TW200921222A - Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays - Google Patents

Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays Download PDF

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TW200921222A
TW200921222A TW97140762A TW97140762A TW200921222A TW 200921222 A TW200921222 A TW 200921222A TW 97140762 A TW97140762 A TW 97140762A TW 97140762 A TW97140762 A TW 97140762A TW 200921222 A TW200921222 A TW 200921222A
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liquid crystal
manufactured
acrylate
meth
weight
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TW97140762A
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TWI463225B (en
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Shinshi Yamaguchi
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Sekisui Chemical Co Ltd
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    • 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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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention aims at providing a sealing material for liquid crystal dispensing method which dose not contaminate a liquid crystal when used in the production of liquid crystal displays by the dispenser method even if a component of the sealing material is dissolved in the liquid crystal and which makes it possible to produce liquid crystal displays excellent in display quality and reliability. A sealing material for liquid crystal dispensing method which contains both a curable resin and a photo-radical initiator, wherein the photo-radical initiator is one which does not precipitate from a liquid crystal as tested by dissolving the initiator completely in the liquid crystal in a concentration of 4 wt% at 120 DEG C and allowing the resulting solution to stand at -20 DEG C for 144 hours and which exhibits an absorptivity of 50mL/gcm or above as determined at 405 nm in a solvent.

Description

200921222 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種液晶滴下法用密封劑，其在用於滴 下法之液晶顯示it件之製造時，即便密封劑成分溶出至液 晶，亦可防止引起液晶污染，從而可製造顯示品質及可靠 性優異之液晶顯示元件。又，本發明係關於一種上下導通 材料及液晶顯示元件。 【先前技術】 於先前之液晶顯示元件之製造方法中，首先，藉由網 版印刷，於兩片附電極之透明基板中之任一者上形成密封 圖案（其設置有使用熱硬化性密封劑之液晶注入口），於6〇 〜100 C進行預烘烤，使密封劑中之溶劑乾燥。繼而，挟持 著間隔件使兩片基板相對向，對準後進行貼合，於110〜220 C進行10 90为鐘之熱壓，調整密封劑附近之間隙後，於 I, 洪箱中以UO〜22。。。加…2〇分鐘，使密封二硬 化。最後’自液晶注入口注入液晶，最後使用封口劑將液 晶注入口加以密封，從而製造液晶顯示元件。 然而，於該製造方法中，存在如下問題：產生因加執 而產生之變形所導致之位置偏移、間隙之不均、以及密封 W與基板之密著性之降低等；殘留溶劑進行熱膨脹而產生 氣泡’導致產生間隙之不均或密封通道（seal);密封 硬化需要長時間；預烘烤製程繁雜；由於溶劑之揮發而導 致密封劑之可使用時間變短；液晶之注入較花時間等。尤 200921222 其’於近年來之大型液晶顯示裝i中，液晶之注入非 時間而成為較大問題。 匕 針對此，目前已對被稱為滴下法（使用由硬化型樹脂組 成物所構成之密封齊"之液晶顯示元件之製造方法進行研 九。於滴下法中’首先，藉由網版印刷等，於2片附電極 之透明基板中之—者上形成長方形狀之密封圖案。繼而， 於冶封劑未硬化之狀態下，於透明基板之框内整個面上滴[Technical Field] The present invention relates to a liquid crystal dropping method sealing agent which can be used for the production of a liquid crystal display member for dropping, even if the sealant component is eluted to the liquid crystal. Preventing liquid crystal contamination, it is possible to manufacture liquid crystal display elements with excellent display quality and reliability. Further, the present invention relates to a vertical conduction material and a liquid crystal display element. [Prior Art] In the prior art method of manufacturing a liquid crystal display device, first, a seal pattern (which is provided with a thermosetting sealant) is formed on one of two transparent substrates with electrodes by screen printing The liquid crystal injection port is pre-baked at 6 〇 to 100 C to dry the solvent in the sealant. Then, holding the spacers so that the two substrates are facing each other, and then aligning them after bonding, and performing a hot pressing of 10 90 for a clock at 110 to 220 C, adjusting the gap near the sealant, and then, in the I, the water tank, UO ~twenty two. . . Add 2 minutes to harden the seal. Finally, liquid crystal is injected from the liquid crystal injection port, and finally, the liquid crystal injection port is sealed with a sealing agent to manufacture a liquid crystal display element. However, in this manufacturing method, there are problems in that positional displacement due to the deformation due to the addition, unevenness in the gap, and deterioration in the adhesion between the sealing W and the substrate are caused, and the residual solvent is thermally expanded. The generation of bubbles 'causes unevenness of the gap or seals; seal hardening takes a long time; the prebaking process is complicated; the usable time of the sealant is shortened due to the volatilization of the solvent; the injection of the liquid crystal takes time, etc. . In 200921222, in the large-scale liquid crystal display device i in recent years, the injection of liquid crystal has become a big problem. In view of this, a method of manufacturing a liquid crystal display element called a dropping method (using a sealed resin composition composed of a hardened resin composition) has been studied. In the dropping method, first, by screen printing And a rectangular sealing pattern is formed on the two transparent substrates with electrodes. Then, in the state where the sealing agent is not hardened, the entire surface of the transparent substrate is dropped.

下塗佈液晶之微小_，然、後立即重疊另—片透明基板，對 密封劑照射紫外線而進行預硬化。其後，i需要於液晶退 火時加熱’進—步進行硬化，從而製成液晶顯示元件。若 於減壓下貼合基板，則可以極高之效率製造液晶顯示元 件7後期待該滴下法會成為液晶顯示裝置之製造方法之 主流。 作為用於滴下法中之液晶滴下法用密封劑，由於可獲 付间接著性，故通常使用環氧樹脂作為熱硬化性成分。然 而於利用滴下法所製造之液晶顯示元件十存在容易產生 由液晶之配向紊亂所導致之色斑等之顯示不良的問題。一 般認為其原因在於 於滴下法之步驟上，未硬化狀態之液 晶滴下法用密封劑會直接接觸於液晶，而於密封劑完全硬 化前，密封劑成分會溶出至液晶。 _為解決上述問題，例如於專利文獻i、專利文獻2中揭 不有使用對液晶之溶解性低之成分的液晶滴下法用密封 片J上述雄、封劑由於成分不溶出至液晶，故認為其不會產 生液晶污染。 200921222 然而，即便於使用上述密 &在封劑且利用滴下法來製造液 晶顯不元件之情形時，實ρες μ 貝味上’有時亦會引起液晶污染， 而無法製造色斑較少且高品皙阁 间00質圖像之液晶顯示元件。 〔專利文獻丨〕日本專利第3583326號 〔專利文獻2〕曰本專利胜μ。λ λ， I扪特開2001-133794號公報 【發明内容】 發明所欲解決之^翻 本發明之目的在於提供一種液晶滴下法用密封劑，其 f用於滴下法之液晶顯示元件之製造時，即便密封劑成分 溶出至液晶，亦可防止引起液晶污染，從而可製造顯示品 質及可靠性優異之液晶顯示元件。 解決問部之乎坪 本發月係種液晶滴下法用密封劑，其含有硬化性樹 月胃旨與光自由基起始劑，上述光自由基起始劑係以相對於液 曰曰重量4之’辰度於120 C完全溶解後，於_2〇°c放置144 J時後仍未自上述液晶析出者；上述光自由基起始劑，其 於冷劑中所測定之於4〇5 nm之吸光係數為5〇 mL/g. 以 上。 以下對本發明進行詳細說明。 本發明者等人銳意研究，結果發現，藉由使用對液晶 之;谷解f生南者作為用於液晶滴下法用密封劑中之光自由基 起始劑’可防止引起液晶污染，從*可獲得可實現顯示品 質及可罪性優異之液晶顯示元件之液晶滴下法用密封劑， 200921222 從而完成本發明。 本發明之液晶滴下法用密封劑含有光自由基起始劑， 該光自由基起始劑係以相對於液晶4重量％之濃度於12〇亡 完全溶解後，於-2(TC放置144小時後仍未自上述液晶析出 者。 以往，於液晶滴下法用密封劑中，為了防止液晶污染， 而使用對液晶之溶解性低之光自由基起始劑。然而，存在 即便使用上述光自由基起始劑，亦無法充分地防止液晶污 染之問題。 本發明者等人發現，藉由使用對液晶之溶解性高之光 自由基起始劑，可防止液晶污染。 上述光自由基起始劑，其於溶劑中所測定之於4〇5打瓜 之吸光係數之下限為50mL/g.cm。若吸光係數未滿5〇 mL/g‘cm，則利用可見光的密封劑會硬化而變得不充分。上 述吸光係數之較佳下限為70 mL/g . cm。 上述吸光係數由於具有越高則反應性越高之傾向，故 其並無特別上限。 再者，作為上述溶劑，若為可溶解上述光自由基起始 劑，且在所測定之吸收波長下並無吸光者，則無特別限定。 具體而言例如使用乙腈、甲酵等。 上述光自由基起始劑較佳為不吸收5〇〇 nm以上之波長 的光。若上述光自由基起始劑吸收5〇〇 nm以上之波長的 光，則有時於黃色燈光下亦會產生反應，密封劑之處理性 會變差。 200921222 上述光自由基起始劑之熔點之較佳上限為85。〇。若上 述光自由基起始劑之熔點超過85〇C，則有時使其以相對於 液bb 4重量農度於120C完全溶解後，於_2〇°c放置144 小時後，光自由基起始劑會自液晶析出，而引起液晶污染。 上述光自由基起始劑之熔點之更佳上限為8〇<t。作為上述 光自由基起始劑之熔點之下限，並無特別限定，但於液晶 滴下法中有於常溫下連接未硬化密封劑與液晶之步驟，為 了儘可能抑制該光自由基起始劑溶出至液晶，較佳下限為 30。(：。 作為上述光自由基起始劑，例如可列舉㈣（⑽⑹ 化合物。具體而！ ’例#可列舉由下述式⑴所表示 之U2·辛H_[4_(笨硫基）_2_(〇_苯甲酿基則等。作為由 述弋（1)所表不之肟酯化合物之市售品，例如可列舉 IRGACURE OXE01 (汽巴精化公司製造）等。The liquid crystal is coated with a small amount of _, and immediately afterwards, another transparent substrate is superposed, and the sealing agent is pre-cured by irradiating ultraviolet rays. Thereafter, i needs to be heated while the liquid crystal is annealed to be hardened to form a liquid crystal display element. When the substrate is bonded under reduced pressure, the liquid crystal display element 7 can be manufactured with extremely high efficiency, and it is expected that the dropping method will become the mainstream of the manufacturing method of the liquid crystal display device. As a sealant for a liquid crystal dropping method used in a dropping method, since an interlaminar property can be obtained, an epoxy resin is usually used as a thermosetting component. However, the liquid crystal display element manufactured by the dropping method has a problem that display defects such as stains caused by alignment disorder of the liquid crystal are liable to occur. The reason is generally considered to be that, in the step of the dropping method, the liquid crystal dropping method for the uncured state directly contacts the liquid crystal, and the sealant component is eluted to the liquid crystal before the sealant is completely hardened. In order to solve the above problem, for example, in the sealing sheet J for a liquid crystal dropping method using a component having a low solubility in liquid crystal, the above-mentioned male and sealing agents are not eluted into the liquid crystal, and therefore, It does not cause liquid crystal contamination. 200921222 However, even when the above-mentioned dense & sealant is used and the liquid crystal display element is manufactured by the dropping method, the actual ρες μ bet taste sometimes causes liquid crystal contamination, and it is impossible to manufacture a small amount of color spots. A liquid crystal display element with a 00-quality image between the high-quality cabinets. [Patent Document 日本] Japanese Patent No. 3583326 [Patent Document 2] This patent wins μ. λ λ, 扪 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 Even if the sealant component is eluted to the liquid crystal, liquid crystal contamination can be prevented, and a liquid crystal display element excellent in display quality and reliability can be manufactured. The invention relates to a sealing agent for a liquid crystal dropping method, which comprises a hardening tree and a photoradical initiator, and the above photoradical initiator is based on the weight of the liquid helium. After the "Chen degree is completely dissolved in 120 C, it is not precipitated from the above liquid crystal after leaving 144 J at _2 ° ° C; the above photoradical initiator, which is determined in the refrigerant at 4 〇 5 The absorption coefficient of nm is 5 〇mL/g. or more. The invention is described in detail below. The present inventors have intensively studied and found that it is possible to prevent liquid crystal contamination by using a liquid radical initiator in a liquid crystal dropping method for a liquid crystal by using a liquid crystal. A liquid crystal dropping method sealing agent capable of realizing a liquid crystal display element excellent in display quality and sinfulness is obtained, and the present invention has been completed in 200921222. The sealing agent for liquid crystal dropping method of the present invention contains a photoradical initiator which is completely dissolved in 12 concentrations relative to the liquid crystal at a concentration of 4% by weight, and is placed at -2 (TC is placed for 144 hours). In the sealing agent for liquid crystal dropping method, a photoradical initiator which has low solubility in liquid crystal is used in order to prevent liquid crystal contamination. However, even if the above-mentioned photoradical is used, The present inventors have found that the problem of liquid crystal contamination is not sufficiently prevented. The present inventors have found that liquid crystal contamination can be prevented by using a photoradical initiator which has high solubility in liquid crystal. The lower limit of the absorption coefficient of the 4 〇 5 瓜 melon measured in the solvent is 50 mL/g.cm. If the absorption coefficient is less than 5 〇 mL/g 'cm, the sealant using visible light is hardened and becomes insufficient. The preferred lower limit of the above-mentioned light absorption coefficient is 70 mL/g. cm. The higher the absorption coefficient is, the higher the reactivity is, and therefore there is no particular upper limit. Further, as the solvent, the above solvent is soluble. Freedom of light The initiator is not particularly limited as long as it does not absorb light at the measured absorption wavelength. Specifically, for example, acetonitrile, methylcellulose or the like is used. The above photoradical initiator preferably does not absorb 5 Å or more. Light of the wavelength. If the photoradical initiator absorbs light having a wavelength of 5 〇〇 nm or more, a reaction may occur under a yellow light, and the sealant may become less rational. The preferred upper limit of the melting point of the initiator is 85. If the melting point of the above photoradical initiator exceeds 85 ° C, it may be completely dissolved at 120 C with respect to the liquid bb 4 weight. After 1/2 〇 °c is left for 144 hours, the photoradical initiator will precipitate from the liquid crystal and cause liquid crystal contamination. The upper limit of the melting point of the above photoradical initiator is 8 〇 < t. The lower limit of the melting point of the radical initiator is not particularly limited. However, in the liquid crystal dropping method, the step of connecting the uncured sealant and the liquid crystal at normal temperature is employed, and in order to suppress the dissolution of the photoradical initiator to the liquid crystal as much as possible, The lower limit is 30. (:. as above The photoradical initiator is, for example, a compound of (4) ((10)(6). Specifically, 'Example #', U2·Xin H_[4_(stupyl)_2_(〇_苯甲甲基) represented by the following formula (1) For example, IRGACURE OXE01 (manufactured by Ciba Specialty Chemicals Co., Ltd.), etc., may be mentioned as a commercial item of the oxime ester compound which is represented by the above (1).

