200809355 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種液晶密封劑以及使用其之液晶顯示單 元，該液晶密封劑係用以接著TFT基板與（：1?基板，以及用 以將液晶封入至内部。 【先前技術】 近年來，液晶顯示單元亦向電視等大型顯示晝面展開應 用，於多用途中增長需要。該液晶顯示單元藉由下述之^ 法製造：於以樹脂固著之上下玻璃基板中封入液晶。又， 近年來，已實用化有液晶滴下工法，該液晶滴下工法係於 以樹脂作成之堰中滴下液晶，其後進行貼合而將樹脂硬 化於任何之製造方法中，藉由與液晶直接接觸之液晶密 封劑接著上下基板，且封入液晶。因此，要求液晶密封劑 具有即使與液晶接觸亦不污染液晶之特性。同時自生產線 速度之觀點考慮，要求其係快速硬化、且可使用時間長 者。又，生產之面板的長期可靠性亦為重要之問題，特別 疋耐屬可罪性亦成為密封劑所要求之特性。 作為具備該等特性之密封劑，；見已提出有各種提案（專 利文獻丨、專利文獻2、專利文獻3、專利文獻4、專利文獻 5)，但仍未出現實質上具備該所有特性者。又，高精細化 不斷推進之今天的液晶面板市場中，要求密封劑之特性的 進v提网，亦存在密封劑之特性未能滿足其進步的問 題。 [專利文獻1]曰本專利第2754004號 121410.doc 200809355 [專利文獻2]曰本專利第35 83326號 [專利文獻3]曰本專利特開2001-89743號公報 [專利文獻4]日本專利特開平ΐ〇·273644 [專利文獻5]日本專利特開2004-61925號公報 【發明内容】 [發明所欲解決之問題] 本發明係提供一種液晶密封劑，該液晶密封劑貫穿工序 對液晶之污染性低，塗佈於基板之作業性、適用期優異， 且於耐濕可靠性方面亦優異。 [解決問題之技術手段] 本發明者等為解決上述問題而反覆努力研究之結果，想 到併用芳香族醯肼化合物以及脂肪族醯肼化合物作為熱硬 化劑成分，而完成本發明。 即，本發明係關於下述（1)〜(9)者。 (1) 一種液晶密封劑，其特徵在於含有：（a)環氧樹脂、 (b)芳香族醯肼化合物以及（c)脂肪族醯肼化合物。 (2) 如上述（1)之液晶密封劑，其中（b)成分係芳香族二醯 肼，（c)成分係脂肪族二醯肼。 (3) 如上述（1)或（2)之液晶密封劑，其中除（a)成分、（b)成 分以及（c)成分以外，亦含有（句光硬化性樹脂以及（e)光自 由基聚合引發劑。 (4) 如上述（3)之液晶密封劑，其中（幻成分係丙烯酸樹 脂。 (5) 如上述（3)或（4)之液晶密封劑，其中（d)成分係環氧丙 121410.doc 200809355 婦酸酯樹脂 (6)如上述（1)至（5)任一項中之液晶密封劑，其中進而含 有（0矽烷偶合劑。 ' 其中進而含 其中黏度為 ⑺如上述⑴至⑹任一項中之液晶密封劑 有（g)平均粒徑為3 μιη以下之無機填充劑。 (8) 如上述（1)至⑺任一項中之液晶密封劑 250 Pa · s以下。 (9) -種液晶顯示單元，其係以硬化物密封，該硬化物 係將如上述⑴至⑻任-項中之液晶㈣劑硬化而獲得。 【實施方式】 以下，對本發明加以詳細說明。200809355 IX. The invention relates to a liquid crystal sealing agent and a liquid crystal display unit using the same, which is used for following a TFT substrate and a (:1? substrate, and In the recent years, the liquid crystal display unit has been developed for use in a large-sized display surface such as a television, and has been required for multi-purpose use. The liquid crystal display unit is manufactured by the following method: fixing with a resin Liquid crystal is sealed in the upper and lower glass substrates. In recent years, a liquid crystal dropping method has been put into practical use, which is a method in which a liquid crystal is dropped into a crucible made of a resin, and then bonded to each other to cure the resin. The liquid crystal sealing agent which is in direct contact with the liquid crystal is then attached to the upper and lower substrates, and the liquid crystal is sealed. Therefore, the liquid crystal sealing agent is required to have a characteristic of not contaminating the liquid crystal even if it is in contact with the liquid crystal, and is required to be fast from the viewpoint of production line speed. Hardened and long-lasting. Moreover, the long-term reliability of the panels produced is also important. In particular, it is a smothering property that is required for a sealant. As a sealant having such characteristics, various proposals have been made (Patent Document 专利, Patent Document 2, Patent Document 3, Patent Document 4) Patent Document 5), but it does not appear to have all of these characteristics. In addition, in today's liquid crystal panel market where high definition is progressing, the characteristics of the sealant are required to be introduced into the net, and the characteristics of the sealant are also present. The problem of the progress of the invention is not satisfied. [Patent Document 1] Japanese Patent No. 2754004, No. 200141055, Japanese Patent Application No. H. [Patent Document 4] Japanese Patent Laid-Open No. 273644 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2004-61925 [Draft of the Invention] [Problems to be Solved by the Invention] The present invention provides a liquid crystal sealing agent which is liquid crystal. In the sealant penetration step, the contamination of the liquid crystal is low, and the workability and application period of the substrate are excellent, and the moisture resistance reliability is also excellent. [Technical means for solving the problem] The present invention has been made in view of the above-mentioned problems, and it has been considered that the aromatic hydrazine compound and the aliphatic hydrazine compound are used as the thermosetting agent component. The present invention relates to the following (1) to (9). (1) A liquid crystal sealing agent comprising: (a) an epoxy resin, (b) an aromatic cerium compound, and (c) an aliphatic cerium compound. (2) A liquid crystal sealing agent as described in (1) above. (b) The component (b) is an aromatic diterpene, and the component (c) is an aliphatic diterpene. (3) The liquid crystal sealing agent of (1) or (2) above, wherein (a) component, (b) In addition to the component and the component (c), the phrase photocurable resin and (e) photoradical polymerization initiator are also contained. (4) The liquid crystal sealing agent according to the above (3), wherein (the magic component is an acrylic resin. (5) The liquid crystal sealing agent of (3) or (4) above, wherein the component (d) is a propylene oxide 121410.doc The liquid crystal sealing agent according to any one of the above (1) to (5), which further contains (0 decane coupling agent, wherein the viscosity further is (7) as in any one of the above (1) to (6). The liquid crystal sealing agent of the present invention has (g) an inorganic filler having an average particle diameter of 3 μm or less. (8) The liquid crystal sealing agent in any one of the above (1) to (7) is less than 250 Pa·s. (9) - A liquid crystal display unit obtained by curing a liquid crystal (four) agent according to any one of the above (1) to (8). The embodiment of the present invention will be described in detail below.
