TW200831541A - Sealant for liquid crystal display device and liquid crystal display device - Google Patents
Sealant for liquid crystal display device and liquid crystal display device Download PDFInfo
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- TW200831541A TW200831541A TW096149359A TW96149359A TW200831541A TW 200831541 A TW200831541 A TW 200831541A TW 096149359 A TW096149359 A TW 096149359A TW 96149359 A TW96149359 A TW 96149359A TW 200831541 A TW200831541 A TW 200831541A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic groups
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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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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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
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
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- 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
- G02F1/1341—Filling or closing of cells
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
Abstract
Description
200831541 九、發明說明 【發明所屬之技術領域】 本發明係關於放射線硬化性樹脂組成物。詳而言之， 係關於適用於液晶顯示元件用封閉劑之放射線硬化性樹脂 組成物及使用其之液晶顯示元件。 【先前技術】 φ 液晶顯示胞等液晶顯示元件，係於相隔既定間隔而相 對向之兩片附電極之透明基板之間，封入液晶所形成者。 以往，於製造液晶顯示胞之際，首先於兩片附電極之透明 基板之一者，藉由網版印刷，使用熱硬化性封閉劑，於封 入液晶之範圍的外圍，形成設置有液晶注入口之圖型。接 著，夾著間隔物使另一透明基板相對向而進行對準以將兩 片基板貼合，加熱使封閉劑硬化。接著，由液晶注入口注 入液晶後，將液晶注入口以封口劑密封。如此之方法，一 • 般係稱爲液晶注入方式。 液晶注入方式，有步驟多、製造效率低、因熱應變造 _ 成基板位置偏移、間隔的偏差、封閉劑與基板之密合性不 充分等問題。 作爲解決液晶注入方式之問題點的手段，現今係提出 稱爲液晶滴下方式之方法，而於液晶封閉劑之硬化係以光 熱硬化倂用法爲主流。該液晶滴下方式，首先，於兩片之 附電極之透明基板之一，藉由網版印刷，以液晶封閉劑， 於封入液晶之範圍的外圍形成長方形的框。此時，不設置 -5- 200831541 液晶注入口。接著，於封閉劑未硬化的狀態下’將液晶滴 下塗布至該框內整面’並立即將另一透明基板疊合壓接’ 對液晶封閉劑部分照射紫外線使其預硬化。之後，於液晶 退火時加熱再使封閉劑硬化以製造液晶胞者。 液晶滴下方式，步驟少可有效率地製造液晶胞，亦適 於大型面板的製造。又，由於以紫外線進行預硬化，故可 防止因熱應變所造成之基板位置偏移，提昇封閉劑與基板 ^ 之密合性。 然而，於液晶滴下方式，有未硬化狀態之液晶封閉劑 與液晶接觸的階段，故液晶封閉劑的成分會溶解至液晶而 污染液晶，使液晶之比電阻降低而產生不良情形，是其問 題（專利文獻1 )。 以減低因未硬化之液晶封閉劑成分對液晶之污染、提 昇硬化性等目的，配合各種成分之硬化性組成物被提出（ 例如，專利文獻2〜7 )。 # 然而，近年來，要求液晶顯示元件之狹額緣化，由於 狹額緣化，液晶封閉劑與黑矩陣或配線等重疊的情形增多 . 。於該部分，由於未以紫外線照射液晶封閉劑，故封閉劑 殘留有未硬化之部分，由於其與液晶接觸而使液晶封閉劑 成分溶出，而產生液晶被污染之問題。 專利文獻1 :日本特開2001-133794號公報 專利文獻2:日本特開2004-37937號公報 專利文獻3 :日本特開2003-28004號公報 專利文獻4 :日本特開2005-263 987號公報 -6 - 200831541 專利文獻5:日本特開2005-6065ι號公報 專利文獻6 :日本特開2006-3048 ι號公報 專利文獻7 :日本特開2 0 0 6 - 5 8 4 6 6號公報 【發明內容】 本發明係有鑑於上述問題所完成者，其目的在於提供 一種硬化性樹脂組成物，其對液晶可減低污染性，即使因 φ 配線等而成爲陰影的部分，亦可得充分之硬化性，可因應 狹額緣化。 爲了達成上述目的，本發明人等努力硏究的結果發現 ，藉由於（甲基）丙烯酸單體、局部丙烯酸化環氧樹脂、 潛在型環氧硬化劑、無機微粒子、矽烷耦合劑，使用具有 肟酯構造之高感度之光自由基起始劑，可得對液晶之污染 性低、且即使因配線等而成爲陰影的部分亦顯示良好硬化 性之硬化性樹脂組成物，而完成本發明。 φ 亦即，本發明，係提供下述之硬化性樹脂組成物、其 所構成之液晶封閉劑、及使用其之液晶顯示元件。 1 · 一種硬化性組成物，其係含有下述成分（A )〜 (D)： ^ (A)具有乙烯性不飽合基之化合物、 (B) 局部（甲基）丙烯酸化之環氧樹脂、 (C) 環氧硬化劑、 (D) 具有肟酯構造之光自由基聚合起始劑。[Technical Field] The present invention relates to a radiation curable resin composition. More specifically, it relates to a radiation curable resin composition suitable for a blocking agent for a liquid crystal display element and a liquid crystal display element using the same. [Prior Art] A liquid crystal display element such as a liquid crystal display cell is formed by encapsulating a liquid crystal between two transparent substrates which are opposed to each other at a predetermined interval. Conventionally, in the production of a liquid crystal display cell, a liquid crystal injection port is formed on the periphery of a range in which a liquid crystal is sealed by screen printing using a thermosetting sealing agent in one of two transparent substrates with electrodes. The pattern. Next, the other transparent substrate is aligned with the spacer interposed therebetween to bond the two substrates, and heating causes the blocking agent to harden. Next, after the liquid crystal was injected from the liquid crystal injection port, the liquid crystal injection port was sealed with a sealing agent. Such a method is generally referred to as a liquid crystal injection method. The liquid crystal injection method has many problems such as a large number of steps, low manufacturing efficiency, misalignment of the substrate due to thermal strain, variation in the interval, and insufficient adhesion between the blocking agent and the substrate. As a means for solving the problem of the liquid crystal injection method, a method called a liquid crystal dropping method has been proposed, and a curing method of a liquid crystal blocking agent is mainly used for photothermal curing. In the liquid crystal dropping method, first, a rectangular frame is formed on one of the transparent substrates of the two electrodes by screen printing, and a liquid crystal blocking agent is formed on the periphery of the range in which the liquid crystal is sealed. At this time, the -5-200831541 liquid crystal injection port is not set. Next, the liquid crystal is dropped onto the entire surface of the frame in a state where the blocking agent is not cured, and the other transparent substrate is immediately laminated and pressure-bonded. Thereafter, it is heated during the annealing of the liquid crystal to harden the blocking agent to produce a liquid crystal cell. The liquid crystal dropping method can produce liquid crystal cells with less efficiency, and is also suitable for the manufacture of large panels. Further, since the pre-curing is performed by ultraviolet rays, the positional deviation of the substrate due to thermal strain can be prevented, and the adhesion between the blocking agent and the substrate can be improved. However, in the liquid crystal dropping method, there is a stage in which the liquid crystal blocking agent in an uncured state is in contact with the liquid crystal, so that the components of the liquid crystal blocking agent are dissolved in the liquid crystal to contaminate the liquid crystal, and the specific resistance of the liquid crystal is lowered to cause a problem, which is a problem ( Patent Document 1). A curable composition containing various components is proposed for the purpose of reducing the contamination of the liquid crystal by the uncured liquid crystal blocking agent component, and improving the curability (for example, Patent Documents 2 to 7). # However, in recent years, there has been a demand for a narrow marginalization of a liquid crystal display element, and a situation in which a liquid crystal blocking agent overlaps with a black matrix or wiring is increased due to a narrow marginalization. In this portion, since the liquid crystal blocking agent is not irradiated with ultraviolet rays, the uncured portion remains in the blocking agent, and the liquid crystal blocking agent component is eluted due to contact with the liquid crystal, thereby causing a problem that the liquid crystal is contaminated. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2004-03737 (Patent Document No. JP-A-2003-37937) 6 - 200831541 Patent Document 5: Japanese Laid-Open Patent Publication No. 2005-6065 No. Patent Document 6: JP-A-2006-3048 PCT Patent Publication No. JP-A No. 2000-58 No. The present invention has been made in view of the above problems, and an object of the present invention is to provide a curable resin composition which can reduce contamination to a liquid crystal, and can be sufficiently cured even if it is shaded by φ wiring or the like. Can be used in response to narrow margins. In order to achieve the above object, the inventors of the present invention have found that the use of a (meth)acrylic monomer, a partially acrylated epoxy resin, a latent epoxy hardener, inorganic fine particles, and a decane coupling agent has been used. The high-sensitivity photo-radical initiator of the ester structure is a curable resin composition which exhibits low curability to liquid crystals and exhibits good curability even in a portion which is shaded by wiring or the like, and has completed the present invention. In other words, the present invention provides a curable resin composition described below, a liquid crystal blocking agent comprising the same, and a liquid crystal display element using the same. 1 . A curable composition comprising the following components (A) to (D): ^ (A) a compound having an ethylenic unsaturated group, and (B) a partially (meth)acrylated epoxy resin (C) an epoxy hardener, (D) a photoradical polymerization initiator having an oxime ester structure.