200921222 重里％，則有時硬化會不充 合姦斗、* B a 古超過10重量％，則有時 會產生液晶污染’對基板 〗有吁 把捽#丨夕人曰 耆力會降低。上述光自由基 起始劑之含量之更佳下限 量％。 垔量/〇，更佳上限為5.0重 發明之液晶滴下法用密封劑含有硬化性樹脂。 作為上述硬化性樹脂並無特別限定，較 丙婦基與環氧基。藉由具有上述 (' 另工延g月t基，先前之液晶滴下 法用密封劑可經過光硬化、熱硬化之兩個階段之硬化。 ^另外，於上述硬化性樹脂中，於具有（甲基）丙烯基與環 氧基之情形時’環氧基相對於（甲基）丙烯基與環氧基之總量 之比率的較佳上限為40莫耳。/(^若超過4〇莫耳％，則存在 對液晶之溶解性變高，引起於面板上產生色斑之污染之情 形。更佳上限為30莫耳％。 作為上述硬化性樹脂，並無特別限定，例如可列舉·· 使具有經基之化合物與（甲基）丙烯酸反應所得之酯化合 物、使（甲基）丙烯酸與環氧化合物反應所得之環氧（甲基）丙 烯酸酯、以及使具有羥基之（甲基）丙烯酸衍生物與異氰酸醋 反應所得之（甲基）丙烯酸胺基甲酸酯等。 作為上述使具有羥基之化合物與（甲基）丙烯酸反應所 得之酯化合物，並無特別限定’作為單官能者，例如可列 舉：（曱基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲 基）丙烯酸4-羥丁酯、（甲基）丙烯酸2-羥丁酯、（甲基）丙烯 酸異丁酯、（曱基）丙烯酸第三丁酯、（甲基）丙烯酸異辛酯、（曱 基）丙烯酸月桂酯、（甲基）丙烯酸硬脂酯、（甲基）丙烯酸異冰 200921222 片酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸2-甲氧基乙酯、 曱氧基乙二醇（甲基）丙烯酸酯、（曱基）丙烯酸2-乙氧基乙 酯、（甲基）丙烯酸四氫糠酯、（甲基）丙烯酸苄酯、乙基卡必 醇（曱基）丙烯酸酯、（曱基）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、醯亞胺（曱基）丙烯酸酯、（甲基）丙烯酸 曱酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丁酯、（甲基）丙 烯酸丙酯、（曱基）丙烯酸正丁酯、（甲基）丙烯酸環己酯、（曱 基）丙烯酸2-乙基己酯、（甲基）丙烯酸正辛酯、（曱基）丙烯酸 異壬醋、（甲基）丙烯酸異十四烷基酯、（曱基）丙烯酸2_ 丁氧 基乙酯、2-(曱基）丙烯酸苯氧基乙酯、（甲基）丙烯酸雙環戊 稀基S曰、（曱基）丙烯酸異癸酯、曱基丙稀酸二乙胺基乙酯、 曱基丙烯酸二甲胺基乙酯、2_(甲基）丙烯醯氧基乙基琥珀 酸、2-(甲基）丙烯醯氧基乙基六氳鄰笨二曱酸、2_(甲基）丙 烯醯氧基乙基2-羥基丙基鄰苯二甲酸酯、（曱基）丙烯酸縮水 甘油醋、2-(曱基）丙烯醯氧基乙基磷酸酯等。 又，於上述使具有羥基之化合物與（甲基）丙烯酸反應所 得之醋化合物中’作為二官能者，並無特別限^，例如可 列舉.1,4_ 丁二醇二（甲基）丙烯酸酯、1，3-丁二醇二（甲基） 婦酉曰1,6 -己—醇二（甲基）丙烯酸醋、1，9_壬二酵二（甲 基）丙烯酸酯、I，10-癸二醇二（甲基）丙烯酸酯、2·正丁基_2_ 乙基-1，3-丙一醇二（甲基）丙烯酸酯、二丙二醇二（甲基）丙烯 200921222 酸酯、三丙二醇二（甲基）丙烯酸酯、聚丙二醇二（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A二（甲基）丙烯酸酯、環氧乙烷加成 雙酚A二（曱基）丙烯酸酯、環氧乙烷加成雙酚F二（曱基） 丙烯酸酯、二羥曱基二環戊二烯二（曱基）丙烯酸酯、L3 •丁 二醇二（曱基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、環氧 乙烷改質異三聚氰酸二（曱基）丙浠酸酯、2-羥基-3-丙烯醯氧 基丙基二（曱基）丙烯酸酯、碳酸酯二醇二（曱基）丙烯酸酯、 聚醚二醇二（甲基）丙烯酸酯、聚酯二醇二（曱基）丙烯酸酯、 聚己内酯二醇二（曱基）丙烯酸酯、聚丁二烯二醇二（甲基）丙 烯酸酯等。 另外，於上述使具有羥基之化合物與（甲基）丙烯酸反應 所得之酯化合物中’作為三官能以上者，並無特別限定， 例如可列舉：季戊四醇三（甲基）丙烯酸酯、三羥甲基丙烷三 f (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（曱基）丙烯酸酯、己内 δ旨改質三羥曱基丙烷三（曱基）丙烯酸酯、環氧乙烷加成異三 聚氰酸三（曱基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、 二季戊四醇六（曱基）丙烯酸酯、二（三羥曱基丙烷）四（甲基） 丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、丙三醇三（甲基）丙 烯酸酯、環氧丙烷加成丙三醇三（甲基）丙烯酸酯、三（甲基） 丙烯醯氧基乙基磷酸酯等。 作為上述使（甲基）丙烯酸與環氧化合物反應所得之環 12 200921222 氧（甲基）丙烯酸酯，並無特別限定，例如可藉由依照常法， 使（甲基）丙烯酸與環氧樹脂於鹼性觸媒存在之條件下進行 反應而獲得。 於成為用以合成上述環氧（甲基）丙烯酸酯之原料之環 氧化合物中，作為市售品，例如可列舉：EPIKOTE 828EL、 EPIKOTE 1004 (均為 Japan Epoxy Resins 公司製造）等之 雙酚A型環氧樹脂；EPIKOTE 806、EPIKOTE 4004 (均為 Japan Epoxy Resins公司製造）等之雙盼F型環氧樹脂； R-710等之雙酚E型環氧樹脂；EPICLON EXA1514 (大曰 本油墨公司製造）等之雙酚S型環氧樹脂；RE-810NM (曰 本化藥公司製造）等之2,2'-二烯丙基雙酚A型環氧樹脂； EPICLON EXA7015 (大曰本油墨公司製造）等之氫化雙酚 型環氧樹脂；EP-4000S (旭電化公司製造）等之環氧丙烷 加成雙酚A型環氧樹脂；EX-201 (長瀨化成公司製造）等 之間苯二酚型環氧樹脂；EPIKOTE YX-4000H ( Japan Epoxy Resins公司製造）等之聯苯型環氧樹脂；YSLV-50TE (東 都化成公司製造）等之硫化物型環氧樹脂；YSLV-80DE (東 都化成公司製造）等之聯苯醚型環氧樹脂；EP-4088S (旭 電化公司製造）等之二環戊二烯型環氧樹脂；EPICLON HP4032、EPICLON EXA-4700 (均為大曰本油墨公司製造） 等之萘型環氧樹脂；EPICLON N-770(大曰本油墨公司製造） 等之苯酚酚醛清漆型環氧樹脂；EPICLON N-670-EXP-S (大 曰本油墨公司製造）等之鄰曱酚酚醛清漆型環氧樹脂； EPICLON HP7200 (大日本油墨公司製造）等之二環戊二烯 13 200921222 酚醛清漆型環氧樹脂；NC-3000P (日本化藥公司製造）等 之聯苯酚醛清漆型環氧樹脂；ESN-165S (東都化成公司製 造）等之萘酚酚醛清漆型環氧樹脂；EPIKOTE 630 ( Japan Epoxy Resins公司製造）、EPICLON 430 (大日本油墨公司 製造）、TETRAD-X (三菱瓦斯化學公司製造）等之縮水甘 油胺型環氧樹脂；ZX-1542(東都化成公司製造）、EPICLON 726 (大曰本油墨公司製造）、EPOLIGHT 80MFA (共榮社 化學公司製造）、DENACOL EX-611 (長瀨化成公司製造） 等之烷基多元醇型環氧樹脂；YR-450、YR-207 (均為東都 化成公司製造）、EPOLEAD PB ( Daicel化學公司製造）等 之橡膠改質型環氧樹脂；DENACOL EX-147(長瀨化成公司 製造）等之縮水甘油酯化合物；EPIKOTE YL-7000 ( Japan Epoxy Resins公司製造）等之雙盼A型環硫樹脂，此外可 列舉：YDC-1312、YSLV-80XY、YSLV-90CR (均為東都化 成公司製造）、XAC4151(旭化成公司製造）、EPIKOTE 103 卜 EPIKOTE 1032(均為 Japan Epoxy Resins 公司製造）、 EXA-7120 (大曰本油墨公司製造）、TEPIC (日產化學公 司製造）等。 另外，作為上述環氧（曱基）丙烯酸酯之市售品，例如可 歹丨J 舉：EBECRYL 3700、EBECRYL 3600、EBECRYL 3701、 EBECRYL 3703 、 EBECRYL 3200 、 EBECRYL 3201 、 EBECRYL 3702、EBECRYL 3412、EBECRYL 860、EBECRYL RDX63 182、EBECRYL 6040、EBECRYL 3800 (均為 Daicel UCB 公司製造）；EA-1020、EA-1010、EA-5520、EA-5323、 14 200921222 EA-CHD、EMA-1020 (均為新中村化學工業公司製造）； EPOXY ESTER M-600A > EPOXY ESTER 40EM > EPOXY ESTER 70PA、EPOXY ESTER 200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、EPOXY ESTER 3002A、 EPOXY ESTER 1600A、EPOXY ESTER 3000M、EPOXY ESTER 3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA(均為共榮社化學公司製造）；DENACOL ACRYLATE DA-141 、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-91 1 (均為長瀨化成公司製造）等。 作為上述使具有羥基之（曱基）丙烯酸衍生物與異氰酸 酯反應所得之（甲基）丙烯酸胺基甲酸酯，並無特別限定，例 如可藉由使2當量之具有羥基之（甲基）丙烯酸衍生物與1當 量之具有2個異氰酸酯基之化合物，於作為觸媒的錫系化 合物存在之條件下進行反應而獲得。 作為成為上述（甲基）丙烯酸胺基甲酸酯之原料之異氰 酸酯，並無特別限定，例如可列舉：異佛酮二異氰酸酯、 2,4-曱苯二異氰酸酯、2,6-曱苯二異氰酸酯、六亞曱基二異 氰酸酯、三曱基六亞甲基二異氰酸酯、二苯基甲烷-4,4’-二 異氰酸酯（MDI)、氫化MDI、聚合MDI、1,5-萘二異氰酸 酯、降冰片烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二亞 曱基二異氰酸酯（XDI )、氫化XDI、離胺酸二異氰酸酯、 三苯曱烷三異氰酸酯、三（異氰酸酯基苯基）硫代磷酸酯、四 甲基二甲苯二異氰酸酯、1,6,10-十一烷三異氰酸酯等。 另外，作為上述異氰酸酯，例如亦可使用由乙二酵、 15 200921222 丙三醇、山槊醇、三羥曱基丙烷、（聚）丙二醇、碳酸脂二醇、 聚醚二醇、聚酯二醇、聚己内酯二醇等之多元醇與過剩之 異氰酸酯的反應所得之鏈被延長之異氰酸酯化合物。 作為上述具有羥基之（甲基）丙烯酸衍生物，並無特別限 定，例如可列舉：（甲基）丙烯酸2-羥乙酯、（曱基）丙烯酸2-羥丙酯、（甲基）丙烯酸4_羥丁酯、（甲基）丙烯酸2_羥丁酯等 之市售品；或乙二醇、丙二醇、1，3 -丙二醇、1,3 -丁二醇、 1,4-丁二醇、聚乙二醇等二元醇之單（曱基）丙烯酸酯；三羥 甲基乙烷、三羥曱基丙烷、丙三醇等三元醇之單（曱基）丙烯 酸酯；或二（甲基）丙烯酸酯、雙酚A改質環氧（曱基）丙烯酸 酯等之環氧（甲基）丙烯酸酯等。 另外，作為上述（甲基）丙烯酸胺基甲酸酯之市售品，例 如可列舉：M-1100、M-1200、M-1210、M-1600 (均為東亞 合成公司製造）；EBECRYL 230 ' EBECRYL 270 ' EBECRYL 4858、EBECRYL 8402、EBECRYL 8804、EBECRYL 8803、 EBECRYL 8807、EBECRYL 9260、EBECRYL 1290、 EBECRYL 5129、EBECRYL 4842、EBECRYL 210、EBECRYL 4827、EBECRYL 6700、EBECRYL 220、EBECRYL 2220(均 為 Daicel UCB 公司製造）；ART RESIN UN-9000H、ART RESIN UN-9000A、ART RESIN UN-7100、ART RESIN UN-1255、ART RESIN UN-330、ART RESIN UN-3320HB、 ART RESIN UN-1200TPK、ART RESIN SH-500B (均為根上 工業公司製造）；U-122P、U-108A、U-340P、U-4HA、U-6HA、 U-324A、U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、 16 200921222 U-2HA、U-2PHA、UA-4100、UA-7100、UA-4200、UA-4400、 UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、 U-340A、U-108、U-6H、UA-4000 (均為新中村化學工業公 司製造）；AH-600、AT-600、UA-306H、AI-600、UA-101T、 UA-101I、UA-306T、UA-306I 等。200921222% of the weight, sometimes hardening will not be filled with treacherous, * B a ancient more than 10% by weight, sometimes liquid crystal pollution will occur on the substrate 〗 〖After the 捽#丨夕人曰 耆力 will be reduced. A more preferable lower limit of the content of the above photoradical initiator. The amount of enthalpy/twist is more preferably 5.0. The sealant for liquid crystal dropping method of the invention contains a curable resin. The curable resin is not particularly limited, and is preferably a propyl group or an epoxy group. By having the above-mentioned (the other liquid crystal dropping method sealant can be hardened by two steps of photohardening and thermal hardening. ^ In addition, in the above curable resin, it has (a In the case of a propylene group and an epoxy group, a preferred upper limit of the ratio of the epoxy group to the total amount of the (meth) propylene group and the epoxy group is 40 moles. / (^ if more than 4 moles In the case of %, the solubility in the liquid crystal is high, and the stain on the panel is contaminated. The upper limit is preferably 30 mol%. The curable resin is not particularly limited, and for example, An ester compound obtained by reacting a compound having a trans group with (meth)acrylic acid, an epoxy (meth) acrylate obtained by reacting a (meth)acrylic acid with an epoxy compound, and a (meth)acrylic acid derived from a hydroxyl group The (meth)acrylic acid urethane obtained by reacting the compound with isocyanic acid vinegar, etc. The ester compound obtained by reacting the compound having a hydroxyl group with (meth)acrylic acid is not particularly limited as a monofunctional one. E.g Listed: (mercapto) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (methyl) Isobutyl acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobutyl (meth) acrylate 200921222 Ester, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, nonoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, ethyl carbitol (decyl) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (A) Acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, ( 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl methacrylate, decyl imido(meth) acrylate, Ethyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, cyclohexyl (meth)acrylate , (mercapto) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, isodecanoic acid (mercapto) acrylate, isotetradecyl (meth) acrylate, 2- butyl (meth) acrylate Oxyethyl ester, phenoxyethyl 2-(indenyl)acrylate, dicyclopentanyl (meth)acrylate, isodecyl (decyl) acrylate, diethylaminoethyl decyl acrylate , dimethylaminoethyl methacrylate, 2-(meth) propylene methoxyethyl succinic acid, 2-(methyl) propylene oxyethyl hexamethylene phthalate, 2-(methyl) Acryloxyethyl 2-hydroxypropyl phthalate, (mercapto)acrylic acid glycidic vinegar, 2-(indenyl) propylene methoxyethyl phosphate, and the like. Further, the vinegar compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid is not particularly limited as a difunctional one, and for example, 1,4-butanediol di(meth)acrylate is exemplified. , 1,3-butanediol di(methyl) women's and women's vinegar 1,6-hexanol di(meth)acrylic acid vinegar, 1,9-壬 diyle di(meth)acrylate, I,10- Decanediol di(meth)acrylate, 2·n-butyl 2_ethyl-1,3-propanol di(meth)acrylate, dipropylene glycol di(meth)propylene 200921222 acid ester, tripropylene glycol Di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(methyl) Acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol A bis(indenyl) acrylate, epoxy Ethane addition bisphenol F bis(indenyl) acrylate, dihydroxyindenyl dicyclopentadienyl di(indenyl) acrylate, L3 • butanediol di(曱) Acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified bis(indenyl)propionate, 2-hydroxy-3-propenyloxypropyl (Mercapto) acrylate, carbonate diol di(indenyl) acrylate, polyether diol di(meth) acrylate, polyester diol di(indenyl) acrylate, polycaprolactone diol II (fluorenyl) acrylate, polybutadiene diol di(meth) acrylate, and the like. In addition, the ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid is not particularly limited as a trifunctional or higher one, and examples thereof include pentaerythritol tri(meth)acrylate and trimethylol group. Propane trif (meth) acrylate, propylene oxide addition trimethylolpropane tri(meth) propylene & acid ester, ethylene oxide addition trimethylolpropane tri(decyl) acrylate, Δ-modified trishydroxypropyl propane tris(fluorenyl) acrylate, ethylene oxide addition of tris(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa(indenyl)acrylate, bis(trihydroxydecylpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition c Triol tri(meth)acrylate, tris(meth)acryloxyethyl phosphate, and the like. The ring 12 200921222 oxygen (meth) acrylate obtained by reacting (meth)acrylic acid with an epoxy compound is not particularly limited, and for example, (meth)acrylic acid and epoxy resin can be obtained by a usual method. It is obtained by carrying out a reaction in the presence of a basic catalyst. In the epoxy compound which is a raw material for the synthesis of the epoxy (meth) acrylate, for example, bisphenol A such as EPIKOTE 828EL or EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.) may be mentioned as a commercial product. Epoxy resin; EPIKOTE 806, EPIKOTE 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.), etc. F-type epoxy resin; R-710 and other bisphenol E-type epoxy resin; EPICLON EXA1514 (大曰本墨公司Manufacture of bisphenol S type epoxy resin, etc.; 2,2'-diallyl bisphenol A type epoxy resin such as RE-810NM (manufactured by Sakamoto Chemical Co., Ltd.); EPICLON EXA7015 (大曰本墨公司Manufactured by hydrogenated bisphenol type epoxy resin; propylene oxide addition bisphenol A type epoxy resin such as EP-4000S (made by Asahi Kasei Co., Ltd.); benzene between EX-201 (manufactured by Changchun Chemical Co., Ltd.) Diphenol type epoxy resin; biphenyl type epoxy resin such as EPIKOTE YX-4000H (made by Japan Epoxy Resins Co., Ltd.); sulfide type epoxy resin of YSLV-50TE (made by Toho Chemical Co., Ltd.); YSLV-80DE (East Capital Diphenyl ether type epoxy resin manufactured by Huacheng Company; E Dicyclopentadiene type epoxy resin such as P-4088S (made by Asahi Kasei Co., Ltd.); naphthalene type epoxy resin such as EPICLON HP4032, EPICLON EXA-4700 (all manufactured by Otsuka Ink Co., Ltd.); EPICLON N-770 A phenol novolac type epoxy resin such as Eplon N-670-EXP-S (manufactured by Otsuka Ink Co., Ltd.); EPICLON HP7200 (large) Dicyclopentadiene 13 manufactured by Nippon Ink Co., Ltd. 200921222 Novolac type epoxy resin; AC-3000P (manufactured by Nippon Kayaku Co., Ltd.), such as biphenolic varnish type epoxy resin; ESN-165S (manufactured by Dongdu Chemical Co., Ltd.) ) a naphthol novolac type epoxy resin; a glycidylamine type epoxy resin such as EPIKOTE 630 (manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON 430 (manufactured by Dainippon Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Resin; alkyl group such as ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), EPICLON 726 (manufactured by Otsuka Ink Co., Ltd.), EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.) Alcohol type epoxy resin; YR-450, YR-207 (all manufactured by Dongdu Chemical Co., Ltd.), EPOLEAD PB (manufactured by Daicel Chemical Co., Ltd.), rubber modified epoxy resin; DENACOL EX-147 (Changfu Chemical Company) Manufactured by a glycidyl ester compound, such as a glycidyl ester compound such as EPIKOTE YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.), etc., in addition, YDC-1312, YSLV-80XY, and YSLV-90CR (both are Dongdu Huacheng) Manufactured by the company, XAC4151 (manufactured by Asahi Kasei Corporation), EPIKOTE 103, EPIKOTE 1032 (both manufactured by Japan Epoxy Resins Co., Ltd.), EXA-7120 (manufactured by Otsuka Ink Co., Ltd.), TEPIC (manufactured by Nissan Chemical Co., Ltd.), and the like. Further, as a commercially available product of the above epoxy (fluorenyl) acrylate, for example, EBECRYL 3700, EBECRYL 3600, EBECRYL 3701, EBECRYL 3703, EBECRYL 3200, EBECRYL 3201, EBECRYL 3702, EBECRYL 3412, EBECRYL 860 , EBECRYL RDX63 182, EBECRYL 6040, EBECRYL 3800 (both manufactured by Daicel UCB); EA-1020, EA-1010, EA-5520, EA-5323, 14 200921222 EA-CHD, EMA-1020 (all Xinzhongcun Chemical EPOXY ESTER M-600A > EPOXY ESTER 40EM > EPOXY ESTER 70PA, EPOXY ESTER 200PA, EPOXY ESTER 80MFA, EPOXY ESTER 3002M, EPOXY ESTER 3002A, EPOXY ESTER 1600A, EPOXY ESTER 3000M, EPOXY ESTER 3000A, EPOXY ESTER 200EA, EPOXY ESTER 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.); DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-91 1 (all manufactured by Nagase Chemical Co., Ltd.). The (meth)acrylic acid urethane obtained by reacting the (fluorenyl)acrylic acid derivative having a hydroxyl group with an isocyanate is not particularly limited, and for example, 2 equivalents of a (meth)acrylic acid having a hydroxyl group can be obtained. The derivative is obtained by reacting one equivalent of a compound having two isocyanate groups in the presence of a tin-based compound as a catalyst. The isocyanate which is a raw material of the above (meth)acrylic acid urethane is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-nonyl diisocyanate, and 2,6-nonyl diisocyanate. , hexamethylene diisocyanate, tridecyl hexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornene Alkyl diisocyanate, tolidine diisocyanate, phenyldiamidylene diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenyl decane triisocyanate, tris(isocyanate phenyl) thiophosphate, four Methyl xylene diisocyanate, 1,6,10-undecane triisocyanate, and the like. Further, as the above isocyanate, for example, ethylene glycolate, 15 200921222 glycerin, behenyl alcohol, trihydrocarbyl propane, (poly)propylene glycol, carbonate diol, polyether diol, polyester diol can also be used. A chain extended isocyanate compound obtained by reacting a polyhydric alcohol such as polycaprolactone diol with an excess of isocyanate. The (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 4. a commercial product such as hydroxybutyl ester or 2-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, a mono(indenyl) acrylate of a glycol such as polyethylene glycol; a mono(indenyl) acrylate of a triol such as trimethylolethane, trihydroxymethylpropane or glycerin; or Epoxy (meth) acrylate such as acrylate or bisphenol A modified epoxy (fluorenyl) acrylate. In addition, examples of the commercially available (meth)acrylic acid urethane include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.); EBECRYL 230' EBECRYL 270 ' EBECRYL 4858, EBECRYL 8402, EBECRYL 8804, EBECRYL 8803, EBECRYL 8807, EBECRYL 9260, EBECRYL 1290, EBECRYL 5129, EBECRYL 4842, EBECRYL 210, EBECRYL 4827, EBECRYL 6700, EBECRYL 220, EBECRYL 2220 (all are Daicel UCB companies) Manufacturing); ART RESIN UN-9000H, ART RESIN UN-9000A, ART RESIN UN-7100, ART RESIN UN-1255, ART RESIN UN-330, ART RESIN UN-3320HB, ART RESIN UN-1200TPK, ART RESIN SH-500B (All manufactured by Gensei Industrial Co., Ltd.); U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U -6LPA, 16 200921222 U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U -122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); AH-600, AT-600, UA-306H, AI-600, UA-101T, UA -1 01I, UA-306T, UA-306I, etc.