作為本發明中使用之環氧樹脂（a)，並無特別之限定，較 的疋g月匕以上之j衣氧樹脂，例如可列舉•·雙A 樹脂、雙酚F型環氧樹脂、雙 雙酚8型J哀氧樹脂、苯酚酚醛清 漆型環氧樹脂、甲盼紛酸清漆型環氧樹脂、雙盼A㈣清 2' 雙__清漆型環氧樹脂、脂環族環氧 t脂肪族鏈狀環氧樹脂、縮水甘油醋型環氧樹脂、缩 水甘油胺型環氧樹脂、乙内酿脲型環氧樹脂、显酸 酯型環氧樹脂、具有/、一象虱酉文 氧樹r , w 架之苯㈣料漆型環 乳树月曰，另外，可列舉：二官 物、-官# g & …員之二環氧丙醚化 物一1此％頰之二環氧丙醚化物、 氫化物等。該等之中，自液…及該4之南化物、 决祕 自液日日$染性之觀點考岸，#從土 為雙紛型環氧樹脂、㈣清漆型環氧樹腊。〜更好者 又’本發明中使用之環氧樹脂的水解性氯量為_ppm 121410.doc 200809355 以下，較好的是300 ppm以下。若水解性氯量多於6〇〇 PPm，則液晶密封劑對液晶之污染性成為問題。水解性氯 量例如可藉由如下之方衫量：將約G.5 g之環氧樹脂溶解 於20 ml之二你中’於5 mlu ⑽乙醇溶液中回流 3〇分鐘之後’狀G1 _酸銀溶液滴定。該環氧樹脂⑷於 液晶密封劑中所占之含量為5〜5〇重量％左右。 又，本發明中使用之(b)成A ’若為芳香族醮肼化合 物’則無特別之限定，例如可列舉：水揚酸酿拼、苯甲酸 醯肼、1-萘甲酸醯肼、對苯二甲酸二醯肼、間苯二甲酸二 酿肼、萘甲酸二酿肼、2,…二醢肼、以苯三醯 肼、1，4,5,8-萘甲酸四醯肼、均苯四甲酸四醯肼等。於本 2 Ί硬化反隸與潛在性之平衡考慮，較好的是2 吕此之4香族二崎，特職好的可列舉間苯二甲酸二酿 肼。 ^拉本發明中使用之⑷成分，若為脂肪族酿肼化合物， :無:：之限定，例如可列舉：甲酿肼、乙酿肼、丙酿 文-醢肼、丙二酸二酿肼、仙酸二酿肼、戊二酸 一醯肼、己二酸二醯肼、庚二 肼、洒；?； _ . ^ •一醯肼、i，4-環己烷二醯 肼屬石酸二醯肼、蘋果酸二醯肼、亞胺 肼、N，N，·伸己基雙半卡肼 "黾一醯 酸三酿肼:基三醋 異丙基乙内醯脲等具有，胺& (基咬乙基）·5· 等。於太… 内酿脲骨架之二酿肼類 :二自硬化反應性與潛在性之平衡考慮3 〜之月曰肪族二醯肼，特別較好的可列舉己二酸 121410.doc 200809355 二醯肼。 、該等醢肼化合物之平均粒徑若過大，則成為於製造狹間 隙之液晶單元時貼合上下玻璃基板時未能很好形成間隙等 不良原因，故較好的是3 μιη以下，更好的是2 pm以下。 又，同樣最大粒徑較好的是8 μιη以下，更好的是5 以 下。該粒徑可藉由雷射繞射•散射式粒度分布測定器（乾 式）（Seishin Enteri>rise股份有限公司製造，lms_3〇)進行 定。The epoxy resin (a) used in the present invention is not particularly limited, and examples thereof include a double epoxy resin, a bisphenol F epoxy resin, and both of them. Phenol type 8 J sulphur resin, phenol novolak type epoxy resin, yoke varnish type epoxy resin, double hop A (four) clear 2' double _ varnish type epoxy resin, alicyclic epoxy t aliphatic chain Epoxy resin, glycidol vinegar type epoxy resin, glycidylamine type epoxy resin, B-urethane type epoxy resin, acid ester type epoxy resin, with /, like a porphyrin tree r, w Benzene (four) paint-type ring-shaped milk saplings, in addition, can be cited: Erguan, - official # g & ... member of the diepoxypropyl ether - 1% of the cheek diepoxypropyl ether , hydride, etc. Among these, from the liquid ... and the 4 South, the secret of the day from the point of view of the dyeing of the shore, # from the soil is a double-type epoxy resin, (four) varnish-type epoxy tree wax. Further, the amount of the hydrolyzable chlorine of the epoxy resin used in the present invention is _ppm 121410.doc 200809355 or less, preferably 300 ppm or less. When the amount of hydrolyzable chlorine is more than 6 〇〇 PPm, the contamination of the liquid crystal by the liquid crystal sealing agent becomes a problem. The amount of hydrolyzable chlorine can be, for example, the amount of the square shirt: dissolve about G.5 g of the epoxy resin in 20 ml of two of you're refluxed in a 5 mlu (10) ethanol solution for 3 minutes after the 'G1 _ acid Silver solution titration. The content of the epoxy resin (4) in the liquid crystal sealing agent is about 5 to 5 % by weight. Further, (b) used in the present invention is not particularly limited as long as it is an aromatic hydrazine compound, and examples thereof include salicylic acid brewing, benzoic acid hydrazine, and 1-naphthoic acid hydrazine. Diterpene phthalic acid, isophthalic acid di-buttered, naphthoic acid di-branched, 2,... diterpene, benzotriazole, 1,4,5,8-naphthoic acid tetraterpene, benzene Tetraformic acid tetradecene and the like. In the balance between the hardening and the potential of the 2nd Ί, it is better to use the 2 fragrant two saki of the 2 s, and the special job is to mention the isophthalic acid. ^The component (4) used in the present invention, if it is an aliphatic sputum compound, is not limited to:, for example, it can be exemplified by: a brewed glutinous rice, a brewed glutinous rice, a propyl granule, a malonic acid, and a malonic acid. , 仙 二 二 肼, glutaric acid 醯肼, adipic acid dioxime, 庚 肼, sprinkle;?; _ . ^ • 醯肼, i, 4-cyclohexane diterpenoid Diterpenoids, diterpenoid malate, imine oxime, N, N, · hexyl bis-carbamate " 黾一醯酸三肼肼: base triacetate isopropyl carbendazim, amine &; (base bite ethyl) · 5 · and so on.于太... The second brewing of the urea skeleton: the balance between the two self-hardening reactivity and the potential. 3 ~ The moon 曰 族 醯肼 醯肼 醯肼, particularly good can be listed adipic acid 121410.doc 200809355 二醯Hey. When the average particle diameter of the ruthenium compound is too large, it is a cause of failure in forming a gap between the upper and lower glass substrates when the liquid crystal cell is formed in a narrow gap, and therefore it is preferably 3 μm or less. It is below 2 pm. Further, the same maximum particle diameter is preferably 8 μηη or less, more preferably 5 or less. The particle diameter can be determined by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enteri >rise Co., Ltd., lms_3〇).
