201100933 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之黏度為 lOOPa· s以下之液晶密封劑，並且因未經過乾燥步驟或預 烤(pre-bake)步驟，故液晶不會滲入密封部中；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】 〇 近年來液晶顯示單元（liquid crystal display cell)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（takt 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 〇於玻璃基板後，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 使樹脂硬化之液晶滴入工法也正在貫用化。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，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。 其次，在密封劑未硬化之狀態下將液晶之微小液滴予以滴 加塗佈於透明基板之密封圖案之框内全面後，立刻將另一 3 321934 201100933 =基板貼合，而製作液晶單元， 外線而進行預硬化。然後m而 你达曰抑-、要在減壓下進行將基板貼合而製 =:了，則可以極高效率製造液晶顯， ^此滴人讀已逐漸成為液晶顯示元件之製造方法之主 流0 當藉由液晶滴入工法來製造液晶顯示元件時，有 問題.所製得之液晶顧；_ 生液晶渗入密封圖案‘中= 案發生變形’而產 黏产μ〜Γ 解決此_之枝有例如使用 =度較·所使用者更高之密封劑來形成密封圓案， ==:’而導致在進行分配時之乾涸、斷線等；良 ==此外，近年來為了更進一步縮短產距時間 开 ==分配速度或更容易地藉由網版印刷 劑成雄、封圖案’因此而要求更低黏度且無滲入現象之密封 元之問題，在專利文獻1中，有在進行製作液晶單 象之報止則妙未硬化之密封圖案增黏而防止滲入現 =::Γ ’尚無關於下述之液晶密封劑的前例:剛 ;;=，度為_。以下之低黏度，並且即使在 5 a度也不會極度上升的用於液 曰曰滴入工法之液晶密封劑。 粒子ί專利文獻2及3中，有包含橡膠狀聚合物微 子之液4封劑之報告4此等2份公報之情形中，皆 321934 4 201100933 並非初期黏度為lOOP.a· s以下者。在專利文獻4中，有包 含核殼(core-shell)構造交聯橡膠與特定馬來醯亞胺化合物 之液晶密封劑之報告，但初期黏度超過l〇〇Pa · s。在專利 文獻5中，有包含核殼構造交聯橡膠之液晶密封劑之報 告’但初期黏度超過l〇〇Pa· s。並且，尚無關於下述作用 之報告：為了抑制在光硬化時不容易照射到uv之遮光部 分之密封劑成分在熱硬化時溶出於液晶中，而使用橡膠狀 聚合物微粒子，以發揮做為預烤時之增黏成分之作用。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕日本特開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2〇〇7_262253號公報 〔專利文獻4〕日本特開2005 —2015號公報 〔專利文獻5〕國際公開2〇〇4/419〇〇號小冊 ❹【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 入密封劑中之滲入覌象，而提供一種經減少滲入現象之液 晶密封劑及使用該密封劑的液晶顯示單元。 (解決課題的手段） 本發明^等進行致力研究後，結果發現一種使用具有 核忒構城/ 脂微粒子的硬化性樹脂組成物，該硬化性樹 脂組成物係初期黏度為l〇〇pa · s以下者，且在分配式塗 5 321934 201100933 佈、網版印刷塗佈之任—者之情形下的塗佈性皆優良，並 且在經過增黏過程後維持下之黏度，同時可形成單 凡間隙_gap)。此外，也發現藉由使用該硬化性樹⑻且 成物即可防止進行液晶滴^法時之滲人現象，遂完成本 發明。換言之，本發明係有關下述〇)至（ιι)者。 ⑴-種液晶密封劑，係包含（a)具有核殼構造之 樹脂微粒子’且❹E難度計測狀坑之黏 lOOPa · s以下者。 ⑺如前述⑴之液晶密封劑，其中，復包含成分 (b )光硬化樹月旨。 (3 )如刖述（2 )之液晶密封劑，其中，成分（匕） 光硬化樹脂係環氧（甲基）丙烯酸酯樹脂。 (4 )如削述（3 )之液晶密封劑，其中，在環氧（曱 基）丙烯酸酯樹脂中包含50質量％以上的間苯二酚二環氧 丙基醚與丙烯酸之反應生成物。 (5) 如前述〇)至（4)中任一項之液晶密封劑， 其中’復包含成分（c)石夕烧柄合劑。 (6) 如前述（5)之液晶密封劑，其中，包含(胺 基乙基）-3-胺基丙基三曱氧基矽烷做為成分（c)矽烷耦 合劑。 (7) 如前述（丨）至（6)中任一項之液晶密封劑， 其中，復包含（d)光自由基聚合起始劑。 (8) 如前述（1)至（7)中任一項之液晶密封劑， 其中’復包含（e)熱硬化樹脂及/或（f)熱硬化劑。 321934 6 201100933 (9)如前述⑴之液晶密封劑，其中，成分⑷熱 硬化樹脂係環氧樹脂，&八< # 成刀（f)熱硬化齊J係有機醯肼201100933 VI. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal sealing agent which is excellent in dispensing property and can correspond to a liquid crystal sealing having a viscosity of 100 Pa·s or less for screen printing. The liquid crystal does not penetrate into the sealing portion because the drying step or the pre-bake step is not performed; and the present invention relates to a liquid crystal display unit using the sealing agent. [Prior Art] In recent years, liquid crystal display cells have also been applied to large-scale display such as televisions, and the demand for multi-purpose 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 takt time (time per step). In the production of a liquid crystal display device, conventionally, it has been produced by coating a liquid crystal sealing agent on a glass substrate by a method such as dispensing coating or screen printing, sealing it to form a unit, and vacuuming it. After the liquid crystal is injected into the cell from the liquid crystal injection port provided in a part of the environment, the liquid crystal injection port is sealed with 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 being used. In the liquid crystal dropping method, first, a rectangular sealing pattern composed of an uncured sealant is formed by dispensing one of two transparent substrates with electrodes. Next, after the liquid droplets of the liquid crystal are dripped and applied to the frame of the sealing pattern of the transparent substrate in a state where the sealing agent is not hardened, the other 3 321934 201100933 = substrate is bonded to form a liquid crystal cell. Pre-hardening on the outside line. Then m and you reach the suppression -, under the pressure reduction, the substrate is bonded and made =:, then the liquid crystal display can be manufactured with high efficiency. ^ This drop has gradually become the mainstream of the manufacturing method of liquid crystal display elements. 0 When the liquid crystal display element is manufactured by the liquid crystal dropping method, there is a problem. The liquid crystal produced by the liquid crystal is infiltrated into the seal pattern 'the case is deformed' and the stick is produced μ~Γ For example, a sealing agent with a higher degree than the user is used to form a sealing case, ==: ', resulting in drying, breaking, etc. during dispensing; good == In addition, in recent years, in order to further shorten the production In the case of the time opening == distribution speed or more easily by the screen printing agent, the sealing pattern is required to require a lower viscosity and no penetration phenomenon, in Patent Document 1, a liquid crystal sheet is being produced. As for the report, the seal pattern is not hardened to increase the adhesion and prevent penetration. =::Γ 'There is no previous example of the following liquid crystal sealant: just;;=, degree is _. The following liquid crystal sealant for liquid helium dropping method, which has a low viscosity and does not rise extremely even at 5 degrees. Particles ί Patent Documents 2 and 3, there are reports of liquid silicone sealants containing rubbery polymer microparticles. 4 In the case of these two publications, all of them are 321934 4 201100933, and the initial viscosity is not less than 100 p.a·s. Patent Document 4 discloses a liquid crystal sealant comprising a core-shell structure crosslinked rubber and a specific maleimide compound, but the initial viscosity exceeds 10 ÅPa · s. In Patent Document 5, there is a report of a liquid crystal sealing agent comprising a core-shell structured crosslinked rubber, but the initial viscosity exceeds 10 ÅPa·s. Further, there is no report on the effect of the following: in order to suppress the sealant component which is not easily irradiated to the light-shielding portion of the uv at the time of photo-curing, it is dissolved in the liquid crystal at the time of heat curing, and rubber-like polymer microparticles are used to serve as The role of the viscosity-increasing component in pre-baking. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2008-275670 (Patent Document 2) JP-A-2007-219039 (Patent Document 3) JP-A-H07-262253 [Patent Document 4] Japanese Laid-Open Patent Publication No. 2005-2015 (Patent Document 5) International Publication No. 4/4 〇〇 小 ❹ 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 ( ( ( ( In the liquid crystal dropping method, the liquid crystal penetrates into the sealant, and a liquid crystal sealing agent which reduces the penetration phenomenon and a liquid crystal display unit using the sealing agent are provided. (Means for Solving the Problem) After intensively studying the present invention, it was found that a curable resin composition having a core structure/lipid fine particle having an initial viscosity of l〇〇pa·s was used. The following, and in the case of the distribution coating 5 321934 201100933 cloth, screen printing coating, the coating properties are excellent, and after the viscosity-increasing process to maintain the viscosity, while forming a single gap _gap). Further, it has been found that the use of the curable tree (8) can prevent the phenomenon of infiltration during the liquid crystal dropping method, and the present invention has been completed. In other words, the present invention relates to the following 〇) to (ι). (1) A liquid crystal sealing agent comprising (a) resin fine particles having a core-shell structure and having a viscosity of 100 Pa·s or less. (7) The liquid crystal sealing agent according to the above (1), wherein the component (b) is photohardened. (3) The liquid crystal sealing agent of (2), wherein the component (匕) photocurable resin is an epoxy (meth) acrylate resin. (4) The liquid crystal sealing agent of (3), which contains 50% by mass or more of a reaction product of resorcinol diglycidyl ether and acrylic acid in an epoxy (meth) acrylate resin. (5) The liquid crystal sealing agent according to any one of the above items, wherein the compound comprises (c) a stone stalk mixture. (6) A liquid crystal sealing agent according to the above (5), which comprises (aminoethyl)-3-aminopropyltrimethoxy decane as a component (c) decane coupling agent. (7) The liquid crystal sealing agent according to any one of (a) to (6), wherein (d) a photoradical polymerization initiator is further contained. (8) The liquid crystal sealing agent according to any one of the above (1) to (7), wherein the composite comprises (e) a thermosetting resin and/or (f) a thermal curing agent. 321934 6 201100933 (9) The liquid crystal sealing agent according to the above (1), wherein the component (4) is a thermosetting resin-based epoxy resin, & eight <
Chydrazide) ° (⑻如則述⑴至（9)中任一項之液晶密封劑， 其中’復包含（g)平均粒徑為3//m以下之無機填料。 (U ) —種液晶顯示單元，係以前述（丨）至（中 任-項之液晶密封劑硬化而得之硬化物加以密封者。 _ (發明的效果） 〇 ^本發明之液晶密封劑係即使經過預烤步驟仍維持一 疋以下之黏度’因此，可形成單元間隙。除此之外，具有 f進行液aB滴人J1法時使液晶渗人密封劑中之程度為相當 >、的效果。因此’經由使用此密封劑，即可使分配式塗佈、 、周版印刷塗佈所耗費之時間縮短，而可容易地製造液晶顯 不面板。 【實施方式】 D 以下’詳細說明本發明。 本發明中所使用之具有核殼構造之樹脂微粒子（a)係 無特別限定，可使用例如：具有由具有橡膠彈性之樹脂所 構成之核心粒子及形成於該核心粒子之表面之由樹脂所構 成之外殼層者。具體而言，較佳係一種微粒子，其為粒子 之核心部分與外殼部分具有不同性質之聚合物，且為在粒 子狀之橡膠之外部具有接枝層的核殼系微粒子、或由橡膠 狀t ά物之核心與玻壤狀聚合物之外殼所構成的核殼系微 粒子。核心部分可舉例如：丁二烯系橡膠、丙烯酸系橡膠、 321934 7 201100933 石夕氧(silicone)—丙稀酸系複合橡膠' 或使聚合性單體聚人 而成之核殼丙烯酸系共聚物等。此聚合性單體之例子可舉 例如：（曱基）丙烯酸正丙酯、（甲基）丙烯酸正丁_、（甲 基）丙蝉酸2-乙基己酯、（曱基）丙稀酸正癸酯等（曱其） 丙烯酸系單體；苯乙烯、乙烯基曱笨、α-曱基苯乙歸等芳 香族乙烯系化合物；丙烯腈、曱基丙烯腈等氰乙烯化合物； 二氰亞乙烯(vinylidene cyanide)、（甲基）丙烯酸2_羥基乙 酯 '(甲基）丙烯酸3-羥基丁酯、富馬酸2_羥基乙酯、羥 基丁基乙烯基醚、馬來酸單丁酯、曱基丙烯酸丁氧基乙酯 等。並且，可舉例如：乙二醇二（甲基）丙烯酸酯、丁二 醇二（曱基）丙烯酸酯、三羥甲基丙烷二（甲基）丙烯酸 酉曰一輕甲基丙烧二（甲基）丙烯酸g旨、己二醇二（甲基） 丙烯酸酯、己二醇三（甲基）丙烯酸酯、寡聚（二（甲基） 丙烯酸伸乙醋）寡聚（三（甲基）丙烯酸伸乙醋）等具有 2個以上反應性基之交聯性單體；二乙烯基苯等芳香族二 乙烯系單豸偏苯二甲酸二烯丙_、三婦丙基異氰酸醋等， 使用從此等中選出之i種或2種以上者。當使用具有核 殼構造之樹賴粒子以外之微粒子及增測時，無法在短 時間内增黏、或也難以特—定黏度。藉由使用具有核殼 構造之樹賴粒子，即可使液晶密封劑之初期黏度成為 騰⑴以下，且藉由預烤步驟來適度地增黏，也可抑制 液晶渗入密封劑中。具有核殼構造之樹職粒子U)係可 從市場絲得，可舉例如：在粒子狀之橡谬之外部具有接 枝層之一 * RAYON股份有限公司製metablen系列、 321934 8 201100933 或丙烯酸酯共聚物之GANZ化成股份有限公司製F —351 等。再者，關於具有核殼構造之樹脂微粒子（a)之含量， 當令本發明之液晶密封劑整體為100質量％時，係以5質 量％至30質量°/◦為佳、以10質量°/◦至20質量％特佳。 本發明之液晶密封劑係剛調整後之初期黏度為 lOOPa · s以下。若初期黏度為lOOPa · s以下，則分配式 塗佈性優良且可對應於網版印刷。本發明之液晶密封劑雖 藉由預烤步驟來增黏，但即使增黏後黏度也不會急劇上 升。本發明之液晶密封劑係在短時間内增黏，且黏度安定 性優良。此外，由於只要其藉由預烤來增黏後之黏度為 lOOPa· s以上400Pa· s以下，則可形成單元間隙而無問 題地進行後續的貼合，而可製作液晶單元，故本發明之液 晶密封劑以藉由預烤來增黏後之黏度為400Pa.s以下為 佳。經由預烤後之加熱使其完全硬化。藉此，防止在進行 液晶滴入工法時液晶滲入密封劑中之滲入現象。 〇 本發明中所使用之光硬化性樹脂（b)，只要溶出至液 晶中之溶出性低，則並無特別限定，可舉例如：如胺酯 (urethane )丙浠酸酯、（甲基）丙烯酸酯、環氧（曱基） 丙烯酸酯等具有丙烯醯基做為官能基之化合物，具體而言 例如：甲基丙烯酸苄酯、甲基丙烯酸環己酯、甘油二曱基 丙稀酸S旨、甘油三丙浠酸醋、EO改質甘油三丙稀酸醋、 季戊四醇丙烯酸酯、三羥甲基丙烷三丙烯酸酯、參（丙烯 醯氧基乙基）異氰脲酸酯、二季戊四醇六丙烯酸酯、氟甘 胺醇（glycinol)三丙烯酸酯、1，6-己二醇二環氧丙基_丙 9 321934 201100933 烯酸酯等。此外，從液晶污染性之觀點來看，以環氧（甲 基）丙烯酸酯樹脂特佳。此環氧（甲基）丙烯酸酯樹脂可 藉由使丙烯酸或曱基丙烯酸與分子中具有至少2個以上環 氧基之裱氧樹脂進行酯化反應而得到。此合成反應可藉由 一般已知之方法進行。例如：在環氧樹脂中添加預定當量 士之丙烯酸或甲基丙烯酸、以及觸媒（例如节基二甲基胺、 三乙基胺、氣化节基三曱基銨、三苯基膦、三苯基銻等）、 與聚合抑制劑（例如對甲氧基盼、氫醒、曱基氫酉昆、㈣ 哄（。phenothiazine)、二丁細基曱苯等），並在例如8〇至 hoc進㈣化反應。