201042016 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種液晶密封劑，其係分配式（dispense) 塗佈性優良且可對應於網版印刷且黏度為lOOPa· s以下之 液晶密封劑，且為不經過乾燥步驟或預烤步驟，而液晶不 會滲入密封部中的液晶密封劑；並且，本發明係有關使用 該密封劑的液晶顯示單元。 【先前技術】 近年來液晶顯示單元也朝應用於電視等大型顯示晝面 進展，而在多用途上之需求越來越高。因此，關於液晶面 板之製造，為了更加提高量產性，而正逐漸使基板大型化 且縮短產距時間（tack time，每一步驟之時間）。 在製作液晶顯示裝置時，以往一直藉由下述方式來製 作：藉由分配式塗佈或網版印刷等方法將液晶密封劑塗佈 於玻璃基板後，予以密封而形成單元，並在真空環境中從 設置於其一部分之液晶注入口將液晶注入單元内後，使用 密封劑或封口劑將該液晶注入口予以密封（真空注入法）。 此外，將液晶滴入由樹脂製作成之堰中後進行貼合再 使樹脂硬化的液晶滴入工法也正在實用化。在液晶滴入工 法中，首先，於2片附有電極之透明基板中之一者上，藉 由分配而形成長方形之由未硬化密封劑所構成之密封圖 案。接著，在密封劑未硬化之狀態下將液晶之微小液滴滴 入塗佈於透明基板之密封圖案之框内全面後，立刻將另一 透明基板貼合，而製作液晶單元，並對密封圖案部照射紫 4 321935 201042016 、外線而進行預硬化。然後，依需要而加熱，進行主要硬化， 而製作液晶顯示單元。只要在減壓下進行將基板貼合而製 ’ 作液晶單元之步驟，則可以極高效率製造液晶顯示元件， 現今此滴入工法已逐漸成為液晶顯示元件之製造方法之主 流。 當藉由液晶滴入工法來製造液晶顯不7〇件時’有下述 問題：所製得之液晶顯示單元之密封圖案發生變形，而產 生液晶滲入密封圖案中之現象（滲入現象），因而擾亂該密 封圖案附近之液晶之定向。解決此問題之方法有例如使用 黏度較通常所使用者更高之密封劑來形成密封圖案，但有 因分配性惡化，而導致在進行分配時之乾涸、斷線等不良 影響之可能性。此外，近年來為了更進一步縮短產距時間 等之目的而希望可提高分配速度或更容易地藉由網版印刷 形成密封圖案，因此而要求更低黏度且無滲入現象之密封 劑。 〇 關於此問題，在專利文獻1中，有在進行製作液晶單 元之步驟前，藉由預先增加未硬化之密封圖案之黏度而防 止滲入現象之報告。然而，尚無關於初期黏度為1 OOPa · s 以下之低黏度且不經過預烤步驟即直接用於液晶滴入步驟 的液晶密封劑之前例。 此外，在專利文獻2及3中，有經改善液晶污染性之 包含橡膠狀聚合物微粒子之液晶密封劑之報告。但在此等 2份公報之情形，皆並非為初期黏度為l〇〇Pa · s以下者， 並且橡膠狀聚合物微粒子係用於抑制在光硬化時不容易被 5 321935 201042016 uv照射到之遮光部分之密封劑成分在進行熱硬化時溶 液晶中。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻丨〕曰本特開2008-275670號公報 〔專利文獻2〕日本特開2007-219039號公報 〔專利文獻3〕日本特開2007-262253號公報 【發明内容】 (發明欲解決的課題） 本發明之課題為抑制在進行液晶滴入工法時液晶滲入 密封劑中之滲入現象，而提供一種經抑制滲入現象之液曰曰 密封劑及使用該密封劑的液晶顯示單元。 阳 (解決課題的手段） 本發明人等進行致力研究後，結果發現一種包含聚石夕 氧（silicone)橡膠粉末之硬化性樹脂組成物，該硬化性 月曰組成物係即使初期黏度為1 〇〇pa · s以下，也可抑制進疒 液晶滴入工法時之參人現象。此外，也發現，經由在該= 化性樹脂組成物中添加胺基矽烷耦合劑，即可得到更 步防止滲人現象之效果’再經由伕需要而添加球狀填料， 而可提高進行分配式塗佈時之密封之直線性，遂完成林 明。換言之，本發明係有關下述（1)至（1〇)者。 ⑴-種液晶密封劑，係包含（a)聚石夕氧橡膠粉末，且 用E型黏度计測得之25°C時之黏度為1〇〇Pa · s 者0 321935 6 201042016 (2)如前述Ο)之液晶密封劑’其中，復包含（b)胺基；ε夕燒 '耦合劑。 ，（3)如前述（1)之液晶密封劑，其中，復包含（c)球狀填料。 (4) 如前述（1)至（3)中任一項之液晶密封劑，其中，復包 含（d)光硬化樹脂。 (5) 如（4)中任一項之液晶密封劑，其中，（d)光硬化樹脂 係環氧丙稀酸酯。 (6) 如前述（1)至（5)中任一項之液晶密封劑，其中，復包 ^ 含（e)光自由基聚合起始劑。 (7) 如前述（1)至（6)中任一項之液晶密封劑，其中，復包 含（f)熱硬化樹脂及/或（g)熱硬化劑。 (8) 如前述（7)中任一項之液晶密封劑，其中，（f)熱硬化 树月s係環氧樹脂’成分（g)熱硬化劑係有機醯肼 (hydrazide) ° (9) 如前述（1)至（8)中任一項之液晶密封劑，其中，復包 Q 含（h)平均粒徑為3//m以下之無機填料。 (1〇) —種液晶顯示單元’係經使前述（^至^)中任一項之 液晶密封劑硬化而得之硬化物進行密封者。 (發明的效果） 換言之’本發明之液晶密封劑係低黏度，並且不經過 預烤步驟’而具有防止在進行液晶滴入工法時液晶滲入密 封劑中之優良的效果。因此，經由使用此密封劑，即容易 製造出可使分配式塗佈、網版印刷塗佈所耗費之時間縮短 之浪晶顯示面板。 7 321935 201042016 【實施方式】 以下，詳細說明本發明。 本發明之液晶密封劑中所使用之聚矽氧橡膠粉末，只 要為由以矽氧烷鍵之重複做為主鏈之聚合物所構成者，則 無特別限定。聚矽氧粉末一般依彈性率而區分為樹脂粉末 與橡膠粉末，從可抑制液晶滲入密封劑中之觀點來看，特 別是以具有衝擊吸收性之橡膠粉末為佳。以未經交聯聚合 物等被覆表面之聚矽氧橡膠粉末較佳。並且，在本發明中， 聚矽氧橡膠係以使用具有使聚矽氧烷交聯而成之構造者為 佳，聚矽氧烷以直鏈狀之二甲基聚矽氧烷為佳。此外，因 密封劑之製造及使用時進行加熱處理，因此以具有耐熱性 為佳。 本發明之液晶密封劑中所使用之聚矽氧橡膠粉末（a) 之平均粒徑，由於若過大，則在製造間隙狹窄之液晶單元 時，會成為當貼合上下玻璃基板時無法順利形成間隙等之 不良要因，故通常為3/zm以下，且以2/zm以下為佳。此 外，同樣地，最大粒徑通常為8#m以下，且以5/zm以下 為佳。並且，為了良好地形成間隙，以在-50°C至250°C顯 示橡膠彈性為佳。此外，以在液晶污染性方面也良好為佳。 以信越化學工業公司製KMP-594特佳。相對於本發明之液 晶密封劑100質量％ ，其使用量通常為1至20質量％ ，且 以5至15質量％左右為佳。若添加更多，則搖變性增大， 而使塗佈性降低。 本發明之液晶密封劑中所使用之聚矽氧橡膠粉末（a) 8 321935 201042016 係/以與胺基魏輕合_)個為佳。經由仙此等，由於 耐衝擊性提高’故可防止液晶滲人密封劑中。 本發明之液晶密封劑中可使用之胺基石夕烧耗合劑⑻ —般可使用習知物’無特別限定。例如··胺基丙基三 ，石夕烧、胺基丙基三乙氧基㈣、二甲基胺基丙基三甲氧 土石夕，、二乙基縣丙基三曱氧基魏、二丙基胺基丙基 二甲氧基魏、二丁基胺基丙基三甲氧基錢、單丁基胺 Ο Ο 基丙基三甲氧基魏、二辛基胺基丙基三甲氧基魏、二 丁基胺基丙基二甲氧基傾、二丁基胺基丙基單甲氧基石夕 境、-甲基胺基苯基三甲氧基魏、三甲氡基魏基个 兩基苯基胺、三f氧基魏基_r_丙基γ基胺、三甲氧基 石夕烧基个丙基哌<、三甲氧基德基个丙基嗎琳、三 甲氧基料基-卜丙基輕等。此等可使用1種或併用2 種以上。若令本發明之液晶密封劑整體為100質量％，則 鞍基梦_合劑在液晶㈣射所佔之含量為G至3量 %左右。 本發明中之液晶密封劑之初期黏度為1〇〇pa· s以下。 若初期黏度為l〇〇pa· s以下，則分配式塗佈性優良且可對 應於網板印刷，而與面板之生產性大幅相關，且造成有效 的影響。 本發明之液晶密封劑中可使用之球狀填料（c)可舉例 如：氧化石夕（silica)、石夕膠（silica gel)、中空玻璃、碳 黑、高分子聚乙烯等。若為球狀’則由於無論從任何方向 施加攪動壓力皆可整體承受，故可非常安定地揉合。此外， 9 321935 201042016 此填料通常平均粒徑為◦.⑽_至⑽㈣左右，且以〇· 〇1 二至10Am為佳。經由添加此尺寸之球狀填料，即可 而= 旨之搖變性。藉由此等，可進行安定之分配式塗佈， 私㈣之直線性。前述中，由於在樹脂中容易分散， Πΐη水减理切敎佳。可從市場取得信越化 干業I之次微米（submicron)球狀氧化矽粉末χ_24_ 9163Α等。若令本發明之液晶密封劑整體為^⑽質量％， 則其使用量通常為〇至1()質量％，且以質量％丄右 為佳。若添加更多’則料氧橡膠粉末與胺基錢輕 所產生之效果低，而渗入性不良。 本發明之液晶密封劑中可使用之光硬化性樹脂（d)，只 要為溶出至液晶中之溶出性低，則並無特別限定，可舉例、 如：如胺酯（urethane)丙烯酸酯、（甲基）丙烯酸酯、環曱 基）丙烯酸酯等具有丙烯醯基做為官能基之化合物。具體而 δ例如·曱基丙烯酸苄酯、曱基丙烯酸環己酯、甘、、由一曱 基丙烯酸酯、甘油三曱基丙烯酸酯、Ε〇改質廿、a _ θ| ’由二丙稀酸 酉曰、季戊四醇丙烯酸酯、三羥甲基丙烷三丙烯酸酯、參 缚醯氧基乙基）異氰脲酸酉旨、二季戊四醇Α丙稀酸酿、 胺醇（glycinol)三丙烯酸酯等。此外，你游曰、_ 氣 Γ 攸及日日3染性之翻 點來看，以環氧（曱基）丙烯酸酯樹脂特佳。此環& 祝 丙烯酸醋樹脂可藉由使丙烯酸或曱基丙晞酸與二$ 至少2個以上環氧基之環氧樹脂進行§旨化反應 具= 合成反應-般可料已知之方法進行。例如：在環氧樹月匕 中添加預定當量比之丙烯酸或曱基丙橋 q 内烯酸、以及觸媒（例如 321935 10 201042016 爷，一甲基胺、三乙基胺、氯化节基三甲基銨、三苯基膊、 一苯基銻化氫（triphenyi stibine)等）、與聚合抑制劑（例 如對曱氧基苯紛、氫酉昆、甲基氣酿、啡嗟啡 Ohenothiazine)、二丁基羥基甲苯等），在例如8〇至11〇 Ο201042016 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal sealing agent which is excellent in dispensing and coatability and can correspond to screen printing and has a viscosity of 100 Pa·s or less. And a liquid crystal sealing agent which does not permeate into the sealing portion without undergoing a drying step or a pre-baking step; and the present invention relates to a liquid crystal display unit using the sealing agent. [Prior Art] In recent years, liquid crystal display units have also been applied to large-scale displays such as televisions, and the demand for multi-purposes is increasing. Therefore, in order to further improve mass productivity, the production of the liquid crystal panel is gradually increasing the size of the substrate and shortening the tap time (time per step). In the production of a liquid crystal display device, conventionally, a liquid crystal sealing agent is applied to a glass substrate by a method such as dispensing coating or screen printing, and