本發明之液晶密封劑中，成分（b)芳香族醯肼化合物之 含有率，相賴成分⑷環論脂之環氧基的環氧當量，較 好的是0.20〜〇.80當量，特別好的是〇4〜〇 6當量。又成 分⑷脂肪族酿肼化合物之含有率，相對於成分⑷環氧樹 脂之環氧基的環氧當量，較好的狀2G〜G.8Gt量，特別好 的是0.4〜〇·6當量。 本發明中使用之光硬化性樹脂（d)，若向液晶中 性低’則並無特別之限定，若列舉如丙烯酸胺基甲酸醋、 (甲基)丙稀酸醋、環氧(甲基)丙缔酸醋之具有丙婦酿基作 為吕能基之化合物（丙稀酸系樹脂）等，則具體可列舉：甲 ^丙稀酸笨甲自旨、甲基丙烯酸環己§旨、甘油二甲基丙稀酸 三丙烯㈣、職f甘油三丙稀㈣、異戊四 … 一匕甲基丙烷-丙烯酸，、異三聚氰酸三 (丙烯醯氧基乙基）酯、二異戊四丄 二π m 知，、丙烯酸酯、氟乙醇胺 二丙烯酸酯等。該等中自液晶 沾Η供γ 木之硯點考慮，特別好 乳(甲基)丙稀酸醋樹脂。該環氧丙彿酸醋樹脂或環 1214l0.doc 200809355 氧甲基丙烯酸醋拍m，可使分子中具有至少2個環氧基之 環氧樹脂與丙烯酸或甲基丙稀酸進行醋化反應而獲得:該 合成反應可藉由通常已知之方法推ϋ , β 凌進仃。例如：於環氧樹脂 t添加特定當量比之丙烯酸或甲基丙烯酸、觸媒(例如. 二甲节胺、三乙胺、氯化节基三甲基銨、三苯基膦、三苯 基銻等）、聚合抑制劑（例如r對甲氧基苯酚、對苯二酚、 甲基對苯二齡、硫二苯胺、二丁基經基甲苯等），於例如 8::11(TC下進行醋化反應。又，作為分子中具有至少2個 環氧基之環氧樹脂，例如可列舉：雙酚A型環氧樹脂、級 烧基取代之雙紛A型環氧尉脂、環氧烧加成雙紛A型環= 樹脂、雙酚F型環氧樹脂、經烷基取代之雙酚？型環氧樹 脂、環氧燒加成雙㈣型環氧樹脂、雙紛s型環氧樹脂、細 烧基取代之雙W型環氧樹脂、環氧燒加成雙㈣型環氧樹 脂、苯酚㈣清漆型環氧樹脂、甲盼㈣清漆型環氧樹 脂、聯苯型環氧樹脂、萘型環氧樹脂、縮水甘油胺型環氧 樹脂、二環戊二婦型環氧樹脂、聚石夕氧改質環氧樹脂、、胺 基甲酸醋改質環氧樹脂、樹膠改質環氧樹脂等，較好的是 雙酴A型環氧樹脂、經燒基取代之雙紛a㈣氧樹脂、= 氧烷加成雙酚A型環氧樹脂、雙酚F型環氧樹脂、經烷基取 代之雙酚F型環氧樹脂、環氧貌加成雙盼F型環氧樹脂、雙 龄s型％κ樹脂、钱絲代之㈣s型環氧樹脂、環氧燒 加成雙酚S型環氧樹脂。 70 於本發明中’光硬化性樹脂⑷於液晶密封劑中所 含I為20〜8〇重量％左右。 121410.doc 200809355 又’本發明中使用之光自由基聚合引發劑⑷，若為自由 基型引發剤則無特別之限定，例如可列舉：节基二甲美縮 酮、1-羥基環己基苯基酮、二乙基噻噸酮、二苯甲二 乙基蒽酿、2-經基_2_甲基苯丙酮、2_甲基例甲硫基）苯 基]-2-嗎#基-i-丙⑥、2,4,6_三甲基笨甲酿基二苯基鱗氧 化物等。X，藉由使用以下示式⑴所表示之於一分子中兼 具自由基聚合反應性基與自由基產生基的光自由基聚合引 發劑，可實現更低之液晶污染性。 [化1] 七。〜/。〜⑴ 本發明之液晶密封财，⑷成分相對於⑷成分之調配 比，相對於（d)成分100重量份，較好的是（e)成分為〇 〇1〜5 重董份，特別好的是O.iy重量份。若自由基產生型光自 由基聚合引發#]之量少於G.G14|份，則光硬化反應變得 不充分；若多於5重量份，貝,H|發劑之量過多，對液晶之 由引發劑造成之污染或硬化樹月旨特性之降低成為問題。 ，好的是本發明之液晶密封劑含有矽烷偶合劑（f)以提高 接著強度。作為矽烷偶合劑，例如可列舉：3_縮水甘油氧 基丙基三甲氧基矽烷、3_縮水甘油氧基丙基甲基二甲氧基 ，：3'缩水甘油氧基丙基甲基二甲氧基石夕烧、2_(3,4‘ 氧基環己基）乙基三甲氧基錢、Ν·苯基个胺基丙基三甲 氧基矽烷、Ν·(2_胺基乙基）3_胺基丙基甲基二甲氧基矽 121410.doc 12 200809355In the liquid crystal sealing agent of the present invention, the content of the component (b) aromatic cerium compound depends on the epoxy equivalent of the epoxy group of the component (4) ring ester, preferably 0.20 to 〇.80 equivalent, particularly preferably. It is 〇4~〇6 equivalent. Further, the content of the (4) aliphatic stilbene compound is preferably from 2 G to G. 8 Gt, more preferably from 0.4 to 〇 6 equivalents, based on the epoxy equivalent of the epoxy group of the epoxy resin of the component (4). The photocurable resin (d) used in the present invention is not particularly limited as long as it is low in liquid crystallinity, and examples thereof include urethane acrylate, (meth) acrylate vinegar, and epoxy (methyl). The propanol vinegar has a propylene-branched broth as a compound of a ruenenyl group (acrylic resin), and the like, specifically, a propylene glycol, a methacrylic acid, a glycerol Acrylic acid tripropylene (tetra), occupational f glycerin tripropylene (tetra), isovatetrazol... monomethyl propane-acrylic acid, tris(methacryloxyethyl) isocyanurate, diisoamyltetradecyl Two π m know, acrylate, fluoroethanolamine diacrylate, and the like. These are considered to be particularly good for the use of liquid crystals for the purpose of gamma wood, especially milk (meth) acrylic acid vinegar resin. The epoxy propylene vinegar resin or the ring 1214l0.doc 200809355 oxy methacrylate vinegar m, can make the epoxy resin having at least 2 epoxy groups in the molecule and acetal or acrylic acid acetalization reaction Obtained: The synthesis reaction can be deduced by a commonly known method, β 凌 仃. For example, adding a specific equivalent ratio of acrylic acid or methacrylic acid to a solvent (for example, dimethyl sulphate, triethylamine, chlorobenzyltrimethylammonium, triphenylphosphine, triphenylphosphonium) Etc., a polymerization inhibitor (for example, r-p-methoxyphenol, hydroquinone, methyl-p-phenylene, thiodiphenylamine, dibutyl-transmethylbenzene, etc.), for example, at 8::11 (TC) Further, as the epoxy resin having at least two epoxy groups in the molecule, for example, a bisphenol A type epoxy resin, a sulfonate-substituted double-type A-type epoxy resin, and an epoxy burn are mentioned. Addition of double A-ring = resin, bisphenol F-type epoxy resin, alkyl-substituted bisphenol-type epoxy resin, epoxy-fired addition double (four) epoxy resin, double s-type epoxy resin Double W type epoxy resin substituted with fine burning base, epoxy burning addition double (four) type epoxy resin, phenol (four) varnish type epoxy resin, jiapan (four) varnish type epoxy resin, biphenyl type epoxy resin, naphthalene Epoxy resin, glycidylamine epoxy resin, dicyclopentadiene epoxy resin, polyoxo modified epoxy resin, urethane modified vinegar Epoxy resin, gum modified epoxy resin, etc., preferably double bismuth A type epoxy resin, substituted by a burnt base a (tetra) oxy resin, = oxyalkyl addition bisphenol A type epoxy resin, bisphenol F-type epoxy resin, alkyl-substituted bisphenol F-type epoxy resin, epoxy-added double-hop F-type epoxy resin, double-aged s-type %κ resin, Qiansi (4) s-type epoxy resin, In the present invention, the photocurable resin (4) contains about 20 to 8 % by weight of I in the liquid crystal sealing agent. 