又，為進一步抑制本發明之液晶滴下法用密封劑之成 分於硬化前溶出至液晶，上述硬化性樹脂較佳為於丨分子 中具有至少1個氫鍵性官能基。 作為上述氫鍵性官能基並無特別限定，例如可列舉： -OH基、-SH基、-NHR基（R表示芳香族或脂肪族烴，及 該等之衍生物）、-C00H基、_麵〇11基等之官能基；又， 存在於分子内之-NHC0·、·ΝΗ_、_c〇NHC〇、_nh nh 等 之殘基’其中，自導入之容易度考慮，較佳為-0H基。 作為上述1分子中具有至少1個氫鍵性官能基且具有 (甲基)丙稀基之硬化性樹脂，例如可列舉上述(甲基)丙烯酸 胺基曱酸酯或環氧（曱基）丙烯酸酯等。 為了減少硬化時 1分子中具有2 於本發明之液晶滴下法用密封劑中， 之未硬化殘分，上述硬化性樹脂較佳為於 個以上反應性基之化合物。 物作盔μ、+， ，穴力个叫汉應性官能基之化合 作為上述硬化性樹脂。作 分子中且有M ， 述化合物’例如可列舉1 ’、有各為至〉1個之搂 ,,^ 、、 之環乳基與（甲基）丙烯基者。 作為上述1分子中且右 丙婦基之化合物，例如;少1個之環氧基與（曱基) r歹丨舉.使具有2個以上環氧基之 17 200921222 化合物的一部分環氧基與（甲基）丙烯酸反應所得之化合 物、使具有羥基之（甲基）丙烯酸衍生物及縮水甘油與二官能 以上之異氰酸酯反應所得之化合物等。 上述使具有2個以上環氧基之化合物的一部分環氧基 與（甲基）丙烯酸反應所得之化合物，例如可藉由依照常法， 於鹼性觸媒存在之條件下使環氧樹脂與（曱基）丙烯酸反應 而獲得。 作為上述具有2個以上環氧基之化合物，例如可列舉： EPIKOTE 828EL、EPIKOTE 1004 (均為 Japan Epoxy Resins 公司製造）等之雙酚A型環氧樹脂；EPIKOTE 806、EPIKOTE 4004 (均為Japan Epoxy Resins公司製造）等之雙盼F型環 氧樹脂；R-710等之雙酚E型環氧樹脂；EPICLON EXA1514 (大日本油墨公司製造）等之雙酚S型環氧樹脂；RE-810NM (曰本化藥公司製造）等之2,2'-二烯丙基雙酚A型環氧樹 脂；EPICLON EXA7015 (大日本油墨公司製造）等之氫化 雙酚型環氧樹脂；EP-4000S (旭電化公司製造）等之環氧 丙烷加成雙酚A型環氧樹脂；EX-201 (長瀨化成公司製造） 等之間苯二酚型環氧樹脂；EPIKOTE YX-4000H ( Japan Epoxy Resins公司製造）等之聯苯型環氧樹月旨；YSLV-50TE (東都化成公司製造）等之硫醚型環氧樹脂；YSLV-80DE (東都化成公司製造）等之聯苯醚型環氧樹脂；EP-4088S (旭電化公司製造）等之二環戊二烯型環氧樹脂；EPICLON HP4032、EPICLON EXA-4700 (均為大曰本油墨公司製造） 等之萘型環氧樹脂；EPICLON N-770(大曰本油墨公司製造） 18 200921222 等之苯酚酚醛清漆型環氧樹脂；EPICLON N-670-EXP-S (大 曰本油墨公司製造）等之鄰甲酚酚醛清漆型環氧樹脂； EPICLON HP7200 (大曰本油墨公司製造）等之二環戊二烯 酚醛清漆型環氧樹脂；NC-3000P (曰本化藥公司製造）等 之聯苯酚醛清漆型環氧樹脂；ESN-165S (東都化成公司製 造）等之萘笨酚酚醛清漆型環氧樹脂；EPIKOTE 630 ( Japan Epoxy Resins公司製造）、EPICLON 430 (大日本油墨公司 製造）、TETRAD-X (三菱瓦斯化學公司製造）等之縮水甘 油胺型環氧樹脂；ZX-1542(東都化成公司製造）、EPICLON 726 (大曰本油墨公司製造）、EPOLIGHT 80MFA (共榮社 化學公司製造）、DENACOL EX-611 (長瀨化成公司製造） 等之烷基多元醇型環氧樹脂；YR-450、YR-207 (均為東都 化成公司製造）；EPOLEAD PB ( Daicel化學公司製造）等 之橡膠改質型環氧樹脂；DENACOL EX-147(長瀨化成公司 製造）等之縮水甘油酯化合物；EPIKOTE YL-7000 ( Japan Epoxy Resins公司製造）等之雙紛A型環硫樹脂，此外可 列舉：YDC-1312、YSLV-80XY、YSLV-90CR (均為東都化 成公司製造）、XAC4151 (旭化成公司製造）；EPIKOTE 103 1、EPIKOTE 1032(均為 Japan Epoxy Resins 公司製造）； EXA-7120 (大日本油墨公司製造）；TEPIC (日產化學公 司製造）等。 作為上述使具有2個以上環氧基之化合物的一部分環 氧基與（甲基）丙烯酸反應所得之化合物之市售品，例如可列 舉 EBECRYL 1561 ( Daicel UCB 公司製造）等。 19 200921222 作為上述使具有羥基之（曱基）丙烯酸衍生物及縮水甘 油與一官能以上之異氰酸酯反應所得之化合物，例如可藉 由使各為1當量之具有羥基之（甲基）丙烯酸衍生物及縮水 甘油’與1當量之具有2個異氰酸酯基之化合物，於作為 觸媒之錫系化合物存在之條件下進行反應而獲得。 作為上述二官能以上之異氰酸酯，並無特別限定，例 如可列舉：異佛酮二異氰酸酯、2,4-曱苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞曱基二異氰酸酯、三甲基六亞曱基 二異氰酸酯 '二苯基曱烷_4,4，_二異氰酸酯（MDI)、氫化 Μ〇Ι、聚合MDI、1，5-萘二異氰酸酯、降冰片烷二異氰酸酯、 聯甲苯胺二異氰酸酯、苯二亞曱基二異氰酸酯（XDI )、氫 化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、三（異 氣酸醋基笨基）硫代磷酸酯、四甲基二甲苯二異氰酸酯、 U，10·十一烷三異氰酸酯等。 另外，作為上述二官能以上之異氰酸酯，例如亦可使 用由乙二醇、丙三醇、山梨醇、三羥甲基丙烷、（聚）丙二醇、 碳酸自曰—醇、聚醚二醇、聚酯二醇、聚己内酯二醇等之多 元醇與過剩之異氰酸酯的反應所得之鏈被延長之異氰酸酯 化合物。 作為上述具有羥基之（曱基）丙烯酸衍生物，並無特別限 J如可列舉：（甲基）丙稀酸2_經乙醋、（甲基）丙稀酸2_ 里赌、（甲基）丙烯酸4-羥丁酯、（甲基）丙烯酸2-羥丁酯等 之市售品；或乙二醇、丙二醇、1，3-丙二醇、1，3_丁二醇、 1’4_丁二醇、聚乙二醇等二元醇之單（甲基）丙烯酸酯；三羥 20 200921222 曱基乙烷、三羥曱基丙烷、丙三醇等三元醇之單（甲基）丙烯 酸酯或二（甲基）丙烯酸酯；雙酚A改質環氧（甲基）丙烯酸酯 等之環氧（甲基）丙烯酸酯等。 另外，除上述具有（曱基）丙烯基之硬化性樹脂之外，本 發明之密封劑亦可含有具有環氧基之化合物。 作為上述具有環氧基之化合物，並無特別限定，例如 可列舉：表氣酵（epichlorohydrin)衍生物、環式脂肪族環氧 樹脂、由異氰酸酯與縮水甘油之反應所得之化合物等。 作為上述表氣醇衍生物，例如可列舉：EPIK0TE 828EL、EPIKOTE 1004(均為 Japan Epoxy Resins 公司製造） 等之雙酚A型環氧樹脂；EPIKOTE 806、EPIKOTE 4004(均 為Japan Epoxy Resins公司製造）等之雙紛F型環氧樹脂； EPICLON EXA1514 (大曰本油墨公司製造）等之雙酚S型 環氧樹脂；RE-810NM (日本化藥公司製造）等之2,2’-二烯 丙基雙酚A型環氧樹脂；EPICLON EXA7015 (大日本油墨 公司製造）等之氫化雙酚型環氧樹脂；EP-4000S (旭電化 公司製造）等之環氧丙烷加成雙酚A型環氧樹脂；EX-201 (長瀨化成公司製造）等之間苯二酚型環氧樹脂；EPIKOTE YX-4000H ( Japan Epoxy Resins公司製造）等之聯苯型環氧 樹脂；YSLV-50TE (東都化成公司製造）等之硫醚型環氧 樹脂；YSLV-80DE (東都化成公司製造）等之聯苯醚型環 氧樹脂；EP-4088S (旭電化公司製造）等之二環戊二烯型 環氧樹脂；EPICLON HP4032、EPICLON EXA-4700 (均為 大曰本油墨公司製造）等之萘型環氧樹脂；EPICLON N-770 21 200921222 (大日本油墨公司製造）等之苯酚酚醛清漆型環氧樹脂； EPICLON N-670-EXP-S (大曰本油墨公司製造）等之鄰曱 酚酚醛清漆型環氧樹脂；EPICLON HP7200 (大曰本油墨公 司製造）等之二環戊二烯酚醛清漆型環氧樹脂；NC-3000P (曰本化藥公司製造）等之聯苯紛·醛清漆型環氧樹脂； ESN-165S (東都化成公司製造）等之萘酚酚醛清漆型環氧 樹脂；EPIKOTE 630 ( Japan Epoxy Resins 公司製造）； EPICLON 430 (大曰本油墨公司製造）；TETRAD-X (三菱 瓦斯化學公司製造）等之縮水甘油胺型環氧樹脂；ZX-1542 (東都化成公司製造）；EPICLON多元醇型環氧樹脂； YR-45 0、YR-207 (均為東都化成公司製造）；EPOLEAD PB (Daicel化學公司製造）等之橡膠改質型環726 (大曰本油 墨公司製造）、EPOLIGHT 80MFA(共榮社化學公司製造）、 DENACOL EX-611 (長瀨化成公司製造）等之烷基氧樹脂； DENACOL EX-147(長瀨化成公司製造）等之縮水甘油酯化 合物；EPIKOTE YL-7000 ( Japan Epoxy Resins 公司製造） 等之雙酚 A型環硫樹脂，此外可列舉：YDC-1312、 YSLV-80XY、YSLV-90CR (均為東都化成公司製造）； XAC4151 (旭化成公司製造）；EPIKOTE 1031、EPIKOTE 1032 (均為 Japan Epoxy Resins 公司製造）；EXA-7120 (大 曰本油墨公司製造）；TEPIC (日產化學公司製造）等。 另外，作為上述環式脂肪族環氧樹脂，並無特別限定， 作為市售品，例如可列舉：CELLOXIDE 202卜CELLOXIDE 2080、CELLOXIDE 3000、EPOLEAD GT300、EHPE (均為 22 200921222Further, in order to further suppress the elution of the component of the sealing compound for liquid crystal dropping method of the present invention to the liquid crystal before curing, the curable resin preferably has at least one hydrogen bond functional group in the ruthenium molecule. The hydrogen bond functional group is not particularly limited, and examples thereof include an -OH group, a -SH group, and a -NHR group (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof), -C00H group, _ a functional group of a group of 11 or the like; and a residue of -NHC0·,·ΝΗ_, _c〇NHC〇, _nh nh, etc. present in the molecule, wherein from the viewpoint of easiness of introduction, it is preferably -0H group . The curable resin having at least one hydrogen bond functional group in one molecule and having a (meth) acryl group may, for example, be the above-mentioned (meth)acrylic acid amide or decyl acrylate. Ester and the like. In order to reduce the uncured residue of the liquid crystal dropping method sealant of the present invention in one molecule at the time of curing, the curable resin is preferably a compound having more than one reactive group. The object is a helmet, μ, +, and a combination of a group of functional groups called the sclerosing resin. M is a molecule, and the compound 'for example' is exemplified by 1 ', and each of them is a sulfonyl group and a (meth) propylene group. The compound of the above-mentioned one molecule and the dextropropyl group, for example, one less epoxy group and (fluorenyl) ruthenium. A part of the epoxy group of the compound of 200921222 having two or more epoxy groups is A compound obtained by a reaction of (meth)acrylic acid, a compound obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group, and glycidol with a difunctional or higher isocyanate. The compound obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (meth)acrylic acid can be obtained, for example, by an epoxy resin according to a conventional method in the presence of a basic catalyst. Acetyl based on acrylic acid reaction. Examples of the compound having two or more epoxy groups include bisphenol A type epoxy resin such as EPIKOTE 828EL and EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.); EPIKOTE 806 and EPIKOTE 4004 (both Japan Epoxy) Resins company, etc., F-type epoxy resin; bisphenol E-type epoxy resin such as R-710; bisphenol S-type epoxy resin such as EPICLON EXA1514 (manufactured by Dainippon Ink Co., Ltd.); RE-810NM ( 2,2'-diallyl bisphenol A type epoxy resin manufactured by Sakamoto Chemical Co., Ltd.; hydrogenated bisphenol type epoxy resin such as EPICLON EXA7015 (manufactured by Dainippon Ink Co., Ltd.); EP-4000S (旭Ethylene oxide addition bisphenol A type epoxy resin manufactured by Electrochemical Co., Ltd.; EX-201 (manufactured by Changchun Chemical Co., Ltd.), etc. Ethylphenol type epoxy resin; EPIKOTE YX-4000H (Manufactured by Japan Epoxy Resins Co., Ltd.) ) a biphenyl type epoxy resin such as a biphenyl type epoxy resin; a thioether type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.); a diphenyl ether type epoxy resin such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); -4088S (manufactured by Asahi Kasei Co., Ltd.) Resin; Epiclon HP4032, EPICLON EXA-4700 (all manufactured by Otsuka Ink Co., Ltd.); naphthalene type epoxy resin; EPICLON N-770 (manufactured by Otsuka Ink Co., Ltd.) 18 200921222 phenol novolak type epoxy resin ; ortho-cresol novolac type epoxy resin such as EPICLON N-670-EXP-S (manufactured by Otsuka Ink Co., Ltd.); dicyclopentadiene novolac type ring such as EPICLON HP7200 (manufactured by Otsuka Ink Co., Ltd.) Oxygen resin; a non-phenol novolak type epoxy resin such as NC-3000P (manufactured by Sakamoto Chemical Co., Ltd.); a naphthol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.); EPIKOTE 630 (Japan) Glycidylamine type epoxy resin such as EPICLON 430 (manufactured by Dainippon Ink Co., Ltd.), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), ZX-1542 (manufactured by Tosho Kasei Co., Ltd.), EPICLON 726 (large) Alkyl polyol type epoxy resin such as EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) and DENACOL EX-611 (manufactured by Changchun Chemical Co., Ltd.); YR-450, YR-207 (all manufactured) Dongdu Huacheng Rubber modified epoxy resin such as EPOLEAD PB (manufactured by Daicel Chemical Co., Ltd.); glycidyl ester compound such as DENACOL EX-147 (manufactured by Changchun Chemical Co., Ltd.); EPIKOTE YL-7000 (Manufactured by Japan Epoxy Resins Co., Ltd.) ), such as YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Dongdu Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), EPIKOTE 103 1 and EPIKOTE 1032 (both) It is manufactured by Japan Epoxy Resins Co., Ltd.; EXA-7120 (manufactured by Dainippon Ink Co., Ltd.); TEPIC (manufactured by Nissan Chemical Co., Ltd.). The commercially available product obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (meth)acrylic acid, for example, may be EBECRYL 1561 (manufactured by Daicel UCB Co., Ltd.). 19 200921222 The compound obtained by reacting a (hydroxy)acrylic acid derivative having a hydroxyl group and glycidol with a monofunctional or higher isocyanate, for example, by using 1 equivalent of a (meth)acrylic acid derivative having a hydroxyl group and Glycidol' is obtained by reacting one equivalent of a compound having two isocyanate groups in the presence of a tin-based compound as a catalyst. The difunctional or higher isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-nonyl diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, and trimethyl group. Hexamethylene diisocyanate 'diphenylnonane_4,4,-diisocyanate (MDI), hydrazine hydride, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine di Isocyanate, phenylenedifluorene diisocyanate (XDI), hydrogenated XDI, diazonic acid diisocyanate, triphenylmethane triisocyanate, tris(isophthalic acid phenanthryl) phosphorothioate, tetramethyl xylene diisocyanate , U, 10· undecane triisocyanate, and the like. Further, as the above-mentioned difunctional or higher isocyanate, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonic acid-based alcohol, polyether diol, polyester may also be used. A chain-extended isocyanate compound obtained by reacting a polyol such as a diol or a polycaprolactone diol with an excess of isocyanate. The (meth)acrylic acid derivative having a hydroxyl group is not particularly limited as long as it is exemplified by (meth)acrylic acid 2_acetic acid, (meth)acrylic acid 2_ gambling, (methyl) a commercial product such as 4-hydroxybutyl acrylate or 2-hydroxybutyl (meth)acrylate; or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1'4-butadiene a mono(meth)acrylate of a glycol such as an alcohol or a polyethylene glycol; a mono(meth)acrylate of a trihydric alcohol such as trihydroxy 20 200921222 mercaptoethane, trishydroxypropylpropane or glycerin or Di(meth)acrylate; bisphenol A modified epoxy (meth) acrylate such as epoxy (meth) acrylate. Further, the sealant of the present invention may contain a compound having an epoxy group in addition to the above-mentioned curable resin having a (fluorenyl) propylene group. The compound having an epoxy group is not particularly limited, and examples thereof include an epichlorohydrin derivative, a cyclic aliphatic epoxy resin, and a compound obtained by reacting an isocyanate with glycidol. Examples of the surface gas alcohol derivative include bisphenol A type epoxy resins such as EPIK0TE 828EL and EPIKOTE 1004 (all manufactured by Japan Epoxy Resins Co., Ltd.); EPIKOTE 806 and EPIKOTE 4004 (all manufactured by Japan Epoxy Resins Co., Ltd.). Equivalent to F-type epoxy resin; Epiclon EXA1514 (manufactured by Otsuka Ink Co., Ltd.) and other bisphenol S-type epoxy resin; RE-810NM (manufactured by Nippon Kayaku Co., Ltd.), etc. 2,2'-diene Bisphenol A type epoxy resin; hydrogenated bisphenol type epoxy resin such as EPICLON EXA7015 (manufactured by Dainippon Ink Co., Ltd.); propylene oxide addition bisphenol A type epoxy such as EP-4000S (made by Asahi Kasei Co., Ltd.) Resin; biphenyl type epoxy resin such as EX-201 (manufactured by Changchun Chemical Co., Ltd.); biphenyl type epoxy resin such as EPIKOTE YX-4000H (manufactured by Japan Epoxy Resins Co., Ltd.); YSLV-50TE (Dongdu Chemical Co., Ltd.) a thioether type epoxy resin such as a thioether type epoxy resin; a bisphenylene type epoxy resin such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.); and a dicyclopentadiene type epoxy resin such as EP-4088S (manufactured by Asahi Kasei Co., Ltd.) ; EPICLON HP4032, EPICLON EXA-4700 (all Naphthalene type epoxy resin, etc. manufactured by Sakamoto Ink Co., Ltd.; phenol novolak type epoxy resin such as EPICLON N-770 21 200921222 (manufactured by Dainippon Ink Co., Ltd.); EPICLON N-670-EXP-S (大曰本墨O-nonphenol novolac type epoxy resin manufactured by the company; dicyclopentadiene novolac type epoxy resin such as EPICLON HP7200 (manufactured by Otsuka Ink Co., Ltd.); NC-3000P (manufactured by Sakamoto Chemical Co., Ltd.) Ethylene aldehyde varnish type epoxy resin; ESN-165S (made by Dongdu Chemical Co., Ltd.), etc. Company made); Glycidylamine type epoxy resin such as TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.); ZX-1542 (manufactured by Dongdu Chemical Co., Ltd.); EPICLON polyol type epoxy resin; YR-45 0, YR-207 (all manufactured by Dongdu Chemical Co., Ltd.); rubber modified ring 726 (manufactured by Otsuka Ink Co., Ltd.), EPOLIGHT 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and DENACOL EX-611 (made by EPOLEAD PB (manufactured by Daicel Chemical Co., Ltd.)) Changhua Alkyloxy resin, etc. manufactured by the company; a glycidyl ester compound such as DENACOL EX-147 (manufactured by Nagase Chemical Co., Ltd.); a bisphenol A type episulfide resin such as EPIKOTE YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.), For example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Dongdu Chemical Co., Ltd.); XAC4151 (made by Asahi Kasei Corporation); EPIKOTE 1031, EPIKOTE 1032 (all manufactured by Japan Epoxy Resins Co., Ltd.); EXA-7120 (large Manufactured by Sakamoto Ink Co., Ltd.; TEPIC (manufactured by Nissan Chemical Co., Ltd.). In addition, the cyclic aliphatic epoxy resin is not particularly limited, and examples of the commercially available product include CELLOXIDE 202, CELLOXIDE 2080, CELLOXIDE 3000, EPOLEAD GT300, and EHPE (both 22 200921222).