then sealed to form a unit in a vacuum environment. After liquid crystal is injected into the cell from a liquid crystal injection port provided in a part thereof, the liquid crystal injection port is sealed using a sealant or a sealing agent (vacuum injection method). Further, a liquid crystal dropping method in which a liquid crystal is dropped into a crucible made of a resin, bonded, and the resin is cured is also put into practical use. In the liquid crystal dropping method, first, a rectangular sealing pattern composed of an uncured sealant is formed by dispensing on one of two transparent substrates with electrodes. Then, after the fine liquid droplets of the liquid crystal are dropped into the frame of the sealing pattern applied to the transparent substrate in a state where the sealing agent is not cured, the other transparent substrate is bonded immediately to form a liquid crystal cell, and the sealing pattern is formed. The part is irradiated with purple 4 321935 201042016, and the outer line is pre-hardened. Then, it is heated as needed to perform main hardening, and a liquid crystal display unit is produced. The liquid crystal display element can be manufactured with high efficiency as long as the substrate is bonded under reduced pressure to form a liquid crystal cell. Nowadays, the dropping method has gradually become the main method for manufacturing a liquid crystal display element. When the liquid crystal display is manufactured by the liquid crystal dropping method, there is a problem that the sealing pattern of the obtained liquid crystal display unit is deformed to cause a phenomenon in which the liquid crystal penetrates into the sealing pattern (infiltration phenomenon), and thus The orientation of the liquid crystal in the vicinity of the seal pattern is disturbed. A method for solving this problem is to form a seal pattern by using a sealant having a higher viscosity than a usual user, but there is a possibility that the distribution property is deteriorated, which may cause adverse effects such as dryness and disconnection at the time of dispensing. Further, in recent years, in order to further shorten the production time and the like, it is desirable to increase the dispensing speed or to form a seal pattern by screen printing, thereby requiring a sealant having a lower viscosity and no penetration. In this regard, Patent Document 1 discloses a report for preventing the penetration phenomenon by increasing the viscosity of the uncured seal pattern before the step of producing the liquid crystal cell. However, there is no previous example of a liquid crystal sealing agent which has a low viscosity of 1 00 Pa·s or less and is directly used for the liquid crystal dropping step without a pre-bake step. Further, in Patent Documents 2 and 3, there is a report of a liquid crystal sealing agent containing rubber-like polymer fine particles which is improved in liquid crystal contamination. However, in the case of these two publications, it is not the initial viscosity of l〇〇Pa · s or less, and the rubbery polymer microparticles are used to suppress the shading which is not easily irradiated by 5 321935 201042016 uv during photohardening. Part of the sealant component is in the solution crystal during thermal hardening. [PRIOR ART DOCUMENT] [Patent Document] [Patent Document] Japanese Patent Laid-Open Publication No. Hei. No. 2007-225. Disclosure of the Invention (Problems to be Solved by the Invention) An object of the present invention is to suppress a penetration phenomenon of liquid crystal infiltrating into a sealant during a liquid crystal dropping method, and to provide a liquid helium sealant which inhibits penetration and use the sealant LCD unit. YANG (Means for Solving the Problem) After intensive research, the present inventors have found a curable resin composition containing a silicone rubber powder having an initial viscosity of 1 〇. Below 〇pa · s, it is also possible to suppress the participation phenomenon when the liquid crystal is dropped into the method. In addition, it has been found that by adding an amino decane coupling agent to the chemical resin composition, the effect of further preventing the infiltration can be obtained, and the spherical filler can be added as needed, thereby improving the distribution. The linearity of the seal at the time of coating, 遂 completed Lin Ming. In other words, the present invention relates to the following (1) to (1). (1) A liquid crystal sealing agent comprising (a) a polyoxo rubber powder, and the viscosity at 25 ° C measured by an E-type viscometer is 1 〇〇 Pa · s 0 321935 6 201042016 (2) The liquid crystal sealing agent of the above-mentioned ') includes a (b) amine group; an oxime-fired coupling agent. (3) The liquid crystal sealing agent according to (1) above, which further comprises (c) a spherical filler. (4) The liquid crystal sealing agent according to any one of (1) to (3) above which further comprises (d) a photocurable resin. (5) The liquid crystal sealing agent according to any one of (4), wherein (d) the photocurable resin is an epoxy acrylate. (6) The liquid crystal sealing agent according to any one of the above (1) to (5), wherein (e) a photoradical polymerization initiator is contained. (7) The liquid crystal