TW201231488A - Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element - Google Patents

Sealing material for liquid-crystal dropping process, material for vertical conduction, and liquid-crystal display element Download PDF

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TW201231488A
TW201231488A TW100144332A TW100144332A TW201231488A TW 201231488 A TW201231488 A TW 201231488A TW 100144332 A TW100144332 A TW 100144332A TW 100144332 A TW100144332 A TW 100144332A TW 201231488 A TW201231488 A TW 201231488A
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manufactured
liquid crystal
resin
acrylate
meth
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TWI398460B (en
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Takuya Yamamoto
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4035—Hydrazines; Hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C08G59/46—Amides together with other curing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

A purpose of the present invention is to provide a sealing material for use in a liquid-crystal dropping process, the sealing material having excellent storage stability, rarely causing liquid-crystal fouling, and being capable of being sufficiently cured at a low temperature of about 80 C. Another purpose of the invention is to provide: a material for vertical conduction which is obtained using the sealing material for use in a liquid-crystal dropping process; and a liquid-crystal display element. The sealing material, which is for use in a liquid-crystal dropping process, comprises a curable resin, a free-radical heat polymerization initiator, and a heat-curing agent comprising a compound represented by general formula (A). In general formula (A), X represents the structure represented by any of CH2, CH(OH), C(OH)2, C2H4, CH2CH(OH), CH2C(OH)2, C(OH)C(OH), CH2CO, COCO, and NH.

Description

201231488 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種保存穩定性優異、幾乎不引起液晶 污染、且於80°C左右之低溫即可充分硬化之液晶滴下法用 密封劑。又，本發明係關於一種使用該液晶滴下法用密封 劑而製造之上下導通材料及液晶顯示元件。 【先前技術】 近年來，就縮短節拍時間（takt time )、使用液晶量之 最佳化之觀點而言’液晶顯示單元等液晶顯示裝置之製造 方法正在自先前之真空注入方式變成例如專利文獻丨、專利 文獻2中所揭示之使用有密封劑之稱為滴下法的液晶滴下 方式，該密封劑係由含有「（甲基）丙烯酸樹脂等光硬化 性樹脂與光聚合起始劑」、及「環氧樹脂等熱硬化性樹脂 與熱硬化劑」之光、熱併用硬化型樹脂組成物所構成。 於使用由光、熱併用硬化型樹脂組成物所構成之密封 劑之滴下法中，首先，於兩片附帶電極之基板之一者上形 成密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微 小滴滴加至基板之框内’於真空下重合另一基板，對密封 部照射光而進行光硬化性樹脂之硬化（暫時硬化步驟）。 其後’加熱並進行熱硬化性樹脂之硬化，從而製作液晶顯 不面板〇 通常，具有熱硬化性樹脂之密封劑係藉由於l2〇〇c左右 之μ度加熱1小時左右而進行熱硬化，但近年來，由於使 用雖然節能或能高速回應但高溫下之穩定性較差之液晶材 201231488 料，故期望於更低之溫度使密封劑熱硬化。然而，若先# 之密封劑於8 0 °C左右之低溫硬化，則有接著力變低之問 題。作為用以使密封劑於低溫硬化之方法，雖考慮使用炫 點較低之熱硬化劑或硬化促進劑，但若使用熔點較低之熱 硬化劑或硬化促進劑，則有密封劑之適用期變短、密封劑 之保存穩定性變差之問題。 專利文獻1 :日本特開200 1 — 133794號公報 專利文獻2:日本特開平5 — 295087號公報 【發明内容】 本發明之目的在於提供一種保存穩定性優異、幾乎不 引起液晶污染、且於80。(：左右之低溫即可充分硬化之液晶 滴下法用密封劑。又’本發明之目的在於提供一種使用該 液晶滴下法用密封劑而製造之上下導通材料及液晶顯示元 件。 本發明係一種液晶滴下法用密封劑，其含有硬化性樹 脂、熱自由基聚合起始劑、及由下述通式（A)表示之化合 物所構成之熱硬化劑。 Ο Ο h2nhn—c—X—i—nhnh2 (a) 通式（a )中，X 表示 ch2、CH ( 〇H ) 、c ( oh ) 2、 C2H4、CH2CH ( OH)、CH2C ( OH) 2、C ( OH) C ( OH)、 、COCO、NH中之任一者表示之結構。 以下對本發明進行詳述。 201231488 本發明者發現，藉由將熱自由基聚合起始劑與作為熱 硬化劑之通式（A)表示之化合物組合使用，而獲得保存穩 定性優異、幾乎不引起液晶污染、且& 8〇。。左右之低溫即 可充分硬化之液晶滴下法用密封劑，從而完成本發明。 藉由將熱自由基聚合起始劑與作為熱硬化劑之通式 j A)表不之化合物組合使用，而獲得保存穩定性優異、幾 乎不引起液晶污染、且於8(rc左右之低溫即可充分硬化之 液晶滴下法用密封劑之理由被認為如下。 已：若於密封劑中使用熱自由基聚合起始劑，則熱硬 化性提馬，但若熱自由基起始劑未達到某種程度之溫度 (110 C以上），則反應不開始。又，已知由通式⑷表 示之化合物所構成之熱硬化劑與環氧（甲基）丙烯酸酿等 極性較高之樹脂之相容性優異，且於作為熱硬化劑而用於 液晶滴下法用密封劑之情形時幾乎不污染液晶，但若於8〇 它左右之低溫硬化，則所獲得之密封劑的接著力變差。 然而可認為：於將熱自由基聚合起始劑與該熱硬化劑 組合使用之情形時，若與樹脂之相容性較高之該熱硬化劑 達到啊左右之溫度，則溶解開始，由於其溶解熱而使執 自由基聚合起始劑之自由基起始點之溫度降低，故可同時 開始自由基硬化與熱硬化…由於兩者均於室溫下與硬 2性樹脂之反應性較低，故所獲m封㈣ 長且保存穩定性優異者。 本發明之液晶滴下法用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為含有具有（甲基）丙稀酿氧基 201231488 之樹u有環氧基之樹脂，作為上述具彳（甲基）丙稀 酿氧基之樹脂，更佳為於上述硬化性樹脂中含有4G重量％ 之下述式（丨）表示之樹脂及/或下述式（2)表示之 树月曰於本發明之液晶滴下法用密封劑中，由於用作熱硬 化劑之上述通式（A)表示之化合物之極性較高，故與下述 f (1)或下述式（2)表示之極性較高之樹脂的相容性較 高，可藉由將該等組合使用而防止該熱硬化劑於液晶中溶 析，從而抑制液晶污染。就上述觀點而言，尤其是於上述 通式（A)表示之化合物中’亦較佳為將高極性之丙二酸二 醯肼（mal〇nicaciddihydrazide)與作為硬化性樹脂之下述 式（1 )表示之樹脂及/或下述式（2 )表示之樹脂組合使 用。 若上述硬化性樹脂中之下述式（1)表示之樹脂及/或 下述式（2)表示之樹脂的含量未達4〇重量％，則有時所獲 得之密封劑的接著性變差，或引起液晶污染。上述硬化性 樹脂進而較佳為含有60重量％以上之下述式（〇表示之樹 脂及/或下述式（2)表示之樹脂。 〇 OH CH2=CH-C-〇-CH2-CH-CH2 〇[Technical Field] The present invention relates to a liquid crystal dropping method sealant which is excellent in storage stability, hardly causes liquid crystal contamination, and can be sufficiently cured at a low temperature of about 80 °C. Further, the present invention relates to an upper and lower conductive material and a liquid crystal display element produced by using the sealing compound for liquid crystal dropping methods. [Prior Art] In recent years, the manufacturing method of a liquid crystal display device such as a liquid crystal display unit has been changed from the prior vacuum injection method to a patent document, for example, from the viewpoint of shortening the takt time and optimizing the liquid crystal amount. In the liquid crystal dropping method called a dropping method using a sealant disclosed in Patent Document 2, the sealant contains "a photocurable resin such as a (meth)acrylic resin and a photopolymerization initiator", and The thermosetting resin such as an epoxy resin and a thermosetting agent are composed of a light-and-heat-hardening resin composition. In the dropping method using a sealant composed of a light-and-heat-hardened resin composition, first, a seal pattern is formed on one of the two substrates with electrodes. Then, the droplets of the liquid crystal are dropped into the frame of the substrate in a state where the sealant is not cured. The other substrate is superposed under vacuum, and the sealing portion is irradiated with light to cure the photocurable resin (temporary curing step). Then, 'heating and hardening the thermosetting resin to produce a liquid crystal display panel. Usually, the sealant having a thermosetting resin is thermally cured by heating at a degree of about 1 〇〇c for about 1 hour. However, in recent years, it has been desired to thermally harden the sealant at a lower temperature by using a liquid crystal material 201231488 which is energy-saving or capable of high-speed response but has poor stability at high temperatures. However, if the sealant of #先# is hardened at a low temperature of about 80 °C, there is a problem that the adhesive force becomes low. As a method for hardening the sealant at a low temperature, it is considered to use a hot hardener or a hardening accelerator having a lower hue point, but if a hot hardener or a hardening accelerator having a lower melting point is used, the pot life of the sealant is used. Shortening, the storage stability of the sealant is deteriorated. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . (: a sealing compound for liquid crystal dropping method which can be sufficiently hardened at a low temperature on the left and right sides. Further, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealing compound for liquid crystal dropping method. The present invention is a liquid crystal. A sealing agent for a dripping method comprising a curable resin, a thermal radical polymerization initiator, and a thermosetting agent composed of a compound represented by the following formula (A): Ο Ο h2nhn-c-X-i-nhnh2 (a) In the general formula (a), X represents ch2, CH (〇H), c ( oh ) 2, C2H4, CH2CH (OH), CH2C (OH) 2, C (OH) C (OH), COCO The structure is represented by any of the following. The present invention will be described in detail below. 201231488 The present inventors have found that a combination of a thermal radical polymerization initiator and a compound represented by the formula (A) as a thermosetting agent is used. By obtaining a sealing agent for liquid crystal dropping method which is excellent in storage stability, hardly causes liquid crystal contamination, and can be sufficiently hardened at a low temperature of about 3,000 Å. The present invention is completed by thermal radical polymerization. And the formula of the formula j A) as a heat hardener The reason why a liquid crystal dropping method sealant which is excellent in storage stability and hardly causes liquid crystal contamination and which is sufficiently cured at a low temperature of about 8 rc is considered to be as follows. When a thermal radical polymerization initiator is used, the thermosetting property is lifted, but if the thermal radical initiator does not reach a certain temperature (110 C or more), the reaction does not start. (4) The thermal curing agent composed of the compound is excellent in compatibility with a resin having a relatively high polarity such as epoxy (meth)acrylic acid, and is used as a thermal curing agent for a liquid crystal dropping method. It does not contaminate the liquid crystal, but if it is hardened at a low temperature of about 8 Torr, the adhesion of the obtained sealant is deteriorated. However, it can be considered that when the thermal radical polymerization initiator is used in combination with the heat hardener If the thermosetting agent having a high compatibility with the resin reaches a temperature of about 3,000, the dissolution starts, and the temperature of the free radical starting point of the radical polymerization initiator decreases due to the heat of dissolution thereof. with Starting from free radical hardening and thermal hardening... Since both have low reactivity with a hard resin at room temperature, the obtained m (four) length is excellent and the storage stability is excellent. The liquid crystal dropping method sealing agent of the present invention The curable resin is preferably a resin containing an epoxy group having a (meth) acryloxy 201231488, and the above-mentioned resin having a fluorene (meth) propylene oxide group. More preferably, the resin represented by the following formula (丨) containing 4 g% by weight of the curable resin and/or the resin represented by the following formula (2) are used in the sealing compound for liquid crystal dropping method of the present invention, The compound represented by the above formula (A) used as a thermosetting agent has a high polarity, and therefore has high compatibility with a resin having a higher polarity represented by f (1) or the following formula (2). By using these in combination, the thermal curing agent is prevented from being eluted in the liquid crystal, thereby suppressing liquid crystal contamination. From the above viewpoints, in particular, in the compound represented by the above formula (A), it is also preferred to use highly polar malic acid dihydrazide and the following formula (1) as a curable resin. The resin represented by the formula and/or the resin represented by the following formula (2) is used in combination. When the content of the resin represented by the following formula (1) and/or the resin represented by the following formula (2) in the curable resin is less than 4% by weight, the sealability of the obtained sealant may be deteriorated. Or cause liquid crystal contamination. The curable resin further preferably contains 60% by weight or more of the following formula (a resin represented by 〇 and/or a resin represented by the following formula (2). 〇OH CH2=CH-C-〇-CH2-CH-CH2 〇

OH 0 v^^^O-CH2CH-CH2O-C-CH OH Ο 〇-CH2-CH-CH2-〇-C-CH=CH, (1) o OH CH2-CH-C-0-CH2-CH-CH2-〇 ch2 (2) 上述具有（曱基）丙烯醯氧基之樹脂並無特別限定， 例如可列舉：藉由使（曱基）丙烯酸與具有羥基之化合物 201231488 、藉由使（甲基）丙烯酸與環 之環氧（甲基）丙稀酸酯、藉由 (甲基）丙烯酸衍生物進行反應 進行反應所獲得之醋化合物 氧化合物進行反應所獲得之 使異氰酸酯與具有羥基之 所獲知之（曱基）丙烯酸胺曱酸乙酯等。 ”再者，於本說明書巾，所謂上述（甲基）丙稀醢氧基 係才曰丙稀酿氧基或曱基丙稀酿氧基，所謂上述（曱基）丙 烯酸酯係指丙烯酸酯或甲基丙烯酸酯’所謂上述（曱基） 丙烯酸係指丙烯酸或曱基丙烯酸。又，於本說明書中，上 述環氧（甲基）丙烯酸酯表示使環氧樹脂中之所有環氧基 與（甲基）丙烯酸進行反應而成之化合物。 藉由使上述（曱基）丙稀酸與具有經基之化合物進行 反應所獲得之酯化合物並無特別限定，作為單官能酯化合 物’例如可列舉：（甲基）丙烯酸2 —羥基乙酯、（甲基） 丙烯酸2—羥基丙酯、（曱基）丙烯酸4一羥基丁酯、（甲 基）丙烯酸2_羥基丁酯、（甲基）丙烯酸異丁酯、（甲基） 丙浠酸三級丁酯、（甲基）丙烯酸異辛酯、（甲基）丙歸 酸月桂酯、（甲基）丙烯酸硬脂酯、（曱基）丙烯酸異莰 酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸2 —甲氡基乙 酯、（甲基）丙烯酸曱氧基乙二醇_、（甲基）丙缔酸2 —乙氧基乙醋、（甲基）丙烯酸四氫糠酯、（曱基）丙烯 酸苄酯、（曱基）丙烯酸乙基卡必醇酯、（曱基）丙烯酸 苯氧基乙酯、（甲基）丙烯酸苯氧基二乙二醇酯、（甲基） 丙烯酸苯氧基聚乙二醇酯、（甲基）丙烯酸曱氧基聚乙二 醇酯、（甲基）丙烯酸2,2,2 —三氟乙酯、（曱基）丙烯酸 201231488 2,2,3,3—四氟丙酯、（曱基）丙烯酸1H，iH，5H—八氟戊酯、 (甲基）丙烯酸醯亞胺酯、（甲基）丙烯酸曱酯、（甲基） 7烯酸乙酯、（甲基）丙烯酸正丁酯、（曱基）丙烯酸丙 (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、（甲基）丙烯酸異壬酯、（甲基） 丙烯酸異肉豆蔻酯、（甲基）丙烯酸2〜丁氧基乙酯、（甲 基）丙烯酸2—苯氧基乙酯、（甲基）丙烯酸二環戊烯酯' (曱基）丙烯酸異癸酯、（曱基）丙烯酸二乙胺基乙酯、 (甲基）丙烯酸二曱胺基乙酯、琥珀酸2_ (曱基）丙烯醯 氧基乙酯、六氫鄰苯二甲酸2一（甲基）丙烯醯氧基乙酯、 鄰苯二甲酸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 等。 曰 又，作為二官能酯化合物，例如可列舉：1，4 一 丁二醇 二（曱基）丙烯酸酯、1，3- 丁二醇二（曱基）丙烯酸酯、 l6 —己二醇二（甲基）丙烯酸酯、1，9 —壬二醇二（甲基） 丙烯酸酯、M〇 —癸二醇二（甲基）丙烯酸酯、2_正丁基 乙基一 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、聚丙 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）丙稀酸酯、四乙二醇二（甲基）丙烯酸 酯、聚乙二醇二（甲基）丙烯酸酯、經環氧丙烷加成之雙 酹A二（甲基）丙烯酸酯、經環氧乙烷加成之雙酚A二（甲 基）丙烯酸酯、經環氧乙烷加成之雙酚F二（曱基）丙烯 8 201231488 酸酯、二（曱基）丙烯酸二羥曱基二環戊二歸g旨、1，3 一丁 二醇二（曱基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、 經環氧乙烷改質之異三聚氰酸二（甲基）丙烯酸醋、（甲 基）丙烯酸2 —羥基一 3—（曱基）丙烯醯氧基丙酯、碳酸 酯二醇二（甲基）丙烯酸酯、聚醚二醇二（曱基）丙稀酸 酉曰、曰·一醇··一（曱基）丙稀酸酿、聚已内g旨二醇-(甲 基）丙烯酸酯、聚丁二烯二醇二（甲基）丙稀酸醋等。 又’作為二g能以上之醋化合物，例如可列舉：新戍 四醇三（甲基）丙烯酸酯、三羥曱基丙烷三（甲基）丙婦 酸醋、經環氧丙院加成之三經甲基丙院三（曱基）丙烯酸 6曰、經環氧乙烷加成之三羥曱基丙烷三（曱基）丙烯酸酯' 經己内酯改質之三羥甲基丙烷三（甲基）丙烯酸酯、經環 氧乙烷加成之異三聚氰酸三（曱基）丙烯酸酿、二新戊四 醇五（甲基）丙稀酸酯、二新戊四醇六（曱基）丙烯酸g旨、 二（三羥甲基）丙烷四（甲基）丙烯酸酿、新戊四醇四（甲 基）丙烯酸酯、三（甲基）丙橋酿廿、，士 — 、T丞；内沛^甘油醋、經環氧丙烷加 成之三（甲基）丙烯酸甘油酯、磷酸三（ 基乙醋等。 L甲基）丙烯醯氧OH 0 v^^^O-CH2CH-CH2O-C-CH OH Ο 〇-CH2-CH-CH2-〇-C-CH=CH, (1) o OH CH2-CH-C-0-CH2-CH- CH2-〇ch2 (2) The above-mentioned resin having a (fluorenyl) acryloxy group is not particularly limited, and examples thereof include (meth)acrylic acid and a compound having a hydroxyl group 201231488, by (meth) An isocyanate obtained by reacting an epoxy group with an epoxy (meth) acrylate of a ring, an oxo compound oxygen compound obtained by a reaction of a (meth)acrylic acid derivative, and having a hydroxyl group ( Mercapto) Acrylamide ethyl citrate and the like. Further, in the specification sheet, the above-mentioned (meth) acryloxy group is an acryloxy group or a mercapto propylene oxide group, and the above-mentioned (mercapto) acrylate means acrylate or Methacrylate The so-called (mercapto) acrylic refers to acrylic acid or mercaptoacrylic acid. Further, in the present specification, the above epoxy (meth) acrylate means that all epoxy groups in the epoxy resin are The ester compound obtained by reacting the above-mentioned (mercapto)acrylic acid with a compound having a trans group is not particularly limited, and examples of the monofunctional ester compound include, for example, 2-hydroxyethyl ethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate Esters, tert-butyl (meth)propionate, isooctyl (meth)acrylate, lauryl (meth)propionate, stearyl (meth)acrylate, isodecyl (meth)acrylate (meth)acrylic acid cyclohexyl Ester, 2-methylglycolyl (meth)acrylate, methoxyglycol (meth)acrylate, 2-methyl ethoxyacetate 2-ethoxyethyl ketone, tetrahydrogen (meth) acrylate Oxime ester, benzyl (meth) acrylate, ethyl carbitol (mercapto) acrylate, phenoxyethyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, (A) Base) phenoxypolyethylene glycol acrylate, decyloxy polyethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, (mercapto)acrylic acid 201231488 2, 2,3,3-tetrafluoropropyl ester, (mercapto)acrylic acid 1H, iH, 5H-octafluoropentyl ester, benzylimine (meth)acrylate, decyl (meth)acrylate, (methyl) 7 Ethyl acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, Isodecyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate Dicyclopentenyl (meth)acrylate 'isodecyl methacrylate, diethylaminoethyl (meth) acrylate, diamidoethyl (meth) acrylate, succinic acid 2 _ (fluorenyl) ) propylene methoxyethyl ester, hexahydrophthalic acid 2-(methyl) propylene methoxyethyl ester, phthalic acid 2-(methyl) propylene methoxyethyl 2- hydroxypropyl ester, ( Glycidyl methacrylate, 2 - (meth) acryloxy ethoxylate B, etc. Further, as the difunctional ester compound, for example, 1,4 butanediol bis(indenyl) acrylate, 1 , 3-butanediol di(indenyl)acrylate, l6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, M〇-nonanediol II Methyl) acrylate, 2-n-butylethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol ( Methyl) acrylate 'ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol II Methyl) acrylate, polyethylene glycol di(meth) acrylate, bismuth A bis(meth) acrylate added by propylene oxide, bisphenol A bis (addition of ethylene oxide) Acrylate, ethylene oxide addition bisphenol F bis(indenyl) propylene 8 201231488 acid ester, bis(indenyl)acrylic acid dihydroxy fluorenyl dicyclopentane ruthenium, 1,3 butyl Diol bis(mercapto) acrylate, neopentyl glycol di(meth) acrylate, ethylene epoxide modified bis(meth) acrylate vinegar, (meth) acrylate 2 — Hydroxy 3-(indenyl) propylene methoxypropyl ester, carbonate diol di(meth) acrylate, polyether diol bis(indenyl) acrylate bismuth, 曰·1···· The thiol-based glycerin-based (meth) acrylate, polybutadiene diol di(meth) acrylate vinegar, and the like. Further, as the vinegar compound having two or more g, the neodymidine tris(meth)acrylate, trishydroxypropylpropane tris(methyl)propyl acetoacetate, and the addition of the epoxy propylene compound may be mentioned. Trimethyl ketone tris(indenyl)acrylic acid 6 曰, ethylene oxide-added trishydroxypropyl propane tris(mercapto) acrylate 'caprolactone modified trimethylolpropane tri Methyl) acrylate, triiso(cyano)acrylic acid added by ethylene oxide, dipentaerythritol penta(methyl) acrylate, dipentaerythritol hexa Acrylic acid, bis(trimethylol)propane tetra(meth)acrylic acid, neopentyl alcohol tetra(meth)acrylate, tris(methyl)propyl bridge, 士, 丞, T丞; Nai Pei ^ glycerin vinegar, glycerol addition of tris (meth) acrylate, tris (ethyl acetonate, etc. L methyl) propylene oxime

