TW200903119A - Liquid crystal sealing agent, and (meth)acrylic ester compound used therefor and manufacturing method of the same - Google Patents

Abstract

A (meth)acrylic ester compound being liquid at room temperature and having low liquid crystal contaminating property, and a liquid crystal sealing agent including the same are provided. The liquid crystal sealing agent includes a (meth)acrylic ester compound represented by the following general formula (I). In formula (I), Each of A independently represents 2C or 3C alkylene, each of R1-R3 independently represents hydrogen or methyl, and each of X-Z independently represents 2-4C alkylene.

Description

200903119 九、發明說明： 【發明所屬之技術領域】 本發明是關於一種液晶密封劑、該液晶密封劑所使用 的（曱基）丙烯酸酯化合物以及該（曱基）丙烯酸酯化合物的 製造方法。 【先前技術】 近年來，使用液晶顯示面板（亦稱為「液晶面板」）作 為電視、行動電話等各種設備的顯示面板。目前，液晶滴 |Τ ' 、 注方式（one drop fill)由於生產性優異，故用於製造液晶 顯示面板。所謂液晶滴注方式，是指包括以下製程的液晶 顯示面板的製造方法：1)將液晶密封劑（亦簡稱為「密封 劑」）塗佈於液晶面板的基板上，形成用以填充液晶的框（密 封圖案）；2)向上述框内滴注液晶；以及3)進而將成對 的液晶面板的基板貼合（如日本專利特開2002-214626號 公報(之後稱為「專利文獻1」）等）。 利用液晶滴注方式製造液晶面板時，由於尚未硬化的 〇 液晶密封劑與液晶接觸，故液晶密封劑的成分容易溶解在 液晶中而容易污染液晶。若液晶受到液晶密封劑的污染， 則製成液晶面板時會產生顯示不良。此顯示不良一旦產生 則難以改善。因此，期望開發出具有低液晶污染性的液晶 密封劑。 液晶密封劑的原料通常是使用（甲基）丙烯酸酯化合 物。由於上述原因，（甲基）丙烯酸酯化合物必須具有低液 晶污染性。又，為了適當地保持液晶密封劑的黏度，較好 200903119BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal sealing agent, a (fluorenyl) acrylate compound used in the liquid crystal sealing agent, and a method for producing the (fluorenyl) acrylate compound. [Prior Art] In recent years, liquid crystal display panels (also referred to as "liquid crystal panels") have been used as display panels for various devices such as televisions and mobile phones. At present, liquid crystal droplets, one drop fill, and one drop fill are used for manufacturing liquid crystal display panels because of their excellent productivity. The liquid crystal dropping method refers to a method of manufacturing a liquid crystal display panel including the following processes: 1) applying a liquid crystal sealing agent (also referred to simply as "sealant") to a substrate of a liquid crystal panel to form a frame for filling a liquid crystal. (sealing pattern); 2) injecting liquid crystal into the frame; and 3) bonding the substrates of the pair of liquid crystal panels (for example, Japanese Patent Laid-Open Publication No. 2002-214626 (hereinafter referred to as "Patent Document 1") Wait). When the liquid crystal panel is produced by the liquid crystal dropping method, since the liquid crystal sealing agent which has not been hardened is in contact with the liquid crystal, the components of the liquid crystal sealing agent are easily dissolved in the liquid crystal and easily contaminate the liquid crystal. If the liquid crystal is contaminated by the liquid crystal sealing agent, display defects may occur when the liquid crystal panel is formed. This display failure is difficult to improve once it is generated. Therefore, it has been desired to develop a liquid crystal sealing agent having low liquid crystal contamination. The raw material of the liquid crystal sealing agent is usually a (meth) acrylate compound. For the above reasons, the (meth) acrylate compound must have low liquid crystal contamination. Moreover, in order to properly maintain the viscosity of the liquid crystal sealing agent, it is better 200903119

的是f ^基f稀_化合物成為高分子量。 丙細酸s旨化合物。例如，日本 (之後稱為「專利文獻2」）中 同分子I且在常溫下為液狀的（甲基）丙烯酸酯化合 物〆已知導入有己内酯鏈沾―）的（甲基) 曰本專利特公昭61-54788號公報 )中，揭示了一種以式（i)表示 的以異二聚氰酸酯環作為主骨架的化合物；日本專利特開 平7-2996號公報(之後稱為「專利文獻3」）中，揭示了一 種以式（11)表示的以三羥曱基丙烷作為原料的己内酯改 質多元醇聚（甲基）丙烯酸酯化合物。又，日本專利第 3715840號公報(之後稱為「專利文獻4」）中，揭示了一種 以式（iii)表示的以異三聚氰酸酯環作為主骨架的化合物。 [化1] 〇It is the f ^ group f dilute compound that becomes high molecular weight. Propionic acid s is a compound. For example, in Japan (hereinafter referred to as "Patent Document 2"), a (meth) acrylate compound which is a liquid I at room temperature and is known to have a caprolactone chain-introduced (meth) oxime Patent Publication No. Sho 61-54788 discloses a compound having a heterodimer cyanate ring as a main skeleton represented by the formula (i); Japanese Patent Laid-Open No. Hei 7-2996 (hereinafter referred to as "patent" In Document 3"), a caprolactone-modified polyol poly(meth) acrylate compound represented by the formula (11) using trishydroxypropylpropane as a raw material is disclosed. Further, Japanese Patent No. 3715840 (hereinafter referred to as "Patent Document 4") discloses a compound represented by the formula (iii) having a hetero-cyanate ring as a main skeleton. [Chemical 1] 〇

CH2CH20(CCH2CH2CH2CH2CH20)mCCH=CH2 式（i)中，l、m、n為0〜3的整數，l、m、n之合計 為0.5〜3。 [化2] 「cch2ch3 L(CH2OCOCH2(CH2 )3CH2OCOCH=CH2 )3 (ϋ) [化3] (iii) 9 200903119CH2CH20(CCH2CH2CH2CH2CH20)mCCH=CH2 In the formula (i), l, m, and n are integers of 0 to 3, and the total of l, m, and n is 0.5 to 3. [Chemical 2] "cch2ch3 L(CH2OCOCH2(CH2)3CH2OCOCH=CH2)3 (ϋ) [Chemical 3] (iii) 9 200903119

CH2=CCOCH2CH2OCCH2CH2 RCH2=CCOCH2CH2OCCH2CH2 R

0 0 CH2CH2COCH2CH2O^C=CH20 0 CH2CH2COCH2CH2O^C=CH2

0 0 -CH2CH2COCH2CH2OCC=：CH2 R 基 式中，R,為H或 式中，R表示H或CH3基。 然而，上述專利文獻1〜4所揭示的（曱基)丙烯酸酯化 合物，是為了用於塗料或印刷油墨等領域而開發的化合 物。因此，上述文獻中，並無任何將上述（甲基）丙烯酸酯 化合物用於液晶密封劑的記載。 本發明人等預製出使用有專利文獻2所揭示的化合物 的液晶密封劑，並對液晶污染性進行了研究。結果表明， 使用專利文獻2所揭示的化合物的液晶密封劑容易污染液 曰曰專利文獻2所揭不的化合物是藉由己内酯與經基的加 成反應而合成，故己内酯產生聚合反應而難以使化合物中 的己=醋鏈長為—定長度。因此，專利文獻2所揭示的化 合物是具有各種己内酯鏈的化合物的混合物，故可推測， =混合物中所存在的低分子量成分會增大上述液晶污染 因此’先前的於室溫下為液狀且分子量較高 丙烯酸酯化合物，難以改善液晶污染性。 τ 土） 【發明内容】 根據以上内容，本發明之目的在於提供一種於室 為液狀且液晶污染性低的（甲基）丙稀酸醋化合物、^含 有該（甲基）丙烯酸酯化合物的液晶密封劑。 3 200903119 鑒於上述狀況，本發明人等對（曱基）丙烯酸酯化合物 進行了潛心研究，結果發現，以下述通式（I )表示的（曱 基)丙烯酸酯化合物有效降低液晶污染性。亦即，上述課題 可藉由下述本發明而解決。 [1]一種液晶密封劑，其含有以下述通式（I )表示的 (曱基)丙烯酸酯化合物。 [化4]0 0 -CH2CH2COCH2CH2OCC=:CH2 R In the formula, R is H or where R represents H or CH3. However, the (fluorenyl) acrylate compound disclosed in the above Patent Documents 1 to 4 is a compound developed for use in the fields of paints, printing inks and the like. Therefore, in the above documents, there is no description of using the above (meth) acrylate compound as a liquid crystal sealing agent. The present inventors preliminarily produced a liquid crystal sealing agent using the compound disclosed in Patent Document 2, and studied liquid crystal contamination. As a result, it has been found that the liquid crystal sealing agent using the compound disclosed in Patent Document 2 is easily contaminated. The compound disclosed in Patent Document 2 is synthesized by the addition reaction of caprolactone and a mercapto group, so that caprolactone is polymerized. It is difficult to make the vinegar chain length in the compound a constant length. Therefore, the compound disclosed in Patent Document 2 is a mixture of compounds having various caprolactone chains, so it is presumed that the low molecular weight component present in the mixture increases the liquid crystal contamination so that the previous liquid is at room temperature. It is difficult to improve liquid crystal contamination by using an acrylate compound having a relatively high molecular weight. According to the above, an object of the present invention is to provide a (meth)acrylic acid vinegar compound which is liquid in the chamber and has low liquid crystal contamination, and contains the (meth) acrylate compound. Liquid crystal sealant. 3 200903119 In view of the above, the inventors of the present invention conducted intensive studies on a (fluorenyl) acrylate compound, and as a result, found that a (fluorenyl) acrylate compound represented by the following formula (I) is effective in reducing liquid crystal contamination. That is, the above problems can be solved by the present invention described below. [1] A liquid crystal sealing agent containing a (fluorenyl) acrylate compound represented by the following formula (I). [Chemical 4]

〇 II ο Ά. Λ ^a^-〇-x-〇-c-c=ch2 Ν Ν Ri ο人人。 乂、 c-0-y-0-c-c=ch2 〇 r2 式（I )中，A各自獨立為碳數為2或3的亞烷基， R!〜R3各自獨立為氫原子或甲基，X〜Z.各自獨立為碳數 為2〜4的亞燒基。 [2] 如[1]所述之液晶密封劑，其中上述通式（I )中的 A為亞乙基。 [3] 如[1]或[2]所述之液晶密封劑，其中上述（曱基）丙烯 酸酯化合物是選自以下述式（B1)、式（B2)、式（B3)以 及式（E1)表示的化合物族群中的兩種或兩種以上化合物 的混合物，且上述混合物中LBu基的數量與LEt基的數量 之比為70 : 30〜30 : 70。〇 II ο Ά. Λ ^a^-〇-x-〇-c-c=ch2 Ν Ν Ri ο everyone.乂, c-0-y-0-cc=ch2 〇r2 In the formula (I), A each independently represents an alkylene group having 2 or 3 carbon atoms, and R! to R3 are each independently a hydrogen atom or a methyl group, X ~Z. Each independently is a sub-alkyl group having a carbon number of 2 to 4. [2] The liquid crystal sealing agent according to [1], wherein A in the above formula (I) is an ethylene group. [3] The liquid crystal sealing agent according to [1], wherein the (mercapto) acrylate compound is selected from the group consisting of the following formula (B1), formula (B2), formula (B3), and formula (E1) a mixture of two or more compounds in the compound group indicated, and the ratio of the number of LBu groups to the number of LEt groups in the above mixture is 70: 30 to 30: 70.