此外，分子中具有至少2個以上環氧 f之魏樹脂可舉例如型環氧樹脂、絲取代雙The liquid crystal sealing agent of any one of (1) to (9), wherein the composite material contains (g) an inorganic filler having an average particle diameter of 3 / / m or less. (U) - a liquid crystal display unit , which is sealed by the hardened material obtained by hardening the liquid crystal sealing agent of the above-mentioned (丨) to _ (the effect of the invention) 〇 The liquid crystal sealing agent of the present invention is maintained even after the pre-baking step. In the following, the viscosity can be formed. Therefore, the cell gap can be formed by the fact that the degree of liquid crystal infiltration into the sealant is equal to the effect of the liquid aB dripping J1 method. Therefore, by using the sealant The time required for the dispensing coating and the circumferential printing can be shortened, and the liquid crystal display panel can be easily manufactured. [Embodiment] D Hereinafter, the present invention will be described in detail. The resin fine particles (a) of the core-shell structure are not particularly limited, and for example, a core particle composed of a rubber-elastic resin and an outer layer of a resin formed on the surface of the core particle can be used. Words, Preferably, it is a microparticle which is a polymer having a different property from a core portion and a shell portion of the particle, and is a core-shell microparticle having a graft layer outside the particulate rubber or a core of a rubbery t-material Core-shell microparticles composed of a shell of a glassy polymer. The core portion may be, for example, a butadiene rubber or an acrylic rubber, 321934 7 201100933, a silicone-acrylic composite rubber or A core-shell acrylic copolymer obtained by polymerizing a polymerizable monomer, etc. Examples of the polymerizable monomer include n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (methyl) ) 2-ethylhexyl acrylate, n-decyl acrylate, etc. (acrylic acid) monomer; styrene, vinyl styrene, α-mercaptophenyl benzene, etc. a compound; a cyanoethylene compound such as acrylonitrile or mercapto acrylonitrile; vinylidene cyanide, 2-hydroxyethyl (meth)acrylate 3-hydroxybutyl (meth)acrylate, fumaric acid 2 _hydroxyethyl ester, hydroxybutyl vinyl ether, horse Monobutyl acrylate, butoxyethyl methacrylate, etc., and examples thereof include ethylene glycol di(meth)acrylate, butanediol di(decyl)acrylate, and trimethylolpropane di ( Methyl)acrylic acid hydrazine-light methyl propyl bis(meth) acrylate g, hexanediol di(meth) acrylate, hexanediol tri(meth) acrylate, oligo (di(methyl) a cross-linking monomer having two or more reactive groups such as oligo(ethyl acrylate) oligo(tris(meth) acrylate vinegar); an aromatic divinyl phthalic acid such as divinyl benzene When it is used, it is not possible to be short when it is used in the case of the use of the microparticles and the addition of the particles of the core-shell structure. It is difficult to adjust the viscosity during the time. By using the tree-shell structure having a core-shell structure, the initial viscosity of the liquid crystal sealing agent can be made equal to or less than (1), and the pre-bake step can be used to moderately increase the viscosity, and the penetration of the liquid crystal into the sealant can be suppressed. The tree particle U) having a core-shell structure can be obtained from the market, for example, one of the graft layers on the outside of the particle-shaped rubber * MATRON Co., Ltd., metablen series, 321934 8 201100933 or acrylate Copolymer GANZ Chemical Co., Ltd. made F-351 and so on. In addition, when the content of the resin fine particles (a) having a core-shell structure is 100% by mass as a whole, the liquid crystal sealing agent of the present invention is preferably 5 mass% to 30 mass%/◦, and 10 mass%/ ◦ to 20% by mass. The liquid crystal sealing agent of the present invention has an initial viscosity immediately after adjustment of 100 Pa·s or less. When the initial viscosity is 100 Pa·s or less, the dispensing property is excellent and it can correspond to screen printing. Although the liquid crystal sealing agent of the present invention is tackified by the pre-baking step, the viscosity does not rise sharply even after the viscosity is increased. The liquid crystal sealing agent of the present invention is viscous in a short period of time and has excellent viscosity stability. In addition, since the viscosity after the pre-baking is increased to 100 Pa·s or more and 400 Pa·s or less, the cell gap can be formed without any problem, and a liquid crystal cell can be produced. The liquid crystal sealing agent preferably has a viscosity of 400 Pa.s or less after being pre-baked. It is completely hardened by heating after prebaking. Thereby, the penetration of the liquid crystal into the sealant during the liquid crystal dropping method is prevented. The photocurable resin (b) used in the present invention is not particularly limited as long as the elution property in the liquid crystal is low, and examples thereof include, for example, urethane propionate and (methyl). A compound having an acryl fluorenyl group as a functional group such as an acrylate or an epoxy (fluorenyl) acrylate, and specifically, for example, benzyl methacrylate, cyclohexyl methacrylate, or glyceryl dimercapto acrylate , glycerin triacetin, EO modified glycerin triacetate, pentaerythritol acrylate, trimethylolpropane triacrylate, propylene (propylene oxyethyl) isocyanurate, dipentaerythritol hexaacrylate Ester, glycinol triacrylate, 1,6-hexanediol diepoxypropyl-propane 9 321934 201100933 enoate. Further, from the viewpoint of liquid crystal contamination, epoxy (meth) acrylate resin is particularly preferable. The epoxy (meth) acrylate resin can be obtained by esterifying acrylic acid or methacrylic acid with a fluorinated resin having at least two or more epoxy groups in the molecule. This synthesis reaction can be carried out by a generally known method. For example, adding a predetermined equivalent of acrylic acid or methacrylic acid, and a catalyst (for example, benzyl dimethylamine, triethylamine, vaporized benzyltrimethylammonium, triphenylphosphine, three) Phenylhydrazine, etc.), with a polymerization inhibitor (for example, p-methoxy, hydrogen, sulfhydryl, phenothiazine, dibutyl fluorene, etc.), and for example, 8 〇 to hoc Into the (four) reaction. In addition, a Wei resin having at least two epoxy resins in the molecule may, for example, be a type epoxy resin or a silk substitution double
