〇〇〇mj/cm 2 , more preferably 1 〇〇〇 to 3000 mJ/cm 2 °. The temperature of the heat curing is not particularly limited, but preferably, the curing temperature is 70 ° C or higher. It is less than 200 ° C, more preferably 100 ° C or more and less than 150 ° C. Further, the hardening time is preferably 20 minutes or more and less than 3 hours, more preferably 30 minutes or more and less than 2 hours. II. Liquid Crystal Sealant Liquid crystal sealing agent is used to adhere two glass substrates of a liquid crystal display element to protect the inside while preventing liquid crystal from flowing out. The liquid crystal sealing agent of the present invention is characterized by the above-described curable composition of the present invention. Therefore, the liquid crystal sealing agent of the present invention is useful for producing a liquid crystal display element (liquid crystal display cell) which is resistant to liquid crystal contamination, darkness, tensile strength, tensile strength, and the like by a liquid crystal dropping technique. The viscosity of the liquid crystal sealing agent of the present invention is not particularly limited, but is preferably from 10 to 1,000 Pa.s, more preferably from 100 to 500 Pas, from the viewpoints of dispersibility and shape preservability. III. Liquid crystal display element -22- 201003257 The liquid crystal display element of the present invention is characterized by the liquid crystal sealing agent of the present invention described above. Therefore, according to the present invention, it is possible to obtain a liquid crystal display element which is excellent in liquid crystal contamination resistance, excellent in tensile strength, long-term stability, and reliability. The structure of one of the liquid crystal display elements of the present invention shown in Fig. 1 will be described with reference to the structure of the liquid crystal display element of the present invention. As shown in Fig. 1, the liquid crystal display element 1 has a transparent electrode 14 and an alignment film 1 2 'color filter 1 6 between the two glass substrates 1 夹, with the spacers 18 interposed therebetween. The liquid crystal sealing agent maintains the configuration of the liquid crystal 22. The two glass substrates 1 are adhered by the liquid crystal sealing agent 20, and the liquid crystal 22 is sealed and held in the space surrounded by the glass substrate 10 and the liquid crystal sealing agent 20. As can be seen from Fig. 1, since the liquid crystal sealing agent 20 is in direct contact with the liquid crystal 22, the components in the unhardened liquid crystal sealing agent 20 are dissolved in the liquid crystal 22, and the specific resistance of the liquid crystal 22 is lowered, resulting in damage to the liquid crystal display element. Long-term stability and reliability of 1. In the liquid crystal display device of the present invention, the liquid crystal sealing agent of the present invention is used, so that the liquid crystal sealant component which is not cured can be prevented from being dissolved in the liquid crystal, so that it has excellent long-term stability and reliability. The liquid crystal display element of the present invention is preferably produced by a liquid crystal dropping method. Referring to Fig. 2, a description will be given of the manufacturing steps of the liquid crystal display element by the liquid crystal dropping method. A dispenser is used to surround the enclosed liquid crystal on one side of the glass substrate to form a frame of the liquid crystal sealing agent. The line width and film thickness of the liquid crystal sealing agent are usually about 0.1 to 5 mm and about 0.1 to 20 μm, respectively, preferably 〇.5 to -23 to 201003257 3 mm, and 1 to 1 μm. The dispenser of the liquid crystal sealing agent used at this time is exemplified by SHOTminiSL (made by Musashi Engineering Co., Ltd.). After the liquid crystal sealing agent is hardened, liquid crystals are dropped in the frame of the liquid crystal sealing agent, air bubbles are removed, and the like, and the other glass substrate is bonded to each other, and the two glass substrates are pressed together to seal the liquid crystal. Next, ultraviolet rays are irradiated to temporarily cure the liquid crystal sealing agent. The ultraviolet rays used at this time are preferably those having a wavelength of from 200 to 700 nm, and those having a wavelength of from 350 to 700 nm are more preferably used in consideration of damage to the alignment film and the liquid crystal. The ultraviolet light source is preferably a high pressure mercury lamp, a metal halide lamp, an LED or the like. Thereafter, the substrate is heated at 70 to 200 ° C, preferably 90 to 150 ° C for 10 minutes to 5 hours, preferably 30 minutes to 2 hours, to perform liquid crystal annealing, and at the same time, a liquid crystal sealing agent It is completely hardened to obtain a liquid crystal display element. [Examples] Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the examples. Production Example 1 Synthesis of urethane acrylate ((A) component; glycerol-AOI) 75.4 parts of 2-isocyanate ethyl acrylate (Karenz AOI by Showa Denko Co., Ltd.) in a container equipped with a stirrer A solution of 0.1 parts of dibutyltin dilaurate was added to 24.6 parts of glycerin (purified glycerin manufactured by Sakamoto Pharmaceutical Co., Ltd.) at 1 ° C for 1 hour, and then stirred at 60 ° C for 4 hours. And made a reaction solution. The amount of residual isocyanate in the product in the reaction liquid was measured by FT-IR to be 〇·1 mass% or less, and it was confirmed that the reaction system was carried out substantially quantitatively. Further, it was confirmed that a urethane bond and an acrylonitrile group (polymerizable unsaturated group) were contained in the molecule. -24- 201003257 By the above operation, 100 parts of glycerol-AOI were obtained. Example 1 The components shown in Example 1 of the following Table 1 were weighed into a container, and sufficiently mixed using a planetary mixer (THINK Y Mixer, manufactured by Thinky Co., Ltd.). Thereafter, defoaming was carried out under vacuum to obtain a curable composition. Examples 2 to 4 and Comparative Examples 1 to 2 Each of the curable compositions was produced in the same manner as in Example 1 except that the composition shown in Table 1 below was changed. <Evaluation of characteristics of cured product> The following characteristics when the curable composition obtained in the above Examples and Comparative Examples were cured were evaluated. The results obtained are shown in Table 1. 