sealing agent according to any one of (1) to (6) above which further comprises (f) a thermosetting resin and/or (g) a heat hardening agent. (8) The liquid crystal sealing agent according to any one of the above (7), wherein (f) the thermosetting tree s-type epoxy resin 'component (g) the heat hardening agent is hydrazide ° (9) The liquid crystal sealing agent according to any one of the above (1), wherein the compound Q contains (h) an inorganic filler having an average particle diameter of 3 / / m or less. (1) A liquid crystal display unit is a cured product obtained by hardening a liquid crystal sealing agent according to any one of the above (^ to ^). (Effect of the Invention) In other words, the liquid crystal sealing agent of the present invention has a low viscosity and does not undergo the pre-baking step, and has an excellent effect of preventing liquid crystal from penetrating into the sealing agent during the liquid crystal dropping method. Therefore, by using this sealant, it is easy to manufacture a crystal display panel which can shorten the time taken for the dispensing coating or screen printing. 7 321935 201042016 [Embodiment] Hereinafter, the present invention will be described in detail. The polyoxyxylene rubber powder used in the liquid crystal sealing agent of the present invention is not particularly limited as long as it is composed of a polymer having a repeating of a decane bond as a main chain. The polyoxynian powder is generally classified into a resin powder and a rubber powder according to the modulus of elasticity, and is particularly preferably a rubber powder having impact absorption properties from the viewpoint of suppressing penetration of liquid crystal into the sealant. The polyoxyethylene rubber powder coated on the surface without a crosslinked polymer or the like is preferred. Further, in the present invention, the polyoxyxene rubber is preferably one having a structure obtained by crosslinking a polyoxyalkylene oxide, and the polyoxyalkylene oxide is preferably a linear dimethyl polyoxyalkylene. Further, since the sealant is heat-treated at the time of manufacture and use, it is preferable to have heat resistance. When the average particle diameter of the polyoxyxene rubber powder (a) used in the liquid crystal sealing agent of the present invention is too large, when a liquid crystal cell having a narrow gap is produced, a gap cannot be formed smoothly when the upper and lower glass substrates are bonded together. If it is a bad cause, it is usually 3/zm or less, and preferably 2/zm or less. Further, similarly, the maximum particle diameter is usually 8 #m or less, and preferably 5/zm or less. Further, in order to form a gap well, it is preferred to exhibit rubber elasticity at -50 ° C to 250 ° C. In addition, it is also preferable in terms of liquid crystal contamination. KMP-594 is made by Shin-Etsu Chemical Co., Ltd. The amount of use of the liquid crystal sealant of the present invention is usually from 1 to 20% by mass, and preferably from about 5 to 15% by mass, based on 100% by mass of the liquid crystal sealant of the present invention. If more is added, the shake density is increased to lower the coatability. The polyoxyxene rubber powder (a) 8 321935 201042016 used in the liquid crystal sealing agent of the present invention is preferably/lightly combined with an amine group. By this, it is possible to prevent the liquid crystal from penetrating into the sealant because of the improved impact resistance. The amine-based smoldering agent (8) which can be used in the liquid crystal sealing agent of the present invention is generally not particularly limited. For example, · aminopropyl three, Shi Xi burning, aminopropyl triethoxy (tetra), dimethylaminopropyl trimethoxy sulphate, diethyl propyl tridecyloxy Wei, dipropyl Aminopropyl dimethoxy Wei, dibutylaminopropyl trimethoxy money, monobutylamine Ο Ο propyl trimethoxy Wei, dioctylaminopropyl trimethoxy Wei, two Butylated propyl propyl dimethoxy, dibutylaminopropyl monomethoxy sulphate, -methylaminophenyl trimethoxy wei, trimethyl decyl carbyl bis phenylamine, Trif-methoxy-Wiki-r-propyl-gamma-amine, trimethoxy-carbo-propyl propyl pipe, trimethoxy-demethyl propyl phenanthrene, trimethoxy benzyl-propyl propyl, and the like. These may be used alone or in combination of two or more. When the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the content of the saddle-based composition in the liquid crystal (four) is about G to about 3%. The initial viscosity of the liquid crystal sealing agent in the present invention is 1 〇〇pa·s or less. When the initial viscosity is 1 〇〇pa·s or less, the distribution coating property is excellent and can be applied to screen printing, which is greatly related to the productivity of the panel and has an effective influence. The spherical filler (c) which can be used in the liquid crystal sealing agent of the present invention may, for example, be silica, silica gel, hollow glass, carbon black, high molecular polyethylene or the like. In the case of a spherical shape, since the agitation pressure can be applied as a whole regardless of the direction, it can be stably settled. In addition, 9 321935 201042016 This filler usually has an average particle size of ◦.