121410.doc 200809355 Further, in the present invention The photo-radical polymerization initiator (4) to be used is not particularly limited as long as it is a radical-initiated ruthenium, and examples thereof include a stilbene dimethyl ketal, a 1-hydroxycyclohexyl phenyl ketone, and a diethyl thioxanthone. , diphenylmethyldiethyl broth, 2-carbyl 2-methylpropiophenone, 2-methylmethylthio)phenyl]-2-yl#-i-propyl 6, 2, 4, 6_ trimethyl stupidyl diphenyl squamous oxide and the like. X, by using the photoradical polymerization initiator which has a radical polymerization reactive group and a radical generating group in one molecule represented by the following formula (1), lower liquid crystal contamination can be achieved. [Chemical 1] Seven. ~/. (1) The liquid crystal sealing material of the present invention, the compounding ratio of the component (4) to the component (4) is preferably 100% by weight of the component (d), and the component (e) is preferably 〇〇1 to 5 parts by weight, particularly preferably It is O.iy parts by weight. If the amount of radical-generated photoradical polymerization initiation #] is less than G.G14|part, the photohardening reaction becomes insufficient; if more than 5 parts by weight, the amount of shellfish, H|initiator is excessive, and liquid crystal The contamination caused by the initiator or the reduction in the characteristics of the hardened tree becomes a problem. Preferably, the liquid crystal sealing agent of the present invention contains a decane coupling agent (f) to increase the strength. Examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxy, and 3' glycidoxypropylmethyldimethacrylate. Oxyzepine, 2_(3,4'oxycyclohexyl)ethyltrimethoxy ketone, fluorenyl phenylaminopropyltrimethoxy decane, ruthenium (2-aminoethyl) 3-amine Propylmethyldimethoxyfluorene 121410.doc 12 200809355
烷、N_(一2’基乙基)3,基丙基甲基三甲氧基矽烷、3-胺 二二一乙氧基♦烷、基丙基三甲氧基;^貌、乙烯基 :氧基夕燒Ν·(2•(乙烯基节基胺基）乙基）3_胺基丙基三 甲氧基矽烷鹽酸鹽、”基丙烯醯氧基丙基三甲氧基矽 烧、3-乳丙基甲基二甲氧基石夕燒、3_氯丙基三甲氧基石夕烧 等矽烷偶合劑。該等矽烷偶合劑亦可混合使用2種以上。 該等:，為獲得更好之接著強度，較好的是錢偶合劑為 具有胺基之矽烷偶合劑。藉由使用矽烷偶合劑，可獲得接 著強度提同’耐濕可靠性優異之液晶密封劑。該石夕烧偶合 劑（f)於液晶密封劑中所占之含量為〇〇5〜3重量％左右。 作為本發明中可使用之無機填充劑（g)，可列舉：㈣ 二氧化石夕、結晶二氧化石夕、碳化石夕、氮化石夕、氮化领、碳 酉文鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧 化銘、氧化鎮、氧化锆、氫氧化銘、氫氧化鎮、石夕_、 矽酸鋁、矽酸鋁鋰、矽酸錯、鈦酸鋇、玻璃纖維、碳纖 維、一硫化鉬、石棉等，較好的是熔融二氧化矽、結晶二 氧化矽、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲 母、滑石、黏土、氧化鋁、氫氧化鋁、石夕酸鈣、石夕酸鋁7 更好的是熔融二氧化矽、結晶二氧化矽、氧化鋁、滑石。 該等無機填充劑亦可混合使用2種以上。其平均粒徑若過 大，則成為於製造狹間隙之液晶單元時貼合上下玻璃基板 時未能很好形成間隙等不良原因，故較好的是3 以下， 更好的是2 μπι以下。其粒徑可藉由雷射繞射•散射式粒度 分布測定器（乾式）（Seishin Enterprise股份有限公司製造， 121410.doc -13- 200809355 LMS-30)進行測定。 於本發明中使用之無機填充劑（g)於液晶密封劑中之含 量，通常為5〜40重量％，較好的是15〜3〇重量％。於填充劑 之含量低於5重量％之情形時，對玻璃基板之接著強度降 低，且耐濕可靠性亦差，故存在吸濕後之接著強度的降低 亦變大之情形。又，於填充劑之含量多於40重量％之情形 時，填充劑含量過多，故存在難以破碎而變得未能形成液 晶單元之間隙之情形。 翁 ⑨本發明之液晶密封劑中，可進而視需要調配有機溶 劑、有機填充劑以及顏料、勻化劑、消泡劑等添加劑。 本發明之液晶密封劑之黏度，較好的是25〇 pa · s以下。 該黏度以上之情形時，分配性等處理能力差。又，於 Pa · s以下之情形，亦可對應如網版印刷之密封塗佈方 式，對面板之生產性帶來較大影響。 為獲传本發明之液晶密封劑，首先於⑷成分中視需要溶 • 冑混合⑷成分、(e)成分、⑴成分。繼而於該混合物中添 加特疋篁之（g)成分，進而添加特定量之（b)成分、⑷成分 以及視需要添加特定量之有機填充劑、消泡劑、以及勻化 劑等添加劑，藉由公知之混合裝置，例如··三輥研磨機、 砂磨機、球磨機等將其均句混合，藉此可製造本發明之液 晶密封劑。 本發明之液晶單元，係將於基板形成有特定電極之一對 基板，以特定之間隔相對向配置，將其周圍以本發明之液 晶密封劑密封，並於其間隙封入有液晶者。封入之液晶的 121410.doc -14· 200809355 種類並無特別限定。此處，所謂基板，係由含有玻璃、石 夬'塑膠'石夕等至少_者具有透光性之組合的基板構成。 作為其製法係例如於液晶注入方式之情形時，本發明之液 晶挽封劑中’添加玻璃纖維等間隔物（間隙控制材）後，於 該一對基板之一上藉由分注器等塗佈該液晶密封劑。此時 預先開一處至二處用以注入液晶之注入口。其後，貼合另 一玻璃基板’形成間隙。形成間隙後，於9〇〜13〇。〇下硬化 1 2小日守製成空單元，自注入口注入液晶之後，以封口劑 (UV硬化型樹脂）密封注入口，藉此可獲得液晶顯示單元。 又’於液晶滴下方式之情形時，於本發明之液晶密封劑 中添加玻璃纖維等間隔物（間隙控制材）後，於該一對基板 之一上藉由分注器等塗佈該液晶密封劑之後，於該液晶密 封劑之堪之内側滴下液晶，於真空中貼合另一玻璃基板， 形成間隙。形成間隙後，以紫外線照射機對液晶密封部照 射紫外線使其光硬化。紫外線照射量，較好的是5〇〇〜6〇〇〇 mJ/cm2，更妤的是1〇〇〇〜4000 mJ/cm2之照射量較佳。其 後，於90〜130°C下硬化1〜2小時，藉此可獲得本發明之液 晶顯示單元。如此而獲得之本發明之液晶顯示單元，無由 於液晶污染造成之顯示不良，且接著性、耐濕可靠性優 異。作為間隔物，例如可列舉玻璃纖維、二氧化矽顆粒、 聚合物顆粒等。其直徑視需要而不同，通常為2〜8 μιη，較 好的是4〜7 μιη。其使用量，相對於1〇〇重量份之本發明之 液晶密封劑，通常為0.1〜4重量份，較好的是〇·5〜2重量 份，進而較好的是〇·9〜1·5重量份左右。 121410.doc -15 - 200809355 [實施例] 以下藉由實施例對本發明加以更詳細之說明。再者，液 曰曰狯封劑之黏度藉由汉型黏度計（東機產業股份有限公司製 造）測定。 合成例1上述式（1)所表示之光自由基聚合引發劑之合成 於反應容器中加入155 g之甲基丙烯酸2_異氰酸基乙酯 (昭和電工股份有限公司製造、karenz Μ⑴）、22斗g之2-羥 基·4 -羥乙氧基-2·甲基苯丙酮（汽巴精化股份有限公司 (Ciba Specialty Chemicals Co.，Ltd)製造、IRG-2959)，於其 中添加0.76 g之甲基對苯二酚作為聚合抑制劑。將其升溫 至8CTC，保持該狀態攪拌約26小時。將所得之反應液溶解 於甲基異丁基酮與甲苯之混合溶劑，進行水洗。其後，顧 去甲基異丁基酮與甲苯，使用乙酸乙_與正己烧進行再結 曰曰，藉此獲得上述式（丨）所表示之光自由基聚合引發劑。 實施例1 • 將160重量份之雙酚A環氧樹脂（陶氏化學公司（The DowAlkane, N_(a 2'-ylethyl)3, propylpropylmethyltrimethoxydecane, 3-aminedi-diethoxysilane, propyltrimethoxy; morphological, vinyl: oxy Ν烧Ν·(2•(vinylhedylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, “acryloyloxypropyltrimethoxysulfonate, 3-lactide a decane coupling agent such as methyl methoxy methoxy sulphate or 3- chloropropyl trimethoxy sulphide. These decane coupling agents may be used in combination of two or more kinds. For the purpose of obtaining better adhesion strength, Preferably, the money coupling agent is a decane coupling agent having an amine group. By using a decane coupling agent, a liquid crystal sealing agent having the same strength and excellent moisture resistance reliability can be obtained. The sulphur coupling agent (f) is The content of the liquid crystal sealing agent is about 5% by weight to about 5% by weight. The inorganic filler (g) which can be used in the present invention includes (4) sulphur dioxide, crystalline sulphur dioxide, and carbonized stone. , nitriding stone, nitrided collar, carbon strontium calcium, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, oxidation, oxidation town, oxidation Zirconium, Hydroxide, Hydroxide, Shixi _, aluminum citrate, lithium aluminum niobate, bismuth citrate, barium titanate, glass fiber, carbon fiber, molybdenum monosulfide, asbestos, etc., preferably molten dioxide