2.如上述1所記載之硬化性組成物，其中，該（D -7- 200831541 )具有肟酯構造之光自由基聚合起始劑，係以下述通式（ d-1 )表示， 【化2】2. The curable composition according to the above 1, wherein the (D -7-200831541) photoinitiator having an oxime ester structure is represented by the following formula (d-1); 2】
(式中，R1表示氫原子、苯基、碳數1〜1 0之烷基，R2 表示氫原子、苯基、碳數1〜1 〇之烷基，R3表示取代或 非取代之咔唑基、或Ph-S-Ph-CO-基（Ph表示苯基））。 3. 如上述1或2所記載之硬化性組成物，其中，該 (A )具有乙烯性不飽合基之化合物，係具有1個以上之. (甲基）丙烯醯基之化合物。 4. 如上述1〜3中任一項所記載之硬化性組成物，其 中，該（B )局部（甲基）丙烯酸化之環氧樹脂，係對1 分子中至少具有2個以上環氧基之環氧樹脂，使對該環氧 樹脂之環氧基爲30〜80%當量之（甲基）丙烯酸進行酯 化反應所製得。 5·如上述1〜4中任一項所記載之硬化性樹脂組成物_ ’其進一步含有（F)無機微粒子。 6.如上述1〜5中任一項所記載之硬化性樹脂組成物 ，其進一步含有（G )矽烷耦合劑。 7· —種液晶封閉劑，其特徵係，由上述1〜6中任一 200831541 項所記載之硬化性樹脂組成物所構成。 8 · —種液晶顯示元件，其特徵係，使用上述7所記 載之液晶封閉劑所製造。 藉由本發明，可提供一種硬化性樹脂組成物，其對液 晶之污染性低、且即使因配線等而成爲陰影的部分亦顯示 良好硬化性。 藉由本發明，可提供一種液晶封閉劑，其特別適用於 φ 以液晶滴下方法製造液晶顯示元件之際。 藉由本發明，可提供一種液晶顯示元件，其因未硬化 之液晶封閉劑所致之液晶之污染性減低、長期安定性優異 【實施方式】 Ϊ ·硬化性樹脂組成物 本發明之硬化性樹脂組成物（以下，稱爲本發明之組 成物），可包含下述成分（A)〜（H)。下述成分之中 ’ （A )〜（D )爲必需成分，（E )〜（Η )爲視需要配 合之任意成分。 (A) 具有乙烯性不飽合基之化合物、 (B) 局部（甲基）丙烯酸化之環氧樹脂、 (C) 環氧硬化劑、 (D) 具有肟酯構造之光自由基聚合起始劑、 (E )反應性（甲基）丙烯酸聚合物、 (F )無機微粒子、 -9- 200831541 (G)矽烷耦合劑、 (Η )添加劑。 本發明之硬化性樹脂組成物，藉由使用高感度之（D )光自由基聚合起始劑（具有肟酯構造之光自由基聚合起 始劑），即使因配線或黑矩陣使紫外線無法直接照射之遮 蔽部位之弱紫外線散射光，亦可促進（甲基）丙烯醯基之 交聯反應，而可賦予高耐液晶污染性。此處，所謂「高感 φ 度」’係指紫外線之吸光係數大、即使微弱之光亦可產生 自由基之意。 1 ·以下，說明各成分。 (A)具有乙烯性不飽合基之化合物 具有乙烯性不飽合基之化合物，係自由基.聚合成分， 可發揮提昇強度、低線膨脹係數化、及提昇位置安定性等 之效果。乙烯性不飽合基，並無特別限定，可舉例如（甲 # 基）丙烯醯基、乙烯基等，而以（甲基）丙烯醯基較佳。 具有（甲基）丙烯醯基之化合物，可舉例如丙烯酸2 、 一經乙酯、（甲基）丙烯酸2—羥丙酯、（甲基）丙烯酸 4一羥丁酯、（甲基）丙烯酸2—羥丁酯、（甲基）丙烯 酸異丁酯、（甲基）丙烯酸三級丁酯、（甲基）丙烯酸異 辛酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸硬脂醯酯 '(甲基）丙烯酸異冰片酯、（甲基）丙烯酸環己酯、（ 甲基）丙烯酸2—甲氧基乙酯、（甲基）丙烯酸甲氧基乙 二醇酯、（甲基）丙烯酸2 —乙氧基乙酯、（甲基）丙烯 -10- 200831541 酸四氫呋喃酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸乙 基卡必醇酯、（甲基）丙烯酸苯氧基乙酯、（甲基） 酸苯氧基二乙二醇酯、（甲基）丙烯酸苯氧基聚^ 、（甲基）丙烯酸甲氧基聚乙二醇酯、（甲基） 2,2,2—三氟乙酯、（甲基）丙烯酸2,2,3,3〜四氣@ (甲基）丙烯酸1H，1H，5H—八氟戊酯、（甲基 〜醇酯 芮烯酸 酯、 丙燦酸 (甲基）丙烯酸甲酯、（甲基）丙烯酸 φ 甲基）丙烯酸正丁酯、（甲基）丙烯酸丙酯 烯酸正丁酯、（甲基）丙烯酸環己酯、 亞胺酯 申基 (甲基）丙 一乙基己酯、（甲基）丙烯酸正辛酯、（甲基 壬酯、（甲基）丙烯酸異十四烷酯、（甲基 丁氧基乙酯、（甲基）丙烯酸2 —苯氧基乙酯、 烯酸2 骞 2 申基 丙烯酸二環戊烯酯、（甲基）丙烯酸異癸酯、 赛）柯 烯酸二乙基胺基乙酯、（甲基）丙烯酸二甲基胺| > 乙酷、 琥珀酸2—(甲基）丙烯醯氧基乙酯、六氫苯二甲_ 2 (甲基）丙烯醯氧基乙酯、2-羥基丙基苯二甲g 甲基）丙烯醯氧基乙酯、（甲基）丙烯酸環氧丙_、 2 2—（甲基）丙烯醯氧基乙酯、二（甲基）丙烯酸l4 二醇酯、二（甲基）丙烯酸1，3—丁二醇酯、二 丙烯酸1，6—己二醇酯、二（甲基）丙烯酸1， 鱗酸 (甲基 醇 酯、二（甲基）丙烯酸1，10—癸二醇酯、二（甲篡A > 避）两烯 酸2 —正丁基一 2 —乙基一 1，3_丙二醇酯、二（_甘、 π戔）芮 烯酸二丙二醇酯、二（甲基）丙烯酸三丙二醇酯、 I甲基 )丙烯酸聚丙二醇酯、二（甲基）丙烯酸乙二醇_、 -11 - 200831541 甲基）丙烯酸二乙二醇酯、二（甲基）丙烯酸 、二（甲基）丙烯酸聚乙二醇酯、環氧丙烷: 二（甲基）丙烯酸酯、環氧乙烷加成雙酚A 丙烯酸酯、環氧乙烷加成雙酚F二（甲基）丙 (甲基）丙烯酸二羥氧基二環戊二烯酯、二（ 酸1，3—丁二醇酯、二（甲基）丙烯酸新戊二 乙烷變性三聚異氰酸二（甲基）丙烯酸酯、（ φ 酸2 -羥基一 3—(甲基）丙烯醯氧基丙酯、 丙烯酸碳酸酯二醇酯、二（甲基）丙烯酸聚醚 (甲基）丙烯酸聚酯二醇酯、二（甲基）丙烯 二醇酯、二（甲基）丙烯酸聚丁二烯二醇酯、 丙烯酸新戊四醇酯、三（甲基）丙烯酸三羥甲 氧丙烷加成三（甲基）丙烯酸三羥甲基丙酯、 成三（甲基）丙烯酸三羥甲基丙酯、己內酯變 )丙烯酸三羥甲基丙酯、環氧乙烷加成三聚異 φ 基）丙烯酸酯、五（甲基）丙烯酸二新戊四醇 基）丙烯酸二新戊四醇酯、四（甲基）丙烯酸 _ 丙酯、四（甲基）丙烯酸新戊四醇酯、三（甲 甘油酯、環氧丙烷加成三（甲基）丙烯酸甘油 (甲基）丙烯醯氧基乙酯等。 如此之具有（甲基）丙烯醯基之化合物之 舉例如VR-77LC (昭和高分子（股）公司製 (戴協魯塞鐵克（股）公司製）等。 本發明之組成物中之成分（A )之配合量 四乙二醇酯 加成雙酚A 二（甲基） 烯酸酯、二 甲基）丙烯 醇酯、環氧 甲基）丙烯 二（甲基） 二醇酯、二 酸聚己內酯 三（甲基） 基丙酯、環 環氧乙烷加 性三（甲基 氰酸三（甲 酯、六（甲 二三羥甲基 基）丙烯酸 酯、磷酸三 市售品，可 )、EB3700 ，當組成物 -12- 200831541 之固體成分爲100重量％時，爲〇·1〜90重量％、較佳爲 1〜8 0重量％、更佳爲5〜6 0重量％。成分（A )之配合 量若脫離上述0.1〜90重量％之範圍，則照設紫外線時， 無法得到適度之硬度而有容易因熱引起位置偏移之可能性 (B )局部（甲基）丙烯酸化之環氧樹脂 局部（甲基）丙烯酸化之環氧樹脂，係對於1分子中 至少具有2個以上環氧基之環氧樹脂，使（甲基）丙嫌酸 進行酯化反應所得之局部酯化（甲基）丙烯酸環氧酯樹脂 或局部酯化（甲基）丙烯酸環氧酯樹脂。 局部（甲基）丙烯酸化環氧樹脂，具有經光照射而產 生自由基聚合所得到之丙烯酸基，其經由紫外線照射而與 其他自由基聚合成份進行交聯反應，其可使於其後加熱時 未硬化之樹脂形成低黏度化，而爲具有可防止溶出之液晶 的效果之成份。 局部（甲基）丙烯酸化之環氧樹脂，對於1分子中至 少具有2個以上環氧基之環氧樹脂，較佳爲，對該環氧樹 脂之環氧基使30〜80%當量（較佳爲40〜70%當量）之 (甲基）丙烯酸進行酯化反應所得之局部酯化（甲基）丙 烯酸環氧酯樹脂或局部酯化（甲基）丙烯酸環氧酯樹脂。 其之合成反應可以一般周知之方法進行。例如，於環氧樹 脂添加既定當量比之丙烯酸或甲基丙烯酸、觸媒（苄基二 甲胺、三乙胺、苄基三甲基氯化銨、三苯膦、三苯睇等） -13- 200831541 、與聚合防止劑（例如，甲氧醌（methoquinone)、氫醌 、甲基氫醌、吩噻嗪、二丁基羥基甲苯等）進行酯化反應 〇 所得之局部（甲基）丙烯酸化環氧樹脂之（甲基）丙 熗醯基之當量的比率，若未滿總當量之30%，則光硬化 性不足，對液晶之防污性變差。又，當（甲基）丙烯醯基 之當量的比率若超過總當量之80 %時，硬化後對玻璃基 板之黏著強度會下降。又，環氧當量係根據JIS K7236測 定。 局部（甲基）丙烯酸化環氧樹脂之合成原料之環氧樹 脂，只要1分子中至少具有2個以上環氧基即可，並無特 別限定，可舉例如雙酚A型環氧樹脂、雙酚F型環氧樹 脂、N，N —二環氧丙基-對甲苯胺、N，N —二環氧丙基苯胺 、間苯二酚二環氧丙醚、1，6 —己二醇二環氧丙醚、三羥 甲基丙烷三環氧丙醚、聚丙二醇二環氧丙醚、六氫苯二甲 酸酐二環氧丙醚等一般製造、販售之環氧樹脂。該等環氧 樹脂亦可混合2種以上之環氧樹脂使用。本發明所使用之 局部酯化丙烯酸環氧酯樹脂或酯化甲基丙烯酸環氧酯樹脂 之合成原料之環氧樹脂，如上述並無特別限定，但由於樹 脂本身之液晶污染性低及黏度低，而以雙酚A型液狀環 氧樹脂、雙酚F型液狀環氧樹脂較佳。該等液狀環氧樹脂 爲低黏度，故將其作爲原料之液晶封閉劑爲低黏度，而成 爲作業性優異之液晶封閉劑。 局部丙烯酸化環氧樹脂之市售品之例，可舉例如 -14- 200831541 UVA15 61 (戴協魯塞鐵克（股）公司製）、4HBAGE (曰 本化成（股）公司製）等。 局部丙烯酸化環氧樹脂，可單獨使用1種、亦可組合 2種以上使用。(wherein R1 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 10 carbon atoms, R2 represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 1 carbon number, and R3 represents a substituted or unsubstituted carbazolyl group. Or Ph-S-Ph-CO-based (Ph represents phenyl)). 3. The curable composition according to the above 1 or 2, wherein the (A) compound having an ethylenic unsaturated group is a compound having one or more (meth)acrylonyl groups. 4. The curable composition according to any one of the above 1 to 3, wherein the (B) partially (meth) acrylated epoxy resin has at least two or more epoxy groups in one molecule. The epoxy resin is obtained by subjecting the epoxy group of the epoxy resin to 30 to 80% by weight of (meth)acrylic acid for esterification reaction. The curable resin composition _' according to any one of the above 1 to 4, further comprising (F) inorganic fine particles. 6. The curable resin composition according to any one of the above 1 to 5, further comprising (G) a decane coupling agent. A liquid crystal blocking agent comprising the curable resin composition according to any one of the above items 1 to 6 in the above-mentioned. A liquid crystal display device characterized in that it is produced by using the liquid crystal blocking agent described in the above seven. According to the present invention, it is possible to provide a curable resin composition which exhibits low staining property to liquid crystals and exhibits good curability even in a portion which is shaded by wiring or the like. According to the present invention, there can be provided a liquid crystal blocking agent which is particularly suitable for use in the production of a liquid crystal display element by a liquid crystal dropping method. According to the present invention, it is possible to provide a liquid crystal display element which is excellent in contamination property of liquid crystal due to an uncured liquid crystal blocking agent and excellent in long-term stability. [Embodiment] 硬化 · Curable resin composition The curable resin composition of the present invention The following (referred to as a composition of the present invention) may contain the following components (A) to (H). Among the following components, '(A) to (D) are essential components, and (E) to (Η) are optional components to be blended as needed. (A) a compound having an ethylenic unsaturated group, (B) a partially (meth)acrylated epoxy resin, (C) an epoxy hardener, (D) a photoradical polymerization initiation having an oxime ester structure (E) Reactive (meth)acrylic polymer, (F) Inorganic microparticles, -9-200831541 (G) decane coupling agent, (Η) additive. The curable resin composition of the present invention is obtained by using a high-sensitivity (D) photoradical polymerization initiator (a photoradical polymerization initiator having an oxime ester structure), even if ultraviolet rays cannot be directly used due to wiring or a black matrix. The weak ultraviolet light scattered by the shielding portion of the irradiation can also promote the crosslinking reaction of the (meth) acrylonitrile group, and can impart high liquid crystal contamination resistance. Here, the "high-sensitivity φ degree" means that the ultraviolet light absorption coefficient is large, and even a weak light can generate radicals. 