1·Tensile adhesion strength [glass] The spacer particles are dispersed in an amount of 1 part by mass with respect to 100 parts by mass of the curable composition, and placed in the central portion of the slide glass, and the other slide glass is placed. It is superposed in a way of becoming a cross, and is pressed to make it a uniform thickness. After irradiating ultraviolet rays (500 mW/cm2, 3000 mJ/cm2), it was allowed to stand at 120 t for 1 hour to prepare a sample for measuring the tensile adhesion strength. The adhesion strength (N/mm2) of the sample was measured by a tensile tester. If it is 4 N/mm2 or more, the tensile adhesive strength is good. 2. Tensile Adhesive Strength [Alignment Film] OPTMERAL 60101 (a composition for an alignment film made of JSR) was coated on a glass slide as an alignment film 'prebaked at 80 ° C for 2 minutes and then at 200 ° C. Heat in an oven for 60 minutes. The same operation as in 1. was carried out except that the slide glass with the alignment film was used. 3. Liquid crystal phase transition temperature change -25- 201003257 After the curable composition of 0 · 02 5 g was placed in the vial (inner diameter 1 〇 mm), liquid crystal (MLC-6608, manufactured by Merck) was charged at 0.075 g. After irradiating ultraviolet rays (3000 mJ/cm2) from the bottom surface of the sample vial, it was left at 12 (TC for 1 hour. After standing to cool to 25 ° C, the upper clarified product of the liquid crystal was taken out and subjected to DSC measurement (temperature up rate 2 ° C / min). The amount of change was determined from the difference between the measured phase transition temperature and the phase transition temperature of the untreated liquid crystal (blank), and evaluated according to the following evaluation criteria. A : Poor for the blank sample (variation) is less than 〇. 5 °C : B : difference (variation) for blank sample is 0 · 51 or more and less than 1.0 C: difference (variation) is 1.0 °c or more for blank sample 4. The epoxy group reaction rate was determined by IR measurement of the curable composition before curing and the curable composition irradiated with ultraviolet rays (light quantity: 500 mW/cm 2 , irradiation amount: 3000 mJ/cm 2 ) and left at 120 ° C for 1 hour. Using the peak intensity of 1 720 (:1^1 as a reference, the reaction rate of the epoxy group is determined by the intensity reduction rate of the peak of the epoxy group (910 cm·1). The epoxy group reaction rate before hardening is 〇%, calculated as 100% when the peak intensity of the epoxy group after hardening is 0. Epoxy The higher the rate, the better the hardenability of the curable composition. 5. Storage stability The viscosity of the curable composition (used in the E-type viscometer) which was allowed to stand at 23 °C for 2 days, and the initial hardenability composition. The viscosity of the substance is compared with the viscosity increase rate. 〇: The rate of increase is less than 1%% relative to the initial viscosity. X: The rate of increase is 1% or more relative to the initial viscosity. -26- 201003257 6. Dark place For the sclerosing preparation, the glass slide is completely opaquely treated with a light-shielding treatment, and the half-part is light-shielded (2). The resin composition is applied in a point at the center of the D. (2) (At this point, the boundary between the shielded portion and the non-shielded portion of '(2) becomes the center of the sealant. After fully pressing, 'after irradiation with ultraviolet rays (3000 mJ/cm2), it is allowed to stand at 120 °C for 1 hour. Stripping 2 On the slide glass, IR measurement was performed on the inner portion of 0.5 mm from the end of the unshielded portion and the shielding portion, and the reaction rate of the acrylic group was calculated from the following formula, and evaluated according to the following evaluation criteria. Acrylic reaction rate = {1-(hardened acrylic based peak surface /Standard peak area after hardening)/(Acid-based peak area before hardening/reference peak area before hardening)}χ 100 A : The acryl-based reaction rate of 0.5 mm from the end of the shielding portion is 50% or more B : The acryl-based reaction rate of 0.5 mm from the end of the shielding portion is more than 30% and less than 50%, C: the acryl-based reaction rate of 0.5 mm from the end of the shielding portion is less than 30% -27-201003257 Comparative Example 5 35.80 26.60 10.00 1 1 5.40 1.00 1.00 20.00 0.20 100.0 Unable to measure due to gelation Comparative Example 4 35.80 26.60 10.00 1 5.40 1 1.00 1.00 20.00 0.20 100.0 00 ίη rn 〇g X 〇Comparative Example 3 35.80 26.60 10.00 5.40 II 1.00 1.00 20.00 0.20 100.0 Ο) — CN 〇kT) 〇〇Comparative Example 2 32.0 20.8 15.0 1 9.63 0.37 ο ο 20.0 <Ν Ο 100.0 〇— 00 〇00 (Ν 〇〇Comparative Example 1 35.0 20.2 1 15.0 7.32 0.28 ο ο 20.0 CN Ο 100.0 Ο) rn 〇〇〇 Example 4 34.0 20.3 10.0 ο 8.23 0.32 ρ ρ 20.0 < Ν Ο 100.0 ΓΛ — 〇S 〇〇 Example 3 35.0 20.4 〇10.0 7.15 0.30 ο Ο 20.0 CN Ο 100.0 00 un m ... 〇ON Ό 〇〇 Example 2 1- 32.0 22.8 m 7.70 0.30 ο ο 20.0 (Ν Ο 100.0 Os kn Os 〇cn 〇〇 Example 1 35.8 26.6 Ο ο 5.20 0.20 ο ο Η 20.0 (Ν Ο 100.0 VO inch* 〇JO 〇〇 composition (% by mass) ΕΒ3700 Glycerin-ΑΟΙ Araldite ΜΥ721 ΕΧ-1610-Ρ Ajicure UDH-J Ajicure VDH-J 杨杨基醯肼Ν-1919 ΚΙΡ150 ADMAFINE SE3200-SEJ SH6040 Total <hardened matter Characteristics > Tensile Adhesive Strength (N/mm2) [Glass] Tensile Adhesive Strength (N/mm2) [Alignment Membrane] Liquid Crystal Phase Transition Temperature Change Epoxy Reaction Rate (%) Storage Stability Dark Hardenability g O '" gg -8 -8Z, 201003257 The commercially available products in Table 1 indicate the following. (A) component