Daicel化學公司製造）等。 作為上述由異氰酸酯與縮水甘油反應所得之化人物， 並無特別限定，例如可藉由使2當量之縮水甘油與具有2 個異氰酸酯基之化合物，於作為觸媒之錫系化合物^在之 條件下進行反應而獲得。 作為上述異氰酸酯並無特別限定，例如可列舉：異佛 酮二異氰酸酯、2,4-甲苯二異氰酸酯、2 6_甲笨_ τ冬一異氰酸酯、 六亞曱基二異氰酸酯、χ甲基六亞曱基二異氰酸酯、二苯 基曱烷-4,4，-二異氰酸酯（MDI)、氫化Mm、聚合μ〇ι、 1，5-萘二異氰酸酯、降冰片烷二異氰酸酯、聯甲笨胺二異氰 酸醋、苯二亞甲基二異該s| (XDI)、氫化伽、:胺= 二異氰酸醋、三苯甲烷三異氰酸醋、三(異氰酸酷基苯幻 硫代鱗酸輯、四甲基二甲苯二異氰酸酿、M，隊十一院 氰酸酯等。 疋一、 另外’作為上述異氰 丙三醇、山梨醇、三經甲基丙院、(聚)丙二醇、碳酸醋二醇、 聚醚二醇m $己㈣：醇等之多元醇與過剩之 異氰酸酯的反應所得之鏈被延長之異氰酸酯化合物。 本發明之液晶滴下法用密封劑較 削衩佳為進而含有熱硬化 劑。 物 作為上述熱硬化劑並無特別限定 多酚系化合物、酸肝等。 例如可列舉胺化合 作為上述胺化合物 一〜三級胺基之化合物 可列舉1分子中具有1 具體而言，例如可列舉 個以上之 :間苯二 23 200921222 胺、二胺基二苯甲烷等之芳香族胺；2-甲基咪唑、1,2-二甲 基咪唑、1 -氰乙基-2-甲基咪唑等之咪唑化合物；2-曱基咪唑 啉等之咪唑啉化合物；癸二酸二醯肼、間苯二甲酸二醯肼 等之二醯肼化合物；AJICURE PN-23、AJICURE MY-24、 AJICURE VDH (均為 Ajinomoto Fine-Techno 公司製造）等 之胺加合物類；以及二氰二胺等。 作為上述多酚系化合物，並無特別限定，例如可列舉： EPICURE 170、EPICURE YL6065 (均為 Japan Epoxy Resins 公司製造）等之多酚化合物；EPICURE MP402FPI ( Japan Epoxy Resins公司製造）等之紛搭清漆型苯紛樹脂。 作為上述酸酐，並無特別限定，例如可列舉EPICURE YH-306、YH-307 (均為 Japan Epoxy Resins 公司製造）等。 該等熱硬化劑可單獨使用，亦可併用2種以上。其中， 自低溫硬化性及保存穩定性優異之方面考慮，較佳為二醯 肼化合物。 作為上述熱硬化劑之調配量，並無特別限定，相對於 100重量份之上述硬化性樹脂，較佳下限為1重量份，較佳 上限為100重量份。若上述熱硬化劑之調配量未滿1重量 份，則有時上述硬化性樹脂之硬化會變得不充分；若超過 100重量份，則本發明之液晶滴下法用密封劑之保存穩定性 會有惡化之虞，又，製成硬化物時，會有耐濕性降低之虞。 上述熱硬化劑之調配量之更佳上限為20重量份。 本發明之液晶滴下法用密封劑較佳為進而含有矽烷偶 合劑。上述矽烷偶合劑主要具有接著助劑之作用，該接著 24 200921222 助劑係用以將本發明之液# 件基板良好地接著。 滴下法用密封劑與液晶顯示元 作為上述石夕燒偶合劑並無特別限定，例如可列舉. 胺丙基三甲氧基㈣、卜制基三甲氧基錢、7_縮/甘 油氧基丙基三以基錢、卜異氰酸S旨基丙基三f氧基發 烧專。該等錢偶合劑可單獨使用，亦可併用2種以上 :者，上述r'縮水甘油氧基丙基三甲氧基錢係具有環氧 土之化合物，可於不使由滴下法所製造之液晶顯示元件之 顯不品質降低之程度的範圍内使用。 作為上述石夕燒偶合劑之調配量，並無特別限定，相對 於100重量份之上述硬化性樹腊，較佳τ限為G1重量份， 較佳上限為1G重量份。若上述㈣偶合劑之調配量未滿W 重量份，則可能無法充分發揮性能；若超過10重量份，則 會有剩餘之矽烷偶合劑溶出至液晶而使顯示品質降低之 虞。上述矽烷偶合劑之調配量之更佳下限為0 5重量份，更 佳上限為3重量份。 另外，為了藉由應力分散效果來改善接著性、線膨服 係數等之目的，本發明之液晶滴下法用密封劑亦可含有填 充劑。 作為上述填充劑並無特別限定，例如可列舉：滑石、 石棉、二氧化矽、矽藻土、膨潤石、膨潤土、碳酸二碳 酸鎮、氧化铭、蒙脫土、氧化鎮、氧化鈦、氫氧化鎮、氫 氧化鋁、玻璃珠、硫酸鋇、石膏、矽酸鈣、絹雲母、活性 白土等之無機填充劑；或聚i旨微粒子、聚胺基;酸醋微粒 25 200921222 子、乙烯聚合物微粒+、丙#酸聚合物微粒子等之有機填 充劑。 、 曰作為上料充狀懸量，並無㈣^，相對於100 重置份之上述硬化性樹脂，較佳下限為丨重量份，較佳上 限為ΗΚ)重量份。若上述填充劑之調配量未滿1重量份， 則可能無法充分發揮性能。若超過1〇〇重量份，則有使本 發明之液晶滴下法職封劑之拉延性等操作性降低之虞。 上述填充劑之調配量之更佳下限為1〇重量份，更 5〇重量份。 L吏用Ε型黏度計於说所測定之本發明之液晶滴下法 Ρ封劑的黏度之上限為60萬此.S。若上述黏度超過60 顯，則拉延性會不充分，無法藉由滴下法來製造液晶 :，員不…上述黏度之較佳下限為1〇萬mp"，較佳上限 為 45 萬 mPa . s。 作為測疋本發明之液晶滴下法用密封劑之黏度的E型 黏度冲，並無特別限定，例如可列舉㈣似…公司製造之 Dv-m」等。 作為製造本發明之液晶滴下法用密封劑之方法，並無 限定，可列舉如下方法等：即利用先前公知之方法， ^固定量之上述硬化性樹脂、光自由基起始劑、及視需要 二配之上述熱硬化劑、矽烷偶合劑加以混合等。此時， 觸:、所3之離子性雜質，亦可使其與離子吸附性固體接Made by Daicel Chemical Co., Ltd.). The person obtained by the reaction of the isocyanate and the glycidol is not particularly limited. For example, two equivalents of glycidol and a compound having two isocyanate groups can be used as a tin-based compound as a catalyst. Obtained by carrying out the reaction. The isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate, 2,4-toluene diisocyanate, 2 6-methyl benzoate, isohexamethylene diisocyanate, hexamethylene diisocyanate, and fluorenylmethyl hexamethylene fluorene. Diisocyanate, diphenyldecane-4,4,-diisocyanate (MDI), hydrogenated Mm, polymeric μ〇ι, 1,5-naphthalene diisocyanate, norbornane diisocyanate, dimethoprim diisocyanate Sour vinegar, benzene dimethylene diiso s | (XDI), hydrogenated gamma, amine = diisocyanate vinegar, triphenylmethane triisocyanate, tris (isocyanate thiophene thiophene scale Acid series, tetramethyl xylene diisocyanate brewing, M, team eleventh cyanate ester, etc. 疋一, additionally 'as the above-mentioned isocyanide, sorbitol, trimethoprim, (poly Propylene glycol, carbonic acid diol, polyether diol m $hex (IV): a chain extended isocyanate compound obtained by reacting a polyol such as an alcohol with an excess of isocyanate. The sealing agent for liquid crystal dropping method of the present invention is better. Further, the thermosetting agent is further contained. The thermosetting agent is not particularly limited to a polyphenol compound. For example, a compound having an amination group of the above-mentioned amine compound mono- to tertiary amino group may be mentioned as 1 in a molecule, and specific examples thereof include, for example, isophthalene 23 200921222 amine, diamine group II. An aromatic amine such as phenylmethane; an imidazole compound such as 2-methylimidazole, 1,2-dimethylimidazole or 1-cyanoethyl-2-methylimidazole; an imidazoline compound such as 2-mercaptoimidazoline Adipine compounds such as azelaic acid diterpene and isophthalic acid dioxime; amine adducts such as AJICURE PN-23, AJICURE MY-24, AJICURE VDH (all manufactured by Ajinomoto Fine-Techno) The polyphenol-based compound is not particularly limited, and examples thereof include polyphenol compounds such as EPICURE 170 and EPICURE YL6065 (all manufactured by Japan Epoxy Resins Co., Ltd.); EPICURE MP402FPI (Japan Epoxy) The varnish-type benzene resin is not particularly limited, and examples thereof include EPICURE YH-306 and YH-307 (all manufactured by Japan Epoxy Resins Co., Ltd.). Can be separate In addition, it is preferable to use a diterpene compound from the viewpoint of being excellent in low-temperature hardening property and storage stability. The compounding quantity of the said heat-hardening agent is not specifically limited with respect to 100 weight. The lower limit of the curable resin is preferably 1 part by weight, and the upper limit is preferably 100 parts by weight. When the amount of the thermosetting agent is less than 1 part by weight, the curing of the curable resin may not become When it is more than 100 parts by weight, the storage stability of the sealing compound for liquid crystal dropping methods of the present invention may be deteriorated, and when the cured product is formed, the moisture resistance may be lowered. A more preferable upper limit of the amount of the above-mentioned thermosetting agent is 20 parts by weight. The sealing agent for liquid crystal dropping method of the present invention preferably further contains a decane coupling agent. The above-mentioned decane coupling agent mainly has the function of a secondary auxiliary agent, and the subsequent agent is used to satisfactorily carry out the liquid substrate of the present invention. The sealing agent for a dripping method and a liquid crystal display element are not particularly limited as the above-mentioned catalyst, and examples thereof include an aminopropyltrimethoxy group (tetra), a trimethyloxy group, and a 7-condensed/glyceryloxypropyl group. Three base money, isocyanate S-propyl propyl tri-foxy fever. The above-mentioned money coupling agent may be used singly or in combination of two or more kinds thereof. The above-mentioned r' glycidoxypropyltrimethoxy group is a compound having an epoxy earth, and the liquid crystal produced by the dropping method can be prevented. It is used within the range of the degree to which the display element is not degraded. The blending amount of the above-mentioned zebra calcining coupler is not particularly limited, and is preferably a G1 part by weight and a preferred upper limit of 1 G part by weight based on 100 parts by weight of the curable wax. If the amount of the above (4) coupling agent is less than W parts by weight, the performance may not be sufficiently exhibited. If it exceeds 10 parts by weight, the remaining decane coupling agent may be eluted into the liquid crystal to lower the display quality. A more preferred lower limit of the amount of the above decane coupling agent is 0.5 parts by weight, and a more preferred upper limit is 3 parts by weight. Further, in order to improve the adhesion, the linear expansion coefficient, and the like by the stress dispersion effect, the sealing compound for liquid crystal dropping method of the present invention may further contain a filler. The filler is not particularly limited, and examples thereof include talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, carbonic acid carbonate, oxidized melamine, montmorillonite, oxidized town, titanium oxide, and hydroxide. Inorganic fillers such as town, aluminum hydroxide, glass beads, barium sulfate, gypsum, calcium silicate, sericite, activated clay; or microparticles, polyamines; acid vinegar particles 25 200921222, ethylene polymer particles +, organic reagents such as acrylic acid microparticles. And 曰 as the filling amount of the filling, there is no (four) ^, and the lower limit of the above-mentioned curable resin with respect to 100 parts is preferably 丨 by weight, preferably upper 重量) by weight. If the amount of the above filler is less than 1 part by weight, the performance may not be sufficiently exhibited. When the amount is more than 1 part by weight, the workability such as the drawability of the liquid crystal dropping method sealant of the present invention is lowered. A more preferred lower limit of the amount of the above filler is 1 part by weight, more preferably 5 parts by weight. L吏 uses a Ε-type viscometer to determine the viscosity of the liquid crystal dropping method of the present invention. The upper limit of the viscosity of the sealant is 600,000. If the viscosity exceeds 60, the drawability will be insufficient, and the liquid crystal cannot be produced by the dropping method: the lower limit of the viscosity is preferably 10,000 mp", and the upper limit is 450,000 mPa. The E-type viscosity of the viscosity of the sealing agent for a liquid crystal dropping method of the present invention is not particularly limited, and examples thereof include (d) Dv-m manufactured by the company. The method for producing the sealing agent for a liquid crystal dropping method of the present invention is not limited, and examples thereof include a method of using a conventionally known method, a fixed amount of the curable resin, a photoradical initiator, and optionally The above-mentioned thermal hardener and decane coupling agent are mixed and the like. At this point, touch: the ionic impurities of the 3, can also be made with ion-adsorbing solids