1 · The following describes each component. (A) Compound having an ethylenic unsaturated group The compound having an ethylenic unsaturated group is a radical. A polymeric component exhibits an effect of improving strength, low linear expansion coefficient, and improving positional stability. The ethylenic unsaturated group is not particularly limited, and examples thereof include a (methyl group) acrylonitrile group and a vinyl group, and a (meth) acrylonitrile group is preferred. The compound having a (meth) acrylonitrile group may, for example, be acrylic acid 2, monoethyl ester, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or (meth)acrylic acid 2- Hydroxybutyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearate (meth)acrylate Isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, (meth)acrylic acid 2 —ethoxyethyl ester, (meth) propylene-10- 200831541 acid tetrahydrofuran ester, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate , (meth) acid phenoxy diethylene glycol ester, (meth)acrylic acid phenoxy poly(methyl) methacrylate methoxy polyethylene glycol ester, (methyl) 2, 2, 2 - Trifluoroethyl ester, (meth)acrylic acid 2,2,3,3~tetraki@(meth)acrylic acid 1H,1H,5H-octafluoropentyl ester, (A) ~Alcohol ester decenoate, methyl (meth) acrylate, n-butyl methacrylate (meth) acrylate, n-butyl (meth) acrylate, (methyl) Cyclohexyl acrylate, imidate (meth) propyl monoethyl hexyl ester, n-octyl (meth) acrylate, (methyl decyl ester, isotetradecyl (meth) acrylate, (methyl) Butoxyethyl ester, 2-phenoxyethyl (meth)acrylate, dienoic acid 2 骞2 dicyclopentenyl acrylate, isodecyl (meth) acrylate, diethyl ketate Aminoethyl ester, dimethylamine (meth)acrylate| > Ethyl 2-(methyl) propylene methoxyethyl succinate, hexahydrophthalic acid 2 (methyl) propylene decyloxy Ethyl ester, 2-hydroxypropyl phthalate g methyl) propylene methoxyethyl ester, (meth)acrylic acid propylene acrylate, 2 2 - (meth) propylene methoxyethyl ester, di (methyl) ) l4 diol acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol diacrylate, di(meth)acrylic acid 1, tartaric acid (methyl alcohol ester, 1,10-decanediol (meth)acrylate, 2-(methylammonium A > avoidance) 2-n-butyl-2-ethyl-1,3-propanediol ester, two (_gan, π戋) Dipropylene glycol decenoate, tripropylene glycol di(meth)acrylate, polypropylene glycol mono(meth)acrylate, ethylene glycol di(meth)acrylate_, -11 - 200831541 methyl acrylate Alcohol ester, di(meth)acrylic acid, polyethylene glycol di(meth)acrylate, propylene oxide: di(meth)acrylate, ethylene oxide addition bisphenol A acrylate, ethylene oxide Addition of bisphenol F di(methyl)propane (meth)acrylic acid dihydroxyoxydicyclopentadienyl ester, di(acid 1,3-butanediol ester, di(methyl)acrylic acid neopentadiene Denatured trimeric isocyanate di(meth)acrylate, (φ acid 2-hydroxy-3-(meth)acryloxypropyl propyl ester, acrylic carbonate carbonate, di(meth)acrylic polyether ( Methyl) acrylate polyester diol ester, di(meth) propylene glycol ester, poly(butadiene diol) dimethacrylate, pentaerythritol acrylate, Trimethyl methoxy (meth) acrylate is added to trimethylolpropyl tris(meth)acrylate, trimethylolpropyl tris(meth)acrylate, caprolactone to trishydroxypropyl acrylate Ester, ethylene oxide addition trimeric iso- φ) acrylate, pentaerythritol penta (meth) acrylate) dipropopentate, tetra(meth) acrylate propyl, tetra Methyl) neopentyl glycol acrylate, tris(glyceryl ester, propylene oxide addition tris(meth)acrylic acid glycerol (meth) propylene methoxyethyl ester, and the like. Such a compound having a (meth) acrylonitrile group is, for example, VR-77LC (manufactured by Showa Polymer Co., Ltd. (manufactured by Daisuke Rusekeke Co., Ltd.), etc. The components in the composition of the present invention. (A) compounding amount of tetraethylene glycol ester addition bisphenol A di(meth) enoate, dimethyl) propylene glycol ester, epoxy methyl) propylene di(methyl) glycol ester, diacid Polycaprolactone tris(methyl) propyl ester, cycloethylene oxide addition tris(methyl cyanate, methyl hexamethylol methacrylate), phosphoric acid three commercial products, EB3700, when the solid content of the composition -12-200831541 is 100% by weight, it is 〜1 to 90% by weight, preferably 1 to 80% by weight, more preferably 5 to 60% by weight. When the amount of the component (A) is out of the range of 0.1 to 90% by weight, when ultraviolet rays are irradiated, it is impossible to obtain an appropriate hardness and there is a possibility that positional displacement is likely to occur due to heat (B) Partial (meth)acrylic acid Epoxy resin partial (meth) acrylated epoxy resin having at least two rings in one molecule a base-esterified (meth)acrylic epoxy ester resin or a partially esterified (meth)acrylic epoxy ester resin obtained by esterification of (meth)acrylic acid. An acrylated epoxy resin having an acrylic group obtained by radical polymerization by light irradiation, which is crosslinked with other radical polymerization components by ultraviolet irradiation, and can be used as a resin which is not hardened after heating. A component having a low viscosity and having an effect of preventing dissolution of the liquid crystal. The partially (meth) acrylated epoxy resin is preferably an epoxy resin having at least two epoxy groups in one molecule. a partially esterified (meth)acrylic epoxy ester resin obtained by esterification of 30 to 80% equivalent (preferably 40 to 70% equivalent) of (meth)acrylic acid to the epoxy group of the epoxy resin Or a partially esterified (meth)acrylic epoxy ester resin. The synthesis reaction can be carried out by a generally known method. For example, an epoxy resin is added with a given equivalent ratio of acrylic acid or methacrylic acid, and a catalyst (benzyl). Dimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylsulfonium, etc.) -13- 200831541, with polymerization inhibitors (for example, methoquinone, hydroquinone, A The ratio of the equivalent of the (meth) propyl sulfhydryl group of the partially (meth) acrylated epoxy resin obtained by the esterification reaction of the hydrazine, phenothiazine, dibutylhydroxytoluene, etc., if not When the equivalent value is 30%, the photocurability is insufficient, and the antifouling property to the liquid crystal is deteriorated. Further, when the ratio of the equivalent of the (meth)acryl fluorenyl group exceeds 80% of the total equivalent amount, adhesion to the glass substrate after hardening is performed. In addition, the epoxy equivalent is measured in accordance with JIS K7236. The epoxy resin of the synthetic raw material of the partially (meth) acrylated epoxy resin may have at least two or more epoxy groups in one molecule, and Particularly limited, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, N,N-diepoxypropyl-p-toluidine, N,N-diepoxypropyl aniline, isophthalic acid Phenol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triepoxy , General manufacturing polypropylene glycol diglycidyl ether, phthalic anhydride, hexahydrophthalic diglycidyl ether and the like, the epoxy resin sold. These epoxy resins may be used by mixing two or more kinds of epoxy resins. The epoxy resin of the synthetic raw material of the partially esterified acrylate epoxy ester resin or the esterified methacrylic acid epoxy ester resin used in the present invention is not particularly limited as described above, but the liquid crystal contamination of the resin itself is low and the viscosity is low. Further, a bisphenol A type liquid epoxy resin or a bisphenol F type liquid epoxy resin is preferred. Since these liquid epoxy resins have a low viscosity, the liquid crystal sealing agent which is used as a raw material has a low viscosity and is a liquid crystal sealing agent excellent in workability. Examples of commercially available products of the partially acrylated epoxy resin include, for example, -14-200831541 UVA15 61 (manufactured by Daisuke Ruseke Co., Ltd.), 4HBAGE (manufactured by Sigma Chemical Co., Ltd.), and the like. The partially acrylated epoxy resin may be used singly or in combination of two or more.