…藉由使上述（甲基）丙稀酸與環氧化合物進行反應所 ^件之魏（甲基）丙婦酸S旨並無特別限定，例如可列舉 :由按照常法使環氧樹脂與（甲基）丙稀酸於驗性觸媒： 存在下進行反應所獲得者等。上述式（1)表示之樹、 述式（2)表示之樹脂亦可以此種方式獲得。 S 成為用以合成上述環氧（甲基）丙婦酸醋之原料之環 201231488 氧化合物並無特別限定，例 _ ^ 了歹丨舉·雙酚A型環氧樹脂、 又酚F型環氧樹脂、雙酚s 主衣軋樹月曰、2,2’ 一二烯丙某簪 酴A型環氧樹脂、氫化雙 支 夕雒…，… 環氧樹脂、經環氧丙院加成 樹脂、硫化物型環氧樹r 山氧樹月曰、聯苯型環氧 物生衣氧樹月曰、二苯醚型環氧樹脂、 烯型環氧樹脂、蔡型環量谢# ’、 知、本酚齡醛清漆型環氧招丨#、 鄰甲紛祕清漆型環氧樹脂、 &氧樹月日 一展戊一稀紛駿清漆型琪惫 树脂、聯苯酚醛清漆型環氧招 、 < 月冷1 .衣氧樹脂、萘苯酚酚醛清漆型 樹脂 '縮水甘油胺型環氧樹脂、烧基多元醇型環氧㈣ 橡膠改質型環氧樹脂、縮水甘油酯化合物、料曰 (episulfide)樹脂等。 玉衣爪 之市售者，例如可列舉： 二菱化學公司製造）、 作為上述雙酚A型環氧樹脂中The Wei (methyl) benzoic acid S which is obtained by reacting the above (meth)acrylic acid with an epoxy compound is not particularly limited, and examples thereof include an epoxy resin according to a usual method. (Methyl)acrylic acid in an experimental catalyst: those obtained by carrying out a reaction in the presence or the like. The resin represented by the above formula (1) and the resin represented by the above formula (2) can also be obtained in this manner. S is a ring for synthesizing the above-mentioned epoxy (meth) acetoacetate vinegar. 201231488 Oxygen compound is not particularly limited, for example, 歹丨 ^ bisphenol A type epoxy resin, phenol F type epoxy Resin, bisphenol s main clothing, rolling tree, bismuth, 2,2', a diene, propylene, a type of epoxy resin, hydrogenated double yttrium..., epoxy resin, epoxy propylene alloy addition resin, Sulfide type epoxy tree r oxysyllium, biphenyl type epoxy material, oxygen tree sap, diphenyl ether type epoxy resin, ene type epoxy resin, Cai type ring quantity thank you # ', know, The phenolic aldehyde varnish type epoxy 丨 丨 #, 邻 纷 秘 清 清 型 环氧树脂 、 、 、 、 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 氧 稀 稀 稀 稀 稀 稀 稀 稀 稀 稀 稀 稀<Monthly cold 1. Oxygenated resin, naphthol novolac type resin 'Glycidylamine type epoxy resin, alkyl polyol type epoxy (IV) Rubber modified epoxy resin, glycidyl ester compound, material 曰 (episulfide ) Resin, etc. For example, the manufacturer of the jade-pronged claw can be exemplified by the following bisphenol A type epoxy resin.

Epikote828EL、Epikotel〇〇4 (均為 Epiclon850 - S ( DIC 公司製造）等 之市售者，例如可列舉 菱化學公司製造）等。 之市售者，例如可列舉 等。 作為上述雙酚F型環氧樹脂中Epikote 828EL and Epikotel 〇〇 4 (both of which are commercially available from Epiclon 850-S (manufactured by DIC Corporation), for example, manufactured by Ryo Chemical Co., Ltd.). Commercially available persons, for example, may be mentioned. As the above bisphenol F type epoxy resin

Epikote806、Epikote4004 (均為三 作為上述雙酚S型環氧樹脂中Epikote 806, Epikote 4004 (all three as the above bisphenol S type epoxy resin

Epiclon EXA1514 ( DIC 公司製造） 中之市售 造）等。 例如可列 脂中之市 造）等。 作為上述2,2’一二烯丙基雙酚A型環氧樹脂 者，例如可列舉：RE_81〇NM (日本化藥公司^ 作為上述氫化雙酚型環氧樹脂中之市售者， 舉· Epiclon EXA7〇15 ( DIC 公司製造）等。 作為上述經環氧丙烷加成之雙酚A型環氧樹 售者’例如可列舉：EP — 4000S ( ADEKA公司製 201231488 作為上述間苯二酚型環氧樹脂中之市售 |吾考，例如可列 舉：EX- 201 ( Nagase Chemtex 公司製造）等。 作為上述聯苯型環氧樹脂中之市售者，例如可列舉. Epikote YX — 4000H (三菱化學公司製造）等。 牛. 例如可列 例如可列 作為上述硫化物型環氧樹脂中之市售者 舉：YSLV-- 50TE (新曰鐵化學公司製造）等 作為上述二苯醚型環氧樹脂中之市售者 舉：YSLV-- 80DE (新曰鐵化學公司製造）等， 作為上述二環戊二烯型環氧樹脂中 丨吾考，例如可 列舉：EP— 4088S ( ADEKA公司製造）等。 .作為上述萘型環氧樹脂中之市售者，例如可列舉： ^cl〇n HP4032、Epicl〇n ΕχΑ_ 47〇〇 (均為 公司製牛造） 作為上述苯酚酚醛清漆型環氧樹脂中之市售 可列舉：EPicl〇n N — 770 ( mc公司製造）等。 例如 作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售 如可列舉：Epic丨。η Ν_ 67〇—Εχρ_ s ( dic公司製造）等例 作為上述二環戊二烯酚醛清漆型環氧樹脂中之市 者，例如可列舉：Epicl〇n HP72〇〇 ( dic公司製造）等 作為上述聯苯酚醛清漆型環氧樹脂中之市。 可歹1丨集.XTp 項* 例如 幻舉.NC— 3000P (日本化藥公司製造）等。 作為上述萘苯酚酚醛清漆型環氧樹脂 如可列m ψ售者’例 舉.ESN - 165S (新日鐵化學公司製造）等。 作為上述縮水甘油胺型環氧樹脂中之市售者，例如。 一了 201231488 列舉：Epik〇te630 (三菱化學公司製造）、Epicl〇n43〇 ( DIC 公司製造）、TETRAD — X (三菱氣體化學公司製造）等。 作為上述烧基多元醇型環氧樹脂中之市售者，例如可 列舉：ZX- 1542 (新日鐵化學公司製造）、Epicl〇n726 ( DIC 公司製造）' Epolight80MF A(共榮社化學公司製造）、Denac〇1 EX— 61 1 ( Nagase Chemtex 公司製造）等。 作為上述橡膠改質型環氧樹脂中之市售者，例如可列 舉：YR- 450、YR- 207(均為新日鐵化學公司製造）、Ep〇lead PB ( Daicel化學工業公司製造）等。 作為上述縮水甘油酯化合物中之市售者，例如可列 舉.Denacol EX— 147 ( Nagase Chemtex 公司製造）等。 作為上述雙酴A型環硫樹脂中之市售者，例如可列舉： Epikote YL- 7000 (三菱化學公司製造）等。 作為上述％氧樹脂中之其他市售者’例如可列舉：Y D匸 一1312、YSLV—8〇XY、YSLV_9〇CR (均為新日鐵化學公 司製造）、XAC4151 (旭化成公司製造）、Epik〇tel〇31、Epiclon EXA1514 (manufactured by DIC Corporation), etc. For example, it can be made in the market of the grease. As the 2,2'-diallyl bisphenol A type epoxy resin, for example, RE_81〇NM (Nippon Chemical Co., Ltd.) is commercially available as the above-mentioned hydrogenated bisphenol type epoxy resin. Epiclon EXA7〇15 (manufactured by DIC Corporation), etc. As a bisphenol A-type epoxy resin sold by the above-mentioned propylene oxide-added, for example, EP-4000S (201231488 manufactured by ADEKA Co., Ltd.) is used as the resorcinol ring. For example, EX-201 (manufactured by Nagase Chemtex Co., Ltd.), etc., as a commercially available product of the above biphenyl type epoxy resin, for example, Epikote YX — 4000H (Mitsubishi Chemical) For example, it can be listed as a commercially available one of the above-mentioned sulfide-type epoxy resins: YSLV--50TE (manufactured by Shinkai Iron Chemical Co., Ltd.), etc. as the above-mentioned diphenyl ether type epoxy resin. In the case of the above-mentioned dicyclopentadiene type epoxy resin, for example, EP- 4088S (made by ADEKA Co., Ltd.), etc. As the city of the above naphthalene type epoxy resin For example, ^cl〇n HP4032, Epicli〇n ΕχΑ_47〇〇 (both made by the company) can be cited as the commercially available phenol novolac type epoxy resin: EPicl〇n N — 770 ( For example, the above-mentioned o-cresol novolac type epoxy resin is commercially available as Epic®, η Ν _ 67〇-Εχρ_ s (manufactured by dic), and the like as the above dicyclopentadiene. In the case of the novolac type epoxy resin, for example, Epicl〇n HP72® (manufactured by dic) can be used as the above-mentioned biphenol novolak type epoxy resin. 歹1丨集.XTp item* For example, the above-mentioned naphthol novolak-type epoxy resin is exemplified by ESN-165S (manufactured by Nippon Steel Chemical Co., Ltd.). As a commercially available product of the above glycidylamine type epoxy resin, for example, 201231488 is listed as: Epik〇te630 (manufactured by Mitsubishi Chemical Corporation), Epicl〇n43〇 (manufactured by DIC Corporation), TETRAD — X (Mitsubishi Gas Chemical Company) Manufacturing), etc. For example, ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.) and Epicl〇n726 (manufactured by DIC Corporation) Epolight 80MF A (manufactured by Kyoeisha Chemical Co., Ltd.) Denac〇1 EX—61 1 (manufactured by Nagase Chemtex). For example, YR-450, YR-207 (all manufactured by Nippon Steel Chemical Co., Ltd.), Ep〇lead PB (manufactured by Daicel Chemical Industry Co., Ltd.), and the like can be listed as a commercially available one of the rubber-modified epoxy resins. As a commercially available product of the glycidyl ester compound, for example, Denacol EX-147 (manufactured by Nagase Chemtex Co., Ltd.) or the like can be listed. For example, Epikote YL-7000 (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned as a commercially available product of the above-mentioned biguanide A-type sulphur resin. As other commercially available persons of the above-mentioned % oxygen resin, for example, YD匸-1131, YSLV-8〇XY, YSLV_9〇CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), and Epik〇 are mentioned. Tel〇31,