型二,氧樹脂、環氧烷加成雙酚A型環氧樹脂、雙酚F 紛基取代型環氧樹脂' 環氧燒加成雙 環氧樹旨、物S型環氧樹脂、轉取代雙盼S型 輯月日、料燒加成⑽S型環氧樹脂、_ n〇v〇lae)型環氧樹脂、甲㈣ 樹脂、萘型環氧樹r、 衣氧料、聯苯型環氧 歸型環氧樹脂、“改:環氧：：型環氧樹脂、二環戊二 橡膠改質環氧樹腊等，以二A::胺醋改質環氧樹腊、 酚A型環氧樹脂 衣賴脂、烷基取 型環氧樹…型環氧樹磨： 氧樹脂、環梟ρ 、知、燒基取代勢。 衣虱烷加成雙酚8型 '雙酚S型 ，當令本笋明々V I及乳樹脂為佳。在去 伞知明之液晶密封劑整 庄在本發明 疋體為】00質量％時，光硬 中 型環氧樹塘、雙紛s型環氧：樹塘、環氧貌力σ成雙 %明脂、環氧燒加心w—日、垸基取代雙齡S型 321934 201100933 化性樹脂（b)在液晶密封劑中所佔之含量為20質量％至 80質量％左右。 在本發明中，環氧（甲基）丙烯酸酯樹脂係以在環氧 (曱基）丙烯酸酯樹脂整體中包含50質量％以上之間苯二 酚二環氧丙基醚與丙烯酸之反應生成物者為特佳。因間苯 二酚二環氧丙基醚與丙烯酸之反應生成物係液晶污染性優 良且低黏度者，因此，關於使用該反應生成物之本發明之 液晶密封劑之液晶污染性及黏度之特性會更加提高。 〇 為了提高接著強度，本發明之液晶密封劑係以含有矽 烷耦合劑（C)為佳。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乙氧基矽 烷、3-環氧丙氧基丙基曱基二甲氧基矽烷、2- (3,4-環氧環 己基）乙基三曱氧基矽烷、N-苯基-r-胺基丙基三甲氧基 矽烷、N-2-(胺基乙基）-3-胺基丙基曱基二曱氧基矽烷、 N-2-(胺基乙基）-3-胺基丙基二曱氧基砍炫、3-胺基丙基 〇三乙氧基矽烷、3-巯基丙基三曱氧基矽烷、乙烯基三曱氧 基矽烷、N-( 2-(乙烯基苄基胺基）乙基）-3-胺基丙基三 曱氧基矽烷鹽酸鹽、3-甲基丙烯醯氧基丙基三甲氧基矽 烷、3-氯丙基曱基二甲氧基矽烷、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。再者，以其中一者之矽烷耦合劑 為具有胺基之矽烷耦合劑更佳。尤其是以含有N-2-(胺基 乙基）-3 -胺基丙基二曱氧基碎烧做為胺基碎烧耗合劑特 11 321934 201100933 佳。N-2-(胺基乙基）_3-胺基丙基三f氧基矽烷可從市場 上取得（例如：信越化學工業製KBM—6〇3)。經由使用矽 烷耦合劑，即可得到具有強的接著性且塗佈性優良的液晶 密封劑。當令本發明之液晶密封劑整體為1〇〇質量％時阳 如此之矽烷耦合劑（c)在液晶密封劑中所佔之含量宜為 0.05至3質量％ 。 … 此外，本發明中所使用之光自由基聚合起始劑（d)， 只要為自由基型聚合起始劑，則並無特別限定，可舉例如： 节基二曱基縮酮' 1，基環己基苯基酮、二乙基嗟嘲嗣 (diethylthioxanthone )、二苯甲酮、2_乙基蒽醌、孓羥基-2_ 甲基苯丙酮、2-甲基-〔4·(曱硫基）苯基〕_2_嗎啉基小 丙烷、2,4,6-三甲基苄醯基二苯基膦氧化物等。此外，也可 使用2-羥基小〔4- (2-經基乙氧基）苯基〕_2_甲基丙小 酮、或甲基丙烯酸2-異氰酸基乙酯與2_羥基_丨_〔4_ (2_羥 基乙氧基）本基〕-2-甲基丙_ι_酮之反應生成物。 在本發明之液晶密封劑中，關於（d)光自由基聚合 起始劑相對於成分（b)之調配比，相對於（b)成分1〇〇 質量份，（d)光自由基聚合起始劑通常為〇 〇1至2〇質量 份’且以5至15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20 H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會成為問題。 在本發明之液晶密封劑中，也可包含熱硬化樹脂（e) 及熱硬化劑⑴。經由使用熱硬化性樹脂（d)及熱硬化劑 321934 12 201100933 * _⑴，而使液晶污染性良好。此外，接著強度、 測試之可靠性提高。 ^濕熱 ’本發明中可使用之熱硬化樹腊（e)並無特 2官能't縣樹㈣佳，❹：料A _氧 雙齡F型架乳樹脂、雙紛s型環氧樹脂、㈣ 曰 脂、甲酚酚醛型環負榭_ A 土长乳树 衣虱树知、雙酚A酚醛型環氧樹脂、 F齡酸:型環氧樹腊、賠资 ：断 礼则日“式核氧樹脂、脂肪族鏈狀 〇 "yantoin)型環氧樹脂、異氰腺酸酯型環氧樹脂、 具有三紛甲炫骨架之齡祕型環氧樹月旨，其他尚有曰处 紛類之二環氧丙基趟化物、二官能醇類之二環氧丙基^ 物、及該等之齒化物、氫化物等。此等之中’從液晶污毕 性之觀點來看，以雙_環氧樹脂、祕㈣氧樹脂為佳。 此外，做為本發明所使用之熱硬化樹脂 水解性氣量細_鹏以下為佳。若水解二 〇 riPPm’則有液晶密對液晶之污祕會成為問題之可 解絲量可藉由下述方式來定量，例如：使約叫 kc/h/ “旨溶於2〇mL之二卩§烷（di〇xane)中，以1N之 液滴〜乙醇溶液5mL回流30分鐘後’以〇._俩銀溶 該产=當令本發明之液晶密封劑整體為㈣質量％時， 質:氣樹財本發日狀液晶密封射所佔之含量為0至50 貝垔/〇左右。 定，2明之液晶密封劑中可使用之⑺成分並無特別限 吏用固形之有機_。可舉例如：屬於芳香族酸耕 321934 13 201100933 之水揚醯肼、笨甲醯肼、1-萘曱醯肼、對酞酸二醯肼、間 酞酸二醯肼、2,6-萘甲酸二醯肼、2,心吡啶二醯肼、丨,2,4_ 苯二酿拼、1,4,5,8-萘曱酸四醯肼、均笨四曱酸四醯肼等。 此外，脂肪族醯肼化合物可舉例如：甲醯肼、乙醯肼、丙 醯肼、乙二酸二醯肼、丙二酸二醯肼、丁二酸二醯肼、戊 二酸二醯肼、己二酸二醯肼、庚二酸二醢肼、丨，4_環己烷 二醯肼、酒石酸二醯肼、蘋果酸二醯肼、亞胺基二乙酸二Type 2, oxygen resin, alkylene oxide addition bisphenol A epoxy resin, bisphenol F aryl substituted epoxy resin' epoxy burning addition double epoxy resin, S-type epoxy resin, substituting Double-looking S-type series, day-burning, material-fired addition (10) S-type epoxy resin, _ n〇v〇lae) epoxy resin, nail (a) resin, naphthalene epoxy tree r, epoxy, biphenyl epoxy Equivalent epoxy resin, "Change: Epoxy:: Epoxy resin, Dicyclopentadiene rubber modified Epoxy wax, etc., with two A:: amine vinegar modified epoxy wax, phenol A epoxy Resin-coated lyophile, alkyl-type epoxy tree... Epoxy tree mill: Oxygen resin, cyclopentene ρ, known, alkyl group substitution potential. Zeveane addition bisphenol type 8 'bisphenol S type, when this Bamboo shoots 々 VI and milk resin are preferred. The liquid crystal sealant in the umbrella of the umbrella is 00% by mass in the body of the present invention, the light hard medium-sized epoxy tree pond, double s-type epoxy: tree pond, ring Oxygen-producing force σ into double% gelatin, epoxy burning plus heart w-day, thiol-substituted double-aged S-type 321934 201100933 chemical resin (b) in the liquid crystal sealant content of 20% to 80% % or so. In the present invention In the epoxy (meth) acrylate resin, a reaction product containing 50% by mass or more of a benzenediol diepoxypropyl ether and acrylic acid in the entire epoxy (fluorenyl) acrylate resin is used. Preferably, the liquid crystal contamination and viscosity of the liquid crystal sealing agent of the present invention using the reaction product are excellent because the reaction product of resorcinol diglycidyl ether and acrylic acid is excellent in liquid crystal contamination and low in viscosity. The characteristics of the liquid crystal sealing agent of the present invention are preferably a decane coupling agent (C). The decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxy. Decane, 3-glycidoxypropylmercaptodiethoxydecane, 3-glycidoxypropylmercaptodimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxy decane, N-phenyl-r-aminopropyltrimethoxy decane, N-2-(aminoethyl)-3-aminopropyl decyl decyloxydecane, N-2 -(Aminoethyl)-3-aminopropyl decyloxy chop, 3-aminopropyl hydrazine triethoxy decane, 3-mercaptopropyltrimethoxy decane, B Alkenyl trimethoxy decane, N-(2-(vinylbenzylamino)ethyl)-3-aminopropyltrimethoxy decane hydrochloride, 3-methylpropenyloxypropyl a decane coupling agent such as trimethoxy decane, 3-chloropropyl decyl dimethoxy decane or 3-chloropropyl trimethoxy decane. These decane coupling agents may be used in combination of two or more kinds. It is preferred to use two kinds of decane coupling agents to obtain better bonding strength and shaking property. Further, it is more preferable to use one of the decane coupling agents as a decane coupling agent having an amine group, especially containing N-2. -(Aminoethyl)-3-aminopropyldimethoxycarbonyl calcined as an amine-based calcining agent Special 11 321934 201100933 Good. N-2-(aminoethyl)-3-aminopropyltrimethoxysilane is commercially available (for example, Shin-Etsu Chemical Co., Ltd. KBM-6〇3). By using a decane coupling agent, a liquid crystal sealing agent having strong adhesion and excellent coatability can be obtained. When the liquid crystal sealing agent of the present invention is made in an amount of 1% by mass as a whole, the content of the decane coupling agent (c) in the liquid crystal sealing agent is preferably from 0.05 to 3% by mass. In addition, the photoradical polymerization initiator (d) used in the present invention is not particularly limited as long as it is a radical polymerization initiator, and examples thereof include a stilbene dimethyl ketal Cyclohexyl phenyl ketone, diethylthioxanthone, benzophenone, 2-ethyl hydrazine, hydrazine hydroxy-2-methyl acetophenone, 2-methyl-[4·(thiol) Phenyl]_2_morpholinylpropane, 