LBu LEt LEt LEt 9 200903119 (B3) (Hi) (Bl) (B2) 式（Bl)〜式（El)中，A各自獨立為碳數為2或3 的亞烧基’ LBu為以下述式（LBu)表示的基團，LEt為 以下述式（LEt)表示的基團。 [化6] J 〇 (LBu) (LEt) —C-〇~~CH2CH2CH2CH2—ΰ-〒=(3Η2 Η [化7]LBu LEt LEt LEt 9 200903119 (B3) (Hi) (Bl) (B2) In the formula (Bl) to (El), A is independently a sub-alkyl group having a carbon number of 2 or 3, and LBu is represented by the following formula ( The group represented by LBu), LEt is a group represented by the following formula (LEt). [6] J 〇 (LBu) (LEt) — C-〇~~CH2CH2CH2CH2—ΰ-〒=(3Η2 Η [Chem. 7]

Μ 〇 —C-o— CH2CH2—〇-C-C=CH2 ch3 [4]如[η至[3]中任一項所述之液晶密封劑，其中此液 晶密封劑進一步含有環氧樹脂、自由基聚合起始劑、潛伏 性環氧硬化劑（latent epcxy curing agent)、以及填充料。 i_5]如[4]所述之液晶密封劑，其中相對於]〔)〇重量份之 上述（曱基）丙稀酸酯化合物’含有5重量份〜60重量份之 上述環氣樹脂、0.1重量份〜;1〇重量份之上述自由基聚人 起始劑、5重量份〜40重量份之上述潛伏性環氧硬化劑、 以及10重量份〜50重量份之上述填充料。 [6]—種（甲基)丙烯酸酯化合物的製造方法，其是製造 如上述[1]至[3]中任一項所述之（甲基）丙烯酸酯化合物的 方法，包括以下製程. 於三级胺的存在下，使以下述通式（Im)表示的化合 物與以下述通式（Llm)表示的化合物、以下述通式（L2m) 表示的化合物、以及以下述通式（L3m)表示的化合物在 非鹵溶劑中進行酯化反應，且使上述反應中所生成的鹵化 10 200903119 氫作為胺鹽而析出的製程； 於上述反應後對所獲得的反應混合物進行過濾的製 程； 以鹼水溶液清洗藉由上述過濾而將胺鹽除去的反應混 合物，然後分液而獲得有機相的製程；以及 .以純水清洗上述有機相的製程。 [化8]The liquid crystal sealing agent according to any one of [n to [3], wherein the liquid crystal sealing agent further contains an epoxy resin, and a radical polymerization initiation is started. A latent epoxy resin, a filler, and a filler. The liquid crystal sealing agent according to the above [4], wherein the above (indenyl) acrylate compound (containing 5 parts by weight to 60 parts by weight of the above-mentioned ring gas resin, 0.1 weight by weight) And 1 part by weight of the above-mentioned radical polytropic initiator, 5 parts by weight to 40 parts by weight of the above latent epoxy hardener, and 10 parts by weight to 50 parts by weight of the above filler. [6] A method for producing a (meth) acrylate compound, which is a method for producing the (meth) acrylate compound according to any one of the above [1] to [3], which comprises the following process. In the presence of a tertiary amine, a compound represented by the following formula (Im) and a compound represented by the following formula (Llm), a compound represented by the following formula (L2m), and a formula represented by the following formula (L3m) are used. a process in which a compound is subjected to an esterification reaction in a non-halogen solvent, and a halogenated 10 200903119 hydrogen formed in the above reaction is precipitated as an amine salt; a process of filtering the obtained reaction mixture after the above reaction; The process of removing the reaction mixture by removing the amine salt by the above filtration, and then separating the liquid to obtain an organic phase; and the process of washing the above organic phase with pure water. [化8]

〇 Ο π〇 Ο π

Halo ^ 'HaloHalo ^ 'Halo

O^N^OO^N^O

II

A 〇=C、 'Halo (Im) 式（Im)中，A表示碳數為2或3的亞院基，Halo表 示鹵原子。 [化9] 〇 H〇_X_〇*~C-C=CH2 ri (Llm)A 〇=C, 'Halo (Im) In the formula (Im), A represents a sub-compartment having a carbon number of 2 or 3, and Halo represents a halogen atom. [化9] 〇 H〇_X_〇*~C-C=CH2 ri (Llm)

[化 10] 〇 ho-y-o-c-c=ch2 (L2m) [化 11] ο H〇-2-〇-C-C=CH2 r3 ( L3m ) 式（Llm)〜式（L3m)中，&〜113各自獨立表示氫 原子或曱基，X〜Z各自獨立表示碳數為2〜4的亞烷基。 [7]如[6]所述之製造方法，其中上述非鹵溶劑為芳香族 200903119 烴、乙酸乙酯（ethyl acetate)、或甲基異丁基酮（methyl isobutyl ketone ) ° [8] 如[6]或[7]所述之製造方法，其中上述三級胺為〇比 疋（pyridine )、三乙胺（triethylamine )、或二甲基苯胺 (dimethyl aniline )。 [9] 一種（甲基）丙烯酸酯化合物，其是以下述通式（b) 戶斤表示。化ho-yocc=ch2 (L2m) ο H〇-2-〇-CC=CH2 r3 ( L3m ) In the formula (Llm) to (L3m), &~113 are independently represented The hydrogen atom or the fluorenyl group, and X to Z each independently represent an alkylene group having a carbon number of 2 to 4. [7] The production method according to [6], wherein the non-halogen solvent is aromatic 200903119 hydrocarbon, ethyl acetate, or methyl isobutyl ketone [8] as in [ The production method according to [6], wherein the tertiary amine is pyridine, triethylamine, or dimethyl aniline. [9] A (meth) acrylate compound which is represented by the following formula (b).

[化 12] 0 0 0 h2oc-^-o-X2.c^—CH2CH、又 N/CH2CHf_S-0_Xi_0|c=CH2 。。人人 " | 0 0Η20Η2—C—0—X2-〇—C—C=CHp II I ά 〇 R2[0] 0 0 0 h2oc-^-o-X2.c^-CH2CH, and N/CH2CHf_S-0_Xi_0|c=CH2. . Everyone " | 0 0Η20Η2—C—0—X2-〇—C—C=CHp II I ά 〇 R2

B 式（B)中，χ]表示碳數為3或4的亞烷基，&各自 獨立表示碳數為2〜4的亞烷基，&表示氫原子或甲基， R2各自獨立表示氫原子或曱基。 [10]如[9]所述之（甲基）丙烯酸酯化合物，其中上述通 式（B)中的Xi為亞丁基，為氫原子，且&為亞丁基 或亞乙基。 [11] 如[9]或[10]所述之（曱基)丙烯酸酯化合物，其中上 述通式（Β)中的X!以及X2為亞丁基，且Ri以及為氫 原子。 [12] —種液晶顯示面板的製造方法，其包括以下製程： 準備弟一基板的製程，此弟一基板具有由如上述[1] 至[5]中任一項所述之液晶密封劑所形成的密封圖案； 於上述密封圖案未硬化的狀態下，向上述第一基板的 12 2〇〇9〇3i29 的第二基板上滴注液晶 雄封圖案框内或與上述基板相對向 的製程； 將上述第—基板與上述第二基板疊合的製程；以及 使上述液晶密封劑硬化的製程。 曰龜[-13^1種液晶顯示面板，其是藉由如上述[12]所述之液 日日顯不面板的製造方法而獲得。 [發明的效果]B In the formula (B), χ] represents an alkylene group having a carbon number of 3 or 4, & each independently represents an alkylene group having a carbon number of 2 to 4, & represents a hydrogen atom or a methyl group, and R2 each independently represents A hydrogen atom or a sulfhydryl group. [10] The (meth) acrylate compound according to [9], wherein Xi in the above formula (B) is a butylene group, is a hydrogen atom, and & is a butylene or ethylene group. [11] The (fluorenyl) acrylate compound according to [9] or [10], wherein X! and X2 in the above formula (Β) are a butylene group, and Ri is a hydrogen atom. [12] A method of manufacturing a liquid crystal display panel, comprising the following: a process for preparing a substrate, the substrate having a liquid crystal sealing agent according to any one of the above [1] to [5] a sealing pattern formed; in a state in which the sealing pattern is not cured, a process of injecting or facing the liquid crystal male seal pattern frame onto the second substrate of the first substrate 12 2 〇〇 9 〇 3i29; a process of laminating the first substrate and the second substrate; and a process for curing the liquid crystal sealing agent. The tortoise [13] is a liquid crystal display panel obtained by the method for producing a liquid-day panel according to the above [12]. [Effects of the Invention]