本發明之組成物中之成分（B)之配合量，當組成物 之固體成分爲100重量％時，爲0.1〜90重量％、較佳爲 1〜80重量％、更佳爲5〜60重量％。成分（B )之配合 量若脫離上述〇·1〜90重量％之範圍，則照設紫外線時， 無法得到適度之硬度而有容易因熱引起位置偏移之可能性 (C )環氧硬化劑 環氧硬化劑，係用以將含環氧基之化合物交聯、以發 揮黏著性及硬度之效果所配合者。環氧硬化劑，可舉例如 酸性化合物、酸產生劑、鹼性化合物或鹼產生劑等。又， 環氧硬化劑，較佳爲使用硬化劑本身與環氧基進行交聯反 應，而進入交聯之聚合物中之「潛在型環氧硬化劑」。 潛在型環氧硬化劑，可使用周知者，但由以一液型可 提供黏度安定性良好之配合物的觀點考量，以有機酸二醯 肼化合物、咪嗤及其衍生物、二氰二胺、芳香族胺等爲佳 。該等可單獨使用、亦可組合使用。 該等之中，作爲潛在型環氧硬化劑，較佳爲，胺系潛 在型硬化劑、且其熔點或以環球法（根據 JIS K22 07 )所得之軟化點溫度爲10(rc以上者。 -15- 200831541 若使用胺系潛在型硬化劑，則胺之活性氫，會對本發 明之組成物中之具有（甲基）丙烯醯基之其他成分的（甲 基）丙烯醯基，引起熱親核加成反應，故使本發明之組成 物的硬化性提昇。 亦即，胺系潛在型硬化劑，對成分（A )之具有乙烯 性不飽合基之化合物及/或成分（B )之局部（甲基）丙 烯酸化之環氧樹脂兩者皆顯示熱反應特性，故可作爲兩成 φ 分之相溶化成分作用，使液晶顯示面板之顯示特性、黏著 可罪性等面板的可靠性良好，故較佳。 又’熔點或以環球法所得之軟化點溫度之上限値並無 特別限定，但通常爲25 0 °C以下。 係胺系潛在型硬化劑、且其熔點或以環球法所得之軟 化點溫度爲10(TC以上之潛在型環氧硬化劑的具體例，可 舉例如二氰二胺（熔點209 °C )等二氰二胺類；己二酸二 醯肼（熔點1 8 1 t ) 、1，3 -雙（勝基羰乙基）_ 5 —異丙 # 基尿囊素（熔點12〇t)等有機酸二醯肼；2，4 -二胺基一 6 — [2’一乙基咪唑一（1，）]一乙基三吖嗪（熔點215 °C〜 • 22 5 °C ) 、2 —苯基咪唑（熔點137°C〜147°C ) 、2 —苯基 一 4 一甲基咪唑（熔點174 °C〜184 °C) 、2—苯基一 4 -甲 基一 5 —羥基甲基咪唑（熔點191 °C〜195 °C)等咪唑衍生 物等。 又’本發明所使用之潛在型環氧硬化劑，較佳爲，使 用可藉水洗法、再結晶法進行高純度化處理者。 上述胺系潛在型硬化劑之市售品之例，可舉例如雅米 -16- 200831541 求亞VDH、VDH-J、UDH、UDH-J (味之素精細化學（股 )公司製）等。 潛在型環氧硬化劑，可單獨使用1種、亦可組合2種 以上使用。 本發明之組成物中之成分（C )之配合量，當組成物 之固體成分爲100重量％時，爲0.1〜60重量％、較佳爲 1〜50重量％、更佳爲5〜30重量％。成分（C)之配合 m φ 量若少於〇 · 1重量％，則與環氧基之硬化性不充分而有無 法得到充分之硬度及黏著性之虞、且液晶污染可能性有增 高之虞。又，若較60重量％多，則未反應之過剩之硬化 劑使液晶污染可能性有增高之虞。 (D)具有肟酯構造之光自由基聚合起始劑 本發明所使用之光自由基聚合起始劑，係具有肟酯構 造之化合物。具有肟酯構造之化合物，係高感度，即使因 • 配線或黑矩陣等之陰影使紫外線無法直接照射之部位，亦 可藉反射光、散射光、繞射光使本發明之組成物硬化。 • 具有肟酯構造之化合物，較佳爲，以下述通式（d· 1 )所表示之化合物。 【化3】 ΟThe compounding amount of the component (B) in the composition of the present invention is 0.1 to 90% by weight, preferably 1 to 80% by weight, more preferably 5 to 60% by weight, based on 100% by weight of the solid content of the composition. %. When the amount of the component (B) is out of the range of 〇1 to 90% by weight, when ultraviolet rays are applied, an appropriate hardness cannot be obtained, and there is a possibility that the position is likely to be displaced by heat (C) epoxy hardener An epoxy hardener is used to crosslink an epoxy group-containing compound to exhibit adhesion and hardness. The epoxy curing agent may, for example, be an acidic compound, an acid generator, a basic compound or an alkali generating agent. Further, as the epoxy hardener, it is preferred to use a "potential epoxy hardener" which is crosslinked by an epoxy group and enters the crosslinked polymer. A latent epoxy hardener can be used by a well-known person, but it is considered from the viewpoint that a one-liquid type can provide a complex having good viscosity stability, and an organic acid diterpene compound, amidoxime and its derivative, dicyandiamide Aromatic amines are preferred. These may be used singly or in combination. Among these, as the latent epoxy curing agent, an amine-based latent curing agent is preferred, and the melting point or the softening point temperature obtained by the ring and ball method (according to JIS K22 07) is 10 (rc or more). 15- 200831541 If an amine-based latent hardener is used, the active hydrogen of the amine causes thermal nucleophilicity of the (meth) acryloyl group having the other component of the (meth) acrylonitrile group in the composition of the present invention. The addition reaction increases the hardenability of the composition of the present invention. That is, the amine-based latent curing agent, the compound having the ethylenic unsaturated group of the component (A) and/or the component (B) Both of the (meth)acrylated epoxy resins exhibit thermal reaction characteristics, so that they can act as a phase-dissolving component of two parts of φ, and the reliability of the panel such as display characteristics and adhesion of the liquid crystal display panel is good. Further, the upper limit of the melting point or the softening point temperature obtained by the ring and ball method is not particularly limited, but is usually 25 ° C or lower. The chelating amine is a latent curing agent, and its melting point or by the ring and ball method is obtained. Softening point temperature is 10 (TC or higher Specific examples of the latent epoxy curing agent include dicyandiamides such as dicyandiamide (melting point 209 ° C); diammonium adipate (melting point 18 1 t), 1,3 - double (Singapore carbonylethyl) _ 5 —isopropyl # base allantoin (melting point 12〇t) and other organic acid diterpenoids; 2,4-diamino- 6-[2'-ethylimidazole-(1, )] monoethyltriazine (melting point 215 ° C ~ • 22 5 ° C), 2-phenylimidazole (melting point 137 ° C ~ 147 ° C), 2-phenyl-4-methylimidazole (melting point 174) Imidazole derivatives such as 2-phenyl-4-methyl-5-hydroxymethylimidazole (melting point 191 ° C to 195 ° C), etc. Further potential loops used in the present invention The oxygen hardener is preferably a high-purification treatment by a water washing method or a recrystallization method. Examples of the commercially available amine-based latent curing agent include, for example, Jami-16-200831541. , VDH-J, UDH, UDH-J (made by Ajinomoto Fine Chemical Co., Ltd.), etc. The latent epoxy curing agent may be used singly or in combination of two or more. Ingredients (C) The blending amount is 0.1 to 60% by weight, preferably 1 to 50% by weight, more preferably 5 to 30% by weight, based on 100% by weight of the solid content of the composition. If the amount of the component (C) is m φ When the amount is less than 60·1% by weight, the curing property with the epoxy group is insufficient, and sufficient hardness and adhesiveness are not obtained, and the possibility of liquid crystal contamination is increased. Further, if it is more than 60% by weight, Then, the unreacted excess hardener increases the possibility of liquid crystal contamination. (D) Photoradical polymerization initiator having an oxime ester structure. The photoradical polymerization initiator used in the present invention has an oxime ester. Constructed compound. The compound having an oxime ester structure is high in sensitivity, and the composition of the present invention can be cured by reflected light, scattered light, or diffracted light even in a portion where ultraviolet rays cannot be directly irradiated by shading such as wiring or a black matrix. • A compound having an oxime ester structure, preferably a compound represented by the following formula (d-1). 【化3】 Ο