2,4,6-trimethylbenzylidenediphenylphosphine oxide, and the like. In addition, 2-hydroxysuccinic [4-(2-carbylethoxy)phenyl]-2-methylpropanone or 2-isocyanatoethyl methacrylate and 2-hydroxyl-hydrazine can also be used. A reaction product of _[4_(2-hydroxyethoxy)carbenyl]-2-methylpropanone- ketone. In the liquid crystal sealing agent of the present invention, with respect to (d) the ratio of the photoradical polymerization initiator to the component (b), relative to the (b) component of 1 part by mass, (d) photoradical polymerization The starting agent is usually 〇〇1 to 2 parts by mass 'and preferably 5 to 15 parts by mass. If the amount of the radical generating type photoradical polymerization initiator is less than 0.01 parts by mass, the photohardening reaction is insufficient, and if it is more than 20 H, the amount of the initiator is excessive, and the initiator causes contamination of the liquid crystal or hardens the resin. Reduced features can be a problem. In the liquid crystal sealing agent of the present invention, a thermosetting resin (e) and a heat curing agent (1) may be contained. The liquid crystal contamination property is improved by using the thermosetting resin (d) and the heat curing agent 321934 12 201100933 * _(1). In addition, the reliability of the strength and the test is improved. ^Damp heat 'The heat-hardened tree wax (e) which can be used in the present invention has no special 2-functional 'txian tree (four) good, ❹: material A _ oxygen double-age F-type latex resin, double s-type epoxy resin, (4) Rouge, cresol novolac type ring 榭 _ A soil long nipple tree 虱 知 知, bisphenol A phenolic epoxy resin, F-age acid: type epoxy tree wax, compensation: break ceremony Nuclear oxygen resin, aliphatic chain 〇 yantoin type epoxy resin, isocyanate type epoxy resin, three-year-old sleek skeleton, the age of the secret type of epoxy tree, the other is still awkward Di-epoxypropyl halides, di-epoxypropyl groups of difunctional alcohols, and such toothings, hydrides, etc. Among these, from the viewpoint of liquid crystal contamination, Further, it is preferable to use a double-epoxy resin or a secret (tetra) oxy-resin. Further, it is preferred that the thermosetting resin used in the present invention has a hydrolyzable gas content of less than 5%. If the ruthenium riPPm' is hydrolyzed, the liquid crystal is dense against the liquid crystal. The amount of solvable which can be a problem can be quantified by, for example, making a solution called kc/h/"dissolved in 2〇mL of di〇xane, with a 1N solution After the drop-to-ethanol solution 5 mL is refluxed for 30 minutes, the yield of the two liquid crystal sealants of the present invention is (four) mass%, and the content of the liquid crystal sealing shot of the gas tree It is from 0 to 50 垔 / 〇. The component (7) which can be used in the liquid crystal sealing agent of the formula 2 is not particularly limited to the organic substance of the solid form. For example, it belongs to aromatic acid cultivating 321934 13 201100933, water scorpion, scorpion scorpion, 1-naphthoquinone, bismuth citrate, diterpene bismuth, 2,6-naphthoic acid. Diterpenoids, 2, heart pyridine diterpenes, anthracene, 2,4_ benzene hexagram, 1,4,5,8-naphthoic acid tetraterpene, all stupid tetradecanoic acid tetraterpene and the like. Further, examples of the aliphatic hydrazine compound include: formazan, acetamidine, acetonide, bismuth oxalate, diammonium malonate, diterpene succinate, and bismuth glutarate. , diammonium adipate, dipimepyridinium, hydrazine, 4_cyclohexane dioxime, diterpenic tartrate, diterpene malate, iminodiacetic acid
—，x ^ nyarazinocarbonoettiyi ； 5-isopropylhydantoin)等具有纈胺酸尿囊素骨架之二醯肼 類等’攸硬化反應性與潛在性之平衡之觀點來看 ，較佳可-, x ^ nyarazinocarbonoettiyi; 5-isopropylhydantoin), etc., which have a balance between the hydrazine reactivity and the potential of the guanidine allantoin skeleton, etc.
、由於若此等醯肼化合物之平均粒徑過大，則在製造間 H乍之I單TL時’會成為將上下玻璃基板貼合時無法 舉例如2官能之二If the average particle size of the ruthenium compound is too large, it will not be able to be used as a two-component when the upper and lower glass substrates are bonded together during the production of the I TL.
[嶋一30)進行測定。 在本發明之液晶密封射，當令成分[嶋一30) The measurement was carried out. In the liquid crystal sealing shot of the present invention, when the composition
’當令成分（e)之環氧樹脂 成分（f)之芳香族醯肼化合 劑中可使用之無機填料（g) 321934 14 201100933 可舉例如：溶融氧化石夕（silica)、結 化石夕、氮化蝴、碳酸舞、碳酸鎮、石^酸鎖、石夕、:炭化石夕、氮 滑石、黏土、氧化銘、氧化鎮、& '、硫賴、雲母、 化鎮、石夕酸妈、發酸銘、秒酸化錯、氧氧化銘、氳氧 璃纖維、碳纖維、二硫化鉬、石 、，。鈦馱鋇、坡 曰曰乳化石夕、氮化石夕、氮化爛、啜_、硫酸鎖 、、、。 雲母、滑石、黏土、氧化銘、氫氧化銘、石夕賴二= 為佳，以熔融氧化矽、蛀曰氧 ' 酸鋁 〇此等無機填料可混合、滑石更佳。 *，則在製造間隙狹窄之液晶單元時，：===: 基板貼合時無法翻形成間隙等之不㈣0，故宜為3_ 以下且以2/zm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）（smSHIN企業股份有限公司 製’ LMS —30)進行測定。 當令本發明之液晶密封劑整體為1〇〇質量％時，本發 〇明之液晶密封射可㈣之無機填料（g)在液晶密封劑中 之含量通常為5至40質量％，且以15至3〇質量％為佳。 當無機填料之含量低於5 時，由於對於玻璃基板之 接著強度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4〇質量％ 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。 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（leveUng)劑、消泡劑、溶劑等 15 321934 201100933 添加劍。本發日种可使_溶義無特別限定，可舉例如： 丙-醇一乙酸酯等多元醇之二乙酸酯類；二乙二醇單乙基 醚、二丙，醇二甲基醚等多元醇之醚類；二乙二醇單乙基 趟乙酸酯等多元醇乙酸酯類。 為了得到本發明之液晶密封劑，首先，在⑴成分 中依需要而將⑷成分、（e)成分溶解混合。其次，在此 混合物中混合（〇成分’並添加（a)成分、熱硬化劑⑴、 (g)成分、以及依需要之有機填料、消泡劑及塗平劑、溶 劑等後，藉由f知之混合裝置，例如三_機、混砂機、 球磨機等均勾混合’並以金屬網進行過濾，藉此即可製造 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-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 ^塑膠在至少—者具有透光性之組合之基板所 構成。其製法係例如：當為液晶滴人方式時’在本發明之 液晶密封劑中添加破璃纖維等間隔物（ _ 材料）後，㈣-縣板中之_錢时_或網版^ 裝置等塗佈該液晶密封劑後，經過加熱等增黏步驟（預 烤）例如，在90 C進行5至15分鐘之預烤步驟。繼而， 於該液晶密封劑之堰之内側滴入液晶’並在真空中將另一 破璃基板豐合，而進行間隙形成。形成間隙後，藉由紫外 線照射機來對液晶密封部照射紫外線並進行光硬化。紫外 321934 16 201100933 線照射量較佳為500mJ/ 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130°C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。間隔物可舉例如：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//m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％ 。 (液晶滴入工法用之密封劑之調整） 以下述表1所示之比例將各樹脂成分混合攪拌後，將 〇光聚合起始劑加熱溶解。然後，適當添加填料、增黏劑等 並攪拌。然後，藉由三輥磨機使其分散，並以金屬網過濾， 而調製液晶滴入工法用密封劑實施例（1)至（5)、比較例 ⑴至（5)。 