月之液曰曰滴下法用密封劑由於黏度為60萬mPa. S 26 200921222 以下，故為拉延性亦優異者。又，上述硬化性樹脂由於含 有對上述液晶之溶解性高之光自由基起始劑，故於藉由滴 下法製造液晶顯示元件時’可不引起液晶污染而製造出高 品質圖像之液晶顯示元件。 藉由於本發明之液晶滴下法用密封劑中調配導電性微 粒子，可製造上下導通材料。上述含有本發明之液晶滴下 法用密封劑與導電性微粒子之上下導通材料亦係本發明之 作為上述導電性微粒子，並無特別限定，可使用金屬 球、或於樹脂微粒子之表面形成有導電金屬層者等。其中， 於樹月曰微粒子之表面形成有導電金屬層者，因樹脂微粒子 之優異彈性’而可於不損傷透明基板等的情況下實現導電 連接，因此較適合。 使用本發明之液晶滴下法用密封劑及/或本發明之上下 導通材料而形成之液晶顯示元件亦係本發明之一。 作為裝本發明之液晶顯示元件之方法，例如可列舉 具有如下步驟之方法等：即於iT〇 (Indium τίη 〇χί&，氧 化銦錫）薄膜等之2片附電極之透明基板_之—片上，網 =刷本發明之液晶滴下法用密封劑等，再藉由分配器塗 佈等而形成長方形狀之密封圖串 固系之梦驟，於本發明之液晶 :下法用密封劑等未硬化之狀態下，於透明基板之框内整 面上滴下並塗佈液晶之微小滴，然後立即重疊另 明基板之步驟；以及，對 之密封靥垒细ν 月之液曰日滴下法用密封劑等 、圖案Β照射紫外料光，使其預硬化之步驟；以 27 200921222 及對預硬化之密封圖案進行 、+ m 系运仃加熱，使由本發明之液晶滴下 法用岔封劑等所構成之穿封 、 τ偁珉之在封圖案進行正式硬化之步驟。 上述使用本發明之液晶滴 、 日日肩下法用密封劑及/或本發明之 上下導通材料而形成之液ags_ _ 取 < 辰日日顯不几件亦係本發明之一。 發明效杲 根據本發明，可提供一種液晶滴下法用密封劑，其在 ;滴下法之液B日顯不疋件之製造時，即便密封劑成分溶 出至液晶’亦可防止引起液晶㈣，％而可製造出顯示品 質及可靠性優異之液晶顯示元件。 【實施方式】 以下揭示實施例來對本發明進行進一步詳細說明，但 本發明並非僅限定於該等實施例。 <硬化性樹脂之合成> (環氧丙烯酸酯（1)之合成） 使170 g之雙酚Α型環氧樹脂85〇CRp (大日本油墨公 司製造）溶解於500 mLi甲苯中，於該溶液中加入〇」§ 之三苯膦，製成均勻之溶液。於回流攪拌下以2小時於該 洛液中滴下72 g之丙埽酸後，進而回流攪拌8小時。 胃繼而，除去甲苯，藉此獲得全部環氧基變成丙烯醯基 而得之環氧丙烯酸酯（1) (85〇CRP完全改質品）。 (使環氧基之一部分與丙烯酸反應所得之雙紛E型環 氧丙烯酸酯樹脂（部分改質樹脂（2 )之合成）） 使163 g之雙酚E型環氧樹脂R-710 (三井化學公司製 28 200921222 造）溶解於500 mL之甲苯中，於該溶液中加入〇1 g之三 苯膦，製成均勻之溶液。於回流攪拌下以2小時於該溶液 中滴下54g之丙烯酸後，進而回流擾拌6小時。除去甲苯， 藉此獲彳于由75莫耳％之環氧基與丙烯酸反應所得之雙酚E 型環氧丙烯酸酯樹脂（部分改質樹脂（2 ))。 再者，改質率係藉由如下方法測定：使樹脂溶解於鹽 酸-二氧陸圜（HCl-dioxane)溶液中後，使用K〇H來滴定因環 氧基消耗之鹽酸量。 (使環氧基之一部分與丙烯酸反應所得之雙酚F型環 氧丙烯酸酯樹脂（部分改質樹脂（3 )之合成）） 使156 g之雙酚F型環氧樹脂83〇CRp (大日本油墨公 司製造）溶解於500 mLi曱苯中，於該溶液中加入〇」g 之二苯膦，製成均勻之溶液。於回流攪拌下以2小時於該 溶液中滴下54 g之丙烯酸，進而回流攪拌6小時。除去甲 本藉此獲知由75莫耳％之環氧基與丙稀酸反應所得之雙 紛F型環氧丙烯酸酯樹脂（部分改質樹脂（3 ))。 再者，改質率係藉由如下方法測定：使樹脂溶解於鹽 酸-一氧陸圜溶液中後，使用K〇H來滴定因環氧基消耗之鹽 酸量。 (使環氧基之一部分與丙烯酸反應所得之雙酚E型環 氧丙稀酸酯樹脂（部分改質樹脂（4 )之合成）） 使163 g之雙酚E型環氧樹脂R_7丨〇 (三井化學公司製 造）溶解於500 mL之甲苯中，於該溶液中加入〇」g之三 苯膦，製成均勻之溶液。於回流攪拌下以2小時於該溶液 29 200921222 中滴下3 6 g之丙烯酸後，進而回流攪拌6小時。除去甲苯， 藉此獲得由50莫耳％之環氧基與丙烯酸反應所得之雙酚e 型環氧丙烯酸酯樹脂（部分改質樹脂（4 ))。 再者’改質率係藉由如下方法測定：使樹脂溶解於鹽 酸-二氧陸圜溶液中後’使用KOH來滴定因環氧基消耗之鹽 酸量。 (使環氧基之一部分與丙稀酸反應所得之聯苯謎型環 氧丙烯酸酯樹脂（部分改質樹脂（5 )之合成）） 使157 g之聯苯醚型環氧樹脂ySLV_8〇de (新曰鐵化 學公司製造）溶解於500 mLi甲苯中，於該溶液中加入〇」 g之二苯膦’製成均勻之溶液。於回流攪拌下以2小時於該 /奋液中滴下3 6 g之丙烯酸後，進而回流攪拌6小時。除去 曱苯，藉此獲得由50莫耳％之環氧基與丙烯酸反應所得之 雙酚E型環氧丙烯酸酯樹脂（部分改質樹脂（5 ))。 再者，改質率藉由如下方法測定：使樹脂溶解於鹽酸_ 二氡陸圜溶液中後，利用K〇H來滴定經環氧基消耗之鹽酸 量〇 (實施例1 ) 將100重量份之所合成之部分改質樹脂（2) 、2重量 知之光自由基起始劑（汽巴精化公司製造，irgacure ΓΛ "V" Tj Λ 1 \ 16重量份之熱硬化劑（Ajinomoto Fine-Techno =司製造，賴CURE VDH )、3Q重量份之作為填充劑之球 形一氧化矽（Admatechs公司製造，S0_C1)、及2重量份 之砂烧偶合劑（信越化學公司製造，KBM彻）進行調配， 30 200921222 以行星式授拌裝置（Thinky &司製造，去泡練太郎）加以 攪拌後，利用陶瓷三輥研磨機使其均勻地混合，從而獲得 液晶滴下法用密封劑。 (實施例2 ) 將50重量份之所合成之環氧丙烯酸酯、5〇重量 份之所合成之部分改質樹脂（4) 、2重量份之光自由基起 始劑（》工巴精化公司製造，IRGACURE OXEO1 ) 、16重量 伤之熱硬化劑（Ajinomoto Fine-Techno公司製造，AJICURE VDH)、30重量份之作為填充劑之球形二氧化矽（Admatechs 公司製造，SO-C1)、及2重量份之矽烷偶合劑（信越化學 公司製造，KBM403 )進行調配，以行星式攪拌裝置（Thinky 公司製造’去泡練太郎）加以攪拌後，利用陶瓷三輥研磨 機使其均勻地混合，從而獲得液晶滴下法用密封劑。 (實施例3)The sealant for the liquid helium drop method of the month has a viscosity of 600,000 mPa. S 26 200921222 or less, so it is excellent in drawability. Further, since the curable resin contains a photoradical initiator which has high solubility in the liquid crystal, when a liquid crystal display element is produced by a dropping method, a liquid crystal display element which can produce a high-quality image without causing liquid crystal contamination. By the provision of the conductive microparticles in the sealing compound for liquid crystal dropping methods of the present invention, the upper and lower conductive materials can be produced. The above-mentioned conductive fine particles are not particularly limited as long as the above-mentioned conductive fine particles are contained in the present invention, and the conductive particles are formed on the surface of the resin fine particles. Layers and so on. Among them, in the case where a conductive metal layer is formed on the surface of the sapphire particles, it is preferable because the excellent elasticity of the resin fine particles can be electrically connected without damaging the transparent substrate or the like. The liquid crystal display element formed by using the sealing compound for liquid crystal dropping method of the present invention and/or the upper conductive material of the present invention is also one of the present inventions. As a method of mounting the liquid crystal display element of the present invention, for example, a method having the following steps: a transparent substrate of two electrodes with an electrode such as an indium ITO (Indium TiO 2 ) film or the like , the net = the sealing agent for the liquid crystal dropping method of the present invention, and the like, and the rectangular sealing pattern is formed by the dispenser coating, etc., in the liquid crystal of the present invention: the sealing agent for the lower method, etc. In the state of hardening, the liquid droplets are dropped and coated on the entire surface of the transparent substrate, and then the steps of the other substrate are immediately overlapped; and the sealing liquid is sealed and sealed. a step of pre-curing the ultraviolet light by a pattern, a pattern, a pre-hardening step, and a + m system heating method on 27 200921222 and a pre-hardened sealing pattern to form a liquid crystal dropping method of the present invention. The step of sealing and τ 偁珉 in the sealing pattern for formal hardening. The liquid ags_ _ which is formed by using the liquid crystal droplet of the present invention, the sealing agent for the day and shoulder under the sun, and/or the upper and lower conductive materials of the present invention is also one of the inventions. Advantageous Effects of Invention According to the present invention, it is possible to provide a sealing agent for a liquid crystal dropping method, which can prevent liquid crystals from being caused even when a sealant component is eluted to a liquid crystal when the liquid of the dropping method B is produced. Further, a liquid crystal display element excellent in display quality and reliability can be manufactured. [Embodiment] The present invention will be described in further detail below with reference to the embodiments, but the invention is not limited to the embodiments. <Synthesis of Curable Resin> (Synthesis of Epoxy Acrylate (1)) 170 g of a bisphenolphthalein type epoxy resin 85 〇 CRp (manufactured by Dainippon Ink Co., Ltd.) was dissolved in 500 mL of toluene, A solution of triphenylphosphine was added to the solution to prepare a homogeneous solution. Under reflux with stirring, 72 g of propionic acid was added dropwise to the solution, and the mixture was further stirred under reflux for 8 hours. The stomach then removes toluene, thereby obtaining an epoxy acrylate (1) (85 〇 CRP completely modified product) in which all of the epoxy groups are converted into acryloyl groups. (Synthesized E-type epoxy acrylate resin obtained by reacting one part of epoxy group with acrylic acid (synthesis of partially modified resin (2)) 163 g of bisphenol E type epoxy resin R-710 (Mitsui Chemical Co., Ltd.) The company made 28 200921222 was dissolved in 500 mL of toluene, and 1 g of triphenylphosphine was added to the solution to prepare a homogeneous solution. After 54 g of acrylic acid was added dropwise to the solution under reflux for 2 hours, it was further refluxed for 6 hours. Toluene was removed, whereby a bisphenol E type epoxy acrylate resin (partially modified resin (2)) obtained by reacting 75 mol% of an epoxy group with acrylic acid was obtained. Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-dioxane solution (HCl-dioxane), and then using K〇H to titrate the amount of hydrochloric acid consumed by the epoxy group. (a bisphenol F-type epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of a partially modified resin (3))) 156 g of a bisphenol F type epoxy resin 83 〇 CRp (Great Japan The ink company is dissolved in 500 mL of benzene, and diphenylphosphine is added to the solution to prepare a homogeneous solution. To the solution was added dropwise 54 g of acrylic acid under reflux for 2 hours, and the mixture was further stirred under reflux for 6 hours. By removing the nail, a double F-type epoxy acrylate resin (partially modified resin (3)) obtained by reacting 75 mol% of an epoxy group with acrylic acid was known. Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid-oxonium ruthenium solution and then using K 〇 H to titrate the amount of hydrochloric acid consumed by the epoxy group. (a bisphenol E type epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of a partially modified resin (4))) 163 g of a bisphenol E type epoxy resin R_7丨〇 ( Mitsui Chemical Co., Ltd.) was dissolved in 500 mL of toluene, and a solution of triphenylphosphine was added to the solution to prepare a homogeneous solution. After 3 6 g of acrylic acid was added dropwise to the solution 29 200921222 under reflux for 2 hours, the mixture was further stirred under reflux for 6 hours. Toluene was removed, whereby a bisphenol e-type epoxy acrylate resin (partially modified resin (4)) obtained by reacting 50 mol% of an epoxy group with acrylic acid was obtained. Further, the rate of change was measured by dissolving the resin in a hydrochloric acid-dioxane solution, and then using KOH to titrate the amount of hydrochloric acid consumed by the epoxy group. (Biphenyl mystery epoxy acrylate resin obtained by reacting a part of an epoxy group with acrylic acid (synthesis of partially modified resin (5)) 157 g of a diphenyl ether type epoxy resin ySLV_8〇de ( The product was dissolved in 500 mL of toluene, and a solution of bismuth g of diphenylphosphine was added to the solution to prepare a homogeneous solution. After 3 6 g of acrylic acid was dropped into the solution in 2 hours under reflux with stirring, the mixture was further stirred under reflux for 6 hours. The terpene was removed, whereby a bisphenol E type epoxy acrylate resin (partially modified resin (5)) obtained by reacting 50 mol% of an epoxy group with acrylic acid was obtained. Further, the reforming rate was measured by dissolving the resin in a hydrochloric acid solution of hydrazine, and then titrating the amount of hydrochloric acid consumed by the epoxy group by using K〇H (Example 1) 100 parts by weight Part of the modified resin (2), 2 weight known as photoradical initiator (manufactured by Ciba Specialty Chemicals, irgacure ΓΛ "V" Tj Λ 1 \ 16 parts by weight of heat hardener (Ajinomoto Fine- Techno = Manufactured by CURE VDH), 3Q parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., S0_C1), and 2 parts by weight of a sand-burning coupling (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) , 30 200921222 After being stirred by a planetary mixing device (manufactured by Thinky & Division, de-soaked Taro), it was uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for liquid crystal dropping method. 50 parts by weight of the synthesized epoxy acrylate, 5 parts by weight of the synthesized partially modified resin (4), 2 parts by weight of a photoradical initiator ("Immediate Chemical Co., Ltd., IRGACURE" OXEO1), 16 weight injury A thermosetting agent (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) , KBM403) was prepared and stirred by a planetary stirring device (manufactured by Thinky Co., Ltd.), and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for liquid crystal dropping method. )