(10)_ to (10)(4), and preferably 〇· 〇1 2 to 10Am. By adding a spherical filler of this size, it is possible to reduce the deflection. By this, it is possible to carry out the stable distribution coating and the linearity of the private (four). In the foregoing, since the resin is easily dispersed, the Πΐη water is preferably cut. The submicron spherical cerium oxide powder 信24_ 9163Α can be obtained from the market. When the liquid crystal sealing agent of the present invention is made in an amount of (10)% by mass as a whole, it is usually used in an amount of from 〇 to 1 (% by mass), and preferably 3% by mass. If more is added, the effect of the oxygen-based rubber powder and the amine-based light is low, and the penetration is poor. The photocurable resin (d) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited as long as it has a low elution property into the liquid crystal, and examples thereof include, for example, urethane acrylate, A compound having a propylene fluorenyl group as a functional group such as a methyl acrylate or a cyclodecyl acrylate. Specifically, δ, for example, benzyl methacrylate, cyclohexyl methacrylate, glycerol, phthalic acid acrylate, glyceryl tridecyl acrylate, hydrazine modified a, a _ θ| ' from dipropylene Acid bismuth, pentaerythritol acrylate, trimethylolpropane triacrylate, decyloxyethyl)isocyanurate, dipentaerythritol acrylonitrile, glycinol triacrylate, and the like. In addition, it is especially good for epoxy (fluorenyl) acrylate resin in terms of your swimming, _ 气 攸 攸 and day 3 dyeing. The ring & acryl vinegar resin can be carried out by a method of synthesizing an acrylic acid or a mercaptopropionic acid with an epoxy resin having at least two or more epoxy groups. . For example, adding a predetermined equivalent ratio of acrylic acid or mercapto-propyl bridge q-ene acid to the epoxy tree, and a catalyst (for example, 321935 10 201042016, monomethylamine, triethylamine, chlorinated nodal Methylammonium, triphenyl beryllium, triphenyi stibine, etc., and polymerization inhibitors (for example, p-nonyloxybenzene, hydroquinone, methyl aerated, morphine Ohenothiazine), Dibutylhydroxytoluene, etc.), for example, 8〇 to 11〇Ο
Ci^酯化反應。此外’分子中具有至少2個以上環氧基 之％„可舉例如：㈣A型環氧樹脂、烧基取代雙紛 ^裏氧树月曰、環氧烧加成雙紛A型環氧樹脂、雙齡F型 衣氧烧基取代雙齡F型環氧樹脂、環氧餘成雙盼 ==¼月曰 '雙紛s型環氧樹脂、烧基取代雙紛^型環 氧樹脂、環氧燒加成雙紛s型環氧樹脂、紛麟（咖⑽ 型環氧樹脂、甲盼祕型環氧樹脂、聯苯型環氧 、膝月^秦型環氧樹脂、環氧丙基胺型環氧樹脂、二環戍二 橡樹脂、聚石夕氧改質環氧樹脂、胺酯改 質環氧樹脂等，以雙紛A型環氧樹脂、燒基取代雙 型产Γ氧翻旨、環姐加成魏A型環氧樹脂、雙紛F 盼F型環氧樹脂' 環氧燒加成雙 環氧樹月:r二雙紛S型環氧樹脂、燒基取代雙紛s型 ㈣秘H减加成伽s型環氧樹 ，密封劑中，若令本發明之液晶密封劑整體= 月 里％ ，則光硬化性樹脂（d)在液晶密封劑中所’’、、貝 至8〇質量％左右。 厅佔之含量為0 此外’本發明之液晶密封射可㈣ 起始劑（e)，只要為自由基型聚合起始 ^ 土聚曰 定，可舉例如：节基二曱基躺、 貝=無特別限 工基％已基笨基酮、 321935 11 201042016 二乙基0塞嘴酮（(^61;1^11:1^〇又&111±〇1^)、二苯曱酮、2-乙基 蒽醌、2-羥基-2-甲基苯丙酮、2-曱基-[4-(曱硫基）苯基] -2-嗎琳基-1-丙烧、2, 4,6-三曱基苄醢基二苯基膦氧化物 等。此外’也可使用2-羥基-l-[4-(2-羥基乙氧基）苯基]-2- 甲基丙-卜酮、或曱基丙烯酸2-異氰酸基乙基酯與2-羥基 1 [4-(2*'經基乙氧基）苯基]-2-甲基丙-1 —酮之反應生成 物。 在本發明之液晶密封劑中，光自由基聚合起始劑成分 (e)相對於光硬化性樹脂（d)之調配比係，相對於（d)成分 1〇〇質量份，通常為〇.〇1至20質量份，且以5至π質量 份為佳。若自由基產生型光自由基聚合起始劑之量少於 0.01質量份，則光硬化反應不充分，若大於質量份， 則起始劑之量過多，而起始劑對液晶造成污染或硬化樹脂 特性降低而成為問題。 在本發明之液晶密封劑中，也可包含熱硬化樹脂（f) 及/或熱硬化劑（g)。經由使用熱硬化性樹脂（〇及〆或埶 硬化劑ω’而使液晶污染性良好。此外，接著強度、糾 濕熱測試之可靠性提高。 本，明之液晶密封劑中可使用之熱硬化樹月旨⑴並無 以2宫能以上之環氧樹脂為佳，例如：雙酚A 、魏F型環氧_、物s型環氧樹脂、紛 μ樹脂、㈣祕型環氧樹脂、雙紛a轉型環 =:F _型環氧樹脂、脂環式環氧樹脂、脂肪 狀壤讀腊、環氧_型縣樹脂、魏㈣胺型環 321935 12 201042016 氧樹脂、尿囊素（hydantoin)型環氧樹脂、異氰腺酸酯型環 氧樹脂、具有三盼曱烧骨架之驗紛酸型環氡樹脂，其他尚 有二官能紛類之二環氧丙基醚化物、二官能醇類之二環氧 丙基醚化物、及該等之南化物、氫化物等。此等之中，從 液晶污染性之觀點來看，以雙酚型環氧樹脂、酚醛型環氧 樹脂為佳。 此外，可用於本發明之液晶密封劑中之熱硬化樹脂之 ¢)水解性氯量係以600ρρπι以下為佳。若水解性氯量大於 6〇〇Ppm，則液晶密封劑對液晶之污染性有成為問題之可能 性。水解性氣量可藉由下述方式來定量，例如：使約〇 5g 之環氧樹脂溶於20mL之二噚烧（dioxane)中，以in之Κ0Η =乙醇溶液5mL回流30分鐘後，以〇. 01N硝酸銀溶液滴 定。如此之環氧樹脂在液晶密封劑中所佔之含量為5至50 質量％左右。 〇〜本發明之液晶密封劑中可使用之（g)成分並無特別限 弋，宜使用固形之有機醯肼。可舉例如：屬於芳香族醯肼 之水揚醯肼、苯甲醯肼、丨_萘甲醯肼、對酞酸二醯肼、間 軟賤二酿肼、2, 6-萘甲酸二醯肼、2, 6-吡啶二醯肼、1 2 4-〜酿肼、1，4, 5, 8-萘甲酸四醯肼、均苯四曱酸四酸肼尊。 匕外’脂肪族酸拼化合物可舉例如：甲酸肼、乙醢肼、丙 隨胼、草酸二醯肼、丙二酸二酿肼、丁二酸二酿耕、戊二 酉参_ 肼、己二酸二酿肼、庚二酸二酿肼、1，4一環己烧二 酿解、酒石酸二醯肼、蘋果酸二醯肼、亞胺基二乙酸二醯 牌、Ν，Ν’-六亞曱基雙（半卡肼）、檸檬酸三醯肼、氮基乙酸 13 321935 201042016 三醢肼、環己烷三曱酸三醯肼、丨，3_雙（卡肼基乙基 異丙基尿囊素（l，3~bis(hydrazinocarbonoethyl)~5~ i sopropy lhydantoi η)等具有纈胺酸尿囊素骨架之二醯肼 類等，從硬化反應性與潛在性之平衡之觀點來看，較佳可 舉例如2官能之二醯肼，特佳可舉例如間酞酸二醯肼。 若此等醯肼化合物之平均粒徑過大，則在製造間隙狹 窄之液晶單元時，會成為當貼合上下玻璃基板時無法川貝利 形成間隙等之不良要因，故通常為—以下，且以〜 以下為佳。此外，同樣地，最大粒徑通常為以下，且m 以5/zm以下為佳。此粒徑係藉由雷射繞射/散射式粒产八 布測定器（乾式）（股份有限公司如聰企業製，lm^刀 進行測定。 j 在本發明之液晶密封劑中，芳香族_化合物（八 有率係相對於成分⑴之環氧樹脂之環氧基之環氧當量^ 0. 20至〇. 80為佳、以〇. 4至〇· 6特佳。 此外’本發明之液晶密封劑中可使用之無機填料 I舉例如.㈣氧切、結晶氧切、碳切、氮化石夕 氮化爛、碳_、碳酸鎂、硫酸鋇、硫酸詞、雲母、说、 黏土、氧化銘、氧化鎂、氧化結、氫氧化紹、氩氧化：、 、㈣I呂、石夕酸㈣呂、石夕酸錐、欽酸鎖、玻雜、 =纖維、―硫仙、石棉等，赠融氧切、結化秒、 氮化石夕侧、碳關、硫酸鋇、硫酸妈、雲母氧， :土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁為 ：、 氧化砍、結晶氧切、氧化銘、滑石更佳。此等無== 32!935 14 201042016 可混合2種以上使用。若其平均粒徑過大，則在製造間隙 狹窄之液晶單元時，會成為當貼合上下玻璃基板時無法順 利形成間隙等之不良要因，故通常為3/zm以下，且以2μ m以下為佳。粒徑係藉由雷射繞射/散射式粒度分布測定器 (乾式）（股份有限公司SEISHIN企業製，LMS-3 0)進行測定。 本發明中可使用之無機填料在液晶密封劑中之含量通 常為5至40質量％，且以15至30質量％為佳。當無機填 料之含量低於5質量％時，由於對於玻璃基板之接著強度 〇 降低，且耐濕可靠性也不良，故有時吸濕後之接著強度也 大幅降低。此外，當無機填料之含量大於40質量％時，由 於填料之含量過多，故難以壓扁而無法形成液晶單元之間 隙。 為了提高接著強度，本發明之液晶密封劑可含有胺基 矽烷耦合劑以外之矽烷耦合劑。矽烷耦合劑可舉例如：3-環氧丙氧基丙基三曱氧基矽烷、3-環氧丙氧基丙基曱基二 ◎ 曱氧基矽烷、3-環氧丙氧基丙基曱基二曱氧基矽烷、2-(3, 4-環氧環己基）乙基三曱氧基矽烷、N-苯基-r -胺基丙 基三曱氧基發烧、N-(2-胺基乙基）3-胺基丙基甲基二甲氧 基矽烷、N-(2-胺基乙基）3-胺基丙基甲基三甲氧基矽烷、 3 -胺基丙基三乙氧基梦烧、3 -疏基丙基三曱氧基麥烧、乙 烯基三甲氧基矽烷、N-(2-(乙烯基苄基胺基）乙基）3-胺基 丙基三甲氧基矽烷鹽酸鹽、3-曱基丙烯醯氧基丙基三曱氧 基矽烷、3-氣丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基 矽烷等矽烷耦合劑。此等矽烷耦合劑可混合2種以上使 15 321935 201042016 用。