Epik〇tel〇32 (均為三菱化學公司製造）、ΕχΑ—7i2〇(dic 公司製造）、TEPIC (日產化學公司製造）等。 作為上述環氧（甲基）丙烯酸酯，具體而言，例如間 苯二紛型環氧丙烯酸酯可藉由一面送入空氣—面將間苯二 紛型環氧樹脂（Nagase Chemtex公司製造，「Εχ _ 2〇 1 ) 360重量份、作為聚合抑制劑之對甲氧基苯酚2重量份、作 為反應觸媒之三乙胺2重量份、及丙烯酸21〇重量份於9〇 C進行回流攪拌’使其反應5小時而獲得。 12 201231488 作為上述環氧（曱基）丙烯酸酯中之市售者，例如可 列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、 EBECRYL3412 、 EBECRYL3600 、 EBECRYL3700 、 EBECRYL3701 、 EBECRYL3702 、 EBECRYL3703 、 EBECRYL3800、EBECRYL6040、EBECRYLRDX63 182 (均 為 Daicel— Cytec 公司製造）、EA — 1010、EA — 1020、EA —5323、EA — 5 520、EA- CHD、EMA- 1020 (均為新中村 化學工業公司製造）、Epoxy Ester Μ — 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 — 911(均為 Nagase Chemtex 公司製造） 等。 藉由使上述異氰酸酯與具有羥基之（曱基）丙烯酸衍 生物進行反應所獲得之（曱基）丙烯酸胺曱酸乙酯，例如 可藉由使具有2個異氰酸酯基之化合物1當量與具有羥基 之（甲基）丙烯酸衍生物2當量於觸媒量之錫系化合物存 在下進行反應而獲得。 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_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、三甲基六亞甲基二異氰酸酯、二苯 曱烷一4,4’ 一二異氰酸酯（MDI )、氫化MDI、聚合MDI、 13 201231488 1，5 —奈二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰 酸醋 '伸茬基二異氰酸酯（XDI )、氫化XDI、甜菜鹼二異 氛酸醋、三苯甲烷三異氰酸酯、三（異氰酸酯苯基）硫代 碟酸醋、四甲基二子苯二異氰酸酯、十一烷三異氰 酸酯等。 又’上述異氰酸酿並無特別限定，例如亦可使用藉由 乙二醇、甘油、山梨糖醇、三羥甲基丙烷、（聚）丙二醇' 奴酸酯二醇、聚醚二醇、聚酯二醇、聚己内酯二醇等多元 醇與過剩之異氰酸酯之反應而獲得的經鏈延長之異氰酸酯 化合物。 —丙二醇、i，3_ 丁二醇、1，4_ 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2一羥基乙酯、（甲基）丙輝 酸2—羥基丙酯、（甲基）丙烯酸4一羥基丁酯、（甲基） 丙烯酸2—羥基丁醋等之市售品，或乙二醇、丙二醇^ 醇、聚乙二醇等二元s 之早（甲基）丙烯酸酯，三羥甲基乙烷、三羥曱基丙烷 甘油等二兀醇之單（曱基）丙烯酸酯，或二（甲基）丙* 酸_、雙酚A型環氧（甲基）丙烯酸醋等環氧〇 烯酸酯等。 土）ρ 具體而言，上述（甲基）丙稀酸胺甲酸乙酉旨例如 由如下方式而獲得：於三經曱基丙⑦134重量份 s 為聚合抑制劑之BHT0.2重量份、作AΛ ，〗、、加作 里里如、作為反應觸媒之二 二丁基錫0.01重量份、及展蚀肭-gg ^ 久異佛酮一異氰酸酯666重Epik〇tel〇32 (all manufactured by Mitsubishi Chemical Corporation), ΕχΑ-7i2〇 (made by dic company), TEPIC (made by Nissan Chemical Co., Ltd.), etc. As the epoxy (meth) acrylate, specifically, for example, isophthalic epoxy acrylate can be supplied to Nagase Chemtex by air-to-surface. _ _ 2〇1 ) 360 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 21 parts by weight of acrylic acid were reflux-stirred at 9 ° C. 12 201231488 As a commercially available one of the above epoxy (fluorenyl) acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYLRDX63 182 (both manufactured by Daicel-Cytec), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Epoxy Ester Μ — 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 Kyoei Chemical Co., Ltd.), Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA - 911 (both Nagase (manufactured by Nagase Chemtex Co., Ltd.), etc. Ethyl (meth) methacrylate obtained by reacting the above isocyanate with a (mercapto)acrylic acid derivative having a hydroxyl group, for example, by having two isocyanate groups The compound is obtained by reacting a compound having 1 equivalent of a hydroxyl group-containing (meth)acrylic acid derivative with a catalyst amount of a tin-based compound. The isocyanate is not particularly limited, and examples thereof include isophorone diisocyanate and 2, 4_nonyl diisocyanate, 2,6-nonyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diphenyl decane-4,4' diisocyanate (MDI), hydrogenation MDI, polymeric MDI, 13 201231488 1,5 —naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate vine Cyanate ester (XDI), hydrogenated XDI, betaine diiso-acid vinegar, triphenylmethane triisocyanate, tris(isocyanate phenyl) thioglycolic acid vinegar, tetramethyl diphenyl diisocyanate, undecane triisocyanate, etc. . Further, the above-mentioned isocyanic acid is not particularly limited, and for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol 'stearate diol, polyether diol, or the like may be used. A chain-extended isocyanate compound obtained by reacting a polyhydric alcohol such as a polyester diol or a polycaprolactone diol with an excess of isocyanate. —propylene glycol, i,3-butanediol, 1,4— The above-mentioned (meth)acrylic acid derivative having a hydroxyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate and (meth)propionic acid. Commercial products such as 2-hydroxypropyl ester, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl acrylate (meth)acrylate, or binary s such as ethylene glycol, propylene glycol, alcohol, polyethylene glycol, etc. Early (meth) acrylate, mono(mercapto) acrylate of dinonol such as trimethylolethane or trihydroxymethylpropane glycerol, or di(methyl)propionic acid _, bisphenol A type Epoxy enoate such as epoxy (meth) acrylate. Specifically, the above (meth) acrylic acid urethane is obtained, for example, by the following method: 7134 parts by weight of s-trimethyl propyl propyl is 0.2 parts by weight of BHT of a polymerization inhibitor, and is used as A Λ , 〗 〖,, added as Li Riru, 0.01 parts by weight of dibutyltin as reaction catalyst, and etched 肭-gg ^ long isophorone monoisocyanate 666 weight

-面於⑽回流攪拌一面使其反應 P 卉-人，添加内 14 201231488 烯酸2 —羥基乙酯51重量份，一面送入空氣一面於90°C回 流攪拌，使其反應2小時。 作為上述（甲基）丙烯酸胺甲酸乙酯中之市售者，例 如可列舉：Μ - 1100、M — 1200、M — 1210、M - 1600 (均 為東亞合成公司製造）、EBECRYL230、EBECRYL270、 EBECRYL4858 、 EBECRYL8402 、 EBECRYL8804 、 EBECRYL8803 、 EBECRYL8807 、 EBECRYL9260 、 EBECRYL1290 、 EBECRYL5129 、 EBECRYL4842 、 EBECRYL210 、 EBECRYL4827 、 EBECRYL6700 、 EBECRYL220、EBECRYL2220 (均為 Daicel- Cytec 公司製 造）、Artresin UN — 9000H、Artresin UN — 9000A、Artresin UN — 7100、Art resin UN — 1255、Art resin UN — 330、Art resin UN- 3320HB、Artresin UN— 1200TPK、Artresin 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、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 —3 40A、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 — 1011、UA — 306T、UA — 3 061 (均為共榮 社化學公司製造）等。 就反應性之高度而言，上述具有（曱基）丙烯醯氧基 之樹脂較佳為分子中具有2〜3個（甲基）丙烯醯氧基者。 15 201231488 上述硬化性樹脂較佳為含有具有環氧基之樹脂。 上述具有環氧基之樹脂並無特別限定，例如可列舉. 雙紛A型環乳樹脂、雙盼F型環氧樹脂、雙盼$型環氧樹 月曰、’2- 一烯丙基雙酴A型環氧樹腊、氫 脂、經環氧丙院加成之雙…環氧樹腊、間 氧樹脂、聯苯型環氧樹脂、硫化物型環氧樹脂、二苯：： 環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹浐— ㈣清漆型環氧樹脂、”朌盼酸清漆型環氧樹二：： 戍二烯祕清漆型環氧樹脂、聯苯㈣清漆型環: ^紛㈣清漆型環氧樹脂、縮水甘油胺型環氧樹脂、曰 基二元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘㈣ 化&物 '雙酚A型環硫樹脂等。 -曰 作為上述雙酴A型環氧樹脂中之市售者，例如 EP|k〇te828EL、Epik〇tel_ (均為三菱化學公司製造举- The surface was reacted under reflux with stirring at (10), and the mixture was added to a liquid. In addition, 51 parts by weight of 2-hydroxyethyl ethyl acrylate was added to the mixture, and the mixture was stirred at 90 ° C for 2 hours while being sent to the air. As a commercially available product of the above-mentioned (meth)acrylic acid urethane, for example, Μ-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858 , EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL220, EBECRYL2220 (all manufactured by Daicel-Cytec), Artresin UN — 9000H, Artresin UN — 9000A, Artresin UN — 7100 , Art resin UN — 1255, Art resin UN — 330, Art resin UN- 3320HB, Artresin UN — 1200TPK, Artresin 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, 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-3 40A, U-108, U-6H, UA-4000 (all are Xinzhongcun) Manufactured by Chemical Industry Co., Ltd., AH-600, AT-600, UA-306H, AI-600, UA-101T, UA-1091, UA-306T, UA-3061 (all manufactured by Kyoei Chemical Co., Ltd.). The resin having a (fluorenyl) acryloxy group is preferably a polymer having 2 to 3 (meth) acryloxy groups in the molecule in terms of reactivity. 15 201231488 The above curable resin preferably contains a resin having an epoxy group. The epoxy group-containing resin is not particularly limited, and examples thereof include a double-type A-ring latex resin, a double-presence F-type epoxy resin, a double-presence type epoxy tree, and a 2-2-allyl double酴A type epoxy wax, hydrogen grease, double added by epoxy propylene... Epoxy wax, m- oxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl:: epoxy Resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy tree 浐 - (4) varnish type epoxy resin, "Yupan acid varnish type epoxy tree 2:: decadiene varnish type epoxy resin, biphenyl (4) Varnish-type ring: ^Four (four) varnish type epoxy resin, glycidylamine type epoxy resin, mercapto glycol type epoxy resin, rubber modified epoxy resin, shrinking water (four) chemical & 'biphenol A-type sulphur resin, etc. - 曰 is commercially available as the above-mentioned bismuth A type epoxy resin, for example, EP|k〇te828EL, Epik〇tel_ (all manufactured by Mitsubishi Chemical Corporation)

Epiclon850— S ( DIC 公司製造）等。 .作為上述雙0型環氧樹脂中之市售者例如兴 Eplkote806、Epik〇te4004 (均為三菱化學公司製造）等+ 作為上述雙酚S型環氧樹脂中之市售 Π昏f例如可列舉Epiclon850-S (made by DIC) and so on. As a commercial product of the above-mentioned double-type epoxy resin, for example, Eplkote 806, Epik〇te 4004 (all manufactured by Mitsubishi Chemical Corporation), etc., as a commercially available faint f in the above bisphenol S-type epoxy resin, for example,

Epiclon EXA1514 ( DIC 公司製造）等。 马上述2,2，一二烯丙基雙酚a型環氧樹脂中之市 者，例如可列舉：RE—810NM (日本化藥公司製造）等。 作為上述氫化雙酚型環氧樹脂中之市售 I C 4，例如可列 羋.tpiclon EXA7〇15 ( mc 公司製造）等。 作為上述經環氧丙烷加成之雙酚A型淨氧也 展氣樹脂中之节 201231488 售者，例如可列舉：EP_ 4〇〇〇S ( ADEKA公司制、 、 』義造）等。 作為上述間苯二酚型環氧樹脂中之市售 m . FX 9nw XT ’例如可列 举.201 ( Nagase Chemtex 公司製造）等。 作為上述聯苯型環氧樹脂中之市售者， 如可列兴：Epiclon EXA1514 (manufactured by DIC Corporation), etc. In the case of the above-mentioned 2,2, or a diallyl bisphenol a-type epoxy resin, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) may, for example, be mentioned. As the commercially available I C 4 in the hydrogenated bisphenol type epoxy resin, for example, it can be listed as t.tpiclon EXA7〇15 (manufactured by mc company). In the above-mentioned propylene glycol-added bisphenol A-type net oxygen-supplemented gas-supplementing resin, for example, EP_4〇〇〇S (made by ADEKA Co., Ltd.) can be cited. As a commercially available m. FX 9nw XT' in the above-mentioned resorcinol type epoxy resin, for example, 201 (manufactured by Nagase Chemtex Co., Ltd.) or the like can be listed. As a commercial product of the above biphenyl type epoxy resin, such as Lexing:

Epikote YX— 4000H (三菱化學公司製造）等。 牛. 例如可列 例如可列 作為上述硫化物型環氧樹脂中之市售者 舉：YSLV-- 50TE (新曰鐵化學公司製造）等 作為上述二苯醚型環氧樹脂中之市售者 舉：YSLV-- 80DE (新曰鐵化學公司製造）等 作為上述二環戊二烯型環氧樹脂中之市售者，例 。 列舉：EP— 4088S ( ADEKA公司製造）等。 可 作為上述萘型環氧樹脂中之市售者，例如可列舉.Epikote YX—4000H (manufactured by Mitsubishi Chemical Corporation). For example, it can be listed as a commercially available one among the above-mentioned sulfide-type epoxy resins, such as YSLV--50TE (manufactured by Shinkai Iron Chemical Co., Ltd.), etc., as a commercially available product of the above-mentioned diphenyl ether type epoxy resin. For example, YSLV--80DE (manufactured by Shinco Iron Chemical Co., Ltd.) and the like are commercially available as the above-mentioned dicyclopentadiene type epoxy resin. List: EP-4088S (made by ADEKA). As a commercially available one of the above naphthalene type epoxy resins, for example, it can be enumerated.

Epiclon ΗΡ4032、Epiclon ΕΧΑ— 4700 (均為 DIC 公 + 等。 1 1造） 作為上述本紛盼路·清漆型環氧樹脂中之市售去 古可，例如 可列舉：Epiclon N— 770 ( DIC公司製造）等。 作為上述鄰甲酚酚醛清漆型環氧樹脂中之 , | e有，例 如可列舉：EpiclonN— 670 —Exp—S(DIC& 司製造）等。 作為上述二環戊二烯酚醛清漆型環氧樹脂 去 < 市售 ，例如可列舉：Epiclon HP7200 ( DIC公司製造）等 作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例 了列舉.NC—3000P (曰本化藥公司製造）等。 作為上述萘苯酚酚醛清漆型環氧樹脂中之市售 K , ^，例 可列舉：ESN — 1 65S (新曰鐵化學公司製造）等。 17 201231488Epiclon ΗΡ 4032, Epiclon ΕΧΑ — 4700 (both DIC male + etc. 1 1 made) As the above-mentioned commercially available varnish type epoxy resin, for example, Epiclon N-770 (DIC company) Manufacturing) and so on. In the above o-cresol novolac type epoxy resin, |e is, for example, Epiclon N-670-Exp-S (manufactured by DIC & Division). The dicyclopentadiene novolac type epoxy resin is commercially available, and, for example, Epiclon HP7200 (manufactured by DIC Corporation) or the like is commercially available as the biphenyl novolak type epoxy resin. .NC—3000P (manufactured by Sakamoto Chemical Co., Ltd.). The commercially available K, ^ in the above-mentioned naphthol novolac type epoxy resin, for example, ESN - 1 65S (manufactured by Shinki Steel Chemical Co., Ltd.). 17 201231488

作為上述縮水甘油胺型環氧樹脂中之市售者，例如^ 列舉：EPik〇te630 (三菱化學公司製造）、Epiel()n43() ( H 公司製造）、TETRAD— X (三菱氣體化學公司製造）等。 作為上述烷基多元醇型環氧樹脂中之市售者，例如可 列舉：ZX- i 542 (新日鐵化學公司製造）、响1的726㈤c 公司製造）、Ep〇light80MFA(共榮社化學公司製造）、^一 EX— 61 1 ( Nagase Chemtex 公司製造）等。 售者，例如可列 司製造）、Ep〇leadAs a commercially available product of the glycidylamine type epoxy resin, for example, EPik〇te630 (manufactured by Mitsubishi Chemical Corporation), Epiel () n43 (manufactured by H Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.) )Wait. As a commercially available one of the above-mentioned alkyl polyol type epoxy resins, for example, ZX-i 542 (manufactured by Nippon Steel Chemical Co., Ltd.), 726 (five) company of Ring 1 is manufactured, and Ep〇light 80MFA (Kyoeisha Chemical Co., Ltd.) Manufacture), ^-EX-61 1 (manufactured by Nagase Chemtex), etc. The seller, for example, can be manufactured by Essex), Ep〇lead