將1 00重量份之所合成之部分改質樹脂（2 )、5重量 伤之光自由基起始劑（汽巴精化公司製造，jRGACURE OXE01) 、16 重量份之熱硬化劑（Ajinomot〇 Fine_Techno 公司製造，AJICUREVDH) 、30重量份之作為填充劑之球 形二氧化矽（Admatechs公司製造，SO-C1 )、及2重量份 之石夕燒偶合劑（信越化學公司製造，KBM403 )進行調配， 以行星式攪拌裝置（Thinky公司製造，去泡練太郎）加以 攪拌後，利用陶瓷三輥研磨機使其均勻地混合，從而獲得 液晶滴下法用密封劑。 (實施例4) 31 200921222 將50重量份之所合成之環氧丙烯酸酯（1 ) 、5〇重量 份之所合成之部分改質樹脂（4) 、〇.5重量份之光自由基 起始劑（汽巴精化公司製造，IRGACURE OXE01 ) 、16重 直伤之熱硬化劑（Ajinomoto Fine-Techno公司製造，Ajicure VDH )、30重量伤之作為填充劑之球形二氧化破（ 公司製造，S0_C1 )、及2重量份之矽烷偶合劑（信越化學 公司製造，KBM403 )進行調配，以行星式攪拌裝置（Thinky 公司製造，去泡練太郎）加以攪拌後，利用陶瓷三輥研磨 機使其均勻地混合，從而獲得液晶滴下法用密封劑。 (實施例5) 將50重量份之所合成之環氧丙烯酸酯（1) 、重量 份之所合成之部分改質樹脂（4 )、5重量份之光自由基起 始劑（汽巴精化公司製造，IRGACURE OXE01 )、16重量 份之熱硬化劑（Ajinomoto Fine-Techno公司製造，AJICURE VDH)、22重量份之作為填充劑之球形二氧化矽（Adinatechs 公司製造，SO-C1 )與8重量份之滑石、及2重量份之矽烷 偶合劑（信越化學公司製造，KBM403 )進行調配，以行星 式攪拌裝置（Thinky公司製造，去泡練太郎）加以攪拌後， 利用陶瓷三輥研磨機使其均勻地混合，從而獲得液晶滴下 法用密封劑。 (實施例6) 將50重量份之所合成之環氧丙烯酸酯（1 )、5〇重量 份之所合成之部分改質樹脂（4) 、2重量份之光自由基起 始劑（汽巴精化公司製造，IRGACURE OXE01 )、5重量份 32 200921222 之作為熱硬化劑之己二酸二酿肼、3〇重量份之作為填充劑 之球开v 一氧化矽（Admatechs公司製造，)、及2重 量伤之矽烷偶合劑（信越化學公司製造，KBM403 )進行調 配以仃星式攪拌裝置（Thinky公司製造，去泡練太郎） 加以㈣後’利用陶究三輥研磨機使其均句地混合，從而 獲得液晶滴下法用密封劑。 (實施例7 )100 parts by weight of the synthesized partially modified resin (2), 5 weight of the damaged photoradical initiator (manufactured by Ciba Specialty Chemicals Co., jRGACURE OXE01), and 16 parts by weight of the heat hardener (Ajinomot〇 Fine_Techno Manufactured by the company, AJICUREVDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., SO-C1), and 2 parts by weight of Shixia smouldering agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), The planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked) was stirred, and uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for liquid crystal dropping method. (Example 4) 31 200921222 50 parts by weight of the synthesized epoxy acrylate (1), 5 parts by weight of the synthesized partial modified resin (4), 〇. 5 parts by weight of photoradical initiation Agent (manufactured by Ciba Specialty Chemicals Co., Ltd., IRGACURE OXE01), 16-fold direct-acting thermal hardener (Ajicure VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 30-weight wound, spherical dioxide dioxide as a filler (manufactured by the company, S0_C1) And 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), which was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., degassing Ryotaro), and then uniformly ground by a ceramic three-roll mill. Mixing to obtain a sealant for liquid crystal dropping method. (Example 5) 50 parts by weight of the synthesized epoxy acrylate (1), parts by weight of the synthesized partially modified resin (4), and 5 parts by weight of a photoradical initiator (Ciba refined) The company manufactures, IRGACURE OXE01), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), 22 parts by weight of spherical cerium oxide (manufactured by Adinatechs Co., Ltd., SO-C1) and 8 weights. A portion of talc and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) were blended, and stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked), and then a ceramic three-roll mill was used. The mixture was uniformly mixed to obtain a sealant for liquid crystal dropping method. (Example 6) 50 parts by weight of the synthesized epoxy acrylate (1), 5 parts by weight of the synthesized partially modified resin (4), and 2 parts by weight of a photoradical initiator (Ciba Manufactured by Elite Co., Ltd., IRGACURE OXE01), 5 parts by weight of 32, 200921222, adipic acid bismuth as a heat hardener, and 3 parts by weight of a ball-opening cerium oxide (manufactured by Admatechs Co., Ltd.) as a filler. 2 weight-damaged decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended with a comet-type stirring device (manufactured by Thinky Co., Ltd., de-soaked Taro) (4) and then mixed with the three-roller grinder. Thereby, a sealant for liquid crystal dropping method is obtained. (Example 7)