根據本發明提供—紗室溫下為綠且液晶污染性低 铷（甲基）丙烯酸酯化合物、以及含有該（曱基）丙烯酸酯化合 ，的液晶密封劑。本發明的密封劑尤其適合於液晶滴注方 武’可提賴示魏料的液晶顯示面板。 為讓本發明之上述和其他目的、特徵和優點能更明顯 廑，下文特舉較佳實施例，並配合所附圖式，作詳細説 明如下。 【實施方式】 i.(曱基)丙烯酸酯化合物 (1)(曱基)丙烯酸酯化合物 本發明的液晶密封劑含有以下述通式（I )表示的（甲 ，）丙烯酸酯化合物（以下亦稱為「本發明的化合物」）。所 明（甲基）丙烯酸酯化合物，是指丙烯酸或曱基丙烯酸的酯 化物’所謂「（曱基)丙烯酸」是指「丙烯酸或曱基丙烯酸」。 [化 13] 13 200903119 , Μ h2c=c—c-o-z- r3 II •o-c、 τΐ ο A^a-^o-x-o-c-^ch, Γ卞 〇Ι?，2 r2 Γ ο 以通式（I )表示的（甲基）丙烯酸醋化合物，於異三 =猶自旨環上的3個IU子场結有作為錢基團的A， =各個A:有可聚合的有機基團(以下亦稱為「聚 i白,團」i° 為石炭數為2或3的亞絲。所謂 石1 ^立，是指3個A既可不同，亦可全部為相同的基團。 j為2或3的亞絲之例包括曱基亞曱基、K基、亞 ^基，正丙基）、以及亞異两基。其中，A較好的是亞乙 ，其本發_化合^製造轉將於後文中詳述， 乙基之本發明的化合物，原料容易獲取且容易合成。 二合性基團中：R]〜r3 |自獨立表示氫原子或曱 〜Z各自獨立表示碳數為2〜4的亞烧基。本發明中 的付號「〜」包括其兩端的值。 本發明的化合物由於通式（！）中的A、R】〜R3 =處於上述範_，故提供_種於室溫下為液狀，且 曰曰3染十生低的液晶密封劑。進而，藉由使該些A、r〜兑 = 最適化，可提供液晶污染性及絲等= 異的液晶密封劑。以下，就較好Μ+ 等更優 以說^ 恤好的本發明的化合物之例加 本發明的化合物的較好的第〗例為 化合物。該化合物亦稱為化合物Β。 )表不的According to the present invention, there is provided a liquid crystal sealing agent which is green at room temperature and has a liquid crystal contamination low 铷 (meth) acrylate compound and a thiol acrylate compound. The sealant of the present invention is particularly suitable for a liquid crystal display panel in which liquid crystal instillation is used. The above and other objects, features and advantages of the present invention will become more apparent from [Embodiment] i. (Mercapto) acrylate compound (1) (fluorenyl) acrylate compound The liquid crystal sealing agent of the present invention contains an (meth) acrylate compound represented by the following formula (I) (hereinafter also referred to as It is "the compound of the present invention"). The (meth) acrylate compound means an ester of acrylic acid or methacrylic acid. The term "(fluorenyl) acrylate" means "acrylic acid or methacrylic acid". 13 200903119 , Μ h2c=c—coz- r3 II •oc, τΐ ο A^a-^oxoc-^ch, Γ卞〇Ι?, 2 r2 Γ ο is represented by the general formula (I) a methyl acrylate vinegar compound, which has a group as a money group in the three IU sub-fields of the iso-three-subordinate ring, and each A: a polymerizable organic group (hereinafter also referred to as "polyi white" , group "i° is a filament with a charcoal number of 2 or 3. The so-called "stone" refers to three A's which may be different or all of the same group. J is a 2 or 3 example of a filament. Including fluorenyl fluorenyl, K-based, arylene, n-propyl), and hetero-isomeric. Among them, A is preferably Ethylene, and its preparation is described in detail later. The compound of the present invention of ethyl is easy to obtain and easy to synthesize. In the dimeric group: R]~r3 | independently represents a hydrogen atom or 曱~Z each independently represents a sub-alkyl group having a carbon number of 2 to 4. The payout "~" in the present invention includes the values at both ends thereof. Since the compound of the present invention has the above formula (!), A, R] to R3 = in the above-mentioned range, it provides a liquid crystal sealing agent which is liquid at room temperature and has a low dyeing ratio. Further, by optimizing the A, r, and =, it is possible to provide a liquid crystal sealing agent having liquid crystal contamination and silk. In the following, a preferred example of the compound of the present invention which is more preferably Μ+, etc., and a compound of the present invention are compounds. This compound is also known as the compound hydrazine. )

U 200903119 ΔΟ^Ο^ρΐΙ [化 14] H2C=C-^〇-Xr〇-〇-CH2CH2VNAN/CH2CH^t〇-Xr〇_tc=CH2 〇人 R1 I CH2CH2- -c-〇-x2-〇~8-c=ch2 玲2 r 原子 化合物B是通式（I )中的A為亞乙基的化合^B) 式（B)中，R]為氫原子或曱基。其中&車交好的是氣U 200903119 ΔΟ^Ο^ρΐΙ [Chemical 14] H2C=C-^〇-Xr〇-〇-CH2CH2VNAN/CH2CH^t〇-Xr〇_tc=CH2 〇人R1 I CH2CH2- -c-〇-x2-〇 ~8-c=ch2 Ling 2 r The atomic compound B is a compound of the formula (I) wherein A is an ethylene group. In the formula (B), R) is a hydrogen atom or a fluorenyl group. Which & car is good

U 式（B)中，X〗為碳數為3或4的亞貌基。 碳數為3或4的亞烷基之例包括亞丙基（亞正丙美 亞異丙基、亞丁基（亞正丁基）、亞異丁基、亞第二丁^ 以及亞第二丁基。其中，自製成液晶密封劑時的接著忡 異的觀點考慮’較知的是Χι為亞丁基即亞正丁其。 式（B)中’R2各自獨立為氫原子或甲基。 式（B)中，X2各自獨立為碳數為2〜4的亞規基。石山 數為2〜4的亞烷基之例包括甲基亞曱基、亞乙基二^丙= (亞正丙基）、亞異丙基、亞丁基（亞正丁基）、亞異丁基= 亞第二丁基、以及亞第三丁基。其中，較好的是&為亞丁 基或亞乙基。若又2為亞丁基，則製成液晶密封劑時的接 性優異。若X2為亞乙基，㈣錢晶密賴時的耐熱性優 M- ° , ' 又，上述X2既可全部為亞丁基，亦可全部為亞乙基。 進而，其中—個^為亞丁基而另—個&為亞乙基亦可。 :為J丁基且所有χ2均為亞丁基的化合物亦稱為「_ 孓」。又！為亞丁基、其中一個&為亞乙基而另—個&為 15 200903119 亞丁基的化合物亦稱為「2Bu型」。X!為亞丁基且所有X2 均為亞乙基的化合物亦稱為「lBu型」。其中，化合物B 更好的是下示化合物。 [化 15] LB'dLBuIn the formula (B), X is an alkenyl group having a carbon number of 3 or 4. Examples of the alkylene group having a carbon number of 3 or 4 include a propylene group (an n-propylidene isopropyl group, a butylene group (n-n-butyl group), an isobutylene group, a sub-second butyl group, and a sub-second butyl group. Among them, from the viewpoint of the subsequent difference in the preparation of the liquid crystal sealing agent, it is known that Χι is a butylene group, that is, an n-butylene. In the formula (B), 'R2 is each independently a hydrogen atom or a methyl group. In B), each of X2 is independently a subunit having a carbon number of 2 to 4. Examples of an alkylene group having a number of 2 to 4 in the range of a rock include a methyl fluorenylene group, an ethylene propylene group, and a propylene group. ), isopropylidene, butylene (n-n-butyl), isobutylene = sub-tert-butyl, and thirylene. Among them, it is preferred that & is a butylene or ethylene group. When 2 is a butylene group, it is excellent in the contactability when it is made into a liquid-crystal sealing agent. When X2 is ethylene, (4) The heat resistance of the crystal|grain is excellent M- °, and the above X2 can be all Aden. Further, all of them may be ethylene. Further, one of them is a butylene group and the other is an ethylene group. A compound which is a J butyl group and all of which are all a butylene group is also called " _ 孓". Again! Butyl, one of which is ethylene and the other & is 15 200903119 butylene is also known as "2Bu". X! is a butylene and all X2 are ethylene. "lBu type", wherein compound B is more preferably a compound shown below. [Chemical 15] LB'dLBu

N N 。人人。N N . Everyone.

II

A (Bl) (Β2) LBuA (Bl) (Β2) LBu

[化 16] LBu 1 LBu A、N人Ν’ 。人人。[Chem. 16] LBu 1 LBu A, N person Ν'. Everyone.

I 今 LEt [化】7] LEt\ 人/ Ν Ν ο人人。 .Βυ ι A ι LEt (Β3)I Today LEt [Chemical] 7] LEt\ People / Ν Ν ο Everyone. .Βυ ι A ι LEt (Β3)

式（Bl )〜式（Β3)中’LBu以及LEt是以下述式（LBu) 及式（LEt)表示的基團。 [化 18] ——C-Ο——CH2CH2CH2CH2—c=ch2 H (LBu) [化 19] ——0 一〇——CH2CH2~〇—C—C=CH2 ch3 (LEt) 其中，尤其好的是3Bu型且R!以及R2均為氫原子的 16 200903119 -iOJOjpil 以式（Bl)表示的化合物（亦稱為「化合物B1」）。其原 因在於，此化合物在製成液晶密封劑時的接著性極為優異。 化合物B2或化合物B1中LBu基與LEt基的數量之 比較好的是70 : 30〜30 : 7〇。 本發明的化合物的較好的第2例為以式㈤表示的 化合物。該化合物亦簡稱為化合物E。化合物£是通式（工）In the formula (B1) to the formula (Β3), 'LBu and LEt are groups represented by the following formula (LBu) and formula (LEt). [Chem. 18] ——C-Ο——CH2CH2CH2CH2—c=ch2 H (LBu) [Chem. 19] ——0 One 〇——CH2CH2~〇—C—C=CH2 ch3 (LEt) Among them, especially good 3Bu type and R! and R2 are each a hydrogen atom. 16 200903119 -iOJOjpil A compound represented by the formula (Bl) (also referred to as "compound B1"). This is because the compound is extremely excellent in adhesion when it is made into a liquid crystal sealing agent. The amount of the LBu group and the LEt group in the compound B2 or the compound B1 is preferably 70: 30 to 30: 7 Å. A preferred second example of the compound of the present invention is a compound represented by the formula (5). This compound is also referred to simply as Compound E. Compound £ is a general formula

中的A為亞乙基、且聚合性基團L1〜u中χ〜ζ均為亞 乙基的化合物。 " CH2CH2COCH2CH2〇CC=CH2Among them, A is an ethylene group, and the polymerizable group L1 to u is a compound in which χ~ζ is an ethylene group. " CH2CH2COCH2CH2〇CC=CH2

(E 式（E)中各自獨立為氫原子或甲基。 此化5物疋於異二聚氰酸酯環的氮原子上鍵結有 基)丙制基乙氧基)縣乙基的化合物。該 稱為「丙烯酸醋型」。又，該取代 二： =氧進，基。此時的化合物亦稱為「= 代基的一部分為2侧醯基乙： p a 7匕。物亦知為「（甲基）丙烯酸酯型」。 化合物E更好的是甲基丙稀酸」 接著強度優異的液晶穷w # /、京U在於麩供 ㈤）所表示㈣封劑。甲基丙烯酸_是以下式 200903119 [化 21] _?Ha ο ο ο H2C_C~『。—H2cH2C-〇-^：— CH2CH2、nJLn/ CH2CH2—C-〇-CH2CH2-〇-0i-(j>CH2 ° I 0 i? 兄 CH2CH2—C_〇""CH2CH2-〇 - c—〇ch2 ch3 (El)(E wherein each of the formula (E) is independently a hydrogen atom or a methyl group. The compound of the compound 5 is bonded to the nitrogen atom of the heterodimeric cyanate ring.) A compound of the ethyl group) . This is called "acrylic vinegar type". Again, the substitution is two: = oxygen in, base. The compound at this time is also referred to as "the part of the substituent" is a 2-sided thiol group: p a 7 匕. The substance is also known as "(meth) acrylate type". The compound E is more preferably methyl methacrylate. The liquid crystal of the strength is excellent, and then the U is in the bran supply (f)). Methacrylic acid _ is the following formula 200903119 [Chem. 21] _?Ha ο ο ο H2C_C~『. —H2cH2C-〇-^:—CH2CH2, nJLn/CH2CH2—C-〇-CH2CH2-〇-0i-(j>CH2 ° I 0 i? Brother CH2CH2—C_〇""CH2CH2-〇- c—〇 Ch2 ch3 (El)