舉： PB 作為上述橡膠改質型環氧樹脂中之市 YR — 45 0、YR — 207(均為新曰鐵化學公 (Daicel化學工業公司製造）等。 作為上述縮水甘油酷化合物中之市售者例如可歹, 舉：Denacol EX— 147 ( Nagase Chemtex 公司製造」等。 作為上述㈣A型環硫樹脂中之市售者，例如可列舉： Epikote YL- 7000 (三菱化學公司製造）等。 作為上述環氧樹脂中之其他市售者，例如可列舉 —^2、YSLV_8GXY、yslv_9qcr (均為新日鐵化學公 习製造）、xAC4151 (旭化成公司製造）、EpikGtei, EPlk〇te1032 (均為三菱化學公司製造）、EXA- 7120 ( DIC 公司製造）、TEPIC (日產化學公司製造）等。 又，上述具有環氧基之樹脂例如亦可為丨分子中具有 (甲基）6稀醯氧基與環氧基之樹脂。作為此種化合物， :!可列舉藉由使具有2個以上環氧基之化合物之一部分 %乳基與（甲基）丙烯酸進行反應所獲得之部A(甲基） 丙烯酸改質環氧樹脂等。 18 201231488 再者，上述硬化性樹脂亦可為僅含有上述1分子中具 有（〒基）丙締醯氧基與環氧基之樹脂者。 „ ί述部分' Γ © ^·、 刀〈甲基）丙烯酸改質環氧樹脂例如可藉由按 :、、、吊法使氧樹脂與（甲基）丙稀酸於驗性觸媒之存在下 進行反應而獲得。具體而言，例如使苯齡酴路清漆型環氧 十月曰（DIC Α司製造’「Ν - 770」）190 g溶解於曱苯500 mL 中向“液中添加三苯基膦0.1 g而製成均勻之溶液，於 回_拌下用2小時向該溶液中滴加丙浠酸35g後，進而 ，丁 6小時之回流攪拌，其次，去除甲苯，藉此可獲得50 紅 ' &quot;與丙烯馱進行反應而成的苯酚酚醛清漆型 ^分丙稀酸改質環氧樹脂（於此情料50%部分丙稀酸化）。 作為丄述部分（甲基）丙稀酸改質環氧樹脂中之市售 ^ 例如 °Γ 列舉：UVACURE1561 ( Daicel- Cytec 公司製 本發明之液晶滴下法用密封劑較佳為以硬化性樹脂中 之（甲基）丙烯醯氧基斑 5。〜95:5之方文而找基，氧基之比以莫耳比計成為 r^ μ + 式而乜合上述具有（曱基）丙烯醯氧基之樹 月曰與上述具有環氧基之樹脂。 劑 ^之液曰曰滴下法用密封劑含有熱自由基聚合起始 較佳之自由基聚合起始劑之半衰期為料時之溫度的 聚人 &amp;佳之上限4 90°c °乡上述熱自由基 猙得 小時之溫度未逹5(TC，則有時所 X件之液晶滴下法用金 自由料穩^變差。若上述熱 c，起始劑之半衰期為10小時之溫度超過9(TC，則 201231488 有時對本發明之液晶滴下法用密封 d* pq * #4- J-c 更化需要南 &gt;皿且長 時間’對面板之生產性造成影響。 再者，於本說明書令，所謂上述半 度係指於惰性氣體之存在下且 ........ &quot; 分解反應時，執自…人/ 之溫度進行10小時熱 卢…！ 由基聚合起始劑之濃度成為反應前之濃 度的一半時之溫度。 敗 上述熱自由基聚合起始劑並無特別 氮化合物、有機過氧化物等。直了列舉偶 子量為5_〜10萬……中k佳為由數量平均分 氣起始劑。 …偶氣化合物所構成之高分子偶 上述尚分子偶氮起始劑之數量 限為5_，較佳之上限為i。萬。若里的較佳之下 之數量平妁八；旦土 上述向/刀子偶氮起始劑 =^子$未達5_，财時高分子 液晶造成不良影塑。婪μ、+.古八7 , ΪΤ 八早吾扣，a ^ ,L冋刀偶氮起始劑之數量平均 77 口過1 0萬，則有時難以混合 基之樹脂中。卜、十一、7 ”有（甲基）丙烯酸 、^子偶氮起始劑之數量平均分子量的 下限為1萬’更佳之上限為9萬。 砘「即便為由於黑色矩陣等而光照射不到之 =可藉由熱而更加確實地硬化，且極少產生液晶“ 劑較佳為具有聚二甲基 At 稀化氧（p〇lyalkylene 〇xide)單元。 :為上述具有聚晞化氧單元之結構，較佳 烯化氧之結構者。 取乙 作為此種高分子偶氮起始劑，例如可列舉：* 4 ’ 碼氮 201231488 雙（4一氰基戊酸）與聚烷二醇之縮聚物、或4,4，一偶氣雙 (4—氛基戍酸）與末端具有胺基之聚二甲基矽氧烷之縮聚 物等’作為市售者，例如可列舉：vpe-02()1、vPE_Q4()1、 VPE— 060】、vps— 〇501、vps— 1〇〇1 (均為和光純藥工業 公司製造）等。 作為上述高分子偶氮化合物，此外亦可較佳地使用日 本特開2008- 50572號公報或日本特開2〇〇3 — 12784號公 報中所記載之下述通式⑴|示之高分子偶氮化合物1In the above-mentioned rubber-modified epoxy resin, YR-45 0, YR-207 (both manufactured by Daicel Chemical Industry Co., Ltd.), etc. are commercially available as the above-mentioned glycidyl cool compounds. For example, Denacol EX-147 (manufactured by Nagase Chemtex Co., Ltd.), etc., as a commercially available product of the above-mentioned (4) type A episulfide resin, for example, Epikote YL-7000 (manufactured by Mitsubishi Chemical Corporation), etc. Other commercially available epoxy resins include, for example, -2, YSLV_8GXY, yslv_9qcr (all manufactured by Nippon Steel Chemical Co., Ltd.), xAC4151 (made by Asahi Kasei Corporation), EpikGtei, EPlk〇te1032 (all Mitsubishi Chemical Corporation) Manufactured, EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Co., Ltd.), etc. Further, the epoxy group-containing resin may have, for example, a (meth)6-thraceneoxy group and an epoxy group in a ruthenium molecule. The resin of the base. As such a compound, a part of the (meth)acrylic acid obtained by reacting a part of the compound having two or more epoxy groups with (meth)acrylic acid may be mentioned. Epoxy resin, etc. 18 201231488 Further, the curable resin may be one containing only a resin having a (fluorenyl) propyl decyloxy group and an epoxy group in the above-mentioned one molecule. „ 述 部分 part Γ © ^· The knife <meth)acrylic acid modified epoxy resin can be obtained, for example, by reacting an oxygen resin with (meth)acrylic acid in the presence of an inert catalyst according to:,, and a hanging method. For example, 190 g of Benzene lacquer-type epoxy epoxidized October 曰 ("Ν - 770" manufactured by DIC Co., Ltd.) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to the liquid to make a uniform The solution was added dropwise 35 g of propionic acid to the solution under reflux for 2 hours, and then, the mixture was stirred under reflux for 6 hours, and then toluene was removed, whereby 50 red ' &quot; The reaction is a phenol novolak type, which is an acrylic acid-modified epoxy resin (in this case, 50% is partially acidified). As a part of the (meth)acrylic acid modified epoxy resin For sale, for example, °Γ LIST: UVACURE1561 (The seal for liquid crystal dropping method of the present invention manufactured by Daicel-Cytec Co., Ltd. Preferably, the base of the (meth) propylene oxyoxy group in the curable resin is 5 to 95:5, and the ratio of the oxy groups is r^μ + in terms of molar ratio. A resin having a (fluorenyl) acryloxy group and a resin having an epoxy group as described above. The liquid helium dropping method of the agent contains a half-life of a radical polymerization initiator which is preferably initiated by thermal radical polymerization. The temperature of the material is the upper limit of the temperature and the upper limit of the temperature of the above-mentioned hot radicals is less than 5 (TC, sometimes the liquid crystal dropping method of the X piece is stabilized with gold free material. difference. If the above heat c, the half-life of the initiator is 10 hours and the temperature exceeds 9 (TC, then 201231488 sometimes requires the seal of the liquid crystal dropping method of the present invention d*pq*#4-Jc to be South &gt; 'Influence on the productivity of the panel. In addition, in the present specification, the above-mentioned half degree refers to the presence of an inert gas and ..... &quot; decomposition reaction, from ... person / The temperature is maintained for 10 hours. The temperature of the base polymerization initiator is half the concentration before the reaction. The above thermal radical polymerization initiator does not contain a specific nitrogen compound, organic peroxide, etc. The number of the coupled is 5_~100,000... The middle k is preferably the number average gas-separating initiator. The polymer composed of the odor compound is limited to 5_, preferably the number of the above-mentioned molecular azo initiator. The upper limit is i. 10,000. If the number of the best under the ridge is flat, the above-mentioned directional / knife azo starter = ^ child $ is less than 5 _, the polymer liquid crystal caused bad image. 婪μ, + .古八7, ΪΤ eight early wukou, a ^, L 冋 knife azo starter number average 77 If it is over 100,000, it may be difficult to mix the base resin. The lower limit of the number average molecular weight of the (meth)acrylic acid and the azo starter is 10,000'. 90,000. 砘 "Even if it is not irradiated by light due to black matrix or the like = it can be hardened more reliably by heat, and liquid crystal is rarely produced." The agent preferably has polydimethyl at least oxygen (p〇lyalkylene) 〇xide) unit: is a structure having a polyfluorene oxide unit, preferably an alkylene oxide structure. Taking B as such a polymer azo initiator, for example, * 4 ' code nitrogen 201231488 double a polycondensate of (4-cyanovaleric acid) and a polyalkylene glycol, or a polycondensate of 4,4, an azobis(4-antimonylic acid) and a polydimethyloxane having an amine group at the end thereof As a commercially available person, for example, vpe-02()1, vPE_Q4()1, VPE-060], vps-〇501, vps-1〇〇1 (all manufactured by Wako Pure Chemical Industries Co., Ltd.), etc. As the above polymer azo compound, it is also possible to preferably use JP-A-2008-50572 or JP-A-2-3 — Polymer azo compound 1 of the following formula (1)|

式⑴巾，^…^…分別獨立地表示碳原 子數為卜1〇之烧基或氰基，aAb分別獨立為〇〜4之數， A&quot;及A12為高分子鏈，γ&quot;及γ12分別獨立為一 c〇—〇—、 0-C0--、一NH-CO—、—「。一 CO — ΝΗ — 0 —或一S — R22及R23表示之碳原子 乙基、丙基、異丙基、 數為 上述通式（I )中，R12、R13、 1〜10之烷基可列舉：曱基 丁基、二級丁基、三級丁基里 奚 J ^ 呉丁基、戊基、異戊基、三 級戊基、己基、環己基、環p其甲耸 _ 3 w ^ 衣匕基甲基、裱己基乙基、庚基、 異庚基、二級庚基、正辛某、里妾其 _.. 〒丞呉辛基、二級辛基、2~乙基 己基、正壬基、正癸基等。 限定 上述通式（D + ’ A&quot;及A12表示之高分子鏈並無特別 ’例如可列舉：聚環氧乙烯（polyoxirene)鏈、聚亞甲 21 201231488 基鏈、聚醚鏈、聚酯鏈、聚矽氧烷鏈、取/ 取（曱基）丙烯酸 酯鏈、聚苯乙烯一乙酸乙烯酯鏈、聚醯妝 職如鏈、聚醯亞胺鏈、 聚胺甲酸乙酯鏈、聚脲鏈、多肽鏈箄。甘丄 寻其中，較佳為γ丨丨 為一0—CO—且γ 為一CO—0—之化人1 ,, 〈化合物，ΑΗ及Α12表 示之高分子鏈為聚喊鏈及聚酯鏈者，囡杜 因特別廉價且容易製 造故更佳。 上述通式（I)中，於Α1丨及八丨2主取 為I醚鏈之高分子偶 氮化合物中’下述通式（Π)表示之化八 1匕5物，因溶解性較佳 且容易控制聚合起始劑之分子量故更佳。 •R21 (II) 式（II)中，R12、rH、R22The formula (1) towel, ^...^... respectively independently represents the alkyl group or the cyano group having a carbon number of 〇1〇, the aAbs are independently 〇~4, A&quot; and A12 are polymer chains, γ&quot; and γ12 respectively Independently a c〇-〇-, 0-C0--, an NH-CO-,-"-CO- ΝΗ - 0 - or a S - R22 and R23 represent the carbon atom ethyl, propyl, isopropyl The base and the number are in the above formula (I), and the alkyl group of R12, R13, and 1 to 10 may, for example, be a nonylbutyl group, a secondary butyl group, a tertiary butyl sulfonium group, a butyl group, or a pentyl group. Isoamyl, tertiary pentyl, hexyl, cyclohexyl, ring p, 甲 3 w ^ mercaptomethyl, hexylethyl, heptyl, isoheptyl, secondary heptyl, n-xin,妾 妾 妾 妾 基 、 、 、 、 、 、 、 、 、 、 、 、 、 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ There is no particular 'for example, polyoxyl chain, polymethylene 21 201231488 base chain, polyether chain, polyester chain, polyoxyalkylene chain, acyl group, or poly(alkyl) acrylate chain Styrene-vinyl acetate Ester chain, poly- 醯 makeup jobs such as chain, polyimine chain, polyurethane chain, polyurea chain, polypeptide chain 箄. Ganzi find it, preferably γ 丨丨 is a 0-CO- and γ It is a CO-0-chemical person 1, and the compound chain represented by the compound, ruthenium and osmium 12 is a poly-chain and a polyester chain, and the ruthenium is particularly inexpensive and easy to manufacture. Among them, in the polymer azo compound in which I Α 1丨 and 丨 2 are mainly taken as the I ether chain, the following formula (Π) represents the octagonal compound, which is preferred because of its solubility and easy control of polymerization. The molecular weight of the initiator is better. • R21 (II) In formula (II), R12, rH, R22

R 23 a及b與上述通式 相同，R及R21分別獨立地表示碳原子數為卜 Z&quot; ' Z12 ^ Z21 A Z22 ^ Z,| m iA, Μ 烷基 &quot; '別獨立地表示碳原子數為i〜4之伸 烷基，m、n、s及t分別獨立為 iU00之數，m + n之和、 s + t之和分別獨立為2以上。 上述通式（Π)巾，zn、zl2、z 數為1〜4之伸烧基可列舉：亞甲農：Ζ表不之奴原子 “总= 』芈亞甲基、伸乙基、三亞甲基、 伸丙基、亞丙基、異亞㊅基、 基、乙基伸乙基m㈠亞甲基、伸丁基、異伸丁 石齡主, —f基伸乙基等，妒及r2|表示之碳原 子數為1〜24之烷基可列舉. 丁基、幻舉.甲基、乙基、丙基、異丙基、 铋Λ其ρ ^ 兵丁基、戊基、異戊基、三 級戊基、己基、環己基、 衣己基甲基、環己基乙基、庚基、 22 201231488 異庚基、三級庚基、正辛基、異辛基、三級辛基、2— G基 己基、正壬基、正癸基、月桂基、硬脂基、二十二基等。 R11及R21表示之碳原子數為1〜24之烷基為碳原子數 為1〜4者，因反應性較高故較佳。 於上述通式（I)表示之高分子偶氮化合物之All及A。 為聚醋鏈者之中，下述通式（111)表示之化合物，因溶 性較佳且耐水性優異故較佳。 令R 23 a and b are the same as the above formula, and R and R21 each independently represent a carbon atom of Z&quot; 'Z12 ^ Z21 A Z22 ^ Z,| m iA, Μ alkyl&quot; 'do not independently represent a carbon atom The number is alkyl group of i~4, m, n, s and t are each independently the number of iU00, and the sum of m + n and the sum of s + t are independently 2 or more. The above-mentioned general formula (Π) towel, zn, zl2, and the number of z-extensions of 1 to 4 can be enumerated: sub-agricultural: 奴 不 奴 奴 奴 原子 原子 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 总 、 、 、 、 、 a propyl group, a propyl group, a propylene group, an isohexyl group, a benzyl group, an ethyl group, an ethyl group (m), a methyl group, a butyl group, an isobutyl group, an ex-ethyl group, an anthracene group, and a carbon atom represented by r2| The alkyl group having a number of from 1 to 24 may be exemplified by butyl, magical, methyl, ethyl, propyl, isopropyl, 铋Λ^^, pentyl, isopentyl, tertiary pentyl, Hexyl, cyclohexyl, hexylmethyl, cyclohexylethyl, heptyl, 22 201231488 isoheptyl, tertiary heptyl, n-octyl, isooctyl, trioctyl, 2-g hexyl, n- Base, n-decyl, lauryl, stearyl, 222, etc. R11 and R21 represent an alkyl group having 1 to 24 carbon atoms and having a carbon number of 1 to 4, which is highly reactive. It is preferable that All of the polymer azo compounds represented by the above formula (I) and A are a compound represented by the following formula (111) among the polyester chains, and are excellent in solubility and excellent in water resistance. Better.

A ^ 111 (III) ⑴相同，β及P分別獨立地表示碳原子數=述通式 伸烷基’尺31及R41分別獨立地 /〜18之 〜—及U分別獨立為二子:數碳原子數為丨 上述通式（III)中，Z13、Z23矣_ 之伸烷基可列舉：亞曱基 丁之炭原子數為1〜18 丨基、三亞甲其 亞丙基、異亞丙基、四亞甲基、伸丁 伸兩基、 伸乙基、二曱基伸乙基、五亞甲基、:基亞甲異：丁基、乙基 八亞甲基、心錢二基、十亞、亞基、七亞甲基、 十一烷二基、十二亞甲基、丨〜 亞曱基、1,4 ~~ 等，R3丨1 ’ 、十七烷二基、+ \冗 及R表示之碳原子數1〜 /亞甲基 上述通式⑻中之炫基可列舉：作為 破原子數為之坑基為碳::二者。〜1表示之 較高故較佳。 為1〜4者，因反應性 23 201231488 一上述通式（III)中，P及u為20〜100者，因反應性較 高故較佳》 上述有機過氧化物並無特別限定，可較佳地使用半衰 期為10小時之溫度的下限為8〇t且上限為15〇它者。若I 述半衰期為10小時之溫度未達8(rc，則有時所獲得之密封 劑之常溫下之減變得缺乏料性。若上料㈣為10小 時之溫度超過15〇。(：，則有時所獲得之密封劑變得缺乏反應 性’而於贼無法迅速地硬化。上述半衰期為1()小時之溫 度的更佳之下限為loot：，更佳之上限為l3(rc。 再者’於本說明書中，所謂上述半衰期為10小時之溫 度係指熱自由基聚合起始劑之濃度減少為初始值之一半的 時間為1 0小時之溫度。 作為上述有機過氧化物系化合物，具體而言，例如可 列舉：過氧化甲基乙基酮等過氧化酮系 (三級丁基過氧化環己幻等過氧化縮‘合或：或： 乳化異丁酸三級丁酷等過氧化院基醋系化合物、或過氧化 -月桂醯等過氧化二醯基系化合物、或過氧化二碳酸（2 — =基己幻酿等過氧化二碳酸酯系化合物、或過氧化異丙 基…級丁醋等過氧化碳酸醋系化合物、 化二一 三級丁基等過氧化-产其备 …… 4氫過氧化三級戍基 #過氧化氫系化合物等。 為有述熱自由基聚合起始劑’亦可使用市售品，作 為：機過氧化物系化合物之市售品，例如可列舉：以―A ^ 111 (III) (1) The same, β and P respectively represent the number of carbon atoms = the above-mentioned alkylene group 'foot 31' and R41 are independently / 18 ~ ~ and U are independently two sub-numbers: number of carbon atoms The number of the alkyl group of the above formula (III), Z13, Z23矣_ may be exemplified by the number of carbon atoms of the fluorenylene group being 1 to 18 fluorenyl groups, trimethylene propylene group, isopropylidene group, Tetramethylene, butylene, dibasic, ethyl, fluorenylethyl, pentamethylene, ketone: butyl, ethyl octamethyl, erythroyl, ten, Subunit, heptamethylene, undecanediyl, dodecamethylene, fluorene ~ fluorenylene, 1,4 ~~, etc., R3丨1 ', heptadecandiyl, + \ redundancy and R The number of carbon atoms is 1 to /methylene. The stimuli in the above formula (8) can be exemplified by the fact that the number of broken atoms is carbon:: both. ～1 indicates that it is higher and therefore better. In the case of 1 to 4, the reactivity is 23 201231488. In the above formula (III), P and u are 20 to 100, and it is preferred because the reactivity is high. The organic peroxide is not particularly limited. The lower limit of the temperature at which the half-life is 10 hours is 8 〇t and the upper limit is 15 〇. If the temperature at which the half-life is 10 hours is less than 8 (rc), sometimes the decrease in the sealant obtained at room temperature becomes a lack of materiality. If the feed (4) is 10 hours, the temperature exceeds 15 〇. (:, Then the sealant obtained sometimes becomes less reactive' and the thief cannot harden rapidly. The lower limit of the above half-life of 1 () hour is better than the loot: and the upper limit is l3 (rc. In the present specification, the temperature at which the half-life is 10 hours means that the concentration of the thermal radical polymerization initiator is reduced to a temperature of one half of the initial value of 10 hours. For example, a peroxide ketone system such as methyl ethyl ketone peroxide (peroxide peroxide such as a tertiary butyl peroxide ring or a condensed or emulsified isobutyric acid or a tertiary peroxide) a vinegar-based compound, or a bismuth-based compound such as peroxidized-laurel, or a peroxydicarbonate (2 - = a peroxydicarbonate compound such as a kiwi or a isopropyl peroxide grade) Peroxidized carbonated vinegar compound such as butyl vinegar Peroxidation of a ternary butyl group, etc. - Preparation of a hydrogen peroxide compound, a hydrogen peroxide compound, etc. For commercial products of organic peroxide compounds, for example,

㈣職kH、PermekN(均為日油公司製造）Lup_DDM 24 201231488 (Arkema Yoshitomi公司製造）等過氧化酮系化合物，或(4) Peroxyketone compounds such as KH and PermekN (all manufactured by Nippon Oil Co., Ltd.) Lup_DDM 24 201231488 (manufactured by Arkema Yoshitomi Co., Ltd.), or