Cytec(股）製’含雙酚a之環氧基丙烯酸酯例1所合成）甘油-AOI (製造例Cytec (manufactured by the company) epoxide acrylate containing bisphenol a. Synthesis of glycerol-AOI (manufacturing example)

EB 3 70 0 ： Daicel (B)成分EB 3 70 0 : Daicel (B)

AralditeMY721:亨斯邁先進材料股份有限（股）製，多官能環氧基樹脂（分子量：423 )AralditeMY721: Huntsman Advanced Materials Co., Ltd., a polyfunctional epoxy resin (molecular weight: 423)

(C) 成分 EX-1610-P: Nagase ChemteX(股）製，多官能環氧化合物（重量平均分子量（GPC ) : 760 ) (D) 成分(C) Ingredients EX-1610-P: Nagase ChemteX, a polyfunctional epoxy compound (weight average molecular weight (GPC): 760) (D)

AjicureUDH-J: ΑΠΜΟΤΟ FINETECHNO(股）製，潛在型環氧硬化劑AjicureUDH-J: ΑΠΜΟΤΟ FINETECHNO (share) system, potential type epoxy hardener

AjicureVDH-J: AJIMOTO FINETECHNO(股）製，潛在型環氧硬化劑水楊基醯肼：大塚化學（股）製，潛在型環氧硬化劑 (E) 成分 (e-l)N-1919: Adeca(股）公司製，光自由基聚合引發劑 -29- 201003257 (e-2)KIP150: Satomer公司製，光自由基聚合引發劑AjicureVDH-J: AJIMOTO FINETECHNO (share) system, latent epoxy hardener Salicylamine: Daxie Chemical Co., Ltd., latent epoxy hardener (E) Ingredient (el) N-1919: Adeca )Company system, photoradical polymerization initiator -29- 201003257 (e-2) KIP150: Satomer, photoradical polymerization initiator