(d — 1) -17- 200831541 式（d-l )中，Ri，較佳爲，氫原子、苯基、碳數！ 〜1 〇之烷基等。 R2，較佳爲，氫原子、苯基、碳數1〜1 〇之烷基等。 R3，較佳爲，包含取代或非取代之昨唑基之1價之有 機基、Ph-S-Ph-CO -基（Ph表不苯基）等。 又，成分（D )之較佳之具有肟酯構造之化合物，可 舉例如0 -醯基肟系化合物。〇 -醯基肟系化合物，較佳 爲9 . Η. -昨嗤系之0 —醯基脂型聚合起始劑。可舉例如1 一 [9 —乙基一 6 —苯甲醯一9.Η•一昨哩—3 —基]—壬烷一 1，2一壬院一2-后一 ◦一苯甲酸酯、1— [9 —乙基一 6—苯 甲醯一 9·：Η· —咔唑一 3—基]一壬院—1，2 —壬烷一 2—肟一 〇 —乙酸酯、1 一 [9 一乙基一6 —苯甲醯一9·Η·—昨哩一 3 — 基]一戊烷一1，2—戊烷_2 一肟—〇 一乙酸酯、1— [9 一乙 基一 6 —苯甲醯一 9·Η· —咔唑一 3—基]—辛院一 1—酮膀— 〇_乙酸酯、1 一 [9 一乙基一 6 —（2 —甲基苯甲醯）一9·Η. _ _哗一 3 —基]一乙院一1 一画膀一〇 —苯甲酸酯、1一[9 —乙基一 6—（2—甲基苯甲醯）—9·Η·—咔唑一3—基]一 乙烷一1 一酮肟一0 一乙酸醋、1 一 [9一乙基一 6— (1，3,5 —三甲基苯甲醯）一 9·Η•一咔唑一 3—基]一乙烷一 1—酮 肟一 〇一苯甲酸酯、1一 [9一 丁基一 6—（2—甲基苯甲醯） 一 9. Η.-味唑一 3-基]一乙烷一1 一酮肟—〇—苯甲酸酯、 1— [9 一乙基一 6— （2 —甲基一 4 一四氫呋喃基甲氧基苯甲 醯）一 9.Η· —咔唑一 3-基]一乙烷一1—酮肟—〇 —乙酸酯 -18-(d-1) -17- 200831541 In the formula (d-l), Ri, preferably, hydrogen atom, phenyl group, carbon number! ~1 〇 alkyl, etc. R2 is preferably a hydrogen atom, a phenyl group, an alkyl group having 1 to 1 carbon atom, or the like. R3 is preferably a monovalent organic group containing a substituted or unsubstituted oxazolyl group, a Ph-S-Ph-CO- group (Ph-phenephenyl) or the like. Further, the component (D) is preferably a compound having an oxime ester structure, and may, for example, be a quinone-based quinone compound. The hydrazone-based hydrazine compound is preferably 9. Η. For example, 1 -[9-ethyl-6-benzamide-9.Η•一哩哩-3-yl]-decane-1, 2 壬院一2-后一◦1 benzoate , 1-[9-ethyl-6-benzamide-9: Η·-carbazole-3-yl] a brothel - 1,2 - decane - 2 - hydrazine - acetate, 1 [9-Ethyl-6-benzamide-9.Η·-哩哩3-3-基]-Pentane-1,2-pentane_2-肟-〇-acetate, 1-— [9 Monoethyl-6-benzamide-9.Η·-carbazole-3-yl]-Xinyuan-1-ketone bladder-〇-acetate, 1-[9-ethyl-6-(2 — Methyl benzamidine) -9 Η. _ _ 哗 3 3 3 ] 一 3 3 3 一 一 一 一 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯 苯Benzamidine) - 9 · Η · - carbazole - 3 - yl] - ethane - 1 - ketone oxime 0 - acetic acid vinegar, 1 - [1 - ethyl 1-6 - (1, 3, 5 - trimethyl Benzobenzamide)- 9·Η•-carbazole-3-yl]-ethane-1-one-ketooxime-benzoate, 1-mono [9-butyl-6-(2-methylbenzene) Hyperthyroidism) a 9. oxime--oxazole-3-yl]-ethane-1-one ketone肟-〇-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzidine)-9.Η·-carbazole-3-yl] Ethyl-1-ketooxime-indole-acetate-18-
200831541 、：I一 [9 一乙基一6 —（2 —甲基一 4 一四氫呋喃基甲氧 甲醯）—9.H.—咔唑一 3一基]—乙烷一 ！—酮肟—〇 — 醋、乙酮、1 一 [9 —乙基一 6 — [2 —甲基一 4_ (2,2 — 基_ I，3 —二氧戊環（dioxolanyl )) 甲氧基苯甲醯 9·Η· —咔唑—3—基]—、1— (〇 —乙醯基肟）等。 該等0 —醯基肟系化合物之中，特別以1 一 [ 9 一 —6— （2—甲基苯甲醯）—9·Η· —味哇一 3 —基]—乙 1_酮時一 0—乙酸酯、乙酮、1— [9 一乙基—6— [2 — —4— (2,2 - 一甲基一1，3—一 氧戊環（dioxolanyl) 氧基苯甲醯）一9·Η· —昨哩一3 —基]一、1— (〇 一乙 肟）較佳。 具有肟酯構造之化合物之市售品之例，可舉 CGI242、ΟΧΕ01 (汽巴特殊化藥（股）公司製）、Ν, ((股）亞德卡公司製）等。 成分（D)之光自由基聚合起始劑，可單獨使用 、亦可組合2種以上使用。又，亦可組合適當之增感 鏈轉移劑。亦可使用於光自由基起始劑本身附予交聯 者。 本發明之組成物中之成分（D )之配合量，當組 之固體成分爲100重量％時，爲0.01〜20重量％、 爲0·1〜15重量％、更佳爲1〜10重量％。成分（Ε 配合量若少於〇· 01重量％，則與丙烯酸基之交聯性 分而有無法得到充分之硬度及尺寸安定性之虞、且液 染可能性有增高之虞。又，若較20重量％多，則無 基苯 乙酸 二甲 )— 乙基 烷一 甲基 )甲 酸基 例如 1919 1種 劑或 性基 成物 較佳 )之 不充 晶污 法使 -19- 200831541 內部（下部）硬化而使液晶污染可能性有增高之虞。 (E )反應性（甲基）丙烯酸聚合物 ❿ 所謂反應性（甲基）丙烯酸聚合物，係具有下述式（ e-1 )所示之構造、具有1個以上之反應性基、數量平均 分子量爲1 000〜100000之化合物。此處之數量平均分子 量，係指以凝膠滲透層析法所測定之苯乙烯換算之數量平 均分子量。反應性基，可舉例如（甲基）丙烯酸基、環氧 基、羥基、羧酸基、胺基等。 【化4】200831541,: I-[9-ethyl-1-6-(2-methyl-4-tetrahydrofuranylmethoxymethylhydrazine)- 9.H.-carbazole-3-yl]-ethane one! - ketone oxime - hydrazine - vinegar, ethyl ketone, 1 - [9 -ethyl-6-[2-methyl- 4-(2,2-yl)-methoxy, dioxolanyl) methoxy Benzoquinone 9 · Η · - carbazole - 3 - yl] -, 1- (〇 - acetyl hydrazine) and the like. Among these 0-mercapto lanthanide compounds, especially 1 -[ 9 - 6 - (2-methylbenzhydrazide) - 9 · Η · - taste wow - 3 - base] - ethyl ketone 0-acetate, ethyl ketone, 1-[9-ethyl-6-[2 - 4-(2,2-methyl- 1, 3-oxo- oxyxolanyl oxybenzone)醯)一9·Η·—哩一哩3-基]一,1—(〇一乙肟) is preferred. Examples of the commercial product of the compound having an oxime ester structure include CGI242, ΟΧΕ01 (made by Ciba Specialty Chemicals Co., Ltd.), Ν, (made by Yadeka Co., Ltd.), and the like. The photoradical polymerization initiator of the component (D) may be used singly or in combination of two or more. Further, a suitable sensitizing chain transfer agent may be combined. It can also be used in the photoradical initiator itself to be attached to the crosslinker. The compounding amount of the component (D) in the composition of the present invention is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight, based on 100% by weight of the solid content of the group. . When the amount of the component (Ε) is less than 〇·01% by weight, the crosslinkability with the acrylic group may not be sufficient to obtain sufficient hardness and dimensional stability, and the possibility of liquid dyeing may increase. 190-200831541 internal (lower than the 20% by weight, then no phenyl phenyl) meth)-ethylalkanemethyl)carboxylic acid group such as 1919 1 agent or a preferred compound Hardening causes the possibility of liquid crystal contamination to increase. (E) Reactive (meth)acrylic acid polymer 所谓 The reactive (meth)acrylic polymer has a structure represented by the following formula (e-1), has one or more reactive groups, and has an average number A compound having a molecular weight of from 1,000 to 100,000. The number average molecular weight herein refers to the number average molecular weight in terms of styrene in terms of gel permeation chromatography. The reactive group may, for example, be a (meth)acrylic group, an epoxy group, a hydroxyl group, a carboxylic acid group or an amine group. 【化4】
式中，R11，表示無特別限定之有機基，m，表示1〜 20 00之整數，R12、R13，表示含有選自（甲基）丙烯酸基 、環氧基、羥基、羧酸基及胺基之1個以上之反應基之1 價基。反應性基，可僅爲1種、亦可含有複數種。 藉由配合反應性（甲基）丙烯酸聚合物，可更減低因 未硬化之.本發明之組成物所造成之液晶的污染，並且，可 更提昇硬化後之拉伸黏著強度’故較佳。 反應性（甲基）丙烯酸聚合物，可舉例如（甲基）丙 烯酸交聯性丙烯酸聚合物、環氧交聯性丙烯酸聚合物、或 含羥基之丙烯酸聚合物等，該等之中，較佳爲（甲基）丙 -20- 200831541 烯酸交聯性丙烯酸聚合物及含環氧基之丙烯酸聚合物。 (甲基）丙烯酸交聯性丙烯酸聚合物之市售品之例， 可舉例如RC100C、RC200C ((股）卡聶卡公司製）、 BGV-12 (綜硏化學（股）公司製）等。 環氧交聯性丙烯酸聚合物之市售品之例，可舉例如 UG-4000、UG-4010(東亞合成（股）公司製）等。In the formula, R11 represents an organic group which is not particularly limited, m represents an integer of 1 to 200, and R12 and R13 represent a group selected from a (meth)acryl group, an epoxy group, a hydroxyl group, a carboxylic acid group, and an amine group. One valent group of one or more reactive groups. The reactive group may be one type or a plurality of types. By blending the reactive (meth)acrylic polymer, it is possible to further reduce the contamination of the liquid crystal caused by the composition of the present invention which is not hardened, and it is preferable to further increase the tensile adhesive strength after curing. The reactive (meth)acrylic acid polymer may, for example, be a (meth)acrylic acid crosslinkable acrylic polymer, an epoxy crosslinkable acrylic polymer, or a hydroxyl group-containing acrylic polymer, and the like. It is a (meth) propyl-20-200831541 olefin crosslinkable acrylic polymer and an epoxy group-containing acrylic polymer. Examples of commercially available products of the (meth)acrylic acid cross-linking acrylic polymer include RC100C, RC200C (manufactured by Konica Corporation), and BGV-12 (manufactured by Kyowa Chemical Co., Ltd.). Examples of commercially available products of the epoxy cross-linking acrylic polymer include UG-4000 and UG-4010 (manufactured by Toagos Corporation).