Perhexa C、Perhexa MC (均為日油公司製造）、LUperox230 (Arkema Yoshitomi公司製造）等過氧化縮酮系化合物， 或 Perbutyl E、Perhexa 250、Perocta 〇、Perhexyi 〇 (均為 曰油公司製造）等烧基過氧化酯系化合物，或per〇yl L、 Peroyl SA、Peroyl IB (均為曰油公司製造）等過氧化二醯 基系化合物，或 Peroyl TCP、Peroyl opp、per〇yl SBP (均 為曰油公司製造）等過氧化二碳酸酯系化合物，Kayakarub〇n AIC- 75 ( Kayakuakzo 公司製造）、Luperox TBEC ( ArkemaPerhexa C, Perhexa MC (all manufactured by Nippon Oil Co., Ltd.), LUperox230 (manufactured by Arkema Yoshitomi Co., Ltd.), etc., or Perbutyl E, Perhexa 250, Perocta®, Perhexyi® (all manufactured by Oyster Oil Co., Ltd.) a peroxylated ester compound, or a perylene dibasic compound such as per〇yl L, Peroyl SA, or Peroyl IB (all manufactured by Oyster Sauce), or Peroyl TCP, Peroyl opp, per〇yl SBP (both Peroxydicarbonate compound, manufactured by Oyster Oil Co., Ltd., Kayakarub〇n AIC-75 (manufactured by Kayakuakzo Co., Ltd.), Luperox TBEC (Arkema)

Yoshitomi公司製造）等過氧化碳酸酯系化合物，或Luper〇x DI ( Arkema Yoshitomi 公司製造）、Perbutyl D (曰油公司 製造）等過氧化二烷基系化合物，或Permenta H、Percumy p (均為日油公司製造）、Luperox TAH ( Arkema Y〇shit〇mi 公司製造）等過氧化氫系化合物等。 本發明之液晶滴下法用密封劑中之上述熱自由基聚合 起始劑之含量並無特別限定，相對於上述硬化性樹脂1〇〇 重量份’較佳之下限為〇」重量份，較佳之上限為3〇重量 份。若上述熱自由基聚合起始劑之含量未達〇.丨重量份，則 有時變得無法使上述密封劑於8〇t左右之低溫硬化。若上 述熱自由基聚合起始劑之含量超過3G重量份，則有時所獲 得之液晶滴下法用密封劑之黏度變高，而對塗佈作業性等 這成不良’V響。上述熱自由基聚合起始劑之含量的更佳之 下限為〇.~·重量份，更佳之上限為1 0重量份。 本發明之液晶滴下法用密封劑含有由通式（A )表示之 25 201231488 化合物所構成之熱硬化劑。 =上述由通式⑷表示之化合物所構成之熱硬化劑 量亦可充分地進行熱硬化，故可藉由減少相對於 %氧δ篁之摻合量而抑制液晶污染。 ' 作為上述通式（Α)表示之化合物，具體而言，例如可 列舉.丙二酸二醯肼、琥珀酸二醯肼、酒石酸二醢肼、蘋 果酸二醢肼、亞胺基二乙酸二醯肼等。其中，由於丙二酸 -酉肼與高極性樹脂之相容性或熱反應性優異，故可藉由 1 吏用丙二酸二醯肼作為通式⑷表示之化合物，而獲得抑 法!液晶 &gt;可染之效果、熱硬化性、及接著性特別優異之液晶 滴下法用密封劑。 進而’可藉由將上述丙二酸二醢肼與作為硬化性樹脂 之土述式⑴表示之樹脂及/或上述式（2)表示之樹脂 組合使用，而進一步提高抑制液晶污染之效果、熱硬化性 及接著性。 上述由通式（Α)表示之化合物所構成之熱硬化劑之含 量並無特別限定，相對於上述硬化性樹脂1〇〇重量份，較 佳之下限為〇‘5重量份，較佳之上限為ι〇重量份。若上述 由=式(Α)表示之化合物所構成之熱硬化劑之含量未達〇 5 :置：’則有時變得無法使密封劑於8。它左右之低溫硬 右上述由通式（A)表示之化合物所構成之熱硬化劑之 含量超過1G重量份，則有時引起液晶污染，而使所獲得之 :晶顯示元件之顯示性能下降。上述由通式（a)表示之化 合物所構成之熱硬化劑之含量的更佳之下限為1重量份， 26 201231488 更佳之上限為5重量份，進而較佳之下限為1.6重量份，進 而較佳之上限為4.0重量份。 本發明之液晶滴下法用密封劑較佳為含有光自由基聚 合起始劑。上述光自由基聚合起始劑並無特別限定，例如 可較佳地使用二苯曱酮系化合物、苯乙酮系化合物、醯基 氧化膦系化合物、二茂鈦系化合物、將酯系化合物、安息 香醚系化合物、硫雜蒽_ ( thioxanthone )等。 又，作為上述光自由基聚合起始劑中之市售者，例如 可歹丨J 舉：IRGACURE184、IRGACURE369、IRGACURE379、 IRGACURE651 、 IRGACURE819 、 IRGACURE907 、 IRGACURE2959、IRGACUREOXE01、Lucirin TPO (均為 BASF公司製造）、安息香甲醚、安息香乙醚、安息香異丙 醚（以上，均為東京化成工業公司製造）等。其中，就吸 收波段較寬之方面而言，較佳為 IRGACURE651、 IRGACURE819、IRGACURE907、IRGACUREOXEO1 及 Lucirin TPO。該等光自由基聚合起始劑可單獨使用，亦可 併用2種以上。 上述光自由基聚合起始劑之含量並無特別限定，相對 於上述硬化性樹脂1 0 0重量份，較佳之下限為0.1重量份， 較佳之上限為10重量份。若上述光自由基聚合起始劑之含 量未達0.1重量份，則有時變得無法使本發明之液晶滴下法 用密封劑充分硬化。若上述光自由基聚合起始劑之含量超 過10重量份，則有時儲存穩定性下降。 為了提高黏度、藉由應力分散效果而改善接著性、改 27 201231488 善線膨脹係數、進一步提高硬化物之耐濕性等本發明之 液晶滴下法用密封劑較佳為含有填充劑。 =填充，特別限定’例如可列舉：滑石、石棉、 蒙：膨潤石、膨潤土、碳_、碳酸鎖、 氧化紹、蒙脫石、氧化鋅、氧化鐵、氧化鎮 化鈦、氫氧化鎮、氫氧化紹 '乳錫、氧 u喁珠氮化矽、硫酸鋇、 /酉文弼、竭雲母活性白土、氮化I呂等無機填充劑， 或聚酉曰微粒子、聚胺f酸乙g旨微粒子、 子、丙槐舻取人&amp; 乙婦基聚合物微粒 子丙烯酉夂聚合物微粒子等有機填 或密著性，該笤埴古滿丨介1 马了 k问分散性 理。㈣填充劑亦可利用钱偶合劑等實施表面處 本發明之液晶滴下法用密封 劑。上述石夕燒偶合劑主要具有作為用以佳t含有石夕烧偶合 良好地接著之接著助劑之作用。 ㈣劑與基板等 =烧偶合劑並無特別限定，例如 私基丙基三甲氧基石夕院、卜 史用r 「縮水甘油氧基丙基三甲氧基錢等基三甲氧融、 以液晶滴下法用密封劑進而視需要亦可含有用 m黏度之反應性稀釋劑、調整觸 “用 調整面板間隙之聚合物顆粒等間隔物、變劑、用以 —二甲基腺等硬化促進劑、消泡劑、調”:二基―1，1 其他添加劑等。 聚&amp;抑制劑、 製造本發明之液晶滴下法用 定，例如可列舉如下方法等：使用均：法並無特別限 =勻刀散機、均質攪拌 28 201231488 機、萬能混合機、杆s .日人 人 丁星此《機'捏合機、三輥研磨機等混 +.丄 哽化吐樹脂、上述熱自由基聚合起始劑、上 )表不之化合物所構成之熱硬化劑、及 添加之妙烧倘人麻丨# °荨加以混合。此時，為了去除含有之雜 子性雜質，亦可盥施 有之離 Γ 了與離子吸附性固體接觸。 ，可藉由於本發明之液晶滴下法用密封劑中推合 微粒子而製造上下道、s …田材料。又’此種含有本發明之液晶 滴下法用密封劑與導電性 守·电I·生锨粒子之上下導通材料亦為本發 明之一。 上述導電性微粒子並無特別限定，可使用於金屬球、 樹脂微粒子之表面形成有導電金屬層者等。其中，就 由樹脂微粒子之優異之彈性，而可無損透明基板等進料 電連接」1方面而言，於樹脂微粒子之表 屬層者較佳。 金 又’使用本發明之液晶滴下法用密封劑及/或本發明 之上下導通材料而成之液晶顯示元件亦為本發明之一。 作為製造本發明之液晶顯示元件之方法，例如可列舉 具有以下步驟之方法等：藉由網版㈣、分注器塗佈等而 將本發明之液晶滴下法用密封劑等於附有ιτ〇薄膜等電極 的兩透明基板之一者上形志具 — 小成長方形密封圖案之步驟；於 本發明之液晶滴下法用密封劑等未硬化之狀態下將液曰之 微小滴滴加塗佈於透明基板之框内整個面丨， ： 合另一透明基板之步驟；及對本# 、 1令赞月之液晶滴下法用密封 劑等之密封圖案部分照射紫外飨黧 糸卜綠4先而使密封劑暫時硬化 29 201231488 之步驟’及加熱暫時硬化之密封劑而使其正式硬化之步驟。 [發明之效果] 、、據本發明，可提供一種保存穩定性優異、幾乎不引 ::晶：染、且於8。。。左右之低溫即可充分硬化之液晶滴 ^用密封劑。又，根據本發明’可提供一種使用該液晶 滴下法用密封劑而製造之上下導通材料及液晶顯示元件。 【實施方式】 、以下列舉實施例進一步詳細地說明本發明但本發明 並非僅限定於該等實施例。 (A) 間苯二酚型環氧丙烯酸酯之合成 一面送入空氣一面於90 對間苯二酚型環氧樹脂 (Nagase Chemtex 製造，「De_〇1 Εχ_ 2〇1」）⑽〇 重量 份、作為聚合抑制劑之對曱氧基苯酚2重量份、作為反應 觸媒之三乙胺2重量份、及丙烯酸649重量份進行回流攪 拌，並使其反應5小時。為了吸附反應物中之離子性雜質， 而於填充有10重量份之Qualtz與高嶺土之天然結合物 (Hoffmann Mineral公司製造，「si出tin V85」）之管柱中 過濾所獲得之樹脂100重量份，從而獲得間笨二酚型環氧 丙烯酸酯（A )。 (B) 雙酚A型環氧丙烯酸酯之合成 一面送入空氣一面於90°C對雙酚A型環氧樹脂（三菱 化學公司製造’ 「Epikote828EL」）1000重量份、作為聚 合抑制劑之對曱氧基苯酚2重量份、作為反應觸媒之三乙 胺2重量份、及丙烯酸424重量份進行回流攪拌，並使其 30 201231488 反應5小時。為了吸附反應物中之離子性雜質，而於填充 有10重量份之Qualtz與高嶺土之天然結合物（H〇ffmann Mineral公司製造，「SilntinV85」）之管柱中過濾所獲得 之樹脂100重量份，從而獲得雙酚A型環氧丙烯酸酯（B )。 (C) 雙酚F型環氧丙烯酸酯之合成 一面送入空氣一面於90°C對雙酚f型環氧樹脂（DIC 公司製造，「EPiClon830S」）1000重量份、作為聚合抑制 劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺，2重 量份、及丙烯酸462重量份進行回流攪拌，並使其反應5 小時。為了吸附反應物中之離子性雜質，而於填充有1〇重 量份之Qua丨tz與高嶺土之天然結合物（H〇ffmann⑷以… 公司製造，「SUHtin V85」）之管柱中過濾所獲得之樹脂 100重量份，從而獲得雙酚F型環氧丙烯酸酯（C)。 (D) 部分丙烯酸改質雙酚A型環氧樹脂之合成 一面送入空氣一面於901對雙酚A型環氧樹脂（三菱 化學公司製造’ 「Epikote828EL」）1〇〇〇重量份、作為聚 合抑制劑之對曱氧基苯酚2重量份、作為反應觸媒之三乙 胺2重量份、及丙烯酸212重量份進行回流攪拌，並使其 反應5小時。為了吸附反應物中之離子性雜質，而於填充 有10重量份之Qualtz與高嶺土之天然結合物（H〇ffm_ 公司製造，「SiUitinV85j )之管柱中過據所獲得 之樹脂100重量份，從而獲得5〇%部分丙烯酸改質雙酚A 型環氧樹脂（D )。 (E )部分丙烯酸改質雙酚E型環氧樹脂之合成 31 201231488 一面送入空氣一面於90 °C對雙酚E型環氧樹脂（三井 化學公司製造，「Epomik R710」）1〇〇〇重量份、作為聚合 抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2 重量伤、及丙稀酸2 2 1重量份進行回流攪拌，並使其反應5 小時。為了吸附反應物中之離子性雜質，而於填充有1 〇重 量份之Qualtz與高嶺土之天然結合物（Hoffmann Mineral 公司製造，「Sillitin V85」）之管柱中過濾所獲得之樹脂 1 00重量份，從而獲得5〇%部分丙稀酸改質雙盼E型環氧樹 脂（E )。 (F)部分丙烯酸改質二苯趟型環氧樹脂之合成 一面送入空氣一面於90。(：對二苯醚型環氧樹脂（新曰 鐵化學公司製造，「YSLV8〇DE」）1〇〇〇重量份、作為聚 合抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙 胺2重量份、及丙烯酸229重量份進行回流攪拌，並使其 反應5小時。為了吸附反應物中之離子性雜質，而於填充 有10重量份之Qualtz與高嶺土之天然結合物（H〇ffmann Minera丨公司製造，r Simtin V85」）之管柱中過濾所獲得 之樹脂1 00重量份，從而獲得5〇%部分丙烯酸改質二笨喊 型環氧樹脂（F )。 (實施例1〜2 3、比較例1〜8及參考例1 ) 使用行星式攪拌機（Thinky公司製造，「去泡攪拌太 郎」）並按照表1〜6中所記載之摻合比混合各材料後，進 而使用三輥研磨機使其混合，藉此製備實施例1〜23、比較 例1〜8及參考例1之液晶滴下法用密封劑。 32 201231488 〈評價&gt; 以下對貫施例、比較例及失去办丨士 j及參考例中所獲得之液晶滴下 法用密封劑進行評價。將結果示於表丨〜6中。 (面板顯示不均評價1 ) .以晝成正方形之框之方式条丨田八 万式利用分注器將所獲得之液晶 滴下法用密封劑塗佈於形成有读 π、❿欣有透明電極與配向膜之基板上 從而形成密封圖案。將所獲得之液晶滴下法用密封劑打點 於所形成之密封圖案之内部。繼而，將液晶（chisso公司 製造，「JC — 5004LA | )夕 μ |、务 从小滴滴加塗佈於透明基板之 框内整個面上，於真空中盥另 T興另—形成有透明電極與配向膜 之基板重合。解除真空後，傕用厶思太 便用金屬_化物燈對外框密封 部照射30秒100 mW// cm2 砦 之％外線。此時，對打點之液晶 滴下法用密封劑覆蓋光罩以#祜昭1+ _ m aA peroxycarbonate-based compound such as a peroxidized carbonate compound manufactured by Yoshitomi Co., Ltd., or a dialkyl compound such as Luper〇x DI (manufactured by Arkema Yoshitomi Co., Ltd.) or Perbutyl D (manufactured by Oyster Oil Co., Ltd.), or Permenta H or Percumy p (all A hydrogen peroxide-based compound such as Luperox TAH (manufactured by Arkema Y〇shit〇mi Co., Ltd.). The content of the above-mentioned thermal radical polymerization initiator in the sealing compound for liquid crystal dropping method of the present invention is not particularly limited, and a preferred lower limit of the weight of the curable resin is 1% by weight, preferably a upper limit. It is 3 parts by weight. When the content of the above-mentioned thermal radical polymerization initiator is less than 丨.丨 by weight, the above-mentioned sealant may not be cured at a low temperature of about 8 Torr. When the content of the above-mentioned thermal radical polymerization initiator exceeds 3 G by weight, the viscosity of the obtained sealing compound for liquid crystal dropping method may become high, and the coating workability may become undesirable. A more preferred lower limit of the content of the above thermal radical polymerization initiator is 〇.~· parts by weight, and a more preferred upper limit is 10 parts by weight. The sealing compound for liquid crystal dropping methods of the present invention contains a thermosetting agent composed of a compound of the formula 201201488 represented by the general formula (A). = The amount of the thermosetting agent composed of the compound represented by the formula (4) can be sufficiently thermally cured, so that the liquid crystal contamination can be suppressed by reducing the amount of the mixture with respect to % oxygen δ. The compound represented by the above formula (Α), for example, may be exemplified by diammonium malonate, diterpene succinate, diterpene tartrate, diterpene malate, and iminodiacetic acid. Hey. Among them, since malonate-ruthenium is excellent in compatibility or thermal reactivity with a highly polar resin, it is possible to obtain a compound represented by the formula (4) by using bismuth malonate as a compound represented by the formula (4). &gt; A sealant for a liquid crystal dropping method which is excellent in dyeable effect, thermosetting property, and adhesion property. Further, by using the above-mentioned dimer malonate in combination with a resin represented by the above formula (1) as a curable resin and/or a resin represented by the above formula (2), the effect of suppressing liquid crystal contamination and heat can be further improved. Hardenability and adhesion. The content of the thermosetting agent composed of the compound represented by the formula (Α) is not particularly limited, and the lower limit of the curable resin is preferably 〇'5 parts by weight, and preferably the upper limit is ι. 〇 by weight. When the content of the thermosetting agent composed of the compound represented by the formula (Α) is less than 〇 5 : set: ', the sealant may not be obtained at 8. When the content of the thermosetting agent composed of the compound represented by the general formula (A) exceeds 1 G by weight, the liquid crystal contamination may be caused, and the display performance of the crystal display element may be lowered. A more preferred lower limit of the content of the thermosetting agent composed of the compound represented by the formula (a) is 1 part by weight, and a higher limit of 26 201231488 is 5 parts by weight, and a lower limit is preferably 1.6 parts by weight, and further preferably an upper limit. It is 4.0 parts by weight. The sealing agent for liquid crystal dropping method of the present invention preferably contains a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited, and for example, a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an ester compound, or an ester compound can be preferably used. A benzoin ether compound, thioxanthone or the like. Further, as a commercially available one of the above-mentioned photoradical polymerization initiators, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all manufactured by BASF Corporation), Benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether (all of which are manufactured by Tokyo Chemical Industry Co., Ltd.) and the like. Among them, IRGACURE651, IRGACURE819, IRGACURE907, IRGACUREOXEO1 and Lucirin TPO are preferred in terms of a wide absorption band. These photoradical polymerization initiators may be used singly or in combination of two or more. The content of the photoradical polymerization initiator is not particularly limited, and a lower limit is preferably 0.1 part by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the photoradical polymerization initiator is less than 0.1 part by weight, the liquid crystal dropping method sealing agent of the present invention may not be sufficiently cured. When the content of the photoradical polymerization initiator is more than 10 parts by weight, the storage stability may be lowered. In order to improve the viscosity, improve the adhesion by the stress dispersion effect, and improve the moisture expansion coefficient of the cured product, the sealing agent for liquid crystal dropping method of the present invention preferably contains a filler. = filling, particularly limited 'for example, talc, asbestos, Mongolia: bentonite, bentonite, carbon _, carbonic acid lock, oxidized smectite, montmorillonite, zinc oxide, iron oxide, oxidized sedative titanium, oxidized town, hydrogen Oxidizing sulphur 'tin, tin, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, yttrium, etc., inorganic granules, or polyfluorene , sub-, 槐舻 槐舻 & & & & & & & & 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 & & & & & & & & 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机(4) The filler may be applied to the surface of the liquid crystal dropping method sealing agent of the present invention by using a money coupling agent or the like. The above-mentioned stone smelting coupling agent mainly functions as a good continuation aid for the inclusion of the smelting coupling. (4) The agent and the substrate, etc. = the sinter coupling agent is not particularly limited, for example, propyl propyl trimethoxy sylvestre, sir, r, "glycidoxy propyl trimethoxy hydroxy, etc., trimethyl sulfoxide, liquid crystal dropping method The sealant may further contain a reactive diluent having a viscosity of m, and may be adjusted such as a spacer such as a polymer particle having a gap between the adjustment panels, a modifier, a hardening accelerator such as a dimethyl gland, and a defoaming agent. For the liquid crystal dropping method of the present invention, for example, the following methods can be used: the use of the method: the method is not particularly limited = the uniform knife Machine, homogeneous mixing 28 201231488 machine, universal mixer, rod s. Japanese Ding Xing this "machine" kneading machine, three-roll mill, etc. mixed +. 丄哽 吐 吐 resin, the above thermal radical polymerization initiator, The thermal hardening agent composed of the above-mentioned compounds and the added magical burner are mixed with human 丨# °荨. At this time, in order to remove the miscellaneous impurities contained therein, it is also possible to carry out the separation. Ion-adsorbing solid contact. The liquid crystal dropping method uses a sealing agent to push the fine particles to produce a material for the upper and lower channels, and the material for the liquid crystal dropping method, and the conductive sealing material for the liquid crystal dropping method of the present invention and the conductive material. The conductive fine particles are not particularly limited, and can be used for forming a conductive metal layer on the surface of the metal ball or the resin fine particles. Among them, the transparent fine resin can be used without loss of the transparent substrate. In the case of the "infeed electrical connection", it is preferred to be in the surface layer of the resin fine particles. The liquid crystal display element which is 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 inventions. As a method of producing the liquid crystal display element of the present invention, for example, a method having the following steps: a screen (4), a dispenser, or the like is used, and the sealing compound for liquid crystal dropping method of the present invention is equal to a film with an ιτ〇 film. a step of forming a rectangular seal pattern on one of the two transparent substrates of the equal electrode; and applying a fine drop of the liquid helium to the transparent in an unhardened state such as a liquid crystal dropping method of the present invention The entire surface of the substrate is 丨, : the step of combining another transparent substrate; and the sealing pattern of the sealing film such as the liquid crystal dropping method of the present invention is irradiated with ultraviolet ray green 4 first to make the sealing agent The step of temporarily hardening 29 201231488 and the step of heating the temporarily hardened sealant to form a hardening process. [Effects of the Invention] According to the present invention, it is possible to provide an excellent storage stability, and it is hardly etched and dyed at 8. . . Sealant for liquid crystal droplets that can be fully hardened at low temperatures. Further, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element by using the sealing compound for liquid crystal dropping methods. [Embodiment] The present invention will be described in more detail by way of the following examples, but the invention is not limited to the examples. (A) Synthesis of resorcinol-type epoxy acrylate is carried on the air side at 90 pairs of resorcinol type epoxy resin (manufactured by Nagase Chemtex, "De_〇1 Εχ _ 2〇1") (10) 〇 by weight 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 649 parts by weight of acrylic acid were reflux-stirred, and reacted for 5 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the resin obtained by filtration in a column packed with 10 parts by weight of a natural conjugate of Qualtz and kaolin ("Si-tin V85" manufactured by Hoffmann Mineral Co., Ltd.) Thereby, a m-diphenol type epoxy acrylate (A) is obtained. (B) 1000 parts by weight of bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation), which is a polymerization inhibitor, is supplied to the bisphenol A type epoxy acrylate at a temperature of 90 ° C. 2 parts by weight of methoxy phenol, 2 parts by weight of triethylamine as a reaction catalyst, and 424 parts by weight of acrylic acid were reflux-stirred, and reacted at 30 201231488 for 5 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the resin obtained by filtration is packed in a column packed with 10 parts by weight of a natural conjugate of Qualtz and kaolin ("Silntin V85" manufactured by H〇ffmann Mineral Co., Ltd.), Thus, bisphenol A type epoxy acrylate (B) was obtained. (C) The synthesis of bisphenol F-type epoxy acrylate is carried out at 90 ° C on a bisphenol f-type epoxy resin ("EPiClon 830S" manufactured by DIC Corporation), 1000 parts by weight, as a polymerization inhibitor 2 parts by weight of oxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 462 parts by weight of acrylic acid were stirred under reflux and allowed to react for 5 hours. In order to adsorb the ionic impurities in the reactants, it was obtained by filtering in a column packed with a natural conjugate of Qua丨tz and kaolin (H〇ffmann (4) manufactured by the company, "SUHtin V85"). 100 parts by weight of the resin, thereby obtaining a bisphenol F type epoxy acrylate (C). (D) The synthesis of a part of the acrylic acid modified bisphenol A type epoxy resin was carried out in the air and 10,000 parts by weight of bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation). The inhibitor was refluxed with 2 parts by weight of p-methoxyphenol, 2 parts by weight of triethylamine as a reaction catalyst, and 212 parts by weight of acrylic acid, and allowed to react for 5 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the resin obtained by the natural combination of Qualtz and kaolin ("SiUitin V85j" manufactured by H〇ffm_ company) is filled with 10 parts by weight, thereby Obtained 5〇% of partially modified bisphenol A epoxy resin (D). (E) Synthesis of partially acrylic modified bisphenol E epoxy resin 31 201231488 While feeding air to bisphenol E at 90 °C Epoxy resin ("Epomik R710", manufactured by Mitsui Chemicals Co., Ltd.) 1 part by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 3 parts by weight of triethylamine as a reaction catalyst, and C 2 2 parts by weight of dilute acid was stirred under reflux, and allowed to react for 5 hours. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the resin obtained by filtration in a column packed with 1 〇 part by weight of a natural combination of Qualtz and kaolin ("Sillitin V85" manufactured by Hoffmann Mineral Co., Ltd.) was used. Thus, a 5% by weight portion of the acrylic acid-modified double-prepared E-type epoxy resin (E) is obtained. (F) Synthesis of a part of acrylic acid modified diphenyl fluorene type epoxy resin. (: p-diphenyl ether type epoxy resin ("Yellow Iron Chemical Co., Ltd." "YSLV8〇DE") 1 part by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, as a reaction catalyst 2 parts by weight of triethylamine and 229 parts by weight of acrylic acid were stirred under reflux and allowed to react for 5 hours. In order to adsorb the ionic impurities in the reactant, 10 parts by weight of the natural combination of Qualtz and kaolin was filled (H). 100 parts by weight of the resin obtained by filtration of a column manufactured by ffffmann Minera Co., Ltd., r Simtin V85"), thereby obtaining 5 % by weight of a partially modified acrylic acid-based epoxy resin (F ). ～2 3, Comparative Examples 1 to 8 and Reference Example 1) Using a planetary mixer (manufactured by Thinky Co., Ltd., "Defoaming Taro"), and mixing the materials according to the blending ratios shown in Tables 1 to 6, and then using them. The three-roll mill was mixed to prepare the sealing agents for liquid crystal dropping methods of Examples 1 to 23, Comparative Examples 1 to 8, and Reference Example 1. 32 201231488 <Evaluation> The following are examples, comparative examples, and loss. The liquid obtained in the gentleman j and the reference example The crystal dropping method was evaluated with a sealant. The results are shown in Tables 66. (Panel display unevenness evaluation 1). The 丨田80万式式分分器 is obtained by means of a square frame. The liquid crystal dropping method is applied to a substrate on which a transparent electrode and an alignment film are formed, and a seal pattern is formed on the substrate on which the π, ❿, and the transparent film are formed, and the obtained liquid crystal dropping method is applied to the inside of the formed sealing pattern. Then, a liquid crystal (manufactured by Chisso Co., Ltd., "JC — 5004LA | )) was applied dropwise from the droplets to the entire surface of the frame of the transparent substrate, and another vacuum was formed in the vacuum to form a transparent electrode. The substrate of the alignment film is overlapped. After the vacuum is released, the metal-based lamp is irradiated to the outer frame seal portion for 30 seconds and the external line of 100 mW//cm2 is used. At this time, the sealing agent for the liquid crystal dropping method for the dot is used. Covering the mask with #祜昭1+ _ ma