此等之中，為了得到更良好的接著強度及搖變性，以 組合2種矽烷耦合劑使用為佳。經由使用矽烷耦合劑，即 得到具有強的接著強度之液晶密封劑。若令本發明之液晶 密封劑整體為100質量％ ，則如此之矽烷耦合劑之含量通 常為0至3質量％左右。 在本發明之液晶密封劑中，可進一步依需要而調配有 機填料、以及顏料、塗平（1 eve 1 ing)劑、消泡劑、溶劑等 添加劑。 為了得到本發明之液晶密封劑，首先，在（d)成分申依 需要而溶解混合（e)成分、（f)成分。接著，在此混合物中 混合矽炫耦合劑，並添加預定量之（a)成分、（b)成分、（c) 成分、（g)成分、（h)成分、以及依需要之有機填料、消泡 劑、溶劑及塗平劑等後，藉由習知之混合裝置，例如三輥、 混砂機、球磨機等均勻混合，並以金屬網進行過濾，藉此 即可得到本發明之液晶密封劑。 本發明之液晶顯示單元係藉由將於基板形成有預定電 極之一對基板相對向配置成預定間隔，並以本發明之密封 劑將周圍密封後，於其間隙中封入液晶而成者。所封入之 液晶之種類無特別限定。在此，基板係由包括玻璃、石英、 塑膠、矽等且在至少一者具有透光性之組合之基板所構 成。就其製法而言，例如當為液晶滴入方式時，在本發明 之液晶密封劑中添加玻璃纖維等間隔件（spacer)(間隙控 制材料）後，於該一對基板中之一者使用分配器或網版印刷 裝置等塗佈該液晶密封劑。接著，於該液晶密封劑之堰之 16 321935 201042016 内側滴入液晶，並在真空中將另一玻璃基板疊合，而進行 間隙形成。形成間隙後，藉由紫外線照射機而對液晶密封 / 部照射紫外線並進行光硬化。紫外線照射量較佳為500niJ /cm2 至 6000mJ/cm2、更佳為 1000mJ/cm2 至 4000mJ/cm2 之照射量。然後，依需要而在90至13(TC進行硬化1至2 小時，藉此即可得到本發明之液晶顯示單元。如此進行而 得之本發明之液晶顯示單元係無因液晶污染所造成之顯示 _ 不良，且接著性、耐濕可靠性優良者。間隔件可舉例如： Θ 玻璃纖維、氧化矽珠、聚合物珠等。其直徑係依目的而異， 通常為2至8//m，且以4至7/zm為佳。相對於本發明之 液晶密封劑100質量份，其使用量通常為0. 1至4質量份， 且以0.5至2質量份為佳、以0.9至1.5質量份左右更佳。 (實施例） 以下藉由實施例更詳細說明本發明。在實施例中，「份」 係意指質量份，「％」係意指質量％ 。 〇 (液晶滴入工法用之密封劑之調整） 以下述表中所示之比例將各樹脂成分混合攪拌後，使 光聚合起始劑加熱溶解。然後，適當添加填料、增稠劑等 並攪拌。然後，藉由三輥磨機使其分散，並以金屬網（關西 金網股份有限公司製，材質SVS316，斜紋織法（twi 1 ling)， 網眼大小為635篩）過濾，而調製液晶滴入工法用密封劑。 (藉由分配式塗佈而製作單元、評估） 在所調整之液晶滴入工法用密封劑中混合做為間隙劑 之5 # m之玻璃纖維（日本電器硝子股份有限公司製， 17 321935 201042016 PF-50S)並填充於注射器、消泡後，藉由分配器（MUSASHI ENGINEERING公司製，SH0TMASTER 300)以描繪長方形之方 式於玻璃基板上進行塗佈。對於如此製得之密封劑塗佈基 板，將適量之液晶滴入密封框内，並設置於真空貼合裝置 中，在真空中將另一基板疊合。使其回到大氣壓後，以肉 眼確認其直線性。就直線性而言，以未發生斷線與起伏且 線寬固定者為〇，有斷線或起伏之任一者、或是線寬不固 定者為△，有斷線或起伏之任一者且線寬不固定者為X。進 一步觀察10分鐘後，發生密封破裂者為X，有滲入但未破 裂者為△，未滲入、破裂者為〇。 18 321935 201042016Ci^ esterification reaction. In addition, the 'molecule having at least two or more epoxy groups in the molecule' may, for example, be: (4) an A-type epoxy resin, a burn-in-substituted double-difference, an oxygen tree, and an epoxy-fired addition-type A-type epoxy resin. Two-year-old F-type oxyalkylene replaces double-aged F-type epoxy resin, epoxy residual double-looking ==1⁄4月曰' double s-type epoxy resin, burn-in substituted double-type epoxy resin, epoxy Burning and adding double s type epoxy resin, lin (coffee (10) type epoxy resin, acetal type epoxy resin, biphenyl type epoxy, knee month type ^ epoxy type epoxy resin, epoxy propyl amine type Epoxy resin, two-ring ruthenium resin, poly-stone epoxy modified epoxy resin, amine ester modified epoxy resin, etc., with double-type A-type epoxy resin, burning base instead of double-type oxime Ring sister addition Wei A type epoxy resin, double F F Pan type epoxy resin 'Epoxy burning addition double epoxy tree month: r two pairs of S-type epoxy resin, burning base instead of double s type (four) In the sealing agent, if the liquid crystal sealing agent of the present invention has a total of % of the month, the photocurable resin (d) is in the liquid crystal sealing agent. 8〇% by mass. The content of the hall is 0. In addition, the liquid crystal sealing agent (4) of the present invention can be used as a starting agent (e), as long as it is a radical polymerization initiation, for example, a base group, a ruthenium group, a shell = No special limit of work base % base ketone ketone, 321935 11 201042016 diethyl 0 ketamine ((^61; 1^11:1^〇和amp;111±〇1^), benzophenone, 2 -ethyl hydrazine, 2-hydroxy-2-methylpropiophenone, 2-mercapto-[4-(indolyl)phenyl]-2-phenylin-1-propane, 2, 4,6 - tridecylbenzylidenediphenylphosphine oxide, etc. Further, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-butanone can also be used, Or a reaction product of 2-isocyanatoethyl methacrylate with 2-hydroxy 1 [4-(2*'-transethoxy)phenyl]-2-methylpropan-1-one. In the liquid crystal sealing agent of the present invention, the compounding ratio of the photoradical polymerization initiator component (e) to the photocurable resin (d) is usually 〇.〇 with respect to 1 part by mass of the component (d). 1 to 20 parts by mass, and preferably 5 to π parts by mass. If the amount of the radical generating type photoradical polymerization initiator is less than 0.01 parts by mass, photohardening The reaction is insufficient, and if it is more than a part by mass, the amount of the initiator is too large, and the initiator causes contamination of the liquid crystal or the properties of the cured resin are lowered to cause problems. In the liquid crystal sealing agent of the present invention, a thermosetting resin may also be included ( f) and/or a thermosetting agent (g). The use of a thermosetting resin (〇 and 〆 or 埶 hardener ω' makes the liquid crystal contamination good. Further, the reliability of the strength and the enthalpy heat test is improved. The heat-hardening tree that can be used in the liquid crystal sealing agent of Ming Dynasty (1) is not preferable to epoxy resin with more than 2 gongs, for example: bisphenol A, Wei F type epoxy _, s type epoxy resin, 纷μ Resin, (4) secret epoxy resin, double-distribution ring =: F _ type epoxy resin, alicyclic epoxy resin, fat-like soil read wax, epoxy _ type resin, Wei (tetra) amine ring 321935 12 201042016 Oxygen resin, hydantoin type epoxy resin, isocyanate type epoxy resin, acid-type cyclic enamel resin with three-hop smoldering skeleton, and other dicyclic rings An oxypropyl ether compound, a di-epoxypropyl ether compound of a difunctional alcohol, and the like Such as southern chemicals, hydrides and the like. Among