Bismuth, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium alumite, aluminum alumite 7 better It is molten cerium oxide, crystalline cerium oxide, aluminum oxide, and talc. These inorganic fillers may be used in combination of two or more kinds. When the average particle diameter is too large, the upper and lower glasses are bonded to each other when a liquid crystal cell having a narrow gap is formed. When the substrate does not form a gap or the like, it is preferably 3 or less, more preferably 2 μm or less. The particle diameter can be obtained by a laser diffraction/scattering particle size distribution analyzer (dry type) (Seishin) The amount of the inorganic filler (g) used in the present invention in the liquid crystal sealing agent is usually 5 to 40% by weight, preferably, manufactured by Enterprise Co., Ltd., 121410.doc -13 - 200809355 LMS-30). Is 15~3〇% by weight. When the content of the agent is less than 5% by weight, the adhesion strength to the glass substrate is lowered, and the moisture resistance reliability is also poor, so that the decrease in the strength after the moisture absorption is also increased. When the content is more than 40% by weight, the content of the filler is too large, so that there is a case where it is difficult to be broken and the gap of the liquid crystal cell is not formed. In the liquid crystal sealing agent of the present invention, the organic solvent may be further adjusted as needed. The filler of the liquid crystal sealing agent of the present invention is preferably 25 〇pa·s or less. When the viscosity is higher than the above, the handling property such as dispensability is poor. Moreover, in the case of Pa·s or less, it is also possible to correspond to a seal coating method such as screen printing, which has a large influence on the productivity of the panel. In order to obtain the liquid crystal sealing agent of the present invention, first, the component (4), the component (e), and the component (1) are mixed as needed in the component (4). Then, the component (g) is added to the mixture, and a specific amount of the component (b), the component (4), and, if necessary, a specific amount of an organic filler, an antifoaming agent, and a homogenizing agent are added. The liquid crystal sealing agent of the present invention can be produced by mixing them in a well-known mixing device, for example, a three-roll mill, a sand mill, a ball mill or the like. In the liquid crystal cell of the present invention, one of the specific electrodes is formed on the substrate, and the substrate is opposed to each other at a predetermined interval, and the liquid crystal sealing agent of the present invention is sealed around the substrate, and a liquid crystal is sealed in the gap. The type of liquid crystal to be sealed is not limited to 121410.doc -14· 200809355. Here, the substrate is composed of a substrate containing at least a combination of glass, stone, plastic, and the like. In the case of the liquid crystal sealing method of the present invention, for example, a spacer such as a glass fiber (gap control material) is added to the liquid crystal sealing agent of the present invention, and then coated on one of the pair of substrates by a dispenser or the like. The liquid crystal sealing agent is cloth. At this time, one to two openings are opened in advance to inject the liquid crystal. Thereafter, another glass substrate is bonded to form a gap. After the gap is formed, it is 9〇~13〇. After the underarm is hardened, the liquid crystal cell is obtained by injecting the liquid crystal from the injection port and sealing the injection port with a sealing agent (UV hardening resin). In the case of the liquid crystal sealing method, a spacer such as a glass fiber (gap control material) is added to the liquid crystal sealing agent of the present invention, and the liquid crystal sealing is applied to one of the pair of substrates by a dispenser or the like. After the agent, the liquid crystal was dropped on the inside of the liquid crystal sealing agent, and another glass substrate was bonded in a vacuum to form a gap. After the gap is formed, the liquid crystal sealing portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to harden the light. The amount of ultraviolet irradiation is preferably from 5 〇〇 to 6 〇〇〇 mJ/cm 2 , and more preferably from 1 〇〇〇 to 4000 mJ/cm 2 . Thereafter, it is cured at 90 to 130 ° C 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 is free from display defects due to liquid crystal contamination, and excellent in adhesion and moisture resistance. Examples of the spacer include glass fibers, cerium oxide particles, polymer particles, and the like. The diameter varies depending on the need, and is usually 2 to 8 μm, preferably 4 to 7 μm. The amount of the liquid crystal sealing agent of the present invention is usually 0.1 to 4 parts by weight, preferably 5 to 2 parts by weight, more preferably 〇·9 to 1 part by weight per 1 part by weight of the liquid crystal sealing agent of the present invention. About 5 parts by weight. 