早充破照射紫外線。其後於80〇C 進行1小時液晶退火，传游曰、、电 日日'商下法用密封劑熱硬化從而 獲得液晶顯示元件。 於通電狀態下以目測掛所饉 4對所獲侍之液晶顯示元件觀察於 打點之液晶滴下法用密封番丨H、息^ &gt; 在封劑周邊之液晶中所發生之顏色不 均。其結果，將完全無顏色不均之情形評價為「◎」，將 幾乎無顏色不均之情形評㈣「〇」，將稍有顏色不均之 情形評價為「△」，將館且益A 丁上人 -_ f顒具顏色不均之情形評價為「X」。 (面板顯示不均評價2) 以畫成正方形之框之方彳士丨 式利用为注器將所獲得之液晶 滴下法用植封劑塗佈於开{占古、乐nn &amp; 於形成有透明電極與配向膜之基板上 從而形成通封圖案。將戶斤媒媒夕、戌θ 所獲仔之液晶滴下法用密封劑打點 33 201231488 於所形成之密封圖案之内部 製诰，rTr _ 將液晶（Chisso公司 叔 k，| jC_ 5〇〇4LA ) 」^ t微小滴滴加塗佈 框内整個面上，於真空中歲s ^^踅佈於透明基板之 之某柄4 與另一形成有透明電極與配向膜 之基板重合。解除真空後 邱之用金屬南化物燈對外框密封 4 照射 30 秒 1〇〇 mW//cm2 m + 系外線此時，對打點之液.晶 滴下法用密封劑覆蓋光罩 Λ 尤极…、射兔外線。其後於120 匕進仃1小時液晶退火 而n此 使液日日滴下法用密封劑熱硬化從 而獲付液晶顯示元件。 於通電狀態下以目測對所獲得之液晶顯示元件觀察於 打點之液晶滴下法用密封劑周邊之液晶中所發生之顏色不 句…Ί ’將凡全無顏色不均之情形評價&amp;「◎」，將 幾乎無顏色不均之情形評價為「〇」，將稍有顏色不均之Early filling and breaking of ultraviolet rays. Thereafter, the liquid crystal was annealed at 80 ° C for 1 hour, and the liquid crystal display element was obtained by thermal curing with a sealant. In the state of being energized, the visual inspection is carried out. 4 The liquid crystal display element obtained is observed. The liquid crystal dropping method for sealing is used to seal the Panyu H, and the color is uneven in the liquid crystal surrounding the sealing agent. As a result, the case where there is no color unevenness is evaluated as "◎", and the situation in which there is almost no color unevenness is evaluated (4) "〇", and the case of slight color unevenness is evaluated as "△". Ding Shangren-_ f The color unevenness of the cookware was evaluated as "X". (Panel display unevenness evaluation 2) The square of the squared frame is used as a grinder to apply the obtained liquid crystal dropping method with a planting agent to the open {Zhangu, Lenn &amp; The transparent electrode and the substrate of the alignment film form a through-sealing pattern. The liquid crystal dropping method obtained by the household media, 戌 θ, is sealed with a sealant 33 201231488. The inner surface of the formed seal pattern, rTr _ will liquid crystal (Chisso uncle k, | jC_ 5〇〇4LA) ^ t t tiny drops are applied to the entire surface of the coating frame, and a handle 4 which is placed on the transparent substrate in vacuum is overlapped with another substrate on which the transparent electrode and the alignment film are formed. After the vacuum is released, Qiu uses the metallization lamp to seal the outer frame 4 for 30 seconds. 1〇〇mW//cm2 m + is the outer line. At this time, the liquid is applied to the dot. The crystal dripping method covers the mask with a sealant. Shoot the rabbit outside. Thereafter, the liquid crystal was annealed at 120 Torr for 1 hour, and the liquid crystal display element was obtained by heat-hardening the liquid with a sealing agent. In the state of being energized, the liquid crystal display element observed by the liquid crystal display element is visually observed in the liquid crystal in the vicinity of the sealant for liquid crystal dropping method. Ί 'Evaluate the case where there is no color unevenness &amp; "There is almost no color unevenness as "〇", which will be slightly uneven in color.