本發明的化合物亦可含有少量的由（甲基）丙烯醯基聚 合而生成的低聚物成分等雜質，但較好的是高純度。上述 純度較好的是大於等於80%，更好的是大於等於90%，尤 其好的是大於雜95%。純度是㈣彻高效液相層析法 (High Performance Liquid Chromatography，HPLC )公供 時所得科㈣而算出。糾，較好岐化合物齡= 子性雜貝1st少。其原目在於，若液晶密封劑巾存在離子性 雜質，則密封劑之液晶污染性會顯著下降。為了減少離子 性雜質’較好的是藉由_管㈣製使本發_化合物高 純度化。 (2 )(曱基)丙稀酸醋化合物的製造方法 本發明的化合物的製造方法並無特別限定。例如，可 依據上—述專利文獻4所記_方法來製造。該方法是將 1，3,5-三（鹵化甲醯基乙基)異三聚氰酸醋與（甲基)丙烯酸經 烷酯脫鹵化氫並酯化的方法，具體包括以下製程： 使（甲基）丙烯酸羥烷酯及吡啶溶解於氯仿 (chloroform )溶劑中的製程； 於上述混合物中混合1,3,5-三（^化曱酸基乙基)異三 聚氰酸酯，並進行反應的製程； 200903119 反應液，再ί而以1 Ν氣氧化鋼水溶液清洗上述 分離鹽水清洗的清洗製程；以及 然而，仿等而獲得目標化合物的製程。 性雜質，故,= f:獲得的化合物有時含有大量離子 利用上柱精製等加以精製。 大量 r_=:4:::;=:::T-水。法在清洗製‘ 中使用水代替飽和食，於，若在清洗製程 越二:=溶解於氯仿與水兩者中。又’使用徵和食 水:==水，_ Ο ===:::自食鹽水的_子或氣化 清洗製程中使用飽二 方法獲得的化合物含有大量離;性雜質=:祕的 載的=:、=:等試實施了專利文獻_ 用=情形相比有所改善，但尚不充分。一般認' 親媒:物質。可二:物ί有機相與水相之界面處存在兩 、 ’、j此物質主要為吡啶鹽酸鹽。因此可推 19 200903119 測，第二，清洗時的分祕差，是利料散獻4所記載 的方法獲得的化合物含有大量離子性雜質的原因。 _根據上述内容，本發明的化合物較好的是利用以下所 不的方法（以下亦稱為「過濾法」）來製造。 此方法包括如下製程：The compound of the present invention may contain a small amount of impurities such as an oligomer component formed by polymerization of a (meth) acrylonitrile group, but is preferably high in purity. The above purity is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. The purity was calculated by (4) the high-performance liquid Chromatography (HPLC) obtained at the time of public supply. Correction, better 岐 compound age = less than 1st. The original purpose is that if the liquid crystal sealing agent has ionic impurities, the liquid crystal contamination of the sealing agent is remarkably lowered. In order to reduce ionic impurities, it is preferred to make the present invention highly purified by the method of the tube (four). (2) Method for producing (mercapto) acrylic acid vinegar compound The method for producing the compound of the present invention is not particularly limited. For example, it can be manufactured according to the method described in the above-mentioned Patent Document 4. The method comprises the steps of dehydrohalogenating 1,3,5-tris(halomethylideneethyl)iso-cyanuric acid vinegar and (meth)acrylic acid with an alkyl ester, and specifically comprises the following process: a process for dissolving hydroxyalkyl methacrylate and pyridine in a chloroform solvent; mixing 1,3,5-tris(ethyl decanoic acid) isomeric isocyanate in the above mixture, and performing The process of the reaction; 200903119 The reaction solution is further cleaned with a 1 Ν oxidized steel aqueous solution to clean the cleaning process of the above-mentioned separated brine cleaning; and, however, the process of obtaining the target compound is obtained. Sexual impurities, so = f: The obtained compound sometimes contains a large amount of ions and is purified by column purification or the like. A large number of r_=:4:::;=:::T-water. The method uses water instead of saturated food in the cleaning system, if the cleaning process is two: = dissolved in both chloroform and water. Also 'use the levy and water: == water, _ Ο ===::: _ sub-salt or the gasification cleaning process using a saturated method to obtain a large amount of compound; sexual impurities =: secret carrier =:, =: etc. The patent document _ has been improved compared with the case of =, but it is not sufficient. Generally recognized as 'parental: substance. Can be two: the physical phase of the organic phase and the water phase at the interface of two, ', j this substance is mainly pyridine hydrochloride. Therefore, it can be pushed 19 200903119 to measure, and secondly, the difference in the degree of cleaning is the reason why the compound obtained by the method described in the four materials contains a large amount of ionic impurities. According to the above, the compound of the present invention is preferably produced by the following method (hereinafter also referred to as "filtration method"). This method includes the following processes:

υ於三級胺的存在下，使以下述通式（Im)表示的 化合物輿以下述通式（Llm)表示的化合物、以下述通式 (L2m)表示的化合物、以及以下述通式（L3m)表示的 化合物在非齒溶劑中進行酯化反應，且使上述反應中所生 成的鹵化氫作為胺鹽而析出的製程； 2)於上述反應後對所獲得的反應混合物進杆過濾的製 程； ^ 驗水溶液清洗藉由上述過濾而將胺鹽除去的反應 混合物，然後分液而獲得有機相的製程；以及 4)以純水清洗上述有機相的製程。 1 )製程：反應製程 本反應製程中，於三級胺的存在下，使以下述通式 (Ini)表示的U，5_三（鹵化甲酿基乙基)異三聚氮酸酿（以 下亦稱為「化合物Im」）與以下述通式（Um)〜通式 表示的（甲基)丙烯酸舰S旨（以下亦將該些（甲基 ，統稱為「化合她等」)在非鹵溶劑中進= 應。利用本反應製程可獲得本發明的化合物。缺而，利用 =應製㈣獲得的反應混合物，含有作為副產物的以 又[((甲基）丙埽醯基烧氧基)幾基乙基]-5_(2_幾基乙其)異二 20 200903119 聚亂酸Ss、^級胺之_化氫鹽等。In the presence of a tertiary amine, a compound represented by the following formula (Im) is a compound represented by the following formula (Llm), a compound represented by the following formula (L2m), and a formula (L3m) a process in which a compound represented by esterification is carried out in a non-dentate solvent, and a hydrogen halide formed in the above reaction is precipitated as an amine salt; 2) a process of filtering the obtained reaction mixture after the above reaction; The aqueous solution is cleaned by a reaction mixture obtained by removing the amine salt by the above filtration, and then liquid separation to obtain an organic phase; and 4) a process of washing the above organic phase with pure water. 1) Process: Reaction Process In the present reaction process, U,5_tri(halogenated ethylenyl)isotrinitrous acid represented by the following formula (Ini) is used in the presence of a tertiary amine (hereinafter Also known as "Compound Im") and (meth)acrylic acid represented by the following general formula (Um) to formula (hereinafter also referred to as "methyl (collectively referred to as "Chemical Her", etc.) in non-halogen In the solvent, the compound of the present invention can be obtained by the present reaction process. In the absence, the reaction mixture obtained by the method of (4) is used as a by-product to further [((methyl)propenyl alkoxy). Alkylethyl]-5_(2_monomethylidene)iso-di 20 20 200903119 Polysuccinic acid Ss, a hydrazine salt of the amine.

U 三級胺的鹵化氫鹽（亦稱為「三級胺鹽」），在專利文 獻4所减的方法巾亦會生成。於此專利讀所記載的方 法中，由於使用氣仿作為溶劑，故三級胺鹽容易溶解，因 而二級胺鹽溶解於溶射而存在m於本過滤法 中，使用二級胺鹽的溶解度低的非_溶劑作為溶劑，故三 級胺鹽析出而不會溶解於溶劑中。因此’在後製程中，可 藉由過―自反應混合物巾除去三級㈣。不^三級胺鹽 的反應混合物在此後的清洗製程中分液性良好。 本製程具體而言可依照如下方式而實行。 笫1方法 …、、 村冗兮物與非函溶劑混合而成的懸 >于液中、，添加預先將化合物Llm等與三級胺混合而獲得白( 均勻溶液的方法。 第2方法：於上述均勻溶液中，添 物Im與非鹵溶劑的懸浮液的方法。 冗衣侑日〕化口 第3方法：於上述均勻溶液中添加 加粉末狀化合物Im的方法。 傻/小 其中，第1方法由於操作性優異故較好。此時， 均勻溶液可用非i溶劑稀釋之後添加。 ι 本製程為放減應。ϋ此，若反應麵 ^統的溫度過度上升，有時無法穩定地進行反應。因2 f 1方法以及第2方法中於—方㈣㈣ 化’為避免急遽的反應，較好的是以滴 ― 方液體。滴加時的反應系統的温度較好的是^ 21 200903119 適當=至，嚴〜6〇C。滴加時間可根據反應系統的溫度而 熟化本^後，為了使反應結束，較好的是使反應混合物 ς °見、化是使反應混合物的溫度在較好的是5。〇〜15〇The hydrogen halide salt of U tertiary amine (also known as "tribasic amine salt") is also produced in the method towel reduced by Patent Document 4. In the method described in this patent reading, since the gas imitation is used as the solvent, the tertiary amine salt is easily dissolved, so that the secondary amine salt is dissolved in the solvent and the m is present in the filtration method, and the solubility of the secondary amine salt is low. The non-solvent acts as a solvent, so the tertiary amine salt precipitates without being dissolved in the solvent. Therefore, in the post-process, the third stage (four) can be removed by passing the self-reactive mixture. The reaction mixture of the tertiary amine salt was good in liquid separation in the subsequent cleaning process. The process can be carried out in the following manner.笫1 method..., a suspension of a mixture of a redundant material and an inert solvent in a liquid, and a method in which a compound Llm or the like is mixed with a tertiary amine in advance to obtain a white (a homogeneous solution) is added. The second method: A method of adding a suspension of Im and a non-halogen solvent in the above homogeneous solution. The second method of adding a powdered compound Im to the above homogeneous solution is the method of adding a powdery compound Im. The method is preferred because it is excellent in operability. In this case, the homogeneous solution can be added after dilution with a non-i solvent. ι This process is a reduction. Therefore, if the temperature of the reaction surface rises excessively, sometimes it cannot be stably performed. Reaction. Because of the 2 f 1 method and the second method, in order to avoid the irritating reaction, it is preferred to use a liquid. The temperature of the reaction system at the time of dropping is preferably ^ 21 200903119 = to, strict ~ 6 〇 C. The addition time can be matured according to the temperature of the reaction system, in order to complete the reaction, it is better to make the reaction mixture ς °, the reaction is to make the temperature of the reaction mixture better It is 5. 〇~15〇