121410.doc -15 - 200809355 [Examples] Hereinafter, the present invention will be described in more detail by way of examples. Further, the viscosity of the liquid helium sealant was measured by a Han type viscometer (manufactured by Toki Sangyo Co., Ltd.). Synthesis Example 1 Synthesis of Photoradical Polymerization Initiator represented by the above formula (1) Into a reaction vessel, 155 g of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko Co., Ltd., karenz Μ (1)), 22 hydroxy 2-hydroxy-4-acetoxy-2-methylpropiophenone (manufactured by Ciba Specialty Chemicals Co., Ltd., IRG-2959), to which 0.76 g was added Methyl hydroquinone is used as a polymerization inhibitor. The temperature was raised to 8 CTC, and the state was kept stirring for about 26 hours. The obtained reaction solution was dissolved in a mixed solvent of methyl isobutyl ketone and toluene, and washed with water. Thereafter, methyl isobutyl ketone and toluene were removed, and re-cracking was carried out using acetic acid B and n-hexane to obtain a photoradical polymerization initiator represented by the above formula (丨). Example 1 • 160 parts by weight of bisphenol A epoxy resin (The Dow
Chemical Company)製造、DER_332 ;環氧當量為 i75 g/eq) 之％氧丙烯酉欠酉曰、40重量份之作為環氧樹脂之DER_332(陶 氏化學公司製造；環氧當量為175 g/eq)、1()重量份之合成 例1中所獲得之以式⑴所表示之光自由基聚合引發劑（甲基 丙烯酸2·異氰酸基乙酿與2-經基-1例2-經乙氧基）苯 基]_2_甲基丙燒之反應產物）於9G°C下加熱溶解，獲得 :脂液。冷卻至室溫後’添加8重量份之己二酸二醯肼(商 名 S，將大琢化學股份有限公司製造之喷射研磨機 121410.doc •16- 200809355 粉碎等級進而以噴射研磨機微粉碎者）、9重量份之間苯二 甲酸二醯肼（商品名IDH-S ;將大塚化學股份有限公司製造 之噴射研磨機粉碎等級進而以噴射研磨機微粉碎者）、25 重量份之氧化鋁（C.I.KASEI CO.，LTD.製造，SPC-A1，平 均粒徑為1·0 μιη)、5·8重量份之樹膠（羅門哈斯公g(R〇hm and Haas Company)製造、Paral〇id eXL_2655、平均粒徑為Manufactured by Chemical Company, DER_332; % oxypropylene oxime with an epoxy equivalent of i75 g/eq), 40 parts by weight of DER_332 as an epoxy resin (manufactured by The Dow Chemical Company; epoxy equivalent of 175 g/eq , 1 (parts by weight) of the photoradical polymerization initiator represented by the formula (1) obtained in Synthesis Example 1 (methacrylic acid 2 · isocyanate ethyl and 2-carbyl - 1 - 2 The reaction product of ethoxy)phenyl]-2-methylpropanone was dissolved by heating at 9 G ° C to obtain a fat liquid. After cooling to room temperature, '8 parts by weight of diammonium adipate (trade name S, jet mill 121410.doc •16-200809355 manufactured by Otsuka Chemical Co., Ltd.) was pulverized and further pulverized by a jet mill. ), 9 parts by weight of bismuth phthalate (trade name IDH-S; pulverization grade of jet mill manufactured by Otsuka Chemical Co., Ltd. and finely pulverized by jet mill), 25 parts by weight of alumina (CI) Manufactured by KASEI CO., LTD., SPC-A1, average particle size of 1·0 μιη), 5.8 parts by weight of gum (manufactured by R〇hm and Haas Company, Paral〇id eXL_2655, The average particle size is
〇·2〜0·3 μιη)，藉由三棍研磨機進行混練而獲得本發明之液 晶密封劑。液晶密封劑之黏度（以^為19〇 pa · s。 實施例2 於100重量份之作為環氧樹脂之DER_332(陶氏化學公司 製造；環氧當量為175 g/eq)中，添加2〇重量份之己二酸二 醯肼（商品名ADH-S ;將大塚化學股份有限公司製造之喷 射研磨機粉碎等級進而以噴射研磨機微粉碎者）、22·5重量 伤之間苯一甲酸二醯肼（商品名IDH_S ;將大塚化學股份有 限公司製造之喷射研磨機粉碎等級進而以喷射研磨機微粉 碎者）25重畺伤之氧化鋁（CXKASEI CO_，LTD·製造、， SPC AJ，平均粒徑為1〇 μιη)、5·8重量份之樹膠（羅門哈斯 =司（Rohm and Haas Company)製造、Paral〇id EXL 2655、 平均粒徑為0·2〜0.3㈣，藉由三輥研磨機進行混練而獲得 本發明之液晶密封劑。&晶密封劑之黏度（25。〇為11〇 Pa · s 〇 比較例1 奸作為熱硬化劑僅使用8重量份之己二酸：賴，除去間 本—甲酸二醯肼’其他以與實施例!相同之方式進行而獲 12141〇.d〇e -17- 200809355 得液晶密封劑。黏度為160 Pa · s。 比較例2 作為熱硬化劑僅使用9重量份之間苯二甲酸二醯肼，除 去己二酸二醯肼，其他以與實施例1相同之方式進行而獲 得液晶密封劑。黏度為1 60 Pa · s。 比較例3〇·2~0·3 μιη), the liquid crystal sealant of the present invention is obtained by kneading by a three-stick grinder. The viscosity of the liquid crystal sealing agent (in the range of 19 〇 Pa · s. Example 2) In 100 parts by weight of DER_332 (manufactured by The Dow Chemical Co., Ltd.; epoxy equivalent: 175 g/eq) as an epoxy resin, 2 添加 was added. Parts by weight of diammonium adipate (trade name: ADH-S; pulverization grade of jet mill manufactured by Otsuka Chemical Co., Ltd., and finely pulverized by jet mill), and 2,5 weight loss of diphenyl benzoate肼 (product name IDH_S; pulverization grade of jet mill manufactured by Otsuka Chemical Co., Ltd., and finely pulverized by jet mill) 25-injured alumina (manufactured by CXKASEI CO_, LTD., SPC AJ, average particle diameter is 1〇μηη), 5.8 parts by weight of gum (Rohm and Haas Company, Paral〇id EXL 2655, average particle size 0·2~0.3 (4), by a three-roll mill The liquid crystal sealant of the present invention is obtained by kneading. The viscosity of the crystal sealant is (25. 〇 is 11 〇 Pa · s 〇 Comparative Example 1 As a thermal hardener, only 8 parts by weight of adipic acid is used: Ben-formic acid dioxime 'others with the embodiment! In the manner of 12141〇.d〇e -17- 200809355, the liquid crystal sealant was obtained, and the viscosity was 160 Pa · s. Comparative Example 2 As the heat hardener, only 9 parts by weight of dithizone was used. Dioxin diacid, other liquid crystal sealant was obtained in the same manner as in Example 1. The viscosity was 1 60 Pa · s. Comparative Example 3
作為熱硬化劑僅使用18重量份之己二酸二醯肼，除去@ 苯二甲酸二醯肼，其他以與實施例1相同之方式進行而择 得液晶密封劑。黏度為190 Pa · s。 比較例4 作為熱硬化劑僅使用28重量份之水揚酸醯肼（大塚化學 股份有限公司製造），除去己二酸二醯肼以及間笨二 分As the thermosetting agent, only 18 parts by weight of dioxetium adipate was used, and @bisphthalic acid dioxime was removed, and the liquid crystal sealing agent was selected in the same manner as in Example 1. The viscosity is 190 Pa · s. Comparative Example 4 As a thermal curing agent, only 28 parts by weight of lanthanum silicate (manufactured by Otsuka Chemical Co., Ltd.) was used to remove diammonium adipate and two parts.