C一CH2C-CH2

H3C一C一CH3H3C-C-CH3

OH (F) 成分 ADMAFINE SE3200-SEJ : Admatechs(股）製，矽石微粒子 (G) 成分 SH6〇4〇:東麗道康寧（股）公司製，矽烷偶合劑；γ-環氧丙氧基丙基三甲氧基矽烷由表1之結果可知，未倂用成分（Β)及成分（C)的比較例1、2中環氧基的反應率低、拉伸黏著強度不佳。相對於此，可知倂用成分（Β)與成分（C)之環氧化合物的實施例1 〜4之硬化性組成物係在玻璃上、配向膜上同時顯現優良的拉伸黏著強度。而且可知不僅是拉伸黏著強度，液晶相轉位溫度變化及暗處硬化性的平衡均爲優異。產業上之可利用性本發明之液晶密封劑係根據近年來邊緣狹窄化的要求，即使是密封劑部分與配線或黑色矩陣等重疊之紫外線無法直接照射的部分也能充分硬化，因此與基板的密接性高，亦可減低未硬化之液晶密封劑成分導致的液晶污染可能性。若根據本發明，可提供一種液晶密封劑，其係能夠用 30- 201003257 於步驟數少且效率良好地製造液晶顯示元件之液晶滴下方式。【圖式簡單說明】 [第1圖]本發明之液晶顯示元件的剖面模式圖。 [第2圖]液晶滴下技法之槪要表示圖。【主要元件符號說明】 1 液晶顯示元件 10 玻璃基板 12 配向膜 14 透明電極 16 彩色濾光片 1 8 間隔物 20 液晶密封劑 22 液晶 -31 -OH (F) Ingredients ADMAFINE SE3200-SEJ : Admatechs (shares), vermiculite microparticles (G) Ingredients SH6〇4〇: manufactured by Toray Dow Corning Co., Ltd., decane coupling agent; γ-glycidoxypropyl From the results of Table 1, it was found that the epoxy group had a low reaction rate and a poor tensile adhesion strength in Comparative Examples 1 and 2 in which the component (Β) and the component (C) were not used. On the other hand, it is understood that the curable compositions of Examples 1 to 4 of the epoxy compound of the component (C) and the component (C) exhibit excellent tensile strength at the same time on the glass and on the alignment film. Further, it is understood that not only the tensile adhesion strength but also the balance of the liquid crystal phase transposition temperature and the darkness hardenability are excellent. INDUSTRIAL APPLICABILITY The liquid crystal sealing agent of the present invention is sufficiently hardened even in a portion where the ultraviolet ray which is superimposed on the wiring portion and the wiring or the black matrix cannot be directly irradiated, in accordance with the demand for narrowing of the edge in recent years, and thus the substrate is sufficiently cured. The high adhesion can also reduce the possibility of liquid crystal contamination caused by the unhardened liquid crystal sealant component. According to the present invention, it is possible to provide a liquid crystal sealing agent capable of producing a liquid crystal droplet underlying type of a liquid crystal display element with a small number of steps and efficiently using 30-201003257. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A cross-sectional schematic view of a liquid crystal display device of the present invention. [Fig. 2] A diagram showing the liquid crystal dropping technique. [Main component symbol description] 1 Liquid crystal display element 10 Glass substrate 12 Alignment film 14 Transparent electrode 16 Color filter 1 8 Spacer 20 Liquid crystal sealant 22 Liquid crystal -31 -

Claims

201003257 VII. Patent Application Range 1 - A curable composition for liquid crystal encapsulants which contains the following components (A) to (E): (A) a compound having an ethylenically unsaturated group (B) an aromatic ring Oxygen compound (C) An aliphatic epoxy compound (D) epoxy curing agent (E) photoradical polymerization initiator having three or more epoxy groups in one molecule. 2. The curable composition for a liquid crystal sealing agent according to claim 1, wherein the (E) photoradical polymerization initiator contains a compound having a fluorene structure. 3. The curable composition for a liquid crystal sealing agent according to claim 2, wherein the compound having the oxime structure is represented by the following formula (e-Ι), Ο

(wherein R1 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, r2 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, and R3 represents a substituted or unsubstituted carbazolyl group, or Ph-S-Phe-CO-based (Ph represents phenyl, Phe represents phenyl). The curable composition for a liquid crystal sealing agent according to any one of claims 1 to 3, wherein the component (B) and the component (C) are -32 to 201003257 liquid at normal temperature and normal pressure. 5. The curable composition for a liquid crystal sealing agent according to claim 4, wherein the epoxy group equivalent of the component (B) and the component (C) is in the range of 5 Å to 2 Torr. 6. The curable composition for a liquid crystal sealing agent according to claim 5, wherein the compound having the (A) ethylenically unsaturated group is a compound having one or more (meth)acryl fluorenyl groups. 7. The curable composition for liquid crystal encapsulants of claim 6, further comprising (F) inorganic fine particles. A liquid crystal display element produced by using a liquid crystal sealing agent as disclosed in claim 7 of the patent application. -33-