反應性（甲基）丙烯酸聚合物，可單獨使用1種、亦 可組成2種以上使用。 本發明之組成物中之成分（E )之配合量，當組成物 之固體成分爲100重量％時，爲〇〜70重量％、較佳爲〇 〜60重量％、更佳爲〇〜50重量％。成分（E)之配合量 若過多則無法得到充分的強度，尺寸安定性會有惡化之虞 (F )無機微粒子 φ 藉由配合無機微粒子，可成爲高玻璃轉移溫度及低線 膨脹係數，可發揮（改善、改良）提昇尺寸安定性之效果 ，故較佳。 無機微粒子，可舉例如以氧化矽、氧化鋁、氧化鉻、 氧化鎂、碳酸鈣、碳酸鎂、硫酸鋇、滑石、蒙脫石等爲主 成分之粒子，而較佳爲以氧化矽及氧化鋁爲主成分之粒子 〇 無機微粒子之形狀，可爲球狀、棒狀、板狀、纖維狀 、不定型之任一者，又，該等可爲實心狀、中空狀、多孔 -21 - 200831541 質狀。 無機微粒子之數量平均粒徑，通常爲0.001〜10 /i m、較佳爲0 · 0 1〜5 // m之範圍。若超過1 0 // m，則液 晶胞製作時之玻璃基板貼合之間隙形成有無法順利進行之 虞。此處，無機微粒子之數量平均粒徑，係以雷射光繞射 法測定。 無機微粒子，可將粉體狀者直接添加、混合至其他成 φ 分，亦可將作成溶劑分散液者添加、混合至其他成分再將 溶劑蒸餾除去。 無機微粒子之市售品之例，可舉例如亞德馬發因80-El、SO-E2、SO-E3、SO-E4、SO-E5 ((股）亞德馬鐵克 公司製）、8801、3303、8815、8835(大阪化成（股） 公司製）等。 無機微粒子，可單獨使用1種、亦可組成2種以上使 用。 Φ 無機微粒子，亦可以矽烷耦合劑等進行表面處理。藉 由進行如此之表面處理，可提昇與其他成分之相溶性，而 ^ 可提昇組成物中之分散性與機械強度。 本發明之組成物中之成分（F )之配合量，當組成物 之固體成分爲10 0重量％時，爲1〜5〇重量％、較佳爲5 〜40重量％、更佳爲10〜3〇重量％。成分（？）之配合 量若少於1重量％，則尺寸安定性有惡化之虞。又，若超 過50重量％，則液晶胞製作時之玻璃基板貼合之間隙形 成有無法順利進行之虞。 -22- 200831541 (G)矽烷耦合劑 藉由配合矽烷耦合劑，可發揮（改善、改良）提昇黏 著強度之耐久性之效果，故較佳。 矽烷耦合劑，係具有環氧基者，而以具有（甲基）丙 烯醯基者爲佳。 矽烷耦合劑，可單獨使用1種、亦可組成2種以上使 ❿ 用。 具有環氧基之砂院観合劑之例，可舉例如^ -環氧丙 氧基丙基三甲氧矽烷等。該等之矽烷耦合劑之市售品之例 ，可舉例如SH6040 (東雷道康寧（股）公司製）、KBM-403 (信越聚矽氧（股）公司製）等。 具有（甲基）丙烯醯基之矽烷耦合劑之例，可舉例如 r-甲基丙烯氧基丙基三甲氧矽烷等。該等之矽烷耦合劑 之市售品之例，可舉例如SZ6030 (東雷道康寧（股）公 φ 司製）、KBM-503、KBM-5103、（信越聚矽氧（股）公 司製）等。 _ 本發明之組成物中之成分（G )之配合量，當組成物 之固體成分爲100重量％時，爲0.001〜15重量％、較佳 爲0.01〜10重量％、更佳爲0·1〜5重量％。成分（G) 之配合量若少於〇·〇〇1重量％，則有無法得到充分之黏著 耐久性之虞。又，若較15重量％多，則液晶污染性有增 局之虞。 -23- 200831541 (Η)其他添加劑 於本發明之組成物，以可於不損及本發明之效果的範 圍內，配合其他之添加物。該添加劑，可舉例如成分（D )之外之光自由基起始劑、增感劑、鏈轉移劑、消泡劑、 離子捕捉劑、吸水劑、有機微粒子、整平劑、間格物、有 機溶劑等。 Μ φ 2·硬化性樹脂組成物之製造方法 本發明之組成物，係藉由將成分（A )〜（D )、及 視需要之成分（E )〜（Η )置入容器，使用行星式攪拌 機等攪拌機充分混合後，於真空下進行脫泡來製造。 3 ·硬化性樹脂組成物之硬化方法、硬化條件 本發明之組成物，可藉由照射紫外線、或加熱使用其 硬化。 φ 當將本發明之組成物作爲液晶封閉劑、使用液晶滴下 方法時，一般，係藉照射紫外線預硬化後，再藉由加熱正 式硬化。 用以使本發明之組成物硬化所使用之光之波長，並無 ~ 特別限定，但考量配向膜及對液晶之傷害，以3 5 0〜 7 0 0nm較佳。照射線量，較佳爲500〜1 000011^/〇1112、更 佳爲 1 000 〜3 000mJ/cm2 〇 熱硬化之溫度並無特別限定，但較佳之硬化溫度爲 7(TC以上未滿200°C、更佳爲100°C以上未滿150°C。又 -24- 200831541 ，硬化時間’較佳爲20分鐘以上未滿3小時、更佳爲30 分鐘以上未滿2小時。 II.液晶封閉劑 液晶封閉劑，係使用以將液晶顯示元件之兩片玻璃基 板黏著、保護內部並防止液晶流出。The reactive (meth)acrylic polymer may be used singly or in combination of two or more. The compounding amount of the component (E) in the composition of the present invention is from 〇 to 70% by weight, preferably from 〇 to 60% by weight, more preferably from 〇 to 50% by weight, based on 100% by weight of the solid content of the composition. %. When the amount of the component (E) is too large, sufficient strength cannot be obtained, and the dimensional stability is deteriorated. (F) The inorganic fine particles φ can be made into a high glass transition temperature and a low linear expansion coefficient by blending inorganic fine particles. (Improvement, improvement) It is better to improve the effect of dimensional stability. Examples of the inorganic fine particles include particles mainly composed of cerium oxide, aluminum oxide, chromium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite, etc., and preferably cerium oxide and aluminum oxide. The particle of the main component, the shape of the inorganic fine particles, may be any of a spherical shape, a rod shape, a plate shape, a fiber shape, and an amorphous shape, and these may be solid, hollow, or porous - 21 - 201131541 shape. The number average particle diameter of the inorganic fine particles is usually in the range of 0.001 to 10 /i m, preferably 0 · 0 1 to 5 // m. If it exceeds 10 // m, the gap in which the glass substrate is bonded during the production of the liquid crystal cell may not be smoothly formed. Here, the number average particle diameter of the inorganic fine particles is measured by a laser light diffraction method. The inorganic fine particles may be directly added to and mixed with other powders, or may be added as a solvent dispersion, mixed with other components, and the solvent may be distilled off. Examples of the commercial product of the inorganic fine particles include, for example, Yadmafain 80-El, SO-E2, SO-E3, SO-E4, and SO-E5 (manufactured by Yadema Tektronix Co., Ltd.), 8801. 3303, 8815, 8835 (Osaka Chemicals Co., Ltd.). The inorganic fine particles may be used singly or in combination of two or more. Φ Inorganic fine particles can also be surface treated with a decane coupling agent. By performing such a surface treatment, the compatibility with other components can be improved, and the dispersibility and mechanical strength in the composition can be improved. The compounding amount of the component (F) in the composition of the present invention is 1 to 5 % by weight, preferably 5 to 40% by weight, more preferably 10 to 10% by weight, based on 100% by weight of the solid content of the composition. 3〇% by weight. If the blending amount of the component (?) is less than 1% by weight, the dimensional stability may deteriorate. On the other hand, when it exceeds 50% by weight, the gap formed by lamination of the glass substrate at the time of production of the liquid crystal cell may not proceed smoothly. -22- 200831541 (G) Hydrazine coupling agent It is preferable to use a decane coupling agent to improve (improve and improve) the durability of the adhesion strength. The decane coupling agent is those having an epoxy group, and those having a (meth) propylene group are preferred. The decane coupling agent may be used singly or in combination of two or more. Examples of the sand compound chelating agent having an epoxy group include, for example, ?-glycidoxypropyltrimethoxy decane. Examples of such commercially available decane coupling agents include, for example, SH6040 (manufactured by Toray Dow Corning Co., Ltd.) and KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the decane coupling agent having a (meth) acrylonitrile group include, for example, r-methacryloxypropyltrimethoxydecane. Examples of such commercially available decane coupling agents include, for example, SZ6030 (manufactured by Toray Dow Corning Co., Ltd.), KBM-503, KBM-5103, (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. . The compounding amount of the component (G) in the composition of the present invention is 0.001 to 15% by weight, preferably 0.01 to 10% by weight, more preferably 0·1, when the solid content of the composition is 100% by weight. ~ 5 wt%. When the amount of the component (G) is less than 〇·〇〇1% by weight, sufficient adhesion durability cannot be obtained. Further, if it is more than 15% by weight, the liquid crystal contamination is likely to increase. -23- 200831541 (Η) Other Additives In the composition of the present invention, other additives may be blended in such a manner as not to impair the effects of the present invention. The additive may, for example, be a photoradical initiator other than the component (D), a sensitizer, a chain transfer agent, an antifoaming agent, an ion scavenger, a water absorbing agent, an organic fine particle, a leveling agent, a spacer, or an organic Solvents, etc. Μ φ 2·Method for Producing Curable Resin Composition The composition of the present invention is obtained by placing components (A) to (D) and optionally components (E) to (Η) into a container. After the mixer is sufficiently mixed with a stirrer or the like, it is produced by defoaming under vacuum. 3. Curing method and hardening condition of the curable resin composition The composition of the present invention can be cured by irradiation with ultraviolet rays or heating. φ When the composition of the present invention is used as a liquid crystal blocking agent and a liquid crystal dropping method is used, it is generally pre-cured by irradiation with ultraviolet rays and then hardened by heating. The wavelength of the light used to harden the composition of the present invention is not particularly limited, but it is preferable to consider the alignment film and the damage to the liquid crystal to be 305 to 700 nm. The irradiation amount is preferably 500 to 1 0000 11 / 〇 1112, more preferably 1 000 to 3 000 mJ / cm 2 . The temperature of the heat curing is not particularly limited, but the preferred curing temperature is 7 (TC or less is less than 200 ° C). More preferably, it is 100 ° C or more and less than 150 ° C. Also -24-200831541, the hardening time 'is preferably 20 minutes or more and less than 3 hours, more preferably 30 minutes or more and less than 2 hours. II. Liquid crystal sealing agent A liquid crystal blocking agent is used to adhere two glass substrates of a liquid crystal display element to protect the inside and prevent liquid crystal from flowing out.