these, from the viewpoint of liquid crystal contamination, a bisphenol type epoxy resin or a novolac type epoxy resin is preferred. Further, the amount of the hydrolyzable chlorine of the thermosetting resin which can be used in the liquid crystal sealing agent of the present invention is preferably 600 ρρπ or less. If the amount of hydrolyzable chlorine is more than 6 〇〇 Ppm, the liquid crystal sealant may have a problem of contamination of the liquid crystal. The amount of hydrolyzable gas can be quantified by, for example, dissolving about 5 g of the epoxy resin in 20 mL of dioxane, refluxing with 5 mL of in Κ0Η=ethanol solution for 30 minutes, and then 〇. 01N silver nitrate solution titration. The content of such an epoxy resin in the liquid crystal sealing agent is about 5 to 50% by mass. The component (g) which can be used in the liquid crystal sealing agent of the present invention is not particularly limited, and a solid organic hydrazine is preferably used. For example, it belongs to the aromatic scorpion water scorpion, benzamidine, 丨_naphthoquinone, bismuth bismuth ruthenium, ruthenium ruthenium ruthenium, 2,6-naphthoic acid dioxime 2,6-pyridine dioxime, 1 2 4-~ tanning, 1,4,5, 8-naphthoic acid tetraindole, pyromellitic acid tetradecanoate. Examples of the bismuth-aliphatic acid compound include, for example, cesium formate, acetophenone, propyl acetonide, bismuth oxalate, maltetic acid, succinic acid, glutaric acid, glutinous rice ginseng Diacid bismuth, pimelic acid bismuth, 1,4 hexa hexanol diacetate, tartaric acid diterpene, malate diterpenoid, iminodiacetic acid diterpene brand, Ν, Ν'- hexa曱基双(half-calendar), triterpene citrate, nitrogen-based acetic acid 13 321935 201042016 Triterpenoids, trimethyl sulfonium tridecanoate, hydrazine, 3_bis (carboxylethyl isopropyl urine) From the viewpoint of the balance between hardening reactivity and potential, such as cystein (1,3~bis(hydrazinocarbonoethyl)~5~ i sopropy lhydantoi η), etc. For example, a bifunctional diterpene may be mentioned, and for example, diterpenic acid diterpenoid may be mentioned. If the average particle diameter of the antimony compound is too large, when a liquid crystal cell having a narrow gap is produced, it may become a conformation. When the glass substrate is placed up and down, it is not possible to form a gap or the like. Therefore, it is usually - below, and preferably 〜 or less. The maximum particle diameter is usually the following, and m is preferably 5/zm or less. The particle size is produced by a laser diffraction/scattering type granules (dry type) (manufactured by Congcong Co., Ltd.). The lm^ knife is used for the measurement. j In the liquid crystal sealing agent of the present invention, the aromatic-compound (eight rate is based on the epoxy equivalent of the epoxy group of the epoxy resin of the component (1) ^ 0. 20 to 〇. 80 is In addition, the inorganic filler I can be used in the liquid crystal sealing agent of the present invention, for example, (iv) oxygen cutting, crystal oxygen cutting, carbon cutting, nitriding, nitriding, carbon _, magnesium carbonate, barium sulfate, sulfuric acid, mica, said, clay, oxidation, magnesium oxide, oxidation, hydrogen peroxide, argon oxidation:, (4) I Lu, Shi Xi acid (four) Lu, Shixi acid cone, Qin Acid lock, glass miscellaneous, = fiber, sulphur, asbestos, etc., give oxygen cut, chelate second, nitrite side, carbon off, barium sulfate, sulfuric acid mother, mica oxygen, soil, alumina, hydroxide Aluminum, calcium citrate and aluminum citrate are: oxidized, crystal oxygenated, oxidized, talc is better. These are not == 32!935 14 201042 016 can be used in combination of two or more kinds. When the average particle diameter is too large, when a liquid crystal cell having a narrow gap is produced, it is a disadvantage that the gap cannot be formed smoothly when the upper and lower glass substrates are bonded together, and therefore it is usually 3/zm or less. Preferably, it is 2 μm or less. The particle size is measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd., LMS-3 0). The content of the inorganic filler in the liquid crystal sealing agent is usually from 5 to 40% by mass, and preferably from 15 to 30% by mass. When the content of the inorganic filler is less than 5% by mass, the strength 〇 is lowered for the glass substrate, and Since the moisture resistance reliability is also poor, the strength after the moisture absorption is also greatly lowered. Further, when the content of the inorganic filler is more than 40% by mass, since the content of the filler is too large, it is difficult to crush and the liquid crystal cell gap cannot be formed. In order to increase the bonding strength, the liquid crystal sealing agent of the present invention may contain a decane coupling agent other than the amine decane coupling agent. The decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxy decane, 3-glycidoxypropyl fluorenyl bis decyloxydecane, 3-glycidoxypropyl hydrazine. Di-decyloxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxyoxydecane, N-phenyl-r-aminopropyltrimethoxyoxyl, N-(2- Aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyltrimethoxydecane, 3-aminopropyltriethyl Oxymoxy, 3- benzylpropyltrimethoxy smoldering, vinyl trimethoxy