將50重量份之所合成之環氧丙烯酸酯（丨）、重量 份之所合成之部分改質樹脂（4)、25重量份之所合成之部 刀改質樹月曰（5 )、2重量份之光自由基起始劑（汽巴精化 公司製造，IRGACURE OXE01 )、16重量份之熱硬化劑 (Ajinomoto Fine-Techno 公司製造，AJICURE VDH )、3〇 重量份之作為填充劑之球形二氧化矽（Admatechs公司製 ^ ) 及2重置份之石夕烧偶合劑（信越化學公司製 造’ KBM4G3)進行調配，以行星式料裝置（加咖公司 製造’去料太郎）加以㈣後，利㈣曼三輥研磨機使 其均勻地混合，從而獲得液晶滴下法用密封劑。 (實施例8 ) 將50重量伤之所合成之環氧丙烯酸酯（】）、重量 份之所合成之部分改質樹脂（4)、25重量份之所合成之部 分改質樹脂（5)、2重量份之光自由基起始劑（汽巴精化 公司製造’ IRGACURE 0χ謝）、i 〇重量份之作為熱硬化 劑之癸二酸二醯肼、30重 矽（Admatechs公司製造， 量份之作為填充劑之球形二氧化 SO-C1)、及2重量份之矽烷偶 33 200921222 合劑（信越化學公司製造，KBM403 )進行調配，以行星式 攪拌裝置（Thinky公司製造，去泡練太郎）加以搜拌後， 利用陶瓷三輥研磨機使其均勻地混合，從而獲得液晶滴下 法用密封劑。 (比較例1 ) 將100重量份之所合成之部分改質樹脂（2 )、2重量 份之光自由基起始劑（汽巴精化公司製造，daROCIJRE TPO) 、16重量份之熱硬化劑（Ajin〇m〇t〇 Fine Techn〇公 司製造’ AJICURE VDH )、30重量份之作為填充劑之球形 二氧化矽（Admatechs公司製造，SO-C1 )、及2重量份之 矽烷偶合劑（信越化學公司製造，KBM4〇3)進行調配，以 行星式攪拌裝置（Thinky公司製造，去泡練太郎）加以攪 拌後，利用陶瓷三輥研磨機使其均勻地混合，從而獲得液 晶滴下法用密封劑。 (比較例2) 將50重量份之所合成之環氧丙烯酸酯（1) 、5〇重量 份之所合成之部分改質樹脂（3)、2重量份之光自由基起 始劑（汽巴精化公司製造，DAR〇CURE Tp〇 ) 、16重量份 之熱硬化劑（Ajinomoto Fine_Techn〇 公司製造，ajicure VDH)、3〇i^M^_2_Kw(Admatechs 么司製k ’ SO-C1 )、及2重量份之石夕燒偶合劑（信越化學 公司製造，KBM403 )進行調配，以行星式授摔裝置（Thinky 公司製造’去泡練太郎）加以授拌後，利用陶究三棍研磨 機使其均句地混合，從而獲得液晶滴下法用密封劑。 34 200921222 (比較例3) 將50重量份之所合成之環氧丙烯酸酯（1 )、5〇重量 份之所合成之部分改質樹脂（4) 、5重量份之光自由基起50 parts by weight of the synthesized epoxy acrylate (丨), parts by weight of the partially modified resin (4), and 25 parts by weight of the synthesized knives (5), 2 weights a photo radical initiator (IRGACURE OXE01, manufactured by Ciba Specialty Chemicals Co., Ltd.), 16 parts by weight of a heat hardener (AJICURE VDH, manufactured by Ajinomoto Fine-Techno Co., Ltd.), and a spherical weight of 3 parts by weight as a filler. Yttrium oxide (manufactured by Admatechs Co., Ltd.) and 2 refilled Shihsing Coupling Agent (manufactured by Shin-Etsu Chemical Co., Ltd. 'KBM4G3) for blending with a planetary material device (manufactured by Kaji Co., Ltd.) (4) A three-roll mill is uniformly mixed to obtain a sealant for a liquid crystal dropping method. (Example 8) 50 parts by weight of the synthesized epoxy acrylate (), a part by weight of the synthesized partial modified resin (4), 25 parts by weight of the synthesized partially modified resin (5), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals Co., Ltd. 'IRGACURE 0 χ), i 〇 by weight of diterpene sebacate as a thermosetting agent, 30 bismuth (manufactured by Admatechs, Inc.) The spherical SOD (C1) as a filler, and 2 parts by weight of a decane couple 33 200921222 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) were blended and equipped with a planetary stirring device (manufactured by Thinky Co., Ltd. After the mixture was mixed, it was uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for a liquid crystal dropping method. (Comparative Example 1) 100 parts by weight of the synthesized partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, daROCIJRE TPO), and 16 parts by weight of a heat hardener (Ajin 〇m〇t〇Fine Techn〇 manufactures 'AJICURE VDH), 30 parts by weight of spherical cerium oxide (made by Admatechs, SO-C1), and 2 parts by weight of decane coupling agent (Shin-Etsu Chemical) Manufactured by the company, KBM4〇3) was blended, and the mixture was stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., and soaked in Taro), and then uniformly mixed by a ceramic three-roll mill to obtain a sealing agent for liquid crystal dropping method. (Comparative Example 2) 50 parts by weight of the synthesized epoxy acrylate (1), 5 parts by weight of the synthesized partially modified resin (3), and 2 parts by weight of a photoradical initiator (Ciba Made by Jinghua Co., Ltd., DAR〇CURE Tp〇), 16 parts by weight of heat hardener (Ajinomoto Fine_Techn〇, ajicure VDH), 3〇i^M^_2_Kw (Admatechs K'SO-C1), and 2 parts by weight of Shixia Burn Coupling Agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) was blended, and it was mixed with a planetary-type drop device (Thinky Co., Ltd.) The mixture is uniformly mixed to obtain a sealant for liquid crystal dropping method. 34 200921222 (Comparative Example 3) 50 parts by weight of the synthesized epoxy acrylate (1), 5 parts by weight of the synthesized partially modified resin (4), and 5 parts by weight of photoradicals