本發明之液晶封閉劑，其特徵在於，由上述本發明之 硬化性樹脂組成物所構成。因此，本發明之液晶封閉劑， 具備耐液晶污染性、暗部硬化性、拉伸黏著強度等，而適 用於以液晶滴下方法之液晶顯示元件（液晶顯示胞）之製 造。 本發明之液晶封閉劑之黏度，並無特別限定，而由分 配性及形狀保持性之觀點考量，較佳爲10〜lOOOPay、更 佳爲 1 00 〜500Pa*s ° ΙΠ.液晶顯示元件 本發明之液晶顯示元件，其特徵在於，係使用上述本 發明之液晶封閉劑所製造者。因此，藉由本發明，可得耐 液晶污染性、拉伸黏著強度優異、且長期安定性、可靠性 優異之液晶顯示元件。 參照圖1所示之本發明之液晶顯示元件之一實施型態 之示意圖，說明本發明之液晶顯示元件之構造。 液晶顯示元件1，如圖1所示’具有下述構造：於設 置有透明電極1 4、配向膜12、彩色濾光片1 6之兩片玻璃 -25- 200831541 基板1 〇之間，夾持間隔物1 8，而以液晶封閉劑保持液晶 22 °The liquid crystal blocking agent of the present invention is characterized by comprising the above-mentioned curable resin composition of the present invention. Therefore, the liquid crystal blocking agent of the present invention is suitable for the production of a liquid crystal display element (liquid crystal display cell) by a liquid crystal dropping method, which has liquid crystal contamination resistance, dark portion hardenability, tensile adhesion strength and the like. The viscosity of the liquid crystal blocking agent of the present invention is not particularly limited, but is preferably from 10 to 100 opa, more preferably from 100 to 500 Pa*s ° from the viewpoint of dispersibility and shape retention. The liquid crystal display element is characterized by using the liquid crystal blocking agent of the present invention described above. Therefore, according to the present invention, it is possible to obtain a liquid crystal display element which is excellent in liquid crystal contamination resistance, excellent in tensile adhesive strength, and excellent in long-term stability and reliability. The construction of a liquid crystal display element of the present invention will be described with reference to a schematic view showing an embodiment of the liquid crystal display element of the present invention shown in Fig. 1. The liquid crystal display element 1, as shown in FIG. 1, has the following structure: between two sheets of glass - 25 - 200831541 substrate 1 设置 provided with a transparent electrode 14 , an alignment film 12 , and a color filter 16 Spacer 18, while holding liquid crystal 22 ° with liquid crystal blocking agent
藉由液晶封閉劑20，於將兩片玻璃基板1 〇黏著的同 時，將液晶22封入、保存於以玻璃基板1 0與液晶封閉劑 20所圍繞的空間。由圖1可知，液晶封閉劑20，係與液 晶22直接接觸，故若未硬化之液晶封閉劑20中之成分會 溶解至液晶2 2中，則液晶2 2之比電阻降低，結果會損及 液晶顯示元件1之長期安定性、可靠性。 本發明之液晶顯示元件，係使用上述本發明之液晶封 閉劑’故可防止未硬化之液晶封閉劑成分溶解至液晶，因 此長期安定性、可靠性優異。 本發明之液晶顯示元件，較佳爲以液晶滴下方式來製 造。參照圖2，說明以液晶滴下方式之液晶顯示元件之製 造步驟的槪要。 於一玻璃基板上，使用分配器，形成圍繞封入液晶範 圍之液晶封閉劑之框。液晶封閉劑之線寬、膜厚，通常分 別爲〇·1〜5mm、0.1〜20//m左右，較佳爲0.5〜3mm、1 〜1 0 // m。此時所使用之液晶封閉劑之分配器，可舉例如 SHOTminiSL (武藏工程（股）製）等。 於不使液晶封閉劑硬化之下，將液晶滴入至液晶封閉 劑之框中，除去氣泡等後，貼合另一玻璃基板，將兩片玻 璃基板壓接，以將液晶密封。 接著，照射放射線，使液晶封閉劑預硬化。此時所使 用之放射線，較佳爲使用波長200〜700nm者，若考量對 -26- 200831541 配向膜或液晶的傷害，則以使用波長3 50〜700nm者爲更 佳。放射線之光源，較佳爲使用高壓水銀燈、金屬鹵素燈 、LED 等。 之後，將該基板以70〜200°C (較佳爲90〜150°C ) 加熱1 〇分鐘〜5小時（較佳爲3 0分鐘〜2小時）以進行 液晶退火，同時使液晶封閉劑正式硬化，而製得液晶顯示 元件。 [實施例] 以下，舉實施例及比較例以更具體地說明本發明，但 本發明並不限定於該等實施例。 實施例1 將下述表1所示之成分量取至容器中，使用行星式攪 拌機（去泡攪拌太郎，新基公司製）充分混合。之後於真 空下進行脫泡，製造硬化性樹脂組成物。 實施例2〜7及比較例1〜2 除作成下述表1所示之組成以外，與實施例1以同樣 方式製造各硬化性樹脂組成物。 <硬化物之特性評價> 評價使上述實施例及比較例所得之硬化性樹脂組成物 硬化時之下述特性。所得結果示於表1。 •27- 200831541 1. 拉伸黏著強度 取對硬化性樹脂組成物1 〇〇重量份分散1重量份之間 隔物粒子者之載玻片的中央部，將另一載玻片以呈十字型 之方式疊合，壓接使成爲均一之厚度。對其照射紫外線（ 500mW/cm2、3 000mJ/cm2 )後，放置於 120°C1 小時，作 成拉伸黏著強度測定用之樣品。將該樣品以拉伸試驗機測 _ 定黏著強度（N/cm2)。 2. 液晶相轉移溫度變化 於樣品瓶（內徑l〇mm )置入硬化性樹脂組成物 〇.〇25g後，置入液晶（美魯庫公司製mLC-6608) 0.075g 。由該彳永品瓶之底面照射紫外線（3 〇 〇 〇 m J / c m 2 )後，放置 於1 20°C 1小時。放置冷卻至25 °C後，取出液晶之上清部 分’進行DSC (升溫速度2°C /分鐘）測定。由所測定之 # 相轉移溫度與未處理之液晶（空白）之相轉移溫度之差求 出變化量’根據下述評價基準進行評價。 〇：對空白之差爲2.0°C以下 X :對空白之差超過2.0 t 3 .暗部硬化性 準備將載玻片之整面進行遮光處理者（1)、與一半 進行遮光處理者（2 )。於（1 )之中央部將樹脂組成物點 塗布，並貼合（2 )(此時，（2 )之遮蔽部分與非遮蔽部 -28- 200831541 分之邊界成爲封閉劑之中心）。充分壓接後，照射紫外線 (3000mJ/cm2)後，放置於120°C 1小時。將兩片載玻片 剝下，於非遮蔽部分與距遮蔽部分末端1 mm內側之部分 進行IR測定，以下述式計算出丙烯酸反應率，根據下述 評價基準進行評價。 丙烯酸反應率=u-(硬化後之丙烯酸基波峰面積/硬化 # 後之基準波峰面積）/(硬化前之丙烯酸基波峰面積/硬化前 φ 之基準波峰面積）}xl〇〇 〇：距遮蔽部分末端1 mm之部分的丙烯酸反應率爲 5 0 %以上 X :距遮蔽部分末端1 mm之部分的丙烯酸反應率未滿 50% -29- 200831541 【I撇】 1比較例2| 35.53 35.53 | 5.09 I I 1 1 1 1 1 20.30 I 0.25 1 0.25 3.05 100.00 X X 比較例1 25.38 25.38 5.09 1 審 鼠 20.30 1 1 20.30 1 0.25 I 0.25 I 3.05 100.00 5 〇 X 丨實施例7| 25.90 | 25,90 5.18 1 1 1.04 20.73 1 1 20.73 1 0.26 1 0.26 R 100.00 1 1 ΐ 〇 〇 〇 實施例6 35.53 35.53 5.09 1 3.05 1 1 1 1 20.30 1 0.25 1 I 0.25 I 1 100.00 r-H X 〇 實施例5 20.73 20.73 10.36 1 1.04 1 15.53 ft 10.36 —1 20.73 1 0,26 1 I 0.26 I 1 100.00 〇 〇 〇 實施例4 25.90 25.90 5.18 1 1.04 1 1 20.73 1 ί 1 20.73 1 0.26 I 1 0.26 I t 100,00 239 〇 〇 實施例3 25.90 25.90 5.18 i 1.04 t 20.73 1 I 20.73 1 0.26 1 1 0.26 I 1 100.00 〇 〇 實施例2 25.38 」 25.38 _ί | 5.09 i 1 | 3.05 1 1 20.30 1 1 20.30 1 0.25 1 1 0.25 1 1 100.00 〇 〇 實施例1 25.38 25.38 5.09 3.05 1 1 20.30 1 1 20.30 1 0.25 1 | 0.25 1 1 | loo.oo | 〇〇 〇〇 〇 〇 含雙A之丙烯酸環 氧酯 局部丙烯酸化環氧樹 脂 潛在型環氧硬化劑 高感度光起始劑 高感度光起始劑 高感度光起始劑 丙烯酸交聯性丙烯酸 聚合物 丙烯酸交聯性丙烯酸 聚合物 含環氧基之丙烯酸聚 合物 | 氧化矽微粒子 矽烷耦合劑(環氧） 矽烷耦合劑(丙烯酸） 光自由基起始劑 合計 <硬化物之特性> t m im 液晶相轉移溫度變化 暗部硬化性 〇 > UVA1561 雅米求亞VDH-J CGI242 N-1919 OXE01 RC100C BGV-12 UG-4010 亞德馬發因SO-E3 〇 vo 00 SZ6030 KIP150 < g g g 〇 g -30- 200831541 表1中之市售品，係表示下述者。 VR-7 7LC :昭和高分子（股）公司製含雙酚a之丙烯 酸環氧酯 UVA1 561 :戴協魯塞鐵克（股）公司製局部丙烯酸化 環氧樹脂，分子量4 1 4 【化5】The liquid crystal 22 is sealed and stored in a space surrounded by the glass substrate 10 and the liquid crystal blocking agent 20 while the two glass substrates 1 are adhered by the liquid crystal blocking agent 20. As can be seen from Fig. 1, the liquid crystal blocking agent 20 is in direct contact with the liquid crystal 22. Therefore, if the components in the unhardened liquid crystal blocking agent 20 are dissolved in the liquid crystal 2 2, the specific resistance of the liquid crystal 2 2 is lowered, and the result is damaged. Long-term stability and reliability of the liquid crystal display element 1. In the liquid crystal display device of the present invention, the liquid crystal sealing agent of the present invention is used, so that the liquid crystal blocking agent component which is not cured can be prevented from being dissolved in the liquid crystal, and thus the long-term stability and reliability are excellent. The liquid crystal display element of the present invention is preferably produced by a liquid crystal dropping method. Referring to Fig. 2, a summary of the manufacturing steps of the liquid crystal display element in the liquid crystal dropping mode will be described. On a glass substrate, a dispenser is used to form a frame surrounding the liquid crystal blocking agent enclosed in the liquid crystal range. The line width and film thickness of the liquid crystal blocking agent are usually about 1 to 5 mm, about 0.1 to 20/m, preferably 0.5 to 3 mm, and 1 to 1 0 // m. The dispenser of the liquid crystal sealing agent used in this case is, for example, SHOTminiSL (made by Musashi Engineering Co., Ltd.). After the liquid crystal blocking agent is not hardened, the liquid crystal is dropped into the frame of the liquid crystal sealing agent, and after removing bubbles or the like, the other glass substrate is bonded, and the two glass substrates are pressure-bonded to seal the liquid crystal. Next, the radiation is irradiated to pre-harden the liquid crystal blocking agent. The radiation to be used at this time is preferably a wavelength of 200 to 700 nm. If the damage to the alignment film or liquid crystal of -26-200831541 is considered, it is preferably used at a wavelength of from 50 to 700 nm. The radiation source is preferably a high pressure mercury lamp, a metal halide lamp, an LED or the like. Thereafter, the substrate is heated at 70 to 200 ° C (preferably 90 to 150 ° C) for 1 minute to 5 hours (preferably 30 minutes to 2 hours) to perform liquid crystal annealing, and the liquid crystal sealing agent is officially formed. Hardened to produce a liquid crystal display element. [Examples] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples. Example 1 The amounts of the components shown in the following Table 1 were taken into a container, and thoroughly mixed using a planetary agitator (de-bubble stirring Taro, manufactured by Shinki Co., Ltd.). Thereafter, defoaming was carried out under vacuum to produce a curable resin composition. Examples 2 to 7 and Comparative Examples 1 to 2 Each of the curable resin compositions was produced in the same manner as in Example 1 except that the compositions shown in Table 1 below were prepared. <Evaluation of characteristics of cured product> The following characteristics when the curable resin composition obtained in the above Examples and Comparative Examples were cured were evaluated. The results obtained are shown in Table 1. • 27- 200831541 1. Tensile adhesion strength is taken from the center of the glass slide of 1 part by weight of the hardener resin composition, and the other slide is made into a cross shape. The method is superposed and the crimping is made uniform. After irradiating ultraviolet rays (500 mW/cm2, 3 000 mJ/cm2), it was placed at 120 °C for 1 hour to prepare a sample for measuring the tensile adhesion strength. The sample was measured for tensile strength (N/cm2) by a tensile tester. 2. Liquid crystal phase transition temperature change After the curable resin composition 置.〇25g was placed in the vial (inner diameter l〇mm), liquid crystal (mLC-6608, manufactured by Meluku) was placed at 0.075 g. The ultraviolet rays (3 〇 〇 〇 m J / c m 2 ) were irradiated from the bottom surface of the bottle, and placed at 1 20 ° C for 1 hour. After standing to cool to 25 ° C, the supernatant portion of the liquid crystal was taken out and subjected to DSC (temperature up rate 2 ° C / min) measurement. The amount of change was determined from the difference between the measured phase transition temperature and the phase transition temperature of the untreated liquid crystal (blank), and was evaluated based on the following evaluation criteria. 