I 二醯肼，其他以與實施例1相同之方式進行而獲得液曰贫 封劑。黏度為220 Pa · s。 比較例5 作為熱硬化劑僅使用20重量份之己二酸二醯胖， 本一甲酸二酿耕’其他以與實施例2相同之方★、隹/ 八遲行而獲 得液晶密封劑。黏度為50 Pa · s。 比較例6 作為熱硬化劑僅使用22.5重量份之間苯二曱酸二 一"職脚， 除去己二酸二醯肼，其他以與實施例2相同之方式進疒 獲得液晶密封劑。黏度為60 Pa · s。 T而 比較例7 作為熱硬化劑僅使用40重量份之己二酸二醯肼，除去門 121410.doc -18- 200809355 苯二甲酸二醯肼，其他以與實施例2相 得液晶密封劑。黏度為60 Pa · s。 丁而獲 比較例8 二甲酸二醯肼，除 同之方式進行而獲 作為熱硬化劑僅使用45重量份之間笨 去己二酸二醯肼，其他以與實施例2相 得液晶密封劑。黏度為11 〇 Pa · s。 ⑴液晶污染性測試Further, in the same manner as in Example 1, a liquid helium-depleted sealant was obtained. The viscosity is 220 Pa · s. Comparative Example 5 As a thermal curing agent, only 20 parts by weight of adipic acid dihydrate was used, and the present monocarboxylic acid was used to obtain a liquid crystal sealing agent in the same manner as in Example 2, and 隹/8 was delayed. The viscosity is 50 Pa · s. Comparative Example 6 As a thermal curing agent, only 22.5 parts by weight of a phthalic acid was used, and diammonium adipate was removed, and other liquid crystal sealing agents were obtained in the same manner as in Example 2. The viscosity is 60 Pa · s. T Comparative Example 7 As the thermal curing agent, only 40 parts by weight of diamectium adipate was used, and the gate 121410.doc -18-200809355 diterpene phthalate was removed, and the liquid crystal sealing agent was obtained in the same manner as in Example 2. The viscosity is 60 Pa · s. Comparative Example 8 Dioxonium diformate was obtained in the same manner as that used as the thermal hardener, and only 45 parts by weight of stupid adipic acid dioxime was used, and other liquid crystal sealants obtained in the same manner as in Example 2 were obtained. . The viscosity is 11 〇 Pa · s. (1) Liquid crystal contamination test
於樣品瓶中裝入10種密封劑（實施例〗、2以及比較例1 2、3、4、5、6、7、8)各 〇」g，照射 2〇〇〇 _⑽紫1 外 線，使之硬化後，添加i ml液晶（Merck&份有限公司製 造、MLC-6866_100)，投入至120。〇烘箱内i小時其後， 於室溫下放置0.5小時。自處理結束之樣品瓶中僅取出液 晶，置於液體電極LE21(安藤電氣製造）中，藉由愛德萬測 試股份有限公司（ADVANTEST CORPORATION)製造之靜 電計R-8340測定於測定電壓1〇 ¥下4分鐘後之液晶的比電 阻值，評估液晶污染性。將其結果示於表i。 (H)接著強度測試 於100 g所得之液晶密封劑中添加！ g<5 μηι玻璃纖維作 為間隔物進行混合攪拌。將該液晶密封劑塗佈於5〇 mmx50 mm之玻璃基板上，於該液晶密封劑上貼合j $ mmxl.5 mm之玻璃片，於實施例1以及比較例1、2、3、4 中，猎由uv照射機照射3000 mj/cm2之紫外線，投入至 120 C烘箱中1小時使之硬化；又’於實施例2以及比較例 5 6 7、8中’投入至120°C烘箱中1小時使之硬化。藉由 121410.doc -19- 200809355 西進商事製4之黏結強度試驗機（B〇nd tester)於每分鐘1 〇 mm之速度測定玻璃片之剪切接著強度，評估接著強度。 將其結果示於表1。 (iii) 耐濕可靠性測試 於100 g所传之液晶德、封劑中添加1㊁之$ pm玻璃纖維作 為間隔物進行混合攪拌。將該液晶密封劑塗佈於50 mm><50 mm之玻璃基板上，於該液晶密封劑上貼合15 mmXl·5 mm之玻璃片，於實施例1以及比較例1、2、3、4 中，藉由UV照射機照射3000 mJ/cm2之紫外線，投入至 120°C烘箱中1小時使之硬化；又，於實施例2以及比較例 5 6 7 8中，投入至120 C烘箱中1小時使之硬化。其 後’於溫度12、壓力2 atm、相對濕度loo%之條件放置 24小％後，藉由pCT試驗機測定該玻璃片之剪切接著強度 而評估耐濕可靠性。將其結果示於表！。 (iv) 硬化性測試 於50 mmx50 mm之玻璃基板上放置實施例、比較例之各 液晶密封劑各1 g，將其投入至12〇〇c烘箱中i小時使之硬 化，測定蕭氏D硬度，藉此評估硬化性。將其結果示於表 1 〇 (v) 經時變化測試 將實施例、比較例之各液晶密封劑各約2 g，放置於室 溫25°C下之試驗室中，追蹤黏度變化。將黏度增加率之經 時變化的評估結果示於表1。 、二 [表1] 121410.doc -20- 200809355 表1 黏度液晶污染性接著強度耐濕可靠性硬化性經時變化 (比電阻值） （接著強度） （增黏率） 實施例1 190 Pa · s 〇 〇 〇 〇 〇 實施例2 110 Pa · s 〇 〇 〇 〇 o 比較例1 160 Pa · s 〇 〇 △ X 〇 比較例2 160 Pa · s 〇 〇 〇 X 〇 比較例3 190 Pa · s 〇 〇 〇 X X 比較例4 220 Pa · s 〇 Δ Δ 〇 X 比較例5 50 Pa · s 〇 〇 〇 X 〇 比較例6 60 Pa · s 〇 〇 〇 X 〇 比較例7 60 Pa · s 〇 〇 X 〇 X 比較例8 110 Pa · s 〇 〇 〇 X 〇Ten kinds of sealants (Examples, 2, and Comparative Examples 1, 2, 3, 4, 5, 6, 7, and 8) were placed in the sample vial, and 2〇〇〇_(10) Violet 1 was irradiated. After hardening, i ml liquid crystal (manufactured by Merck & Co., Ltd., MLC-6866_100) was added and charged to 120. After 1 hour in the oven, it was allowed to stand at room temperature for 0.5 hours. Only the liquid crystal was taken out from the vial which was finished by the treatment, and it was placed in the liquid electrode LE21 (manufactured by Ando Electric Co., Ltd.), and the electrometer R-8340 manufactured by ADVANTEST CORPORATION was measured at the measurement voltage 1〇¥ The specific resistance of the liquid crystal after the next 4 minutes was evaluated for liquid crystal contamination. The results are shown in Table i. (H) Next strength test Add to 100 g of the obtained liquid crystal sealant! The g<5 μηι glass fiber was mixed and stirred as a spacer. The liquid crystal sealing agent was coated on a glass substrate of 5 mm×50 mm, and a glass piece of j $ mm×1.5 mm was attached to the liquid crystal sealing agent, and in Example 1 and Comparative Examples 1, 2, 3, and 4. , hunted by UV irradiation machine 3,000 mj / cm2 of ultraviolet light, put into a 120 C oven for 1 hour to harden; and 'in Example 2 and Comparative Example 5 6 7, 8 'into the 120 ° C oven 1 Harden it in hours. The shear