17 321934 201100933 [表1] 實施 例1 實施 例2 實施 例3 實施 例4 實施 例5 比較 例1 比較 例2 比較 例3 比較 例4 比較 例5 ⑴光硬化樹脂 6 16 6 6 6 6 6 6 6 0 (b) (2)光硬化樹脂 10 0 10 7 10 10 10 10 10 0 (3)光硬化樹脂 0 0 0 3 0 0 0 0 0 0 (4)光硬化樹脂 0 0 0 0 ~---- 0 0 0 0 0 10 (e) (5)熱硬化樹脂 4 4 4 4 4 4 4 4 4 0 ⑹熱硬化樹脂 0 0 0 0 0 0 0 0 0 10 (d) ⑺光自由基聚合起始劑 3 3 3 3 3 3 3 3 3 0 ⑻光自由基聚合起始劑 0 0 0 0 0 0 0 0 0 0.2 (c) (9)矽烷耦合劑 0.3 0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0 (10)砍烧麵合劑 0.1 0.1 0 0.1 0.1 0.1 0.1 0.1 0.1 0 (11)熱硬化劑 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0 (12)熱硬化劑 0 0 0 0 0 0 0 0 0 4 (a) (13)F-351S 3 3 3 3 0 0 0 0 0 1 (14)E-901 0 0 0 0 3 0 0 0 0 0 其 /iff (15)F301 0 0 0 0 0 3 0 0 0 0 (16)F-320 0 0 0 0 0 0 3 0 0 0 TO (17)F-340M 0 0 0 0 0 0 0 3 0 0 (g) (18)GELALLMD 0 0 0 0 0 0 0 0 1 0 (19)氧化銘 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 0 其 (20)橡膠 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0 他 (21)氧化矽 0 0 0 0 0 0 0 0 0 5 初期黏度(5rpm) 52.0 88.8 47.5 30.0 52.3 53.7 51.4 60.1 50.2 276.0 搖變性(1 rpm/1 Orpm) 1.12 1.01 1.52 1.40 1.09 1.00 1.14 1.03 1.06 1.07 (1 )雙酚A型環氧丙烯酸酯：r—93100 (曰本化藥 股份有限公司製） (2)間苯二酚二環氧丙基醚與丙烯酸之反應物 18 321934 201100933 (3) 1，6-己二醇二環氧丙基醚丙烯酸酯 (4) 雙酚A型環氧丙烯酸酯：Epikote 828 (japan Epoxy Resins股份有限公司製）與丙烯酸之反應物 (5) 間苯二酚二環氧丙基醚 (6) 雙酚A型環氧：RE—310S (日本化藥股份有限 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 Chemicals 公司 〇製） (8) 1-經基-環己基-苯基酮：Irgacure 184 (Ciba'Inorganic filler (g) which can be used in the aromatic hydrazine compound of the epoxy resin component (f) of the component (e) 321934 14 201100933 For example, a molten oxidized stone, a silicidated stone, a nitrogen Huahua, Carbon Dance, Carbonated Town, Stone, Acid Lock, Shixi, Carbonized Stone, Nitrogen, Clay, Oxidation, Oxidation Town, & ', Sulphur, Mica, Huazhen, Shixi Sour Acidy, second acidification, oxygen oxidation, nitrocellulose fiber, carbon fiber, molybdenum disulfide, stone,. Titanium bismuth, sputum emulsified stone eve, nitriding stone eve, nitriding rotten, 啜 _, sulfuric acid lock,,,. Mica, talc, clay, oxidized Ming, Hydroxide, Shi Xi Lai 2 = better, with molten yttria, yttrium oxide, aluminum sulphate, etc. These inorganic fillers can be mixed and talc is better. * When manufacturing a liquid crystal cell with a narrow gap, :===: When the substrate is bonded, it is not possible to form a gap or the like (4) 0. Therefore, it is preferably 3_ or less and preferably 2/zm or less. The particle size was measured by a laser diffraction/scattering type particle size distribution analyzer (dry type) (manufactured by SmSHIN Co., Ltd. 'LMS-30). When the liquid crystal sealing agent of the present invention is made in an amount of 1% by mass as a whole, the content of the inorganic filler (g) of the liquid crystal sealing agent (4) of the present invention is usually 5 to 40% by mass in the liquid crystal sealing agent, and is 15 to 5% by mass. 3〇% by mass is preferred. When the content of the inorganic filler is less than 5, the subsequent strength to the glass substrate is lowered and the moisture resistance reliability is also poor, so that the adhesion strength after moisture absorption is also largely lowered. Further, when the content of the inorganic filler is more than 4,000 % by mass, the content of the filler is too large, so that it is difficult to form a gap between the liquid crystal cells. In the liquid crystal sealing agent of the present invention, an organic filler, a pigment, a leveUng agent, an antifoaming agent, a solvent, etc. may be further added as needed. 15 321934 201100933 A sword is added. The solute is not particularly limited, and examples thereof include diacetates of polyhydric alcohols such as propylene-alcohol monoacetate; diethylene glycol monoethyl ether, dipropylene, and alcohol dimethyl ether. Polyols such as polyols; polyol acetates such as diethylene glycol monoethyl hydrazine acetate. In order to obtain the liquid crystal sealing agent of the present invention, first, the component (4) and the component (e) are dissolved and mixed as needed in the component (1). Next, in the mixture, the mixture of the component (a), the component (a), the component (g), and the organic filler, the antifoaming agent, the leveling agent, the solvent, and the like are used. Knowing that the mixing device, for example, a three-machine, a sand mixer, a ball mill, etc., is mixed and filtered by a metal mesh, thereby manufacturing the liquid crystal sealing agent of the present invention. The liquid crystal display unit of the present invention is The substrate is formed with a predetermined electrode, and the substrate is disposed at a predetermined interval, and the sealing agent is sealed with the sealing agent of the present invention, and the liquid crystal is sealed in the gap. The type of the liquid crystal to be sealed is not particularly limited. Therefore, the substrate is composed of a substrate including a glass, a stone, and a plastic having at least a combination of light transmissibility. The method is, for example, when the liquid crystal is dropped, the glass is added to the liquid crystal sealing agent of the present invention. After the fiber spacer ( _ material), the liquid crystal sealing agent is applied to the liquid crystal sealing agent, etc. in the (4)-counter plate, and then subjected to a heat-increasing step (pre-bake), for example, at 90 C. 5 to 15 minutes pre- Then, a liquid crystal is poured into the inside of the liquid crystal sealing agent, and another glass substrate is ablated in a vacuum to form a gap. After the gap is formed, the liquid crystal sealing portion is irradiated by an ultraviolet irradiation machine. Ultraviolet light and photohardening. UV 321934 16 201100933 The line irradiation amount is preferably from 500 mJ/cm 2 to 6000 mJ/cm 2 , more preferably from 1000 mJ/cm 2 to 4000 mJ/cm 2 , and then, at 90 to 130 ° C as needed. The liquid crystal display unit of the present invention can be obtained by curing for 1 to 2 hours. The liquid crystal display unit of the present