〇: The difference between the blanks is 2.0 ° C or less. X : The difference between the blanks and the blank is more than 2.0 t 3 . The dark portion is prepared by shading the entire surface of the slide (1) and shading with half (2) . The resin composition is spot-coated at the center of (1) and bonded (2) (at this time, the boundary between the shield portion of (2) and the non-shielding portion -28-200831541 becomes the center of the sealant). After sufficient pressure bonding, ultraviolet rays (3000 mJ/cm2) were irradiated, and then placed at 120 ° C for 1 hour. Two slides were peeled off, and IR measurement was performed on the unmasked portion and a portion 1 mm from the end of the shield portion, and the acrylic acid reaction rate was calculated by the following formula, and evaluated according to the following evaluation criteria. Acrylic acid reaction rate = u - (base area of the acrylic acid after hardening / reference peak area after hardening #) / (base area of the acrylic-based peak before hardening / reference peak area of φ before hardening)} xl 〇〇〇: from the shadow portion The reaction rate of acrylic acid at the end portion of 1 mm is more than 50% X: the reaction rate of acrylic acid at a portion of 1 mm from the end of the masking portion is less than 50% -29- 200831541 [I撇] 1 Comparative Example 2| 35.53 35.53 | 5.09 II 1 1 1 1 1 20.30 I 0.25 1 0.25 3.05 100.00 XX Comparative Example 1 25.38 25.38 5.09 1 Rat 20.30 1 1 20.30 1 0.25 I 0.25 I 3.05 100.00 5 〇X 丨Example 7| 25.90 | 25,90 5.18 1 1 1.04 20.73 1 1 20.73 1 0.26 1 0.26 R 100.00 1 1 ΐ 〇〇〇 Example 6 35.53 35.53 5.09 1 3.05 1 1 1 1 20.30 1 0.25 1 I 0.25 I 1 100.00 rH X 〇Example 5 20.73 20.73 10.36 1 1.04 1 15.53 Ft 10.36 -1 20.73 1 0,26 1 I 0.26 I 1 100.00 〇〇〇Example 4 25.90 25.90 5.18 1 1.04 1 1 20.73 1 ί 1 20.73 1 0.26 I 1 0.26 I t 100,00 239 〇〇Example 3 25.90 25.90 5.18 i 1.04 t 20.73 1 I 20.73 1 0.26 1 1 0.26 I 1 10 0.00 〇〇Example 2 25.38 ” 25.38 _ί | 5.09 i 1 | 3.05 1 1 20.30 1 1 20.30 1 0.25 1 1 0.25 1 1 100.00 〇〇 Example 1 25.38 25.38 5.09 3.05 1 1 20.30 1 1 20.30 1 0.25 1 | 0.25 1 1 | loo.oo | 丙烯酸Acrylic epoxy ester partial acrylated epoxy resin latent epoxy hardener high sensitivity photoinitiator high sensitivity photoinitiator high sensitivity light start Acrylic cross-linking acrylic polymer acrylic cross-linking acrylic polymer epoxy-containing acrylic polymer | cerium oxide micron decane coupling agent (epoxy) decane coupling agent (acrylic acid) photo radical initiator total < hardening Characteristics of the substance > tm im liquid crystal phase transition temperature change darkening hardening 〇> UVA1561 Yami Qiaiya VDH-J CGI242 N-1919 OXE01 RC100C BGV-12 UG-4010 Yademafain SO-E3 〇vo 00 SZ6030 KIP150 <ggg 〇g -30- 200831541 The commercial item in Table 1 shows the following. VR-7 7LC: Acetate epoxy ester containing bisphenol a manufactured by Showa Polymer Co., Ltd. UVA1 561: Partially acrylated epoxy resin manufactured by Daisuke Rusetie Co., Ltd., molecular weight 4 1 4 】
OHOH
UG-4010:東亞合成（股）公司製含環氧基之丙烯酸 聚合物，分子量2900 雅米求亞VDH-J:味之素精細化學（股）公司製潛在 型環氧硬化劑UG-4010: Epoxy-based acrylic acid polymer produced by East Asia Synthetic Co., Ltd., molecular weight 2900 Yami Qiaiya VDH-J: Ajinomoto Fine Chemical Co., Ltd.
【化6】【化6】
NH2 CGI242 :汽巴特殊化藥（股）公司製光自由基聚合 起始劑；艾太引、1-[9-乙基-6-(2-甲基苯甲醯）-91^味 唑-3-基]-1- ( 0、乙醯基肟） 200831541 【化7】NH2 CGI242: Photo-free radical polymerization initiator of Ciba Specialty Chemicals Co., Ltd.; Ai Tai, 1-[9-ethyl-6-(2-methylbenzamide)-91^-oxazole- 3-yl]-1-(0, acetyl group) 200831541 【化7】
φ Ν- 1 9 1 9 :(股）亞德卡公司製光自由基聚合起始劑 【化8】 N-° °Yr21Φ Ν- 1 9 1 9 : (share) Yadeka company photoradical polymerization initiator [Chem. 8] N-° °Yr21
OXEOl :汽巴特殊化藥（股）公司製光聚合起始劑 1，2·辛二酮、1-[4-(苯基硫）-，2-(0-苯甲醯基肟）] 【化9】OXEOl: Photopolymerization initiator of Ciba Specialty Chemicals Co., Ltd. 1,2·octanedione, 1-[4-(phenylsulfanyl)-,2-(0-benzhydrylhydrazine)] 9]
200831541 RC100C ：(股）卡聶卡公司製含丙烯酸基之聚合物 ，分子量24000 [化1 0】200831541 RC100C : (share) Acrylic based polymer made by Konica, with a molecular weight of 24000 [Chemical 1 0]
BGV-12 :綜硏化學（股）公司製含（甲基）丙烯酸 基之聚合物，分子量3 000 SH6040 ：東雷道康寧（股）公司製矽烷耦合劑；r - 環氧丙氧基丙基三甲氧矽烷 SZ6 030 :東雷道康寧（股）公司製矽烷耦合劑；r - 甲基丙烯氧基丙基三甲氧矽烷 • KIP 1 5 0 :三德曼公司製光自由基聚合起始劑 【化1 1】BGV-12: a (meth)acrylic polymer containing a molecular weight of 3 000 SH6040: a decane coupling agent made by Donglei Dow Corning Co., Ltd.; r - glycidoxypropyl trimethyl Oxane SZ6 030: decane coupling agent made by Dongleidao Corning Co., Ltd.; r - methacryloxypropyl trimethoxy decane • KIP 1 5 0 : Photoradical polymerization initiator of Sandman Co., Ltd. 1】
ch3 ICh3 I
-33- 200831541 (η :平均爲約1 · 5 ) 由表1之結果可知，使用高感度光自由基聚合起始劑 之實施例1〜7之硬化性樹脂組成物，顯示優異之暗部硬 化性。-33-200831541 (η: an average of about 1 · 5 ) From the results of Table 1, it is understood that the curable resin composition of Examples 1 to 7 using a high-sensitivity photoradical polymerization initiator exhibits excellent dark portion hardenability. .
本發明之液晶封閉劑，即使於因近年來之狹額緣化之 要求而與配線或黑矩陣等重疊之紫外線無法直接照射之部 分，亦可充分地硬化，故與基板之密合性高，亦可減低因 爲硬化之液晶封閉劑所造成之液晶污染可能性。 藉由本發明，可提供一種適用於液晶滴下方式之液晶 封閉劑，其可步驟少而有效率地製造液晶顯示元件。 【圖式簡單說明】 圖1，係本發明之液晶顯示元件之截面示意圖。 '圖2，係顯示液晶滴下方法之槪要之圖。 【主要元件符號說明】 1 :液晶顯示元件（液晶胞） 1 〇 :玻璃基板 1 2 :配向膜 1 4 :透明電極 1 6 :彩色濾光片 1 8 :間隔物 20 :液晶封閉劑 2 2 :液晶 -34-The liquid crystal blocking agent of the present invention can be sufficiently cured even in a portion which cannot be directly irradiated with ultraviolet rays which overlap with wiring or a black matrix due to the demand for narrow margins in recent years, and therefore has high adhesion to the substrate. It also reduces the possibility of liquid crystal contamination caused by hardened liquid crystal blocking agent. According to the present invention, it is possible to provide a liquid crystal blocking agent which is suitable for a liquid crystal dropping method, which can produce a liquid crystal display element with less steps and efficiently. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a liquid crystal display element of the present invention. Figure 2 shows a schematic diagram of the liquid crystal dropping method. [Description of main component symbols] 1 : Liquid crystal display element (liquid crystal cell) 1 〇: Glass substrate 1 2 : Alignment film 1 4 : Transparent electrode 1 6 : Color filter 1 8 : Spacer 20 : Liquid crystal blocking agent 2 2 : LCD-34-
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW096149359A TW200831541A (en) | 2006-12-28 | 2007-12-21 | Sealant for liquid crystal display device and liquid crystal display device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2008179797A (en) |
| KR (1) | KR20080063139A (en) |
| TW (1) | TW200831541A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928548A (en) * | 2009-06-24 | 2010-12-29 | 三星电子株式会社 | Sealing agent, have its display unit and make the method for this display unit |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008231347A (en) * | 2007-03-23 | 2008-10-02 | Jsr Corp | Curable composition, liquid crystal sealing agent, and liquid crystal display element |
| KR101486619B1 (en) * | 2007-10-25 | 2015-01-26 | 세키스이가가쿠 고교가부시키가이샤 | Sealing material for liquid crystal dispensing method, transfer material and liquid crystal displays |
| JP5343527B2 (en) * | 2008-11-20 | 2013-11-13 | Ｊｓｒ株式会社 | Curable composition, liquid crystal sealant, and liquid crystal display element |
| JP5152868B2 (en) | 2009-06-11 | 2013-02-27 | 日本化薬株式会社 | Visible light curable liquid crystal sealant and liquid crystal display cell using the same |
| JP5778038B2 (en) | 2010-06-28 | 2015-09-16 | 株式会社Adeka | Curable resin composition |
| CN107710060B (en) * | 2016-01-26 | 2021-11-12 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| WO2018225543A1 (en) * | 2017-06-06 | 2018-12-13 | 日本化薬株式会社 | Compound and photocurable composition using same |
| WO2021177316A1 (en) * | 2020-03-03 | 2021-09-10 | 積水化学工業株式会社 | Curable resin composition, sealing agent for display elements, sealing agent for liquid crystal display elements, vertically conductive material, display element, adhesive for electronic components, and electronic component |
| WO2023032543A1 (en) * | 2021-09-03 | 2023-03-09 | 積水化学工業株式会社 | Liquid crystal display element sealant and liquid crystal display element |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG77689A1 (en) * | 1998-06-26 | 2001-01-16 | Ciba Sc Holding Ag | New o-acyloxime photoinitiators |
| JP2005292801A (en) * | 2004-03-09 | 2005-10-20 | Sekisui Chem Co Ltd | Light shielding sealing agent for liquid crystal display element, vertical conducting material, and liquid crystal display element |
| ATE381540T1 (en) * | 2004-08-18 | 2008-01-15 | Ciba Sc Holding Ag | OXIMESTHER PHOTO INITIATORS |
-
2007
- 2007-12-21 TW TW096149359A patent/TW200831541A/en unknown
- 2007-12-25 JP JP2007331479A patent/JP2008179797A/en active Pending
- 2007-12-27 KR KR1020070138368A patent/KR20080063139A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928548A (en) * | 2009-06-24 | 2010-12-29 | 三星电子株式会社 | Sealing agent, have its display unit and make the method for this display unit |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20080063139A (en) | 2008-07-03 |
| JP2008179797A (en) | 2008-08-07 |
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