decane, N-(2-(vinylbenzylamino)ethyl) 3-aminopropyltrimethoxy A decane coupling agent such as decane hydrochloride, 3-mercaptopropenyloxypropyltrimethoxy decane, 3-apropyl propylmethyldimethoxydecane or 3-chloropropyltrimethoxydecane. These decane coupling agents can be used in combination with two or more types for use in 15 321935 201042016. Among these, in order to obtain better bonding strength and shakeability, it is preferred to use two kinds of decane coupling agents in combination. By using a decane coupling agent, a liquid crystal sealing agent having a strong adhesive strength is obtained. When the liquid crystal sealing agent of the present invention is 100% by mass as a whole, the content of the decane coupling agent is usually about 0 to 3% by mass. In the liquid crystal sealing agent of the present invention, an organic filler, an additive such as a pigment, a sizing agent, an antifoaming agent, or a solvent may be further added as needed. In order to obtain the liquid crystal sealing agent of the present invention, first, the component (e) and the component (f) are dissolved and dissolved as required in the component (d). Next, a turmeric coupling agent is mixed in the mixture, and a predetermined amount of the component (a), the component (b), the component (c), the component (g), the component (h), and the organic filler as needed are added. After the foaming agent, the solvent, the leveling agent, and the like are uniformly mixed by a conventional mixing device such as a three-roller, a sand mill, a ball mill, or the like, and filtered with a metal mesh, the liquid crystal sealing agent of the present invention can be obtained. In the liquid crystal display unit of the present invention, the liquid crystal display unit is formed such that a predetermined electrode is formed on the substrate so as to face the substrate at a predetermined interval, and the sealing agent is sealed by the sealing agent of the present invention, and the liquid crystal is sealed in the gap. The type of the liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate including glass, quartz, plastic, tantalum or the like and having a combination of at least one of light transmissive properties. In the method of the method, for example, when a liquid crystal instillation method is used, a spacer (gap control material) such as glass fiber is added to the liquid crystal sealing agent of the present invention, and then one of the pair of substrates is used for distribution. The liquid crystal sealing agent is applied to a device or a screen printing device or the like. Next, liquid crystal was dropped on the inside of the liquid crystal sealing agent 16 321 935 201042016, and another glass substrate was laminated in a vacuum to form a gap. After the gap was formed, the liquid crystal sealing portion was irradiated with ultraviolet rays by an ultraviolet ray irradiator and photocured. The ultraviolet irradiation amount is preferably from 500 niJ /cm 2 to 6000 mJ/cm 2 , more preferably from 1000 mJ/cm 2 to 4000 mJ/cm 2 . Then, if necessary, it is cured at 90 to 13 (TC for 1 to 2 hours, whereby the liquid crystal display unit of the present invention can be obtained. The liquid crystal display unit of the present invention thus obtained has no display due to liquid crystal contamination. _ Defective, and excellent in adhesion and moisture resistance. Examples of the spacer include: Θ glass fiber, cerium oxide beads, polymer beads, etc. The diameter varies depending on the purpose, and is usually 2 to 8/m. And preferably from 4 to 7/zm. The amount of the liquid crystal sealing agent used in the invention is usually from 0.1 to 4 parts by mass, and preferably from 0.5 to 2 parts by mass, from 0.9 to 1.5 parts by mass. The present invention will be described in more detail by way of examples. In the examples, "parts" means mass parts, and "%" means mass%. 〇 (for liquid crystal dropping method) Adjustment of the sealant) The respective resin components are mixed and stirred at a ratio shown in the following table, and then the photopolymerization initiator is heated and dissolved. Then, a filler, a thickener, or the like is appropriately added and stirred, and then, by three rolls. The mill makes it dispersed and is made of metal mesh (Kanxi Jinwang shares) Co., Ltd., material SVS316, twi 1 ling, mesh size 635 sieve), and modulating the liquid crystal into the sealing agent for the process. (Made by means of dispensing coating, evaluation) Adjusted liquid crystal drop-in method is used as a gap agent for 5# m glass fiber (made by Nippon Electric Glass Co., Ltd., 17 321935 201042016 PF-50S) and filled in a syringe, defoamed, by dispensing The device (made by MUSASHI ENGINEERING Co., Ltd., SHOTMASTER 300) is applied to the glass substrate by drawing a rectangular shape. For the sealant-coated substrate thus obtained, an appropriate amount of liquid crystal is dropped into the sealing frame and placed in a vacuum bonding. In the apparatus, the other substrate is superposed in a vacuum, and after returning to atmospheric pressure, the linearity is visually confirmed. In terms of linearity, the line is not broken and the line width is fixed, and the line width is fixed. Any one of the line or the undulation, or the line width is not fixed, △, any one of the broken line or the undulation, and the line width is not fixed, X. After further observation for 10 minutes, the seal rupture is X, there is Infiltration However, those who are not broken are △, those who have not penetrated or broken are 〇. 18 321935 201042016