invention thus obtained has no display defects due to liquid crystal contamination, and is excellent in adhesion and moisture resistance reliability. The spacer may, for example, be glass fiber, cerium oxide beads, polymer beads, etc. The diameter thereof varies depending on the purpose, and is usually 2 to 8/m, and preferably 4 to 7/m. 100 parts by mass of the liquid crystal sealing agent of the invention is usually used in an amount of 0.1 to 4 parts by mass, preferably 0.5 to 2 parts by mass, more preferably about 0.9 to 1.5 parts by mass. (Example) Hereinafter, by way of example The present invention will be described in detail. In the example, "parts" means mass parts, and "%" means mass%. (Adjustment of sealant for liquid crystal dropping method) After mixing and stirring the resin components in the ratio shown in Table 1 below, The calendering polymerization initiator is heated and dissolved, and then, a filler, a tackifier, and the like are appropriately added and stirred, and then dispersed by a three-roll mill and filtered with a metal mesh to prepare a liquid crystal dropping method for a sealing agent for a working method. Examples (1) to (5), Comparative Examples (1) to (5). 17 321934 201100933 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 (1) Photohardenable resin 6 16 6 6 6 6 6 6 6 0 (b) (2) Photohardenable resin 10 0 10 7 10 10 10 10 10 0 (3) Photohardenable resin 0 0 0 3 0 0 0 0 0 0 (4) Photohardenable resin 0 0 0 0 ~---- 0 0 0 0 0 10 (e) (5) Thermosetting resin 4 4 4 4 4 4 4 4 4 0 (6) Thermosetting resin 0 0 0 0 0 0 0 0 0 10 (d) (7) Photoradical polymerization initiator 3 3 3 3 3 3 3 3 3 0 (8) Photoradical polymerization initiator 0 0 0 0 0 0 0 0 0.2 (c) ( 9) decane coupling agent 0.3 0.3 0.4 0.3 0.3 0.3 0.3 0.3 0.3 0 (10) Chopped noodle mixture 0.1 0.1 0 0.1 0.1 0.1 0.1 0.1 0.1 0 (11) Thermal hardener 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0 (12) Thermal hardener 0 0 0 0 0 0 0 0 0 4 (a) (13)F-351S 3 3 3 3 0 0 0 0 0 1 (14)E-901 0 0 0 0 3 0 0 0 0 0 Its /iff (15)F301 0 0 0 0 0 3 0 0 0 0 (16)F-320 0 0 0 0 0 0 3 0 0 0 TO (17)F-340M 0 0 0 0 0 0 0 3 0 0 (g) (18)GELALLMD 0 0 0 0 0 0 0 0 1 0 (19) Oxidation 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 1.25 0 (20) Rubber 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0.26 0 He (21) 矽 0 0 0 0 0 0 0 0 0 5 Initial viscosity (5 rpm) 52.0 88.8 47.5 30.0 52.3 53.7 51.4 60.1 50.2 276.0 Shake variability (1 rpm/1 Orpm) 1.12 1.01 1.52 1.40 1.09 1.00 1.14 1.03 1.06 1.07 (1) Bisphenol A epoxy acrylate: r— 93100 (manufactured by Sakamoto Chemical Co., Ltd.) (2) Reactive reaction of resorcinol diglycidyl ether with acrylic acid 18 321934 201100933 (3) 1,6-hexanediol diepoxypropyl ether acrylate (4) Bisphenol A type epoxy acrylate: Epikote 828 (made by japan Epoxy Resins Co., Ltd.) and Resin reactant (5) Resorcinol diepoxypropyl ether (6) Bisphenol A type epoxy: RE-310S (manufactured by Nippon Kayaku Co., Ltd.) (7) 1-[4- (2 -Hydroxyethoxy)-phenyl]-2-hydroxy-2-mercapto-1-propan-1-one: Irgacure 2959 (manufactured by Ciba Specialty Chemicals Co., Ltd.) (8) 1-Ph-cyclohexyl-benzene Ketone: Irgacure 184 (Ciba
Specialty Chemicals 公司製） (9) 3-環氧丙氧基丙基三曱氧基矽烷：SILA-ACE S 一 510 (CHISSO股份有限公司製） (10) N-2-(胺基乙基）-3-胺基丙基三甲氧基矽烷： KBM—603 (信越化學工業股份有限公司製，KBM—603) 〇 ( 11)間酞酸二醯肼：IDH—S (大塚化學股份有限公 司製） (12) 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） (13) 核殼丙烯酸系共聚物：F —351S (GANZ化成 股份有限公司製） (14) 核殼丁二烯橡膠粒子：METABLENE—901 (三 菱RAYON股份有限公司製） (15) 含環氧基之PMMA : F —301 (GANZ化成股份 19 321934 201100933 有限公司製） (16) PMMA : F — 320 ( GANZ化成股份有限公司製） (17) 丙烯酸系共聚物：F—340 (GANZ化成股份有 限公司製） (18) 雙（曱基亞苄基）山梨糖醇：GELALLMD (新 日本理化股份有限公司製） (19) SPC —A1 ( C_ I.化成股份有限公司製） (20) Paraloid EXL—2655 (大阪化成股份有限公司 製） (21) 氧化矽：SP—1B (扶桑化學工業股份有限公司 製） 在以下表示所調整之各液晶滴入工法用密封劑之評 估項目内容與結果。 (液晶污染性） 於10mL小玻璃瓶（vial bottle)之底部塗佈各液晶滴 入工法用密封劑l〇〇mg後，加入其10倍量之液晶（MLC — 6866— 100: MERCK股份有限公司製）。加熱1小時後， 冷卻30分鐘。冷卻後，藉由傾析將上澄液分離取出後，藉 由數位超高電阻計（R8340’ADVANTEST股份有限公司 製）進行測定，並與由未塗佈密封劑者所得之值做比較。 藉由以下標準進行判定。 •〇：1.0E+ 12以上 • △ : 1.0E+ 11 至 1.0E+ 12 • X : 1,0E + 11 以下 20 321934 r 201100933 (分配性） 將所調整之各液晶滴入工法用密封劑填充於注射器 (syringe)並予以消泡後，藉由分配器（MUSASHI ENGINEERING公司製SHOTMASTER300)於玻璃基板上 以20mm/秒塗佈密封劑後，以肉眼確認形狀。有乾涸、 密封劑斷線等之情形標示為X，無此等情形標示為〇。 (渗入測試） 將按照上述製得之經密封劑塗佈之基板投入設定為 〇 v 90°c之熱風爐中，經過10分鐘後，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。回到大氣壓後，以肉眼確認滲入。觀察10分鐘後，發 生密封破裂者標示為X，未發生者標示為〇。 (印刷性） 以ΕΜΕ消泡機將所調整之各液晶滴入工法用密封劑 消泡後，藉由網版印刷機（NEWLONG精密工業（股）製 〇之LS—150)將密封劑印刷塗佈於玻璃基板。以肉眼確認 塗佈情形。有乾涸、密封劑斷線等之情形標示為X，無此等 情形標不為〇。 (增黏後之黏度） 於玻璃基板將所調整之液晶滴入工法用密封劑塗佈 成面狀並塗佈至40/z m左右，其次，以90它之加熱板加熱 5分鐘、J0分鐘、15分鐘。然後，使各個塗佈基板回到室 溫後’在25°C使用E型黏度計測定密封劑之黏度。 (單元間隙） 21 321934 201100933 在所調整之各液晶滴入工法用密封劑中混合5//m之 間隔物（PF — 50S，曰本電氣硝子股份有限公司製）後， 填充於注射器並消泡後，藉由分配器（MUSASHI ENGINEERING公司製SHOTMASTER 300)而於玻璃基板 上塗佈密封劑。其次，將液晶滴入該塗佈基板，並於相反 側將塗佈有面内間隔物（Natoco spacer KSEB-525F，Natoco 股份有限公司製）之玻璃予以貼合後，經過UV照射、加 熱步驟，而製作單元。藉由液晶特性評估裝置（中央精機 股份有限公司製OMS —NK3)測定所製得之單元之單元間 隙。 [表2] 實施 實施 實施 實施 實施 比較 比較 比較 比較 比較 例1 例2 例3 例4 例5 例1 例2 例3 例4 例5 液晶污染性 〇 〇 〇 Δ 〇 〇 〇一 〇 Δ 〇 分配性 〇 〇 〇 〇 〇 〇 〇 〇 〇 X 渗^^測§式 〇 〇 〇 〇 Δ 〇 〇 〇 X 網版印刷性 〇 Δ Δ △ 〇 〇 〇 〇_ 〇 X 增黏後之黏度 (5rpm/5 分鐘） 128 296 199 118 93 (*) (*) (*) 61 486 增黏後之黏度 (5rpm/10 分鐘） 169 375 269 173 108 (*) r) (*) 75 534 增黏後之黏度 (5rpm/15 分鐘） 208 (*) 293 230 112 (*) (*) (*) 80 577 單元間隙 5.0 5.0 5.0 5.0 5.0 6.8 7色 6.9 5.0 5.0 (* )係指黏度成為6000以上而無法以E型黏度計測定 321934 22 201100933 (產業上之可利用性） 由上述得知，本發明之液晶密封劑係除了滿足可對應 於網版印刷的液晶滴入工法用液晶密封劑所要求之初期黏 度、搖變性以外，液晶污染性、網版印刷性、單元間隙之 形成方式、液晶滲入密封劑中之滲入性等特性也皆優良。 另一方面可得知，比較例係即使初期黏度低，但在進行預 硬化時黏度過度增加而無法形成單元間隙，或者是在進行 ® 預硬化後由於未增黏而使液晶污染性、分配性不良。此外 可得知，初期黏度高之比較例係分配性和網版印刷性不 良。因此，本案發明之液晶密封劑係經由步驟而使對液晶 之污染性低，且於基板塗佈之作業性、液晶滴入工法時之 滲入性、作業性皆優良，而可謂可靠性高者。 【圖式簡單說明】 無。 