It升&quot;平‘ 4 △」’將頗具顏色不均之情形評價為「X」。 (接著強度評價1) 利曰用行星式攪拌裝置於所獲得之液晶滴下法用密封劑 重量伤中使平均粒控5 // m之聚合物顆粒（積水化學工 業公司製造’「Micropearlsp」）3重量份分散而製成均勻 之液體，將極微量取入至附有IT〇電極之無鹼玻璃（“mm X50 mmx〇.7 mmt)之中央部，於其上重合同型之玻璃並 壓開液晶滴下法用密封劑，使用金屬鹵化物燈照射2〇秒1〇〇 mW/ cm之紫外線。其後，於8〇°c加熱i小時，從而獲得 接著試驗片。使用張力計測定該試驗片之接著強度（比較 單位為N/ cm2 )。將接著強度為200 N/ cm2以上之情形評 價為「〇」，將150 N/ cm2以上且未達200 N/ cm2之情形 34 201231488 έ平價為「△」，將未達150N/cm2之情形評價為Γχ」。 (接著強度評價2 ) 利用行星式授拌裝置於所獲得之液晶滴下法用密封劑 1 〇〇重量份中使平均粒徑5 # m之聚合物顆粒（積水化學工 業公司製造，「MiCr0pearl SP」）3重量份分散而製成均勻 之液體，將極微量取入至附有IT0電極之無鹼玻璃（2〇mm x50 mmX〇.7 mmt)之中央部，於其上重合同型之玻璃，並 壓開液晶滴下法用密封劑，使用金屬_化物燈照射2〇秒ι〇〇 紫外線。其後，於12代加熱i小時，從而獲 得接著試驗片。使用張力計測定該試驗片之接著強度（比 較單位為N//cm2)。將接著強度為2〇〇ν/(^2以上之情形 評價為「〇」’將150N/W以上且未達200 N八m2之情 形評價為「△」’冑未達150N/cm2之情形評價為「X」。 (保存穩定性評價） 將所獲得之液晶滴下法用密封劑於溫度 5〇%RH之環境下保存48小 ”、'又 存m 扪用E型黏度計測定黏 度，利用下述式計算出自保存前之黏度起之增點率。 度）增黏率（％)=撕（保存後之黏度）/(保存前之黏 為「〇」，將120%以 ，將130%以上之情形 將增黏率未達12〇%之情形評價 上且未達13〇%之情形評價為「△」 評價為「X」。 35 201231488 【I &lt;】 實施例 卜 § — CN 一 〇 1 v〇 〇 ◎ &lt;1 〇 〇 v〇 § 1 — (N — 〇 1 v〇 ◎ ◎ 〇 〇 Ο § 1 — 〇 1 〇 〇 〇 〇 Ο Tf g 1 (N 一 〇 1 1 〇 〇 〇 〇 〇 ΓΛ S 1 &lt;N — 〇 1 VO 1 1 ◎ ◎ 〇 〇 〇 (Ν g 1 fNJ 一 〇 1 1 1 1 ◎ ◎ 〇 〇 〇 一 § 1 1 一 ίΝ — 〇 1 \0· 1 1 1 I 1 ◎ ◎ 〇 〇 〇 間笨二酚型環氧丙烯酸酯（A) 雙酚A型環氧丙烯酸酯（B) 雙酴F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚A型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二笨醚型環氧樹脂（F) IRGACURE651 (BASF 公司製造） VPE-0201 (分子量約2萬）（和光純藥工業公司製造） VPE—0401 (分子量約3萬）（和光純藥工業公司製造） VPE—0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） PerhexylO (日油公司製造） KBM-403 (信越Silicone公司製造） SO—C2 (Admatechs 公司製造） 2MZA—PW (四國化成工業公司製造） 丙二酸二酿肼（Japan Finechem公司製造） 琥ϊό酸二酿耕（Japan Finechem公司製造） 蘋果酸二酿肼（Japan Finechem公司製造） 酒石酸二酿肼（Japan Hnechem公司製造） AmicureVDH — J (Ajinomoto Fine—Techno 公司製造） 間笨二甲酸二醯肼（大塚化學公司製造） 己二酸二醯肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價丨（於80°c硬化後通電） 面板顯示不均評價2 (於120°c硬化後通電） '接著強度評價1(於80°c硬化後） 接著強度評價2 (於120°C硬化後） 25°C、50%RH、48 小時後 硬化性樹脂 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 其他 面板評價 接著強度評價 保存穩定性評價 熱自由基聚合起始劑 填充劑 熱硬化劑 组成（重量份） 評價 201231488 【&lt;N&lt;】 實施例 1 1 1 1 - is 1 1 1 1 1 — 〇 1 1 1 1 1 1 1 1 〇 ◎ &lt; 〇 〇 (N 1 1 S 1 1 — &lt;N 1 1 1 1 1 - 〇 1 1 1 1 1 1 1 1 〇 ◎ &lt;] 〇 〇 1 ο 1 1 1 — CN 1 1 1 1 1 — 〇 1 v〇 1 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 〇 1 g 1 1 宕 1 — (N 1 1 1 t 1 一 〇 1 SO 1 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 〇\ § 1 1 1 1 — «Ν 1 1 1 1 1 — 〇 1 VO 1 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 00 § 1 1 1 1 — 1 1 1 1 1 — 〇 VO 1 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 | 間笨二吩型環氧丙烯酸酯（A) 雙酚Α型環氧丙烯酸酯（Β) 雙酚F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚A型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二苯醚型環氧樹脂（F) IRGACURE651 ( BASF 公司製造） VPE—0201 (分子量約2萬）（和光純藥工業公司製造） VPE-0401 (分子量約3萬）（和光純藥工業公司製造） VPE —0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） Perhexyl 0 (曰油公司製造） KBM — 403 (信越Silicone公司製造） SO — C2 ( Admatechs 公司） 2MZA—PW (四國化成工業公司製造） 丙二酸二醯肼（Japan Finechem公司製造） 破珀酸二酿肼（Japan Finechem公司製造） 蘋果酸二酿肼（Japan Finechem公司製造） 酒石酸二酿肼（Japan Finechem公司製造） AmicureVDH_J (Ajinomoto Fine—Techno 公司製造） 間苯二甲酸二醯肼（大塚化學公司製造） 己二酸二醯肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價丨（於80°c硬化後通電） 面板顯示不均評價2 (於120°c硬化後通電） 接著強度評價1 (於80°c硬化後） 接著強度評價2 (於120°c硬化後） 25°C、50%RH、48 小時後 硬化性樹脂 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 其他 面板評價 接著強度評價 保存穩定性評價 熱自由基聚合起始劑 填充劑 熱硬化劑 組成（重量份） 評價 201231488 【£&lt;】 實施例 g i 1 - 1 1 1 1 CN — 〇 1 1 1 1 1 1 〇 〇 &lt; 〇 〇 ο g 1 1 — 1 1 1 1 1 一 〇 1 1 1 η 1 1 1 〇 〇 &lt;] 〇 〇 οο g 1 1 - ΓΊ 1 1 1 1 1 — 〇 1 1 ON 1 1 t 1 〇 〇 &lt; 〇 〇 卜 g 1 1 一 1 1 1 1 1 — 〇 1 1 00 1 1 1 1 1 〇 〇 &lt; 〇 〇 § 1 1 - η 1 1 1 1 1 — 〇 1 vq 1 ! 1 1 1 ◎ ◎ 〇 〇 〇 〇 〇 1 1 — &lt;Ν 1 1 1 1 1 — 〇 1 v〇 1 ! 1 1 1 ! 〇 ◎ &lt; 〇 〇 § Ο 1 1 1 — 1 1 1 1 1 — 〇 1 so 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 間笨二酚型環氧丙烯酸酯（A) 雙酚Α型環氧丙烯酸酯（Β) 雙酚F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚Α型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二苯蜮型環氧樹脂（F) IRGACURE651 ( BASF 公司製造） VPE—0201 (分子量約2萬）（和光純藥工業公司製造） |VPE —0401 (分子量約3萬）（和光純藥工業公司製造） VPE-0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） Perhexyl 0 (曰油公司製造） KBM —403 (信越Silicone公司製造） SO — C2 (Admatechs 公司製造） 2MZA—PW (四國化成工業公司製造） 丙二酸二酿肼（Japan Finechem公司製造） 破ίό酸二酿耕（JapanFinechem公司製造） 蘋果酸二醒肼（Japan Finechem公司製造） 酒石酸二酿肼（Japan Finechem公司製造） AmicureVDH — J (Ajinomoto Fine—Techno 公司製造） 間笨二甲酸二醯肼（大塚化學公司製造） 己二酸二醯肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價丨（於80°C硬化後通電） 面板顯示不均評價2 (於120°c硬化後通電） 接著強度評價1 (於80°c硬化後） 接著強度評價2 (於120°c硬化後） 25°C、50%RH、48 小時後 硬化性樹脂 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 其他 面板評價 4 ti: Μ 4 7 保存穩定性評價 熱自由基聚合起始劑 填充劑 熱硬化劑 ii 組成（重量份） 評價 201231488 【寸&lt;】 實施例 (N g 1 1 1 1 一 ΓΊ 1 1 1 1 一 〇 1 〇 00 1 1 1 1 1 1 〇 ◎ 〇 〇 〇 fS &lt;N 1 1 1 1 — (N 1 1 1 1 1 — 〇 1 P — 1 1 1 1 1 1 ◎ ◎ 〇 〇 〇 5 g 1 1 1 1 一 ίΝ 1 1 1 1 1 一 〇 1 v〇 〇 1 1 1 1 1 1 〇 〇 &lt;] 〇 〇 1 問笨二酚型璟氧丙烯酸酯（A) 雙酚A型環氧丙烯酸酯（B) 雙酚F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚A型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二笨醚型環氧樹脂（F) 1RGACURE651 ( BASF 公司製造） VPE—0201 (分子量約2萬）（和光純藥工業公司製造） VPE-0401 (分子量約3萬）（和光純藥工業公司製造） VPE-0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） Perhexyl 0(日油公司製造） KBM—403 (信越Silicone公司製造） SO—C2 (Admatechs 公司製造） 2MZA—PW (四國化成工業公司製造） 丙二酸二酿肼（Japan Finechem公司製造） 號拍酸二酿肼（Japan Finechem公司製造） 蘋果酸二酿肼（Japan Finechem公司製造） 酒石酸二酿耕（Japan Finechem公司製造） AmicureVDH — J (Ajinomoto Fine —Techno 公司製造） 間苯二甲酸二醯肼（大塚化學公司製造） 己二酸二醯肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價1 (於80°C硬化後通電） 面板顯示不均評價2 (於120°c硬化後通電） 接著強度評價丨（於80°C硬化後） 接著強度評價2 (於120°C硬化後） 25°C、50%RH、48 小時後 硬化性継 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 1 其他 面板評價 4 X 保存穩定性評價 熱自由基聚合起始劑 填充劑 熱硬化劑 ίί 組成（重量份） 評價It rises &quot;Ping ‘4 △’’ evaluates the situation of uneven color as “X”. (Following the strength evaluation 1) 曰 聚合物 聚合物 行星 行星 行星 行星 行星 行星 行星 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物 聚合物The parts are dispersed to make a uniform liquid, and a very small amount is taken into the central part of the alkali-free glass ("mm X50 mmx〇.7 mmt") with the IT 〇 electrode, on which the contract type glass is pressed and opened. The liquid crystal dropping method was irradiated with a metal halide lamp using a metal halide lamp for 2 〇〇 1 mW/cm of ultraviolet rays, and then heated at 8 ° C for 1 hour to obtain a test piece. The test piece was measured using a tensiometer. The subsequent strength (comparison unit is N/cm2). The case where the subsequent strength is 200 N/cm2 or more is evaluated as "〇", and the case where the temperature is 150 N/cm2 or more and less than 200 N/cm2 34 201231488 έ parity is " △", the case where the temperature is less than 150 N/cm2 is evaluated as "Γχ". (Following the strength evaluation 2) Polymer particles having an average particle diameter of 5 # m in the weight fraction of the sealant for liquid crystal dropping method obtained by the planetary mixing device (manufactured by Sekisui Chemical Co., Ltd., "MiCr0pearl SP") 3 parts by weight of the dispersion to make a uniform liquid, and a very small amount is taken into the central portion of the alkali-free glass (2〇mm x 50 mm×〇.7 mmt) with the IT0 electrode, on which the contract type glass is And the liquid crystal dropping method is used to seal the sealant, and the metal _ crystallization lamp is used to illuminate for 2 sec. Thereafter, it was heated in the 12th generation for i hours, thereby obtaining a test piece. The strength of the test piece was measured using a tensiometer (comparison unit is N//cm2). When the strength is 2〇〇ν/(^2 or more, it is evaluated as "〇"', and the case where 150N/W or more and less than 200 N8 m2 is evaluated as "△"' is not evaluated as 150N/cm2. It is "X". (Evaluation of storage stability) The obtained liquid crystal dropping method is stored in a temperature of 5 〇 % RH for 48 hours, and the viscosity is measured by an E-type viscometer. The formula calculates the increase rate from the viscosity before storage. Degree) the viscosity increase rate (%) = tear (viscosity after storage) / (the viscosity before storage is "〇", will be 120%, will be more than 130% In the case where the viscosity increase rate is less than 12%, the case is evaluated as "△" and the evaluation is "X". 35 201231488 [I &lt;] Example § - CN 〇 1 V〇〇◎ &lt;1 〇〇v〇§ 1 — (N — 〇1 v〇◎ ◎ 〇〇Ο § 1 — 〇1 〇〇〇〇Ο Tf g 1 (N 〇 1 1 〇〇〇〇〇 ΓΛ S 1 &lt;N - 〇1 VO 1 1 ◎ ◎ 〇〇〇(Ν g 1 f NJ 一〇1 1 1 1 ◎ ◎ 〇〇〇一§ 1 1 Ν Ν — 〇1 \0· 1 1 1 I 1 ◎ ◎ 笨 笨 二 二 phenolic epoxy acrylate (A) Bisphenol A type Epoxy acrylate (B) Double 酴F type epoxy acrylate (C) Partial acrylic modified bisphenol A type epoxy resin (D) Partial acrylic modified bisphenol E type epoxy resin (E) Partial acrylic acid modification Diphenyl ether type epoxy resin (F) IRGACURE651 (manufactured by BASF Corporation) VPE-0201 (molecular weight: approximately 20,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE—0401 (molecular weight: approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE—0601 (molecular weight: about 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS —0501 (molecular weight: approximately 40,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight: approximately 80,000) (manufactured by Wako Pure Chemical Industries, Ltd.) ) PerhexylO (manufactured by Nippon Oil Co., Ltd.) KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) SO-C2 (manufactured by Admatechs Co., Ltd.) 2MZA-PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Malonic acid, second brewed (made by Japan Finechem Co., Ltd.) Acid two farming (Japan Finechem Manufactured) Malic acid, second brewed (made by Japan Finechem), tartaric acid, kiwi (manufactured by Japan Hnechem Co., Ltd.) Amicure VDH — J (manufactured by Ajinomoto Fine-Techno), diammonium dicarboxylate (manufactured by Otsuka Chemical Co., Ltd.) Adipic acid Ershi (manufactured by Otsuka Chemical Co., Ltd.) Sebacate of azelaic acid (manufactured by Otsuka Chemical Co., Ltd.) Panel display unevenness evaluation 通电 (energized after hardening at 80 ° c) Panel display unevenness evaluation 2 (powered at 120 ° c hardening) ) 'Next strength evaluation 1 (after 80 ° C hardening) Next strength evaluation 2 (after hardening at 120 ° C) 25 ° C, 50% RH, 48 hours post-curing resin photoradical polymerization initiator polymer couple Nitrogen starter organic peroxide decane coupling agent cerium oxide hardening accelerator Compounds represented by the general formula (A) Evaluation of other panels Next strength evaluation Storage stability evaluation Thermal radical polymerization initiator Filler Thermal hardener composition (weight Part) Evaluation 201231488 [&lt;N&lt;] Example 1 1 1 1 - is 1 1 1 1 1 - 〇1 1 1 1 1 1 1 1 〇◎ &lt; 〇〇(N 1 1 S 1 1 — &lt;N 1 1 1 1 1 - 〇1 1 1 1 1 1 1 1 〇◎ &lt;] 〇〇1 ο 1 1 1 — CN 1 1 1 1 1 — 〇1 v〇1 1 1 1 1 1 1 ◎ ◎ 〇〇〇〇1 g 1 1宕1 — (N 1 1 1 t 1 〇 1 SO 1 1 1 1 1 1 1 ◎ ◎ 〇〇〇〇\ § 1 1 1 1 — «Ν 1 1 1 1 1 — 〇1 VO 1 1 1 1 1 1 1 ◎ ◎ 〇〇〇00 § 1 1 1 1 — 1 1 1 1 1 — 〇 VO 1 1 1 1 1 1 1 ◎ ◎ 〇〇〇 | 笨 二 二 环氧 epoxy acrylate (A) Bisphenolphthalein Epoxy acrylate (Β) Bisphenol F epoxy acrylate (C) Partial acrylic modified bisphenol A epoxy resin (D) Partial acrylic modified bisphenol E epoxy resin (E) Partial acrylic acid modification Ethylene diphenyl ether type epoxy resin (F) IRGACURE651 (manufactured by BASF Corporation) VPE—0201 (molecular weight: approximately 20,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE-0401 (molecular weight: approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE —0601 (molecular weight: about 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS —0501 (molecular weight: approximately 40,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight: approximately 80,000) (Wakako Pure Chemical Industries Co., Ltd.) system ) Perhexyl 0 (manufactured by Soybean Oil Co., Ltd.) KBM — 403 (manufactured by Shin-Etsu Silicone Co., Ltd.) SO — C2 (Admatechs) 2MZA—PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Dimethyl malonate (manufactured by Japan Finechem Co., Ltd.) Acidic glutinous rice (manufactured by Japan Finechem Co., Ltd.) Malic acid kiwi (manufactured by Japan Finechem Co., Ltd.) tartaric acid kiwi (manufactured by Japan Finechem Co., Ltd.) Amicure VDH_J (manufactured by Ajinomoto Fine-Techno Co., Ltd.) Manufactured by the company) Dibenzoate (manufactured by Otsuka Chemical Co., Ltd.) Sebacate of azelaic acid (manufactured by Otsuka Chemical Co., Ltd.) Panel display unevenness evaluation 通电 (energized after hardening at 80 ° C) Panel display unevenness evaluation 2 ( After 120°c hardening, the power is applied.) Then, the strength is evaluated 1 (after hardening at 80 °C). Then, the strength is evaluated 2 (after hardening at 120 °C). The photoradical polymerization of the curable resin starts at 25 ° C, 50% RH, and 48 hours. Starting agent, polymer azo initiator, organic peroxide, decane coupling agent, cerium oxide hardening accelerator, other panel evaluation of compound represented by general formula (A) Strength Evaluation Storage Stability Evaluation Thermal Radical Polymerization Starter Filler Thermal Hardener Composition (Parts by Weight) Evaluation 201231488 [£&lt;] Example gi 1 - 1 1 1 1 CN — 〇1 1 1 1 1 1 〇〇 &lt; 〇〇ο g 1 1 — 1 1 1 1 1 〇 1 1 1 η 1 1 1 〇〇&lt;] 〇〇οο g 1 1 - ΓΊ 1 1 1 1 1 — 〇1 1 ON 1 1 t 1 〇〇&lt; 〇〇卜g 1 1 1 1 1 1 1 1 — 〇1 1 00 1 1 1 1 1 〇〇&lt; 〇〇§ 1 1 - η 1 1 1 1 1 — 〇1 vq 1 ! 1 1 1 ◎ ◎ 〇〇〇〇〇1 1 — &lt;Ν 1 1 1 1 1 — 〇1 v〇1 ! 1 1 1 ! 〇◎ &lt; 〇〇§ Ο 1 1 1 — 1 1 1 1 1 — 〇1 So 1 1 1 1 1 1 ◎ ◎ 笨 笨 二 酚 phenol epoxy acrylate (A) Bisphenol oxime epoxy acrylate (Β) Bisphenol F epoxy acrylate (C) Partial acrylic acid modification Bisphenolphthalein type epoxy resin (D) Partially acrylic modified bisphenol E type epoxy resin (E) Partially acrylic modified diphenyl fluorene type epoxy resin (F) IRGACURE651 (BAS V manufactured by Company F) VPE—0201 (molecular weight: approximately 20,000) (manufactured by Wako Pure Chemical Industries, Ltd.) | VPE — 0401 (molecular weight approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE-0601 (molecular weight approximately 30,000) (and Manufactured by Wako Pure Chemical Industries, Ltd.) VPS —0501 (molecular weight: approximately 40,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight: approximately 80,000) (manufactured by Wako Pure Chemical Industries, Ltd.) Perhexyl 0 (manufactured by Oyster Oil Co., Ltd.) KBM — 403 (manufactured by Shin-Etsu Silicone Co., Ltd.) SO — C2 (manufactured by Admatechs) 2MZA—PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Malonic acid, second brewed (made by Japan Finechem), broken yoghurt (made by Japan Finechem), apple Acid awake (manufactured by Japan Finechem Co., Ltd.) tartaric acid kiwi (manufactured by Japan Finechem Co., Ltd.) Amicure VDH — J (manufactured by Ajinomoto Fine-Techno Co., Ltd.) bismuth dicarboxylate (manufactured by Otsuka Chemical Co., Ltd.) (Manufactured by Otsuka Chemical Co., Ltd.) Sebacate of azelaic acid (manufactured by Otsuka Chemical Co., Ltd.) Panel display unevenness evaluation 丨 (energized after hardening at 80 ° C) Uneven evaluation 2 (energized after hardening at 120 °C) Then strength evaluation 1 (after hardening at 80 °c) Then strength evaluation 2 (after hardening at 120 °c) 25 ° C, 50% RH, 48 hours post-curing Resin photoradical polymerization initiator, polymer azo initiator, organic peroxide, decane coupling agent, cerium oxide hardening accelerator, other panel evaluation of compound represented by general formula (A) 4 ti: Μ 4 7 Storage stability evaluation heat Free radical polymerization initiator filler thermosetting agent ii composition (parts by weight) evaluation 201231488 [inch &lt;] Example (N g 1 1 1 1 ΓΊ 1 1 1 1 〇 1 〇 00 1 1 1 1 1 1 〇◎ 〇〇〇fS &lt;N 1 1 1 1 — (N 1 1 1 1 1 - 〇1 P - 1 1 1 1 1 1 ◎ ◎ 〇〇〇5 g 1 1 1 1 1 Ν 1 1 1 1 1一〇1 v〇〇1 1 1 1 1 1 〇〇&lt;] 〇〇1 Asking stupid phenolic oxime acrylate (A) Bisphenol A epoxy acrylate (B) Bisphenol F epoxy acrylate Ester (C) Partially modified bisphenol A type epoxy resin (D) Partially modified bisphenol E type ring Oxygen resin (E) Partially modified acrylic diether ether type epoxy resin (F) 1RGACURE651 (manufactured by BASF Corporation) VPE—0201 (molecular weight: approximately 20,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE-0401 (molecular weight approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE-0601 (molecular weight: approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS — 0501 (molecular weight: approximately 40,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight approximately 8) Wan) (manufactured by Wako Pure Chemical Industries Co., Ltd.) Perhexyl 0 (manufactured by Nippon Oil Co., Ltd.) KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) SO-C2 (manufactured by Admatechs Co., Ltd.) 2MZA-PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Malonic acid II肼 肼 (made by Japan Finechem Co., Ltd.) 拍 二 二 肼 (made by Japan Finechem) malic acid 肼 肼 (made by Japan Finechem) tartaric acid arable (made by Japan Finechem) AmicureVDH — J (Ajinomoto Fine — Techno Manufacture) Diisophthalic acid dioxime (manufactured by Otsuka Chemical Co., Ltd.) Dioxane dipic acid (manufactured by Otsuka Chemical Co., Ltd.) Sebacate adipic acid (Otsuka Chemical Co., Ltd.) Manufacture) Panel display unevenness evaluation 1 (energized after hardening at 80 °C) Panel display unevenness evaluation 2 (energized after hardening at 120 °C) Then strength evaluation 丨 (after hardening at 80 °C) Then strength evaluation 2 (in After curing at 120 ° C) After 25 ° C, 50% RH, 48 hours, hardenable photopolymerization initiator, polymer azo initiator, organic peroxide, decane coupling agent, cerium oxide hardening accelerator, A) Compound 1 indicated Other panel evaluation 4 X Storage stability evaluation Thermal radical polymerization initiator Filler Thermal hardener ίί Composition (parts by weight) Evaluation