7，室溫〜_的範圍内保持為大致固定而進行。 杯的^化4間是以反應混合物中的化合物Im Α致完全消 2 、、士式而調整，較好的是〇1小時〜15小時，更好的是 短？ί〜7小時。反應溫度或熟化溫度越高，熟化時間越 ，若反應溫度或熟化溫度高，則（曱基）丙烯醯基 σ能會聚合，故較好的是降低反應溫度或熟化溫度，且延 化時間。上述反應的進度，例如，可對熟化開始後每 次經過任意時間所提取的反應混合物進行HPLC分析而求 出。 ' [原料] 化合物Im即1，3,5-三（鹵化曱醯基烷基)異三聚氰酸 酯，是將1，3,5-三（2-羧基烷基）異三聚氰酸酯7. The room temperature 〜 is kept substantially constant within the range of _. The 4 of the cup is adjusted by the compound Im in the reaction mixture, and is preferably adjusted to be 1 hour to 15 hours, more preferably short. ί~7 hours. The higher the reaction temperature or the aging temperature, the higher the aging time. If the reaction temperature or the aging temperature is high, the fluorenyl ruthenium σ can be polymerized. Therefore, it is preferred to lower the reaction temperature or the aging temperature and to extend the time. The progress of the above reaction can be determined, for example, by HPLC analysis of the reaction mixture extracted every time after the start of aging. '[Materials] The compound Im, 1,3,5-tris(haloalkylidenealkyl)isophthalocyanate, is 1,3,5-tris(2-carboxyalkyl)isocyanuric acid. ester

(l，3,5-tris(2-carboxyl alkyl)isocyanurate)的鲮酸進行醯鹵 化而獲得的醯鹵，以式（Im)所表示。 [化 22] 〇The hydrazine halide obtained by halogenation of decanoic acid of (l,3,5-tris(2-carboxyl alkyl)isocyanurate) is represented by the formula (Im). [化22] 〇

0 C'Halo (Im) 式（Im)中，A表示碳數為2或3的亞烷基，Halo表 22 200903119 示鹵原子。碳數為2或3的亞烷基之例包括上文已述之基 上述鹵tl素之例包括氯、溴以及碘。其中，鹵元素較 好的是氯。此種醯氣是以如下方式獲得：在N，N_二甲基^ 醯胺（Ν,Ν-dimethylformamide)溶劑下，使 ι,35_:(2 幾 基烷基)異二聚氰酸酯與碳醯氯（ph〇sgene )、草醯氯（收^ chloride)或亞硫醯氯（thionyl chloride)反應。 化合物Im巾，多數情況下主要含有u•雙⑽化 基院基)-5·(2·縣垸基)異三聚氰酸g旨作為雜質。此雜質具 有絲。此化合物亦稱為「Im的雜f」。Im的雜f在本^ 雙[((曱細烯輸完氧 基域]_5♦絲絲)異三__。該财物亦稱 為I的副產物」，由於具有缓基故容易溶解於驗水溶液中。 於本過歧巾’錢製程巾祕切料狀應混合物， ^該絲存纽反應混合物巾，顺清洗時的分 液性下降。根據上述内容，化合物Im的純度較 = 更好岐大於等於93%，尤其好的是大於等 々上述純度是根據肌C分析時所獲得的峰 ==合物Im的純度可藉由以下方式求出:添:: :=生為醯胺化合物之後，進行Ηρΐχ分析。具體而 :將1，3,5-二（鹵化甲醯基嫁基)異三聚氮酸醋的峰面射 ^里將二雜質即雙，甲酿基絲)·5_(2遍基 絲)旨的峰面積設為a2、將其他的溶劑以外 23 200903119 的雜質峰設為a3時，以{ai/ (al+a2 + a3)} χ1㈧ 化合物Im的純度。 鼻 化合物Llm、L2m以及L3m是分子内具有羥基及 基)丙烯醯基的化合物，亦即（甲基）丙烯酸羥烷酯， 式所表示。 [化 23]0 C'Halo (Im) In the formula (Im), A represents an alkylene group having 2 or 3 carbon atoms, and Halo Table 22 200903119 shows a halogen atom. Examples of the alkylene group having 2 or 3 carbon atoms include the groups described above. Examples of the above halogenated compounds include chlorine, bromine and iodine. Among them, the halogen element is preferably chlorine. The helium gas is obtained by reacting iota, 35_: (2 alkylalkyl) isomeric cyanate with N,N-dimethylformamide solvent. Carbon 醯 (gene), grass chlorinated (chloride) or thionyl chloride. In many cases, the compound Im towel mainly contains u•bis(10)-based base)-5·(2·county-based)iso-cyanuric acid g as an impurity. This impurity has a wire. This compound is also referred to as "Im's miscellaneous f". Im's miscellaneous f is in this ^ bis [((曱 输 输 输 输 输 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _. In the aqueous solution, in the present invention, the mixture of the waste process of the 'money process towel' should be mixed, and the liquid distribution of the silk reaction mixture is reduced. The purity of the compound Im is better than that of the above. It is equal to 93%, particularly preferably greater than or equal to 々. The above purity is obtained according to the peak of the muscle C analysis = the purity of the compound Im can be obtained by: adding:: := after the production of the guanamine compound, Carry out Ηρΐχ analysis. Specifically: the peak of the 1,3,5-di(halogenated carbaryl-based) sulphuric acid sulphuric acid sulphur will be the second impurity, ie, the double-stranded, the base of the ketone)·5_(2 The peak area of the basal filament is set to a2, and the impurity peak of 23 200903119 is set to a3 other than the other solvent, and the purity of the compound Im is {ai/ (al+a2 + a3)} χ1 (eight). The nasal compounds Llm, L2m and L3m are compounds having a hydroxy group and a propylene group in the molecule, that is, a hydroxyalkyl (meth) acrylate, represented by the formula. [Chem. 23]

HO "〇""0 *~C=CH2 Ri (Llm) μ υ ho-y-〇-c-c=ch2 ho-z-o-c^c-ch 心 r3 2HO "〇""0 *~C=CH2 Ri (Llm) μ υ ho-y-〇-c-c=ch2 ho-z-o-c^c-ch heart r3 2