strength of the glass piece was measured at a speed of 1 〇 mm per minute by means of a bonding strength tester (B〇nd tester) of 121410.doc -19- 200809355, and the subsequent strength was evaluated. The results are shown in Table 1. (iii) Moisture resistance reliability test Add 1 or 2 of pm glass fiber as a spacer in 100 g of the liquid crystal and sealant. The liquid crystal sealing agent was applied onto a glass substrate of 50 mm > 50 mm, and a glass piece of 15 mm×1.5 mm was attached to the liquid crystal sealing agent, and in Example 1 and Comparative Examples 1, 2, and 3, In 4, ultraviolet rays of 3000 mJ/cm 2 were irradiated by a UV irradiator, and they were put into an oven at 120 ° C for 1 hour to be hardened; in addition, in Example 2 and Comparative Example 5 6 7 8 , they were put into a 120 C oven. Harden it in 1 hour. Thereafter, after leaving at 24% under the conditions of temperature 12, pressure 2 atm, and relative humidity loo%, the shear strength of the glass piece was measured by a pCT tester to evaluate the moisture resistance reliability. Show the results on the table! . (iv) Sturability test: 1 g of each liquid crystal sealant of the examples and the comparative examples was placed on a glass substrate of 50 mm×50 mm, and it was put into a 12 〇〇c oven for 1 hour to be hardened, and the D hardness was measured. Thereby, the sclerosis is evaluated. The results are shown in Table 1. 〇 (v) Time-dependent change test Each liquid crystal sealing agent of each of the examples and the comparative examples was placed in a test chamber at room temperature of 25 ° C to trace the change in viscosity. The evaluation results of the change in the viscosity increase rate are shown in Table 1. 2 [Table 1] 121410.doc -20- 200809355 Table 1 Viscosity liquid crystal contamination followed by strength moisture resistance reliability hardening change with time (specific resistance value) (continuous strength) (tackifying ratio) Example 1 190 Pa · s 〇〇〇〇〇 Example 2 110 Pa · s 〇〇〇〇o Comparative Example 1 160 Pa · s 〇〇 △ X 〇 Comparative Example 2 160 Pa · s 〇〇〇 X 〇 Comparative Example 3 190 Pa · s 〇 〇〇 XX Comparative Example 4 220 Pa · s 〇 Δ Δ 〇 X Comparative Example 5 50 Pa · s 〇〇〇 X 〇 Comparative Example 6 60 Pa · s 〇〇〇 X 〇 Comparative Example 7 60 Pa · s 〇〇X 〇 X Comparative Example 8 110 Pa · s 〇〇〇X 〇
註）上述各測定值之評估基準如下所述。 比電阻值： 〇1.0E+12以上 △ 1·0Ε+11 〜1.0E+12 X 1.0Ε+11 以下 接著強度： 〇60 MPa以上 △ 20 MPa〜60 MPa X 20 MPa以下 硬度（蕭氏D硬度）： 〇60以上 △ 20 〜60 X 20以下 121410.doc -21 - 200809355 黏度增加率： 〇增黏率為20%以下 △增黏率為20%〜40% X增黏率為40%以上 、如表1所示，液晶污染性、接著強度之液晶密封劑所要 求之基本特性於實施例、比較例中皆良好。然而，關於硬 化陡經B守變化、对濕可靠性之特性，於比較例中並益兼 冑各特牲者，但於實施例中皆滿^各特性。因此，本發明 之液晶密封劑可謂貫穿工序對液晶之污染性低，塗佈於基 板上之作業性、經時穩定性優異，且耐濕可靠性亦優異 者。 5 [產業上之可利用性] 本發明之液晶密封劑，對液晶之污染性低，塗佈於基板 上之作業性，適用期優異，具有速硬化性，且具有良好之 適用期，進而硬化物之耐濕可靠性亦優異。因此，藉由使 m 用該密封劑，可容易地製造可靠性優異之液晶顯示面板。 121410.doc -22 -Note) The evaluation criteria for each of the above measured values are as follows. Specific resistance value: 〇1.0E+12 or more △1·0Ε+11 ～1.0E+12 X 1.0Ε+11 The following strength: 〇60 MPa or more △20 MPa~60 MPa X 20 MPa or less hardness (Shore D hardness) ): 〇60 or more △ 20 ～ 60 X 20 or less 121410.doc -21 - 200809355 Viscosity increase rate: 〇 viscosity increase rate is 20% or less △ viscosity increase rate is 20% to 40% X viscosity increase rate is 40% or more, As shown in Table 1, the basic characteristics required for the liquid crystal sealing agent of liquid crystal contamination and adhesion strength were good in both the examples and the comparative examples. However, the characteristics of the hardening stability and the wet reliability are better in the comparative examples than in the comparative examples, but in the examples, the characteristics are all sufficient. Therefore, the liquid crystal sealing agent of the present invention has a low contamination property to liquid crystal in the penetration step, is excellent in workability and stability over time applied to the substrate, and is excellent in moisture resistance reliability. 5 [Industrial Applicability] The liquid crystal sealing agent of the present invention has low contamination to liquid crystals, has excellent workability on a substrate, has excellent pot life, is fast-curable, has a good pot life, and is hardened. The moisture resistance reliability of the material is also excellent. Therefore, by using the sealant for m, a liquid crystal display panel excellent in reliability can be easily manufactured. 121410.doc -22 -