始劑（汽巴精化公司製造，DAROCURE 1173)、16重量份 之熱硬化劑（Ajinomoto Fine-Techno 公司製造，ajicure VDH)、30重量份之作為填充劑之球形二氧化矽（Admatechs 公司製造，SO-C1)、及2重量份之矽烷偶合劑（信越化學 公司製造，KBM403 )進行調配，以行星式攪拌裝置（Thinky 公司製造’去泡練太郎）加以攪拌後，利用陶竟三輥研磨 機使其均勻地混合’從而獲得液晶滴下法用密封劑。 (比較例4) 將100重量份之所合成之部分改質樹脂（2 )、2重量 份之光自由基起始劑（汽巴精化公司製造，irgacure 819)、16重量份之熱硬化劑（Ajin〇m〇t〇 Fine Techn〇公司 製造，AJICUREVDH)、3〇重量份之作為填充劑之球形二 氧化矽（Admatechs公司製造，s〇_C1 )、及2重量份之矽 烷偶合劑（信越化學公司製造，KBM4〇3)進行調配，以行 星式攪拌裝置（Thinky公司製造，去泡練太郎）加以攪拌， 利用陶竟三輥研磨機使其均句地混合，從而獲得液晶滴下 法用密封劑。 (比較例5 ) 將1 00重量伤之所合成之部分改質樹脂（2 )、2重量 伤之光自由基起始劑（汽巴精化公司製造， 379 ) 16重量伤之熱硬化劑（Ajinomoto Fine-Techno公司 35 200921222 製造，AJICURE VDH ) 、30重量份之作為填充劑之球形二 氧化石夕（Admatechs公司製造’SO-C1)、及2重量份之梦 烷偶合劑（信越化學公司製造，KBM403 )進行調配，以行 星式攪拌裝置（Thinky公司製造，去泡練太郎）加以攪拌 後，利用陶瓷三輥研磨機使其均勻地混合，從而獲得液晶 滴下法用密封劑。 <光自由基起始劑之評價> 對實施例及比較例中使用之光自由基起始劑，進行以 下評價。 將結果示於表1及表2中。 (1 )光自由基起始劑之液晶溶解性之評價 於玻璃製樣品瓶中加入0.5 g之液晶及固定量之光自由 基起始劑’以使該光自由基起始劑相對於該液晶成為4重 量％。蓋上樣品瓶之蓋子，將其於120°C之烘箱中放置1小 時。1小時後自烘箱中取出，於_20。(：放置144小時，以目 視觀察光自由基起始劑之析出狀態。 再者’液晶係分別使用MLC-6609 ( VA，Merck公司製 造）及 ZN-5〇〇1LA ( TN，Chisso 公司製造）。 (2 )光自由基起始劑之吸光係數之測定 使 1 Μ 耳之 DAROCURE TPO 及 IRGACURE OXE01 溶 解於1L之乙腈中，將所得之溶液加入至1 cm之石英槽中， 使用分光光度計，測定405 nm之吸光係數。 使 1 莫耳之 DAROCURE 1173、IRGACURE 819 及 mGACUKE 379溶解於1 L之甲醇中，將所得之溶液加入至 36 200921222 1 cm之石英槽中，使用分光光度計，測定405 nm之吸光係 數。 再者，若將槽長設為1 [cm]、莫耳濃度設為c [mol/L]、 莫耳吸光係數設為ε [L/mol. cm]，則根據lambert-beer定 律，莫耳吸光度=eel。 [表1]Starting agent (manufactured by Ciba Specialty Chemicals Co., Ltd., DAROCURE 1173), 16 parts by weight of a heat hardener (manufactured by Ajinomoto Fine-Techno Co., ajicure VDH), 30 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd.) SO-C1), and 2 parts by weight of a decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) were blended, and the mixture was stirred by a planetary stirring device (Thinky Co., Ltd.), and the ceramic three-roll mill was used. It is uniformly mixed' to obtain a sealant for liquid crystal dropping method. (Comparative Example 4) 100 parts by weight of the synthesized partially modified resin (2), 2 parts by weight of a photoradical initiator (manufactured by Ciba Specialty Chemicals, irgacure 819), and 16 parts by weight of a heat hardener (Ajin 〇m〇t〇Fine Techn〇 company, AJICUREVDH), 3 parts by weight of spherical cerium oxide (manufactured by Admatechs Co., Ltd., s〇_C1), and 2 parts by weight of decane coupling agent (Shin-Etsu Manufactured by a chemical company, KBM4〇3), blended with a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked Taro), and uniformly mixed with a ceramic three-roll mill to obtain a liquid crystal dropping method seal. Agent. (Comparative Example 5) A part of the modified resin (2) synthesized by the weight of 100 Å, and a photoradical initiator of 2 weights of the wound (manufactured by Ciba Specialty Chemicals Co., Ltd., 379) Ajinomoto Fine-Techno Corporation 35 200921222 Manufactured, AJICURE VDH), 30 parts by weight of spherical sulphur dioxide as a filler ("SO-C1" manufactured by Admatechs Co., Ltd.), and 2 parts by weight of a montane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.) , KBM403) was blended, and stirred by a planetary stirring device (manufactured by Thinky Co., Ltd., de-soaked), and then uniformly mixed by a ceramic three-roll mill to obtain a sealant for liquid crystal dropping method. <Evaluation of Photoradical Starting Agent> The photoradical initiators used in the examples and the comparative examples were evaluated as follows. The results are shown in Tables 1 and 2. (1) Evaluation of liquid crystal solubility of a photoradical initiator in a glass sample vial by adding 0.5 g of liquid crystal and a fixed amount of photoradical initiator ' to make the photoradical initiator relative to the liquid crystal It became 4% by weight. Cover the vial and place it in an oven at 120 ° C for 1 hour. After 1 hour, it was taken out of the oven at -20. (: The crystallization was carried out for 144 hours to visually observe the precipitation state of the photoradical initiator. Further, the liquid crystal system used MLC-6609 (VA, manufactured by Merck) and ZN-5〇〇1LA (TN, manufactured by Chisso Co., Ltd.). (2) Determination of the absorption coefficient of the photoradical initiator The 1 Μ DAROCURE TPO and IRGACURE OXE01 were dissolved in 1 L of acetonitrile, and the resulting solution was added to a 1 cm quartz cell using a spectrophotometer. The absorbance at 405 nm was measured. 1 mole of DAROCURE 1173, IRGACURE 819 and mGACUKE 379 were dissolved in 1 L of methanol, and the resulting solution was added to a quartz cell of 36 200921222 1 cm, and a spectrophotometer was used to measure 405. The absorption coefficient of nm. Further, if the groove length is set to 1 [cm], the molar concentration is c [mol/L], and the molar absorption coefficient is set to ε [L/mol. cm], then according to lambert- Beer's law, Mohr absorbance = eel. [Table 1]

光自由基起始劑 吸光係數 熔點 DAROCURE TPO 165mL/g*cm (乙腈中） 88 〜92°C IRGACURE OXE01 101.6mL/g*cm (乙腈中） 40 〜42°G DAROCURE 1173 0mL/g，cm (甲醇中） 4°C IRGACURE 819 899 mL/g · cm (甲醇中） 127〜133°C IRGACURE 379 280mL/g.cm (曱醇中） 110 〜114°CPhotoradical Initiator Absorbance Coefficient DAROCURE TPO 165mL/g*cm (in acetonitrile) 88~92°C IRGACURE OXE01 101.6mL/g*cm (in acetonitrile) 40~42°G DAROCURE 1173 0mL/g,cm ( Methanol) 4°C IRGACURE 819 899 mL/g · cm (in methanol) 127~133°C IRGACURE 379 280mL/g.cm (in methanol) 110 ~114°C

[表2] 光自由基起始劑 -20。(：144小時後（4\¥%) VA：MLC-6609( Merck) TN ： ZN-5001LA (Chisso) DAROCURE TPO 析出 析出 IRGACURE OXEOl 無 無 DAROCURE 1173 無 無 IRGACURE 819 析出 析出 IRGACURE 379 析出 析出 <液晶滴下法用密封劑之評價> 對實施例1〜8及比較例1〜5中所製作之液晶滴下法 37 200921222 用密封劑進行以下評價。 將結果示於表3中。 (1 )硬化性之評價 將液晶顯示元件用密封劑夾入玻璃中。於該狀態下， 以波長為405 nm之光的照射量成為3〇〇〇 mJ/cm2之方式照 射光此外’於照射時使用400 nm之截止濾光鏡。其後， 使用 FT-IR ( F〇urier Transform infrared，傅立葉變換紅外 線）之分析方法來測定丙烯基之反應率。將丙烯基之反應 率未滿50%者評價為rx」，5〇〜7〇%者評價為「△」，超 過70%者評價為「〇」。 (2 )液晶顯示面板評價（色斑評價） 於配向膜及附電極之透明基板之一者上，使用分配器 以畫長方形框之方式塗佈液晶顯示元件用密封劑。繼而， 滴下液晶（Merck公司製造，「ZN-5001LA」），貼合另一 片基板之後，以100 mW/cm2照射高壓水銀燈3〇秒，使其 硬化。此時，使用400 nm之截止濾光鏡，繼而，於12〇它 使其熱硬化1小時，從而製成液晶顯示面板。 對於所得之液晶顯示面板（樣品數為5個），以目視 來確認液晶顯示面板剛製成後於密封劑附近之液晶配向^ 礼。配向紊亂係根據顯示部之色斑而判斷，依據色斑之程 度，以◎(完全無色斑）、〇（有微量色斑）、△(有少 許色斑）、χ(有大量色斑）4個階段進行評價。再者，= 價為◎、〇之液晶顯示面板係於實際應用上完全無問； 水準。 38 200921222 (垒¥侧) Ιε tiM^i 5 1 〇 1 1 1 1 1 I I (Ν 1 1 1 CN X 〇 财交例 4 1 〇 1 1 1 I 1 1 (Ν I I 1 1 (N X 〇 tb|交例 3 1 1 1 1 1 »〇 1 1 1 (N X X 丨tbfe例 2 1 1 1 (N 1 1 1 CN <3 〇 ! t嫩例 1 1 Ο 1 1 CS 1 1 1 1 <N <] 〇 雜例 8 1 _ 1 CN νΊ (Ν 1 CN I 1 ο 〇 1 CN ◎ 〇 7 1 fN »〇 (Ν 1 (N 1 1 1 CN ◎ 〇 細列 1 6 1 1 1 (N I 1 1 CS ◎ 〇 細列 1 ? 1 I 1 yri 1 1 00 (N ◎ 〇 雜例 4 1 1 1 Ο Ό 1 1 1 (N 〇 < 例 3 1 ο 1 1 1 »η 1 1 1 CN 〇 〇 細列 一 2 1 i 1 (Ν i 1 1 CS ◎ 〇 tim 1 1 ο r—t 1 1 CN 1 1 1 CS 〇 〇 環氧丙烯酸酯（1) 部分改質樹脂（2) 部分改質樹脂（3) 部分改質樹脂（4) 部分改質樹脂（5) DAROCURE TPO IRGACURE ΟΧΕΟΙ DAROCURE 1173 IRGACURE 819 IRGACURE 379 AJICURE VDH 己二酸二醯肼 癸二酸二醯肼 SO-C1 KBM403 色斑評價 硬化性評價 硬化性 樹脂 光反應 起始知J 11 填充劑 矽烷 偶合劑 6ε 200921222 法用密封劑，其在 即便密封劑成分溶 而可製造顯示品質 產業上之可利用性 根據本發明，可提供一種液晶滴下 用於滴下法之液晶顯示元件之製造時， 出之液晶，亦可防止引起液晶污染，從 及可靠性優異之液晶顯示元件。 【圖式簡單說明】 無 【主要元件符號說明】[Table 2] Photoradical initiator -20. (: 144 hours later (4\¥%) VA: MLC-6609 (Merck) TN: ZN-5001LA (Chisso) DAROCURE TPO Precipitation precipitation IRGACURE OXEOl No DAROCURE 1173 No IRGACURE 819 Precipitation precipitation IRGACURE 379 Precipitation precipitation < Evaluation of the sealing agent for the dropping method> The liquid crystal dropping method 37 200921222 produced in Examples 1 to 8 and Comparative Examples 1 to 5 was subjected to the following evaluation with a sealant. The results are shown in Table 3. (1) Curability In this state, the liquid crystal display element sealing agent is sandwiched between the glass. In this state, the irradiation amount of light having a wavelength of 405 nm is 3 〇〇〇mJ/cm 2 , and the light is used. The filter was cut off. Then, the reaction rate of the propylene group was measured by an analytical method of FT-IR (F〇urier Transform infrared). The reaction rate of the propylene group was less than 50%, and it was evaluated as rx". 5〇~7〇% was evaluated as "△", and more than 70% was evaluated as "〇". (2) Liquid crystal display panel evaluation (color spot evaluation) Used on one of the alignment film and the transparent substrate with electrodes Dispenser A liquid crystal display element sealing agent was applied in the form of a frame. Then, liquid crystal (manufactured by Merck Co., Ltd., "ZN-5001LA") was dropped, and another substrate was bonded thereto, and then the high pressure mercury lamp was irradiated at 100 mW/cm 2 for 3 seconds. Hardening. At this time, a 400 nm cut-off filter was used, and then it was thermally cured at 12 Torr for 1 hour to prepare a liquid crystal display panel. For the obtained liquid crystal display panel (the number of samples was 5), visually To confirm the liquid crystal alignment of the liquid crystal display panel immediately after the sealing agent is formed. The alignment disorder is judged according to the color unevenness of the display portion, and according to the degree of the color plaque, ◎ (completely no stain), 〇 (with trace amount) The color spots, △ (a little stain), and χ (have a large number of stains) were evaluated in four stages. Furthermore, the price of ◎, 〇, the liquid crystal display panel is completely unquestioned in practical applications; 200921222 (base ¥ side) Ιε tiM^i 5 1 〇1 1 1 1 1 II (Ν 1 1 1 CN X 〇财交交4 1 〇1 1 1 I 1 1 (Ν II 1 1 (NX 〇tb| Example 3 1 1 1 1 1 »〇1 1 1 (NXX 丨tbfe Example 2 1 1 1 (N 1 1 1 CN ≪3 〇! t tender example 1 1 Ο 1 1 CS 1 1 1 1 <N <] 〇 8 8 1 _ 1 CN Ί Ί (Ν 1 CN I 1 ο 〇 1 CN ◎ 〇 7 1 fN »〇 (Ν 1 (N 1 1 1 CN ◎ 〇 列 1 6 1 1 1 (NI 1 1 CS ◎ 〇 列 1 1 1 1 1 1 yri 1 1 00 (N ◎ 〇 4 4 1 1 1 Ο Ό 1 1 1 (N 〇 < Example 3 1 ο 1 1 1 » η 1 1 1 CN 〇〇 列 1 2 1 i 1 (Ν i 1 1 CS ◎ 〇tim 1 1 ο r — t 1 1 CN 1 1 1 CS Epoxy acrylate (1) partially modified resin (2) partially modified resin (3) partially modified resin (4) partially modified resin (5) DAROCURE TPO IRGACURE ΟΧΕΟΙ DAROCURE 1173 IRGACURE 819 IRGACURE 379 AJICURE VDH Diacid diphthalic acid diterpene SO-C1 KBM403 Color spot evaluation Hardenability evaluation Curing resin Photoreaction start knowledge J 11 Filler decane coupling agent 6ε 200921222 Process sealant, which dissolves even in the sealant component And the manufacturing property of the display quality can be provided according to the present invention, and a liquid crystal dropping liquid for dropping can be provided. At the time of manufacture of a crystal display element, a liquid crystal can be prevented from causing liquid crystal contamination, and a liquid crystal display element excellent in reliability. [Simple description of the diagram] None [Main component symbol description]

Claims (1)

200921222 十、申請專利範圍： 白二種液晶滴下法用密封劑’其係含有硬化性樹脂與光 自由基起始劑者，其特徵在於： 以先 於：=:劑係以相對於液晶為4重量%之漢度 晶析出者於.2Gt放置144小時後仍未自該液 該光自由基起始劑，其於溶劑中所測定之於 吸光係數為5〇mL/g.cm以上。 之 ―2.如申請專利範固第1項之液晶滴下法用密封劑，其中 起劑為i，2-辛二剩1例苯硫基）-2_(0_苯甲醯基 肟）]0 二申請專利範圍第1項或第2項之液晶滴下法用密封 化性樹脂具有（甲基）丙稀基與環氧基，環氧基之 比率相對於（甲基）丙烯基與環氧基之總量為40莫耳％以下。 4. -種上下導通材料’係含有申請專利範圍第卜3項 中任-項之液晶滴下法用密封劑與導電性微粒子。 5. —種液晶顯示元伴，总你m + 士 士 件係使用申請專利範圍第丨〜3項 中任一項之液晶滴下法用密封劑及/或令請專利範圍第4項 之上下導通材料而形成。 十一、圓式：200921222 X. Patent application scope: White two kinds of liquid crystal dropping method sealant's which contain a curable resin and a photo radical initiator, which are characterized by: before: =: the agent is relative to the liquid crystal 4 The weight % of the eutectic crystallizer was not subjected to the photoradical initiator of the solution after being placed at .2 Gt for 144 hours, and the absorbance coefficient was determined to be 5 〇mL/g.cm or more in the solvent. -2. If applying for the patent of Fan Gu 1st, the sealing agent for liquid crystal dropping method, wherein the starting agent is i, 2-octyl, 1 case of phenylthio)-2_(0_benzylidene fluorenyl)]0 2. The sealing resin for liquid crystal dropping method of claim 1 or 2 has a (meth) propyl group and an epoxy group, and the ratio of the epoxy groups is relative to the (meth) propylene group and the epoxy group. The total amount is 40 mol% or less. 4. The above-mentioned upper and lower conductive material' is a sealing compound for liquid crystal dropping method and conductive fine particles according to any one of the above-mentioned items. 5. A kind of liquid crystal display element companion, the total m + 士士件 is used in the liquid crystal dropping method sealant of any one of the application scopes 丨~3, and/or the patent scope is turned on. Formed from materials. Eleven, round:
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