(L2m) (L3m) 式（Llm)〜式（L3m)中，各自獨立表示々 原子或曱基，X〜Z各自獨立表示碳數為2〜4的亞烷基氧 該些化合物之例包括丙烯酸4-經丁酯 '(曱其）石、^ 参生乙S曰、以及〔曱基）内烤酸2-經異丙醋等，但並無々！ 限定。 ’’’、何別 化合物Llm〜化合物L3m可全部相同，亦可全部 同，或，亦可部分相同。 於化合物Llm〜化合物L3m全部相同之情形時，可 得如上述化合物B1或化合物E1之化合物。 又 所謂化合物Llm〜化合物L3m部分相同，例如是异t L2m與L3m相同而與Llm不同的情形。於此情形時，可 獲得如上述化合物B2或化合物B3之化合物。此時，例如 若使化合物Llm的莫耳（mol)數與化合物L2m的莫耳數 為1 : 1，則可獲得選自由上述化合物B1〜化合物£ 1所組 成的族群中的兩種或兩種以上化合物的混合物，且該混合 物中源自化合物Llm的基團與源自化合物L2m的基團的 24 200903119 數量比為l : 1。 對中所使用的化合等的合計莫耳數，相 =)匕a物Im的莫耳數較好的是2倍〜6倍，更好的是3 :;莫:數2好的是3倍〜3.3倍。若化合物Um等的 i製產範圍’則下述清洗製程中的清洗效率以及 ，化δ物Llm等的合計莫耳數少於上 物的精製產率會下降。又，若化合物= ^十f耳數〉'於上述下限值，則於化合物Im # i位、3位、 於Sit土f結物匕曱醯基乙基不會全部被酯化。由 〜H 為兩親媒性，故有時此制清洗製程中的 Γ另—方面，若化合物Um等的合計莫耳數 值’則有時反應混合液中會殘留未反應的化 等，導致此制清洗製程巾的清洗次數增加。 [非ii溶劑] 、所謂非南溶劑，是指不含_元素的有機溶劑。如上所 迷，由於非鹵溶劑難以溶解本製程中所生成的三級胺鹽， =藉由此後的過濾製程可自反應混合物中容易地除去三級 胺鹽。因此’如上所述，此後的清洗製程中的分液性提高。 又，非鹵溶劑若使用與水或鹼水溶液的相溶性低的溶劑， 進-步提高此分液性。若分液性高，則無需如專利文 2 4般在清洗巾使用飽和錢水。0此，藉由制非函溶 釗，可減少目標化合物中的離子性雜質的含量。 根據上述内容，本發明的非鹵溶劑更好的是與三級胺 25 200903119 鹽、水、以及鹼水溶液的相溶性低。此種溶劑之例包括： 烴；二苯醚（diphenyl ether)等醚類；乙酸乙酯等酯類·· 以及曱基異丁基酮、甲基乙基酮等酮類。 、， 其中，本發明的非齒溶劑較好的是非極性的烴。煙的 具體例包括：r苯（t〇i職e)、：f苯（xylene) “族 烴；以及己院（hexane)、庚垸（heptan〇、辛燒（〇ctan)、、 癸院（de圓）等脂肪族烴。尤其，若非鹵溶劑為 則由於與後製程中制的水共沸，故容易自有機相中將水 餾去。非鹵溶劑亦可組合使用多種。 非齒溶劑的使用量並無特別限定，為了高效率地進行 反應，較好的是以非產溶劑中的化合物im的濃幻 ^里％ (wt%)〜6G wt%之方式進行調整，更好的是以成 為iO wt%〜3) wt%之方式進行調整。 〜 [三級胺] 所謂三級胺，是指氨的氫原子經3個烴基所 Ο 合物。三級胺捕獲（t 、山 ^ C P)由源自化合物Im的_原子與源 自化合物Um㈣氫原子所生成_化氳。 以及寺·定。三級胺之例包㈣、三甲胺、 合物中，^二級㊅右將一級或二級以下的胺添加於反應混 因此，三級^好吨會與_反應’故欠佳。 所有_化氫成32=是，使反應混合物中所生成的 战馬取:鹽的充分 二 耳數相對於化合物—級知的莫 的莫耳數較好的是2倍〜6倍，更好 26 200903119 的是3倍〜4倍，尤其好的是3倍〜3 3倍。 2) 製程：過濾製程 本過濾•巾，對υ反應餘巾所獲得的反應混合 ”濾。藉此’可容易地除去反應混合物中析出的吼 °疋鹽等三級胺鹽。過濾反應混合物的方法 ，過濾等公知的方法。於使用過義之情形時; 态的孔徑極小，則可除去微細的三級胺鹽等，但有時會花 費較長的過料間。因此，過濾H的孔徑可考作性而 適當地設定。 μ 3) 製程：驗水溶液清洗製程 Ο 本製程中，以氫氧化鈉等鹼水溶液清洗藉由上述過濾 而將胺鹽除去的反應混合物。清洗時，可進行如下操作& 為一個循環，即，於上述反應混合物中添加鹼水溶液/之後， 振盪並靜置一定時間，分液為水相及有機相。此時，水相 中’萃取出存在於反應混合物中的Γι的副產物」的鈉鹽、 未反應的化合物lm經中和而生成的酸等的納鹽。如上所 述，由於已自反應混合物中將大部分的三級胺鹽除去，故 本製程中清洗時的分液性高。進而，若使用甲苯等非極性 的非鹵溶劑作為溶劑，則分液性進一步提高。由於目標化 合物存在於有機相_，故分液後將水相當作廢棄物而僅回 收有機相。 本發明的方法中所使用的驗水溶液較好的是驗性益機 化合物的水溶液。鹼性無機化合物之例包括氫氧化鈉、、气 氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、以及碳酸氫鉀。虱 27 2〇〇9〇3ii9 鹼水溶液的濃度、使用量、以及清洗水數，若以可充 分地清洗反應混合物之方式而適當毁定即W。例如，若使 用反應混合物的1/3重量左右的濃度為丨yt%驗水溶液， 則可充分清洗反應混合物。 為了提高反應混合物的分液性’較好的是，在添加驗 水溶液之前的反應混合物中，視需要添加f苯或二甲笨等 芳香族烴、乙酸乙酯、曱基異丁基鲷、或f基乙基酮。、 利用驗水溶液對反應混合物、或有機祠的清洗較好的 是反覆進行。例如，可將上述的—個楯環反覆進行多次。 於利用鹼水溶液反覆清洗有機相之情形時，較好的 是，-邊對有機相中ί的副產物即3,3_替(甲基柄婦醒基 烷氧基)幾基絲]_5·㈣基絲)異三聚象酸醋的濃度進 ^控-邊進行清洗。i _產物 除 Ο 3機i目進行分析而求出。具體而言，是將由帆」 二1，3,5·三⑽化甲酿基院基)異三聚氰駿酯的峰· % x、將1的副產物的峰面積設為少將其他的溶 質峰域合計值設為㈡時，以{x2/〇d= 的所鼻出的值。清洗較好的是反覆進行直至I 的田產物的置小於等於1%為止。 主 4)製程：純水清洗製程 此，純水清洗前製程中所獲得的有機相。藉 洗無法除二雜的驗水溶液除去’並且可將鹼清 質中，包含化合⑻T1除去。料洗無法除去的雜 iln等（甲基）丙烯酸羥烷酯。純水清洗 28 2〇〇9〇3li9 旦f使用的純水量並無特別限定 里左右，則可獲得優異的清洗效果。右為有機相的I/3重 利用純水對有軸的 之化合物Llm等的C好的疋，-邊對有機相中 -邊進行。化二的導電度進崎 機相進行HPLC分析而t山 /辰&疋對除去了溶劑的有 析所得的㈣是將由肌c分 外的峰面積的蜱和机A 、 積°又為y〗、將除此以 積日7，和5又為y2(除去溶 +y2)} 所算出的值。 ;^ u {yl/(y1 導電度可利用通常的方法而 中所含的離子性雜f的由於導電度與水相 性雜質的濃度的指標。 歹1，故成為有機相中的離子 w等的合計!至上述有機相中的化合物 於hs/cm為止。、寺灰1/0、且水相的導電度小於等 關於上述3)製程及4)制和 程後反覆進行4)製程，介衣私’既可在反覆進行3)製 Ζ 亦可反覆交替進行3)製程及4) 長、=，右考慮到清洗效率，騎好的是前者的方法。 [濃縮] 好的!經充分清洗的有機相中單離出目標化合物，單離較 於，:農縮有，:而進行。濃縮有機相的裝置之例包括蒸 縮請，較好喊財機相中添加聚合抑制劑等。 ： Chydr〇qmnone).4-^T^ 4’ 以及 2,4_第三丁基-苯盼（2,4_t_bytul_phen〇l) ' 29 200903119 甲氧基笨齡等盼類。 一單離出的目標化合物即1,3,5-三[(4-(甲基）丙烯醯基烷 氧，)幾基烧基]異三聚氰酸酯的純度是藉由HPLC分析而 測定。該純度是將目標化合物的峰面積設為ml、將除此以 外=雜質的總峰面積設為⑽時，以丨ml/(ml+m2)卜1〇〇 所算出的值。以此種方式測定的目標化合物的純度較好 是大於等於90%。 2.密封劑 所明液晶顯示面板，是指在兩片透明的基板之間封入 （液晶）而形成的面板狀農置。將用以封入濟 稱為密封劑或液晶密封劑。通f ,液晶顯示面板 卜定_隔而貼合1在此空間内封入 2而以，因此，液晶密封劑（亦簡释為「密封劑」 作用以貼合兩片基板的接著劑。 、 (1)(甲基)丙烯酸酯化合物 Ο 本發明的密封劑含有上述本發明的化合物作為主 为。密封劑可單獨含有上文已述的化合 肯叮人古夕 二二上Γ密封劑含有多種不同化合物的情形時， 較好的疋’ 3有選自以（B1)、（B2) 物:群中的兩種或兩種以上化合物的混合物。 二合物中的LBU基的數量與歸的數量 ==η30〜3°:70,更好的是_〜4_ 、疋· 5〇。其原因在於，含有此種、人物的宓封 劑的接著性極為優異。 種此。物〕…封 30 2〇〇9〇3ii9 LBu基的數量與LEt基的數量之比處於上述 混(L2m) (L3m) In the formula (Llm) to (L3m), each independently represents a ruthenium atom or a ruthenium group, and X to Z each independently represent an alkylene oxide having a carbon number of 2 to 4, and examples of the compound include acrylic acid. 4-butyl ketone '(曱其)石, ^ 参生乙 S曰, and [曱基) baking acid 2- isopropyl vinegar, etc., but no 々! limited. The compound Llm to the compound L3m may be all the same, may be the same, or may be partially identical. When the compound Llm to the compound L3m are all the same, a compound such as the above compound B1 or the compound E1 can be obtained. Further, the compounds Llm to L3m are partially identical, and for example, the case where the different t L2m is the same as L3m and is different from Llm. In this case, a compound such as the above compound B2 or compound B3 can be obtained. In this case, for example, if the number of moles of the compound Llm and the number of moles of the compound L2m are 1:1, two or two kinds selected from the group consisting of the above-mentioned compound B1 to the compound £1 can be obtained. A mixture of the above compounds, and the ratio of the group derived from the compound Llm to the group derived from the compound L2m in the mixture is 1:1. The total number of moles of the compound used in the pair, the phase =) the molar number of the substance Im is preferably 2 times to 6 times, more preferably 3:; Mo: the number 2 is preferably 3 times ~3.3 times. When the production range of the compound Um or the like is ', the cleaning efficiency in the following cleaning process and the total number of moles of the δ-Llm or the like are less than the purification yield of the substrate. Further, when the compound = ^10 f ears>' is at the above lower limit, all of the compounds Im#i, 3, and Sit's thiol ethyl groups are not esterified. Since ~H is amphiphilic, in some cases in the cleaning process, if the total molar value of the compound Um or the like is the case, unreacted reaction may remain in the reaction mixture, resulting in this. The number of cleanings of the cleaning process towel is increased. [Non-ii solvent], a non-Southern solvent, refers to an organic solvent that does not contain an _ element. As described above, since the non-halogen solvent is difficult to dissolve the tertiary amine salt formed in the process, the tertiary amine salt can be easily removed from the reaction mixture by the subsequent filtration process. Therefore, as described above, the liquid separation property in the subsequent cleaning process is improved. Further, when a solvent having a low compatibility with water or an aqueous alkali solution is used as the non-halogen solvent, the liquid separation property is further improved. If the liquid separation property is high, it is not necessary to use saturated water in the cleaning towel as in the patent document. 0, by dissolving oxime, the content of ionic impurities in the target compound can be reduced. In view of the above, the non-halogen solvent of the present invention is preferably less compatible with the tertiary amine 25 200903119 salt, water, and aqueous alkali solution. Examples of such a solvent include: hydrocarbons; ethers such as diphenyl ether; esters such as ethyl acetate; and ketones such as mercaptoisobutyl ketone and methyl ethyl ketone. Among them, the non-dentate solvent of the present invention is preferably a non-polar hydrocarbon. Specific examples of the smoke include: r benzene (t〇i job e), : f benzene (xylene) "hydrocarbon; and hexane, heptan (heptan〇, 辛烧(〇ctan), 癸院( In particular, if the non-halogen solvent is azeotroped with water produced in the post-process, it is easy to distill water from the organic phase. Non-halogen solvents may also be used in combination. The amount of use is not particularly limited, and in order to carry out the reaction efficiently, it is preferred to adjust the concentration of the compound im in the non-producing solvent (% by weight) to 6 G wt%, more preferably It is adjusted in such a manner that it becomes iO wt% to 3) wt%. [Triad amine] The term "tribasic amine" means a hydrogen atom of ammonia via three hydrocarbon groups. The tertiary amine is trapped (t, mountain ^ CP ) from the _ atom derived from the compound Im and the hydride derived from the compound Um (tetra) hydrogen atom. And the case of the temple. The tertiary amine is included in the package (IV), trimethylamine, and the compound The amine below the second level is added to the reaction mixture. Therefore, the third stage ^ good ton will react with _, so it is not good. All _ hydrogen is 32 = yes, so that the reaction mixture The generated horses are taken: the full number of ears of the salt is 2 to 6 times better than the compound-level, and the number of the moles is preferably 2 times to 4 times, and more preferably 26 times. 3 times ~ 3 3 times. 2) Process: Filtration process This filter/towel is mixed with the reaction obtained by the reaction waste. By this, the tertiary amine salt such as the cerium salt precipitated in the reaction mixture can be easily removed. A method of filtering the reaction mixture, filtration, and the like are known. In the case of uselessness; when the pore size of the state is extremely small, fine tertiary amine salts and the like can be removed, but sometimes it takes a long time between the excess materials. Therefore, the aperture of the filtered H can be set as appropriate. μ 3) Process: Aqueous solution cleaning process Ο In the process, the reaction mixture in which the amine salt is removed by the above filtration is washed with an aqueous alkali solution such as sodium hydroxide. In the case of washing, the following operations can be carried out. In one cycle, an aqueous alkali solution is added to the above reaction mixture, and then shaken and allowed to stand for a certain period of time, and the liquid phase is separated into an aqueous phase and an organic phase. At this time, a sodium salt of an acid such as a sodium salt which is a by-product of oxime present in the reaction mixture and an unreacted compound lm is neutralized in the aqueous phase. As described above, since most of the tertiary amine salts have been removed from the reaction mixture, the liquid separation property in the cleaning process is high. Further, when a nonpolar non-halogen solvent such as toluene is used as the solvent, the liquid separation property is further improved. Since the target compound is present in the organic phase, the water is equivalent to waste and only the organic phase is recovered after liquid separation. The aqueous solution used in the method of the present invention is preferably an aqueous solution of a probiotic compound. Examples of the basic inorganic compound include sodium hydroxide, potassium oxyhydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate.虱 27 2〇〇9〇3ii9 The concentration, amount of use, and amount of washing water of the aqueous alkali solution are appropriately determined by washing the reaction mixture sufficiently. For example, if a concentration of about 1/3 by weight of the reaction mixture is used as the 丨yt% aqueous solution, the reaction mixture can be sufficiently washed. In order to increase the liquid separation property of the reaction mixture, it is preferred to add an aromatic hydrocarbon such as f benzene or dimethyl benzene, ethyl acetate, decyl isobutyl hydrazine, or the like, in the reaction mixture before the addition of the aqueous solution. F-ethyl ethyl ketone. Preferably, the cleaning of the reaction mixture or the organic hydrazine by the aqueous solution is repeated. For example, the above-mentioned one ring can be repeatedly performed multiple times. In the case of repeatedly washing the organic phase with an aqueous alkali solution, it is preferred that the side product of the organic phase is ί, which is a 3,3 _ (methyl ketone) base ketone] _5· (4) The basis of the base wire) isotrimeric acid vinegar is cleaned. i _ product was determined by analyzing the Ο 3 machine i mesh. Specifically, it is a peak of the isomeric melamine ester from the sails of the two 1, 3, 5, and three (10) bases, and the peak area of the by-product of 1 is made small. When the total value of the peak region is (2), the value of the nose is {x2/〇d=. It is preferred to carry out the cleaning until the amount of the field product of I is less than or equal to 1%. Main 4) Process: Pure water cleaning process This is the organic phase obtained in the process before pure water cleaning. It is removed by washing the aqueous solution which cannot be removed, and the alkali (8) T1 can be removed from the alkali. The hydroxyalkyl (meth) acrylate such as hetero iln which cannot be removed is washed. Pure water cleaning 28 2〇〇9〇3li9 The amount of pure water used in f is not particularly limited. The right is the I/3 of the organic phase. The pure water is used for the C of the compound Llm having the axis, and the side is carried out in the organic phase. The conductivity of the second phase is analyzed by HPLC in the phase of the phase, and the analysis of the solvent is removed. The fourth (4) is the peak area of the peak area of the muscle c, and the product A and the product are again y. 〗, the value calculated by dividing day 7 and 5 as y2 (removing dissolution + y2)}. ;^ u {yl/(y1 Conductivity can be measured by the conductivity of the ionic impurity f contained in the usual method and the concentration of the aqueous phase impurity. 歹1, it becomes the ion w in the organic phase. Total! The compound in the above organic phase is hs/cm, the temple ash is 1/0, and the conductivity of the aqueous phase is less than that in the above 3) process and 4) after the process and 4) process, clothing Private 'can be repeated 3) can also be repeated alternately 3) process and 4) long, =, right to consider the cleaning efficiency, riding is the former method. [Concentration] Good! The organic compound in the fully cleaned organic phase is separated from the target compound, and the separation is simpler than: Examples of the apparatus for concentrating the organic phase include steaming, and it is preferable to add a polymerization inhibitor to the fuel phase. : Chydr〇qmnone).4-^T^ 4' and 2,4_t-butyl-benzene (2,4_t_bytul_phen〇l) ' 29 200903119 The methoxy group is expectant. The purity of a single target compound, 1,3,5-tri[(4-(methyl)propenylalkoxy), alkoxyalkyl]isocyanate, was determined by HPLC analysis. . The purity is a value calculated by 丨ml/(ml+m2)b when the peak area of the target compound is ml and the total peak area of the impurity other than the impurity is (10). The purity of the target compound measured in this manner is preferably 90% or more. 2. Sealant The liquid crystal display panel is a panel-shaped agricultural device formed by encapsulating (liquid crystal) between two transparent substrates. It is used to seal the sealant or liquid crystal sealant. Passing f, the liquid crystal display panel is defined as a spacer 1 which is sealed in this space. Therefore, the liquid crystal sealing agent (also simply referred to as "sealant" acts to bond the adhesive of the two substrates. 1) (Meth) acrylate compound Ο The sealant of the present invention contains the above-mentioned compound of the present invention as a main component. The sealant may separately contain the above-mentioned compound Kensin Gu Er Er 2 Shangyu sealant containing a plurality of different In the case of a compound, preferred 疋'3 has a mixture of two or more compounds selected from the group consisting of (B1) and (B2): the number of LBU groups in the dimer and the amount of the compound. ==η30~3°: 70, more preferably _~4_, 疋·5〇. The reason is that the sealant containing such a person and the character is extremely excellent in adhesion. 〇〇9〇3ii9 The ratio of the number of LBu groups to the number of LEt groups is in the above mixture