6C 201231488 【二】 比較例 § 1 一 &lt;N 一 〇 1 1 1 1 〇〇 (N X 〇 X 〇 〇 ΡΛ 1 一 1 1 — 〇 1 1 1 (N X 〇 X 〇 &lt; fN g 1 1 1 — 1 1 - 〇 I 1 1 CM X 〇 X 0 X — § 1 1 t — CM 1 1 — 〇 t 1 00 cn 1 ◎ ◎ &lt;1 X 間笨二酚型環氧丙烯酸酯（A) 雙酚A型環氧丙烯酸酯（B) 雙酚F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚A型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二笨醚型環氧樹脂（F) IRGACURE651 ( BASF 公司製造） VPE-0201 (分子量約2萬）（和光純藥工業公司製造） VPE —0401 (分子量約3萬）（和光純藥工業公司製造） VPE—0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） Perhexy丨Ο (曰油公司製造） KBM —403 (信越Silicone公司製造） SO—C2 (Admatechs 公司製造） 2MZA—PW (四國化成工業公司製造） 丙二酸二酿耕（Japan Finechem公司製造） 破ίά酸二臨耕（JapanFinechem公司製造） 蘋果酸二酿拼（Japan Finechem公司製造） 酒石酸二醯耕（Japan Hnechem公司製造） Amicure VDH — J ( Ajinomoto F&quot;ine—Techno 公司製造） 間笨二甲酸二醯肼（大塚化學公司製造） 己二酸二醖肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價丨（於80°c硬化後通電） 面板顯示不均評價2 (於120°C硬化後通電） 接著強度評價1 (於80°c硬化後） 接著強度評價2 (於120ΐ硬化後） 25°C、50%RH、48 小時後 硬化性樹脂 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 其他 面板評價 接著強度評價 保存穩定性評價 熱自由基聚合起始劑 填充劑 熱硬化劑 組成（重量份） 評價 201231488 【9&lt;】 1參考例1 — g 1 1 1 — ίΝ t — 〇 (N 1 1 1 1 1 1 ◎ ◎ 〇 〇 X 比較例 00 g 1 1 1 — ίΝ 1 1 1 — 〇 (N 1 1 1 t 1 1 1 00 (Ν 〇 ◎ 〇 〇 X 卜 g 1 1 1 — 1 1 1 1 — 〇 (N 1 1 1 1 1 1 &lt;Ν 〇 ◎ 〇 〇 X § 1 1 1 — CN 1 1 1 一 〇 (N 1 1 1 1 [ τΤ (Ν 1 〇 ◎ &lt; &lt;3 X § 1 1 1 一 (N 1 t — 〇 1 1 1 t 00 rn 1 1 ◎ ◎ &lt;] &lt; X 間笨二酚型環氧丙烯酸酯（A) 雙酚A型環氧丙烯酸65 (13) 雙酚F型環氧丙烯酸酯（C) 部分丙烯酸改質雙酚A型環氧樹脂（D) 部分丙烯酸改質雙酚E型環氧樹脂（E) 部分丙烯酸改質二笨醚型環氧樹脂（F) 1RGACURE651 (BASF 公司製造） VPE—0201 (分子量約2萬）（和光純藥工業公司製造） VPE—〇4〇1 (分子量約3萬）（和光純藥工業公司製造） VPE-0601 (分子量約3萬）（和光純藥工業公司製造） VPS —0501 (分子量約4萬）（和光純藥工業公司製造） VPS—1001 (分子量約8萬）（和光純藥工業公司製造） Perhexy丨0 (曰油公司製造） KBM —403 (信越Silicone公司製造） SO —C2 (Admatechs 公司製造） 2MZA—PW (四國化成工業公司製造） 丙二酸二酿肼（Japan Finechem公司製造） 號拍酸二酿肼（Japan Finechem公司製造） 蘋果酸二酿肼（Japan Finechem公司製造） 酒石酸二酿肼（Japan Finechem公司製造） Amicure VDH—J ( Ajinomoto Fine—Techno 公司製造） 間苯二甲酸二醯肼（大塚化學公司製造） 己二酸二醯肼（大塚化學公司製造） 癸二酸二醯肼（大塚化學公司製造） 面板顯示不均評價1 (於80°C硬化後通電） 面板顯示不均評價2 (於120°C硬化後通電） 接著強度評價1 (於80°C硬化後） 接著強度評價2 (於120°C硬化後） 25°C、50%RH、48 小時後 1 硬化性樹脂 光自由基聚合起始劑 高分子偶氮起始劑 有機過氧化物 矽烷偶合劑 填充劑 二氧化矽 硬化促進劑 通式（A)表示之化合物 I 其他 面板評價 接著強度評價 保存穩定性評價 熱自由基聚合起始劑 熱硬化劑 組成（重量份） 評價 201231488 [產業上之可利用性] 起液：據Γ明，可提供一種保存穩定性優異、幾乎不引 下法^、且於80c左右之低溫即可充分硬化之液晶滴 用密封劑。又，根據本發明，可提供一種使用該液晶 滴下法田^ 用畨封劑而製造之上下導通材料及液晶顯示元件。 【圖式簡單說明】 無 【主要元件符號說明】 無 426C 201231488 [2] Comparative example § 1 1 &lt;N 〇 1 1 1 1 〇〇 (NX 〇X 〇〇ΡΛ 1 1-1 1 - 〇1 1 1 (NX 〇X 〇&lt; fN g 1 1 1 — 1 1 - 〇I 1 1 CM X 〇X 0 X — § 1 1 t — CM 1 1 — 〇t 1 00 cn 1 ◎ ◎ &lt;1 X styrene-based epoxy acrylate (A) Bisphenol A Epoxy acrylate (B) Bisphenol F epoxy acrylate (C) Partial acrylic modified bisphenol A epoxy resin (D) Partial acrylic modified bisphenol E epoxy resin (E) Partial acrylic acid modification Isopropyl ether epoxy resin (F) IRGACURE651 (manufactured by BASF Corporation) VPE-0201 (molecular weight: approximately 20,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE — 0401 (molecular weight: approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE—0601 (molecular weight: about 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS — 0501 (molecular weight: approximately 40,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight: approximately 80,000) (Wakako Pure Chemical Industries Co., Ltd.) Manufacturing) Perhexy丨Ο (manufactured by Oyster Company) KBM — 403 (Shin-Etsu Silicone造) SO-C2 (manufactured by Admatechs) 2MZA-PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Malonic acid two brewing (manufactured by Japan Finechem Co., Ltd.) ά ά 二 临 ( ( (made by Japan Finechem Co., Ltd.) Made by Japan Finechem Co., Ltd.) Aminoure VDH — J (Ajinomoto F&quot; manufactured by Ajinomoto F&quot; Manufactured by a chemical company) Azelaic acid diterpene (manufactured by Otsuka Chemical Co., Ltd.) Panel display unevenness evaluation 丨 (energized after hardening at 80 ° C) Panel display unevenness evaluation 2 (energized after hardening at 120 ° C) Then strength evaluation 1 (after hardening at 80 ° C) Next strength evaluation 2 (after 120 ΐ hardening) 25 ° C, 50% RH, 48 hours post-curing resin photoradical polymerization starter polymer azo initiator organic peroxide Decane coupling agent cerium oxide hardening accelerator Compounds represented by the general formula (A) Evaluation of other panels Next strength evaluation Storage stability evaluation Thermal radical polymerization initiator filler Composition of heat hardener (parts by weight) Evaluation 201231488 [9&lt;] 1 Reference Example 1 - g 1 1 1 - Ν t - 〇 (N 1 1 1 1 1 1 ◎ ◎ 〇〇 X Comparative Example 00 g 1 1 1 - Ν 1 1 1 — 〇 (N 1 1 1 t 1 1 1 00 (Ν 〇 ◎ 〇〇 X 卜 g 1 1 1 — 1 1 1 1 — 〇 (N 1 1 1 1 1 1 &lt;Ν 〇◎ 〇〇X § 1 1 1 — CN 1 1 1 一〇(N 1 1 1 1 [ τΤ (Ν 1 〇 ◎ &lt;&lt;3 X § 1 1 1 1 (N 1 t — 〇1 1 1 t 00 rn 1 1 ◎ ◎ &lt;] &lt; X between stupid phenolic epoxy acrylate (A) Bisphenol A epoxy acrylate 65 (13) Bisphenol F epoxy acrylate (C) Partial acrylic modified bisphenol A ring Oxygen resin (D) Partially modified acrylic bisphenol E type epoxy resin (E) Partially modified acrylic diether ether type epoxy resin (F) 1RGACURE651 (manufactured by BASF Corporation) VPE—0201 (molecular weight approximately 20,000) (and Manufactured by Wako Pure Chemical Industries, Ltd.) VPE—〇4〇1 (molecular weight: approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPE-0601 (molecular weight approximately 30,000) (manufactured by Wako Pure Chemical Industries, Ltd.) VPS — 0501 (molecular weight approximately 4 (manufactured by Wako Pure Chemical Industries, Ltd.) VPS—1001 (molecular weight: approximately 80,000) (manufactured by Wako Pure Chemical Industries, Ltd.) Perhexy丨0 (manufactured by Soybean Oil Co., Ltd.) KBM — 403 (manufactured by Shin-Etsu Silicone) SO-C2 (Admatechs Manufactured) 2MZA-PW (manufactured by Shikoku Chemical Industry Co., Ltd.) Malonic acid kiwi (manufactured by Japan Finechem Co., Ltd.) 拍 二 二 肼 (made by Japan Finechem) Malic acid yoghurt (made by Japan Finechem) tartaric acid肼 肼 (made by Japan Finechem) Amicure VDH—J (manufactured by Ajinomoto Fine-Techno Co., Ltd.) Isophthalic acid dioxime (manufactured by Otsuka Chemical Co., Ltd.) Adipic acid dioxime (manufactured by Otsuka Chemical Co., Ltd.) Sebacate肼 (manufactured by Otsuka Chemical Co., Ltd.) Panel display unevenness evaluation 1 (energized after hardening at 80 °C) Panel display unevenness evaluation 2 (energized after hardening at 120 °C) Then strength evaluation 1 (after hardening at 80 °C) Strength evaluation 2 (after hardening at 120 °C) 25 ° C, 50% RH, 48 hours 1 Curing resin photoradical polymerization initiator, polymer azo initiator, organic peroxide 矽Alkane coupling agent filler cerium oxide hardening accelerator Compound I represented by the general formula (A) Evaluation of other panels Next strength evaluation Storage stability evaluation Thermal radical polymerization initiator Thermal curing agent composition (parts by weight) Evaluation 201231488 [Industrial UTILITY: According to the stipulation, it is possible to provide a liquid crystal sealing agent which is excellent in storage stability, hardly leads to a method, and can be sufficiently cured at a low temperature of about 80 c. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element by using the liquid crystal dropping method. [Simple diagram description] None [Main component symbol description] None 42

Claims (1)

201231488 • 七、申請專利範圍： 1. 一種液晶滴下法用密封劑’含有硬化性樹脂、熱自由 基聚合起始劑、及由下述通式（A)表示之化合物構成的熱 硬化劑， 0 0 H2NHN-C-X-C-NHNH2 (A) 通式（A )中，X 表示 CH2、CH ( OH ) 、（：（ OH ) 2、 C2H4 &gt; CH2CH ( OH) &gt; CH2C ( OH) 2 ' C ( OH) c ( 〇h) CH2CO、COCO、NH中之任一者表示的結構。 2. 如申請專利範圍第1項之液晶滴下法用密封劑，其 中，通式（A)表示之化合物為丙二酸二醯肼 dihydrazide) ° 3. 如申請專利範圍第1或2項之液晶滴下法用密封劑， 其中，硬化性樹脂含有4〇重量％以上之下述式（1 )表示的 樹脂及/或下述式（2 )表示的樹脂， QH3 ·/=&gt; OH q 〇-CH2-CH-CH2-〇-i-cn=CH， CH2=CH-C-〇-CH2CH-CH2〇201231488 • VII. Patent application scope: 1. A liquid crystal dropping method sealant 'containing a curable resin, a thermal radical polymerization initiator, and a thermosetting agent composed of a compound represented by the following formula (A), 0 0 H2NHN-CXC-NHNH2 (A) In the formula (A), X represents CH2, CH(OH), (:(OH)2, C2H4&gt; CH2CH(OH) &gt; CH2C(OH) 2' C (OH c ( 〇h) The structure represented by any one of CH2CO, COCO, and NH. 2. The sealing agent for liquid crystal dropping method according to Item 1 of the patent application, wherein the compound represented by the formula (A) is C 3. The liquid crystal dropping method sealant according to the first or second aspect of the invention, wherein the curable resin contains 4% by weight or more of the resin represented by the following formula (1) and/or The resin represented by the following formula (2), QH3 ·/=&gt; OH q 〇-CH2-CH-CH2-〇-i-cn=CH, CH2=CH-C-〇-CH2CH-CH2〇 (1)(1) (2) 4.如申請專利範圍第丨、2哎3頂 次j貝之液晶滴下法用密封 劑’其中’熱自由基聚合起始劑係數量 Ί尔双里十均分子量為5〇〇〇 〜10萬之高分子偶氮化合物。 5 ·如申請專利範圍第4項 貝之欣日日滴下法用密封劑，其 43 201231488 中，高分子偶氮化合物具有聚二曱基矽氧烷單元或聚烯化 氧(polyalkylene oxide )單元 0 6. —種上下導通材料，含有申請專利範圍第1、2、3、 4或5項之液晶滴下法用密封劑與導電性微粒子。 7. —種液晶顯示元件，係使用申請專利範圍第1、2、3、 4或5項之液晶滴下法用密封劑及/或申請專利範圍第6項 之上下導通材料而成。 八、圖式. 無 44(2) 4. If the application scope is 丨, 2哎3 top j, the liquid crystal dropping method sealant 'where 'thermal radical polymerization initiator coefficient Ί尔双里十均分子量为5〇〇〇 ~100,000 polymer azo compounds. 5 · If the patent application scope item 4 is the shell-opening method, the polymer azo compound has a polydidecyloxane unit or a polyalkylene oxide unit. 6. A top-bottom conductive material comprising a sealant for liquid crystal dropping method and conductive fine particles of the first, second, third, fourth or fifth aspect of the patent application. 7. A liquid crystal display element obtained by using a liquid crystal dropping method sealing agent of the first, second, third, fourth or fifthth aspect of the patent application and/or a material for conducting the upper and lower parts of the patent application. Eight, schema. None 44
TW100144332A 2010-12-09 2011-12-02 Liquid crystal drop method sealant, upper and lower conductive material, and liquid crystal display element TWI398460B (en)

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Cited By (1)

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Families Citing this family (9)

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JP5395872B2 (en) * 2011-10-20 2014-01-22 積水化学工業株式会社 Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element
JP2014006324A (en) * 2012-06-22 2014-01-16 Nippon Kayaku Co Ltd Liquid crystal sealing agent and liquid crystal display cell using the same
JP5827752B2 (en) * 2013-06-11 2015-12-02 積水化学工業株式会社 Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element
JP6238850B2 (en) * 2014-07-17 2017-11-29 日本化薬株式会社 Liquid crystal sealant and liquid crystal display cell using the same
JP6588825B2 (en) * 2014-08-07 2019-10-09 積水化学工業株式会社 Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element
JP6730133B2 (en) * 2015-09-02 2020-07-29 積水化学工業株式会社 Liquid crystal display element sealant, vertical conduction material and liquid crystal display element
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WO2017195624A1 (en) * 2016-05-13 2017-11-16 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
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KR101369022B1 (en) * 2006-03-29 2014-02-28 세키스이가가쿠 고교가부시키가이샤 Sealing material for liquid-crystal dropping process, vertical-conduction material, and liquid-crystal display element
JP4974344B2 (en) * 2006-06-19 2012-07-11 日本化薬株式会社 Liquid crystal sealant and liquid crystal display cell using the same
WO2008139736A1 (en) * 2007-05-14 2008-11-20 Mitsui Chemicals, Inc. Liquid crystal panel mounting substrate, and method for producing the same
KR101194202B1 (en) * 2008-04-18 2012-10-25 세키스이가가쿠 고교가부시키가이샤 Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element

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