Q 【主要元件符號說明】 M. ° 23 321934(Chemical Chemicals Co., Ltd.) (9) 3-glycidoxypropyltrimethoxy decane: SILA-ACE S-510 (manufactured by CHISSO Co., Ltd.) (10) N-2-(Aminoethyl)- 3-Aminopropyltrimethoxydecane: KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603) 〇(11) bismuth citrate: IDH-S (manufactured by Otsuka Chemical Co., Ltd.) 12) 1,3-bis(carboxyethyl)-5-isopropyl allantoin: AMICURE VDH (Ajinomoto Fine Techno Co., Ltd.) (13) Core-shell acrylic copolymer: F-351S ( GANZ Chemical Co., Ltd.) (14) Core-shell butadiene rubber particles: METABLENE-901 (Mitsubishi Rayon Co., Ltd.) (15) PMMA with epoxy group: F-301 (GANZ Chemicals Co., Ltd. 19 321934 201100933 Limited (16) PMMA : F — 320 (made by GANZ Chemical Co., Ltd.) (17) Acrylic copolymer: F-340 (manufactured by GANZ Chemical Co., Ltd.) (18) Bis(indenylbenzylidene) Yamanashi Sugar alcohol: GELALLMD (manufactured by Shin-Nippon Chemical Co., Ltd.) (19) SPC-A1 (C_I. Chemical Co., Ltd.) (20) Pa Raloid EXL—2655 (manufactured by Osaka Chemical Industry Co., Ltd.) (21) Antimony Oxide: SP-1B (manufactured by Fuso Chemical Industry Co., Ltd.) The contents and results of evaluation items of each liquid crystal instillation sealant adjusted as shown below are shown below. . (Liquid liquid contamination) After coating each liquid crystal into the bottom of a 10 mL vial bottle, the liquid crystal is added to the sealing agent of the method, and then 10 times the amount of liquid crystal is added (MLC-6866-100: MERCK Co., Ltd. system). After heating for 1 hour, it was cooled for 30 minutes. After cooling, the supernatant liquid was separated by decantation, and then measured by a digital ultra-high resistance meter (manufactured by R8340'ADVANTEST Co., Ltd.), and compared with the value obtained by the uncoated sealant. The judgment is made by the following criteria. • 〇: 1.0E+ 12 or more • △ : 1.0E+ 11 to 1.0E+ 12 • X : 1,0E + 11 or less 20 321934 r 201100933 (Distributive) Fill each syringe with the adjusted liquid crystal into the syringe with a sealant ( After the syringe was defoamed, the sealant was applied to the glass substrate at 20 mm/sec by a dispenser (SHOTMASTER 300 manufactured by MUSASHI ENGINEERING), and the shape was visually confirmed. The case of dryness, sealant breakage, etc. is indicated as X, and no such condition is indicated as 〇. (Infiltration test) The substrate coated with the sealant prepared as described above was placed in a hot air oven set to 〇v 90°c, and after 10 minutes, an appropriate amount of liquid crystal was dropped into the sealed frame' and placed on the vacuum sticker. In the device, another substrate is superposed in a vacuum. After returning to atmospheric pressure, the infiltration was confirmed with the naked eye. After 10 minutes of observation, the seal rupture was marked as X, and the non-occurrence was indicated as 〇. (Printability) After defoaming each of the adjusted liquid crystals into a working sealant by a defoaming machine, the sealant is printed and coated by a screen printing machine (LS-150 manufactured by NEWLONG Precision Industries Co., Ltd.) Covered on a glass substrate. The coating was confirmed with the naked eye. The case of dryness, sealant breakage, etc. is marked as X, and no such condition is marked as 〇. (Adhesiveness after adhesion) The liquid crystal is adjusted to be coated into a planar shape on a glass substrate and applied to a surface of about 40/zm, and then heated by a heating plate of 90 degrees for 5 minutes, J0 minutes, 15 minutes. Then, after returning each coated substrate to room temperature, the viscosity of the sealant was measured at 25 ° C using an E-type viscometer. (cell gap) 21 321934 201100933 After mixing 5/m spacers (PF-50S, manufactured by Sakamoto Electric Glass Co., Ltd.) in each of the adjusted liquid crystal instillation sealants, it is filled in a syringe and defoamed. Thereafter, a sealant was applied onto the glass substrate by a dispenser (SHOTMASTER 300 manufactured by MUSASHI ENGINEERING). Next, the liquid crystal was dropped on the coated substrate, and the glass coated with the in-plane spacer (Natoco spacer KSEB-525F, manufactured by Natoco Co., Ltd.) was bonded to the opposite side, and then subjected to UV irradiation and heating. And the production unit. The cell gap of the obtained unit was measured by a liquid crystal characteristic evaluation apparatus (OMS - NK3, manufactured by Central Seiki Co., Ltd.). [Table 2] Implementation Implementation Implementation Implementation Comparison Comparison Comparative Example 1 Example 2 Case 3 Case 4 Case 5 Case 1 Case 2 Case 3 Case 4 Case 5 Liquid Crystal Contamination 〇〇〇Δ 〇〇〇 〇 〇 〇 Distribution 〇〇〇〇〇〇〇〇〇X 渗 ^ 测 § 〇〇〇〇 〇〇〇 〇〇〇 X 网 印刷 〇 Δ Δ △ 〇〇〇〇 〇 X viscosity after adhesion (5 rpm / 5 min ) 128 296 199 118 93 (*) (*) (*) 61 486 Viscosity after adhesion (5 rpm / 10 min) 169 375 269 173 108 (*) r) (*) 75 534 Viscosity after adhesion (5 rpm /15 minutes) 208 (*) 293 230 112 (*) (*) (*) 80 577 unit gap 5.0 5.0 5.0 5.0 5.0 6.8 7 colors 6.9 5.0 5.0 (*) means the viscosity is 6000 or more and cannot be E-type viscosity Measurements 321934 22 201100933 (Industrial Applicability) From the above, it is known that the liquid crystal sealing agent of the present invention satisfies the initial viscosity and the shakeability required for the liquid crystal sealing agent for liquid crystal dropping method which can correspond to screen printing. In addition, liquid crystal contamination, screen printing, cell gap formation, liquid crystal infiltration into the sealant Infiltration and other characteristics are also excellent. On the other hand, in the comparative example, even if the initial viscosity is low, the viscosity is excessively increased during pre-curing, and the cell gap cannot be formed, or the liquid crystal contamination and distribution are not enhanced due to the pre-hardening. bad. Further, it can be seen that the comparative examples having high initial viscosity are poor in dispensability and screen printing. Therefore, the liquid crystal sealing agent of the present invention has low contamination to liquid crystals through the steps, and is excellent in workability in substrate coating, penetration in liquid crystal dropping method, and workability, and is highly reliable. [Simple description of the diagram] None. Q [Main component symbol description] M. ° 23 321934