5物，可將預先合成的化合物與化合物E1以莫耳比達 到所需值（例如i: υ的方式混合而獲得。又，可 =的化合物的製造方法所述，於作為原料的化合物❿^ 化4L2m之添加量的莫耳比成為所需值（例如工.D f5, the compound which can be synthesized in advance can be obtained by mixing the compound E1 with a molar ratio to a desired value (for example, i: υ. Further, as described in the method for producing a compound which can be used as a raw material, ❿^ The molar ratio of the added amount of 4L2m becomes the desired value (for example, work. D f

U ::件下合成’，得此混合物。以此種方式獲得的混合 ，LBU基的數罝與LEt基的數量之比可藉由核磁共振 、彻clear Magnetic Resonance，NMR)分析而求出。 θ本發明的化合物為液晶密封劑的必需成分*；於刚重 =之液晶密封劑中，較好的是含有5重量份〜9〇重量份 ，發明的化合物，更好的是含有2〇重量份〜6〇重量份 液曰合此含量處於上述範圍内，則可降低 好。夜aa/7#性’液晶顯示面板的顯示特性亦良 本每明中，「〜」包括其兩端的數值。 聚合的r晶密封劑可進—步含有_樹脂、自由基 起始劍、歸錄㈣魏劑、填㈣、其他添加劑。 (2)環氧樹脂 不具是f分子内具有一個或一個以上的環氧基且 氧樹^其例包括以下環氧樹脂/乳树月曰了為么知的壤 得的^香，醇類與表氯醇（epiChk>r〇hydrin)反應所獲 或聚歸基:ί:2==物;由祕清漆型_ 環氧樹炉^類舆表氯醇反應所獲得的苯紛祕清漆型 、曰，本一f 齡樹腊（xy!y：Ienephen〇i resin)的縮水 31 200903119U: Under the composition of ', get this mixture. The ratio of the number of enthalpies of the LBU group to the number of LEt groups obtained in this manner can be determined by nuclear magnetic resonance, clear magnetic resonance, NMR analysis. θ The compound of the present invention is an essential component of the liquid crystal sealing agent*; in the liquid crystal sealing agent of the weight = preferably, it contains 5 parts by weight to 9 parts by weight, the compound of the invention, more preferably 2 parts by weight. When the content of the liquid is in the above range, it can be lowered. The display characteristics of the night aa/7# sex liquid crystal display panel are also good. In each case, "~" includes the numerical values at both ends. The polymerized r-crystal sealant can further contain _resin, free radical starter sword, categorized (four) wei agent, fill (four), and other additives. (2) The epoxy resin does not have one or more epoxy groups in the f molecule, and the oxygen tree, for example, includes the following epoxy resin/milk tree. Epichlorohydrin (epiChk>r〇hydrin) obtained or poly-based: ί:2==; benzoic varnish type obtained from the reaction of smear lacquer type _ epoxy tree furnace曰, the shrinkage of this f-age tree wax (xy!y: Ienephen〇i resin) 31 200903119

甘油鹎化合物類，·三 一 ㈣腊。戊二_環 月曰。又，該些環氧樹浐妒 有夕種該些不同的環氧樹 度化。 軋樹月曰較奸的是藉由分子蒸館法等而高純f 樹脂、雙紛F型^ ，化合物之例包括雙紛A型環氧 型環氧樹月旨、二S型環氧樹月旨、雙盼仙 環氧樹墙的含量為，、以及聯苯型環氧樹脂。 合物較好的是5重目對於⑽重量份之本發明的化 提供接著可紐優異峡封劑， (3)自由基聚合起始劑 =自，聚#觸’是指吸收能量而彦生 劑、：二ί =合起始劑之例包括光自由基;:起： i受到：ίΐί起始劑。所謂光自由基聚合起始劑，是 生分解而由基的化合物’亦即，吸收光能發 劑，是於〜u i 化合物。所謂熱自由基聚合起始 能發生二而J:、而產生自由基的化合物’亦即，吸收熱 , 生自由基種的化合物。本發明的密封劑可 3先自由基聚合起始劑、熱自由絲合起始射的任- 万f兩对〇 別的密封劑所含有的光自由基聚合起始劑並無特 ,¾ Γ-V " Cbenzoin) ♦ G 酮（acet〇phenone )類、二苯甲酮 32 200903119 (benzophenone)類、嗟嘲酮（thioxanthone)類、α_酸義 肟酯（a-ac.yloxime ester )類、苯甲醯甲駿酉匕 (phenylglyoxylate)類、苯偶醯（benzil)類、偶氮系化人 物、二苯硫醚（diphenylsulfide)系化合物、醯基膦氣化物 ΟGlycerol bismuth compounds, · Sany (four) wax.戊二_环月曰. Moreover, the epoxy trees are tempered by the different epoxy densities. The high-purity f resin and the double-type F-type ^ are compounded by the molecular steaming method, and the compound examples include the double-type A-type epoxy type epoxy tree and the two-type epoxy tree. The content of the moon-shaped, double-panned epoxy tree wall is, and the biphenyl type epoxy resin. Preferably, the compound is 5 weights for (10) parts by weight of the present invention to provide the next excellent sealant, (3) free radical polymerization initiator = self, poly # touch' means absorption of energy and Yansheng Agent: two examples of the starting agent include photoradicals;: from: i receives: ίΐί initiator. The photoradical polymerization initiator is a compound which is biodegradable and is a compound which absorbs light energy and is a compound of ~u i . The term "thermal radical polymerization initiation" is a compound which generates two radicals and generates radicals, that is, a compound which absorbs heat and generates radical species. The sealant of the present invention can be used as a photo-radical polymerization initiator which is a free radical polymerization initiator and a hot-free silk-initiator, and is not particularly suitable for a photo-radical polymerization initiator contained in any two pairs of sealants. 3⁄4 Γ -V "Cbenzoin) ♦ G ketone (acet〇phenone), benzophenone 32 200903119 (benzophenone), thioxanthone, a-ac.yloxime ester , phenylglyoxylate, benzil, azo group, diphenylsulfide compound, mercapto phosphide Ο