[表ι] 實施例1 實施例2 實施例3 比較例1 比較例2 · (1)光硬化樹脂 6 6 6 (2)光硬化樹脂 10 10 10 (3)甲基丙烯酸酯改質化合物 12 12 (4)熱硬化樹脂 4 4 4 (5)熱硬化樹脂 2 2 (6)熱硬化樹脂 6 6 (7)光聚合起始劑 3 3 3 0. 4 0. 4 —___________-^ (8)胺基矽烷耦合劑 0. 1 0. 1 (9)矽烷耦合劑 ^ 0. 3 0. 3 0. 3 0· 2 0. 2 (10)熱硬化劑 1.8 J 1.8 1.8 (Π)熱硬化劑 3. 64 3. 64 (12)KMP-594 4 4 4 C13)KMP-600 2 (14)F-351 2 (15)次微米球狀填料 1. 25 1. 25 (16)氧化& 1. 25 1. 25 1. 25 (1Ό橡膠 0. 26 0. 26 0. 26 (18)氧化矽 6. 8 6. 8 初期黏度（lOrpm) 75 80 84 280 279 搖變性（lrpm/10rpm) 1. 48 1. 50 1. 94 1. 12 1. 09 滲入測試 〇 Δ 〇 〇 〇 1 ~ — — — 直線性 〇 〇 △ X X Ο Ο (1) 雙酚Α型環氧丙烯酸酯：R-93100(日本化藥股份有限 公司製） (2) 間;φ； 紛—壤氧丙基謎與丙稀酸之反應物 (3) 甲基丙烯酸酯改質環氧丙烯酸酯：RM_931〇〇(日本化 19 321935 201042016 藥股份有限公司製） (4) 間苯二酚二環氧丙基醚 (5) 酚芳烷基型環氧樹脂：YDF_8170C(東都化成股份有限 公司製） (6) 紛芳烷基型環氧樹脂：EPPN501H(曰本化藥股份有限 公司製） (7) 1-[4-(2-羥基乙氧基）苯基]-2-羥基-2-曱基-1-丙 -1-酮：Irgacure 2959(Ciba Specialty Chemical 公 司製） (8) N-2-(胺基乙基）-3-胺基丙基三甲氧基矽烷：ΚΒΜ-603 (信越化學工業股份有限公司製，ΚΒΜ-603) (9) 3-環氧丙氧基丙基三甲氧基矽烷：siLA-ACE S-510 (CHISS0股份有限公司製） (10) 間酞酸二醯肼：IDH-S(大塚化學股份有限公司製） (11) 1，3-雙（卡肼基乙基）-5-異丙基尿囊素：AMICURE VDH (味之素Fine Techno股份有限公司） (12) 聚矽氧橡膠粉末：kmP-594(信越化學工業股份有限公 司製） (13) 聚矽氧複合粉末：ΚΜΡ-600(信越化學工業股份有限公 司製） (14) 核殼型丙烯酸系共聚物：f-351S(GANZ化成股份有限 公司製） (15) 次微米球狀填料：χ-24-9163Α(信越化學工業股份有 限公司製） 20 321935 201042016 (16) 氧化鋁：SPC-ALCC. I.化成股份有限公司夢） (17) 橡膠：paraloi(i EXL-2655C大阪化成股份有^八s (18) 氧化矽·· SP-1B(扶桑化學工業股份有限公司^^司製） ^石夕氧複合粉末：聚梦氧橡膠粉末之表面經聚石夕氧樹脂 被覆之球狀粉末 (產業上之可利用性） 由上述得知，本發明之液晶密封劑係由於初期黏度 0 低，故塗佈時之直線性優良，並且在液晶滲入密封劑中之 滲入性方面也具有良好的性質。另一方面得知，比較例之 液晶密封劑係由於初期黏度高’故液晶滲入密封劑中之滲 入性方面雖優良，但直線性不良，並未如本發明之液晶密 封劑般滿足任一特性。因此，本案發明之液晶密封劑係歷 經步驟而於基板塗佈之作業性、液晶滴入工法時之滲入性 皆優良’可謂可靠性高者。 【圖式簡單說明】 〇 無。 【主要元件符號說明】 無0 21 321935[Example 1] Example 2 Example 3 Comparative Example 1 Comparative Example 2 (1) Photocurable resin 6 6 6 (2) Photohardenable resin 10 10 10 (3) Methacrylate modified compound 12 12 (4) Thermosetting resin 4 4 4 (5) Thermosetting resin 2 2 (6) Thermosetting resin 6 6 (7) Photopolymerization initiator 3 3 3 0. 4 0. 4 —___________-^ (8) Amine矽 耦合 coupling agent 0. 1 0. 1 (9) decane coupling agent ^ 0. 3 0. 3 0. 3 0 · 2 0. 2 (10) thermal hardener 1.8 J 1.8 1.8 (Π) thermal hardener 3. 64 3. 64 (12) KMP-594 4 4 4 C13) KMP-600 2 (14) F-351 2 (15) sub-micron spherical filler 1. 25 1. 25 (16) Oxidation & 1. 25 1 25 1. 25 (1Ό rubber 0. 26 0. 26 0. 26 (18) yttrium oxide 6. 8 6. 8 Initial viscosity (10 rpm) 75 80 84 280 279 Shake variability (lrpm/10 rpm) 1. 48 1. 50 1. 94 1. 12 1. 09 Infiltration test 〇Δ 〇〇〇1 ~ — — — Linearity 〇〇 △ XX Ο Ο (1) Bisphenolphthalein type epoxy acrylate: R-93100 (Japan Pharmaceutical Co., Ltd.) Co., Ltd.) (2) Between; φ; — - oxypropyl propyl mystery and acrylic acid reactants (3) methacryl Ester-modified epoxy acrylate: RM_931〇〇 (Nippon 19 321935 201042016 Pharmaceutical Co., Ltd.) (4) Resorcinol diepoxypropyl ether (5) Phenol aralkyl type epoxy resin: YDF_8170C ( (6) Argon-based epoxy resin: EPPN501H (manufactured by Sakamoto Chemical Co., Ltd.) (7) 1-[4-(2-Hydroxyethoxy)phenyl]- 2-hydroxy-2-mercapto-1-propan-1-one: Irgacure 2959 (manufactured by Ciba Specialty Chemical Co., Ltd.) (8) N-2-(aminoethyl)-3-aminopropyltrimethoxydecane :ΚΒΜ-603 (made by Shin-Etsu Chemical Co., Ltd., ΚΒΜ-603) (9) 3-glycidoxypropyltrimethoxydecane: siLA-ACE S-510 (manufactured by CHISS0 Co., Ltd.) (10) Diterpenic acid diterpenoid: IDH-S (manufactured by Otsuka Chemical Co., Ltd.) (11) 1,3-bis(carboxyethyl)-5-isopropyl allantoin: AMICURE VDH (Ajinomoto Fine (12) Polyoxyethylene rubber powder: kmP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.) (13) Poly-oxygen composite powder: ΚΜΡ-600 (manufactured by Shin-Etsu Chemical Co., Ltd.) (14) nuclear Shell type acrylic copolymer: f-351S (manufactured by GANZ Kasei Co., Ltd.) (15) Submicron spherical filler: χ-24-9163Α (manufactured by Shin-Etsu Chemical Co., Ltd.) 20 321935 201042016 (16) Alumina: SPC-ALCC. I. Chemicals Co., Ltd. Dream) (17) Rubber: paraloi (i EXL-2655C Osaka Chemicals Co., Ltd. has eight s (18) bismuth oxide · SP-1B (Fusang Chemical Industry Co., Ltd. ^^ Division ^) Xixi oxygen composite powder: the surface of the polyoxyl rubber powder coated with polysulfide resin spherical powder (industrial availability) It is known from the above that the liquid crystal sealing agent of the present invention is due to the initial viscosity When 0 is low, it is excellent in linearity at the time of coating, and also has good properties in terms of penetration of liquid crystal into the sealant. On the other hand, the liquid crystal sealing agent of the comparative example is excellent in the penetration property of the liquid crystal infiltrating into the sealing agent because of the high initial viscosity, but the linearity is poor, and it does not satisfy any characteristic as the liquid crystal sealing agent of the present invention. . Therefore, the liquid crystal sealing agent of the present invention is excellent in the workability in the substrate coating process and the liquid crystal dropping method in the case of the steps. [Simple description of the diagram] 〇 No. [Main component symbol description] None 0 21 321935