(acylphosphine oxide)系化合物、有機色素系化合物、鐵 -酞菁（iron-phthalocyanine)系、安息香類、安息香醚類、 以及蒽覼（anthraquinone )類。本發明的密封劑可含有多 種該些光自由基聚合起始劑。 光自由基聚合起始劑的含量為，相對於100重量份之 本發明的化合物較好的是〇·；[重量份〜10重量份。藉由使 上述含里大於等於0.1重量份，密封劑的光照射硬化性良 好。又，藉由使上述含量小於等於10重量份，可使液晶密 封劑的黏度穩定性良好，從而可在光硬化時獲得均質的硬 化物。 本發明的密封劑所含的熱自由基聚合起始劑並無特別 限定。熱自由基聚合起始劑之例包括有機過氧化物、偶氮 化合物以及取代乙烷化合物。該些化合物可單獨使用或組 合使用。有機過氧化物之例包括過氧化酮、過氧化縮酮 (peroxyketal )、過氧化氫（hydroperoxide )、過氧化二烧 基過氧、過氧化雙乙醯基（diacyl peroxide)、過氧化 一碳酸酯。本發明的密封劑可含有多種該些熱自由基聚合 起始劑。 (4)潛伏性環氧硬化劑 所明潛伏性環氧硬化劑，是指如下的硬化劑：即便混 33 200903119 氧基的狀態下亦幾乎不_ 2潛伏性環氧硬__ 旨硬 限定^__所含有的潛伏性環氧硬 父好的疋分子内具有胺基的胺系潛伏性产:寸別 劑之例包括有機d: 木唾（lmldazole)及 i ϋ °(acylphosphine oxide) compound, organic pigment-based compound, iron-phthalocyanine system, benzoin, benzoin ether, and anthraquinone. The sealant of the present invention may contain a plurality of such photoradical polymerization initiators. The content of the photoradical polymerization initiator is preferably 〇·; [parts by weight to 10 parts by weight based on 100 parts by weight of the compound of the present invention. By setting the above content to 0.1 part by weight or more, the light-curing property of the sealant is good. Further, by setting the above content to 10 parts by weight or less, the viscosity stability of the liquid crystal sealing agent can be improved, and a homogeneous carbide can be obtained at the time of photocuring. The thermal radical polymerization initiator contained in the sealant of the present invention is not particularly limited. Examples of the thermal radical polymerization initiator include organic peroxides, azo compounds, and substituted ethane compounds. These compounds may be used singly or in combination. Examples of organic peroxides include ketone peroxide, peroxyketal, hydroperoxide, peroxydiperoxyperoxy peroxide, diacyl peroxide, peroxymonocarbonate . The sealant of the present invention may contain a plurality of such thermal radical polymerization initiators. (4) Latent epoxy hardener The latent epoxy hardener is the following hardener: even if it is mixed with 33 200903119, the oxygen is hardly _ 2 latent epoxy hard __ __ Contains a latent epoxy hard father, an amine-based amine-based latent property in the molecule: an example of a monomer: organic d: lmldazole and i ϋ °

(dicyandiamide)、芳香族胺、严惫故皙 一氰二胺 脲㈤yam__)她衣氧改質聚胺、以及聚胺基 紗Π環氧魏默其好的是，雜或由環球法所得 。點溫度大於等於75t。含有此歸伏性環氧硬化劑 的，封#j ’於室溫下的黏度穩定性極為優異。因此，即便 為了在基板上描纟會岔封圖案而將此種密封劑長時間填充於 絲網印刷機（screenprinter)或點膠機（dispenser)中，密 封劑的黏度亦穩定，不會損及操作性。(dicyandiamide), aromatic amine, sputum 皙 氰 二 二 胺 ( 五 五 五 五 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她 她The point temperature is greater than or equal to 75t. The seal #j ' with this reductive epoxy hardener is extremely excellent in viscosity stability at room temperature. Therefore, even if the sealant is filled in a screen printer or a dispenser for a long time in order to trace the pattern on the substrate, the viscosity of the sealant is stable and does not damage. Operational.

炫點或由環球法所得的軟化點溫度大於等於75。〇的 胺系潛伏性硬化劑之例包括：二氰二胺（熔點為2〇9〇c) 專一亂一胺類’己一酸二醢脾（adipic acid dihydrazide)(溶 點為181 °C )、1,3-雙（肼基羧乙基）_5-異丙基乙内醯脲 (l,3-bis(hydrazino carboethy 1)-5-isopropyl hydantoin) 點為120°C)等有機酸二醯肼；2,4-二胺基-6-[2’-乙基咪唑 基-(1 丨)]-乙基三嗪（2,4-diamino-6-[2’-ethyl imidazolyl-(l')]-ethyl triazine)(熔點為215°C〜225°C )、2-苯基咪唑（熔點 137°C〜H7°C)等咪唑衍生物。 34 200903119The softening point or the softening point temperature obtained by the ring and ball method is 75 or more. Examples of bismuth amine latent hardeners include: dicyandiamide (melting point 2〇9〇c), a mono-amino acid, adipic acid dihydrazide (melting point 181 °C) , 1, 3-bis(decylcarboxyethyl)_5-isopropylhydantoin (1,3-bis(hydrazino carboethy 1)-5-isopropyl hydantoin), 120 ° C), etc. Bismuth; 2,4-diamino-6-[2'-ethylimidazolyl-(1 丨)]-ethyltriazine (2,4-diamino-6-[2'-ethyl imidazolyl-(l' Imidazole derivatives such as -ethyl triazine) (melting point: 215 ° C to 225 ° C), 2-phenylimidazole (melting point: 137 ° C to H 7 ° C). 34 200903119

潛伏性環氧==12多種該些潛伏性環氧硬化劑。 又化片!ί的含罝為，相對於 旦 t合物較好的是5重量份〜4G重量份=之3本= 罝份〜35重量份。潛伏性環氧硬 、5 的密封劑’提供接著可靠性優里二？： ！處於上述犯圍 種密封劑的黏度稃定性二優m日顯示面板。又，此 氧硬化劑較好:ΐ=;。， ⑴填充^藉由以法、再結晶法等而高純度化。 物的=二控制密封劑的黏度、提高硬化 的財料。^、4並無&別限定’較好的是電子材料用 料:、（、Μί填充料之例包括無機填充料以及有機填充 鎮、例包括碳峡、碳魏、雜鋇、硫酸 Ο 〔 舰_、高嶺土（k施）、滑石（論）、 土 珠（glass beads)、絹雲母（seridte)、活性白土、膨 括^二氮?銘二及氮化石夕。錢填充料之例包 單體的^&酸¥[聚苯乙稀、f基輯酸甲醋與其他 聚脸其:’、苯乙稀與其他單體的共聚物、聚S旨微粒子、 乂 土甲酸乙醋微粒手、以及橡勝微粒子。上述填充料中， =線，脹性、雜減_麵考慮，較好的是無機填 " 透光性的觀點考慮，更好的是二氧化矽、滑石。 填充料的形狀並無特別限定’可為球狀、板狀、針狀 200903119 等固定形狀，或不固定形狀。填充料的含量為，相對於ι〇〇 重置份之本發明的化合物較好的是10重量份〜5〇重旦 .=更好的是％重量份〜45重量份。含有上述範圍的J 充料的密封劑，接著強度優異。 ' (6 )其他添加劑 々本發明的密封劑可視需要含有以下添加劑：矽烷偶合 劑等偶合劑、—分子内含有縮水甘油基及（甲基)丙稀^ f:s 的化合物、離子捕獲劑、離子交換劑、勻平劑、顏料、染 料、熱塑性聚合物、消泡劑等。進而，為了確保所需的單 兀間隙（cell gap)，本發明的密封劑亦可含有間隔物 (spacer)。 〜分子内含有縮水甘油基及（甲基）丙烯醯基的化合 物例如，可使雙紛型環虱樹脂或齡酸清漆型環氧樹脂等 辰氧树月曰與（甲基）内烯酉夂或曱基内烯酸苯酿，於驗性觸媒 ^下反應而獲得。一分子内含有縮水甘油基及（甲基）丙烯醯 ( 基的化合物，亦稱為改質環氧樹脂。由於改質環氧樹脂在 树月曰月呆内兼具環氧基與（甲基）丙稀醯基，故本發明的化 合物與環氧樹脂的相容性優異，因此提供均勻的硬化物。 、為了凋整黏度，本發明的密封劑可含有溶劑。溶劑只 要為^知的溶劑即可。該溶劑之例包括：環己酮等酮溶劑； 一乙一醇一甲_、甲基卡必醇（methyl‘carbitol)、乙基卡 轉、I基卡必醇_賴；二乙三醇二乙酸§|、烧氧基 二乙二醇單乙酸酯等乙酸酯溶劑；以及曱苯、己烷等非極 性溶劑。 36 200903119 於本發明的密封劑含有溶劑之情形時，較好的是，於 液晶顯示面板之製造製程中，於一方的液晶顯示用基板上 形成密封圖案之後，於50°C〜l〇〇°C的溫度下對該液晶密 封劑暫且實施預硬化處理。溶劑之含量為，相對於密封劑 較好的是小於等於20%，更好的是小於等於10%。溶劑的 含量處於該範圍的密封劑，使液晶顯示面板的顯示特性不 易下降。 , 關於密封劑的液晶污染性可根據如下方式評價：依照 下述方式製造液晶顯示面板，根據驅動顯示面板時的顯示 狀態來評價。若液晶受到污染，則顯示面板的液晶的響應 差，顯示狀態不良。Latent epoxy == 12 kinds of these latent epoxy hardeners. Further, the yttrium is preferably 5 parts by weight to 4 parts by weight = 3 parts = 5% by weight to 35 parts by weight. The latent epoxy hard, 5 sealant' provides the reliability of the second? : ! In the above-mentioned perennial sealant, the viscosity is determined by a two-dimensional display panel. Further, the oxygen hardener is preferably: ΐ =;. (1) Filling ^ is highly purified by a method, a recrystallization method, or the like. The second of the material controls the viscosity of the sealant and improves the hardening of the material. ^, 4 is not & not limited 'better is the material used for electronic materials:, (, Μ 填充 filling materials include inorganic fillers and organic filling towns, including carbon gorge, carbon Wei, cesium, barium sulphate [ Ship_, kaolin (k Shi), talc (discussion), earth beads (glass beads), sericite (seridte), activated clay, expanded ^2 Nitrogen? Ming 2 and nitrite eve. Body ^ & acid ¥ [polystyrene, f-based acid methyl vinegar and other poly-face: ', styrene and other monomer copolymer, poly S-microparticles, alumina formate particles And rubber particles. In the above fillers, = line, bulging, impurity reduction _ surface considerations, preferably inorganic filling " light transmission point of view, better is cerium oxide, talc. The shape of the present invention is not particularly limited, and may be a fixed shape such as a spherical shape, a plate shape, or a needle shape of 200903119, or an unfixed shape. The content of the filler is preferably a compound of the present invention with respect to the ι〇〇 replacement portion. 10 parts by weight to 5 〇 heavy denier. = more preferably % by weight to 45 parts by weight. The sealant is then excellent in strength. ' (6) Other additives 密封 The sealant of the present invention may optionally contain the following additives: a coupling agent such as a decane coupling agent, a glycidyl group in the molecule, and (meth) propyl group: a compound of s, an ion trapping agent, an ion exchanger, a leveling agent, a pigment, a dye, a thermoplastic polymer, an antifoaming agent, etc. Further, in order to secure a desired cell gap, the sealant of the present invention is also It may contain a spacer. The compound containing a glycidyl group and a (meth) acrylonitrile group in the molecule may, for example, be a ternary ring-shaped resin or an acid-clear type epoxy resin. (Methyl) enelenyl or decyl enoic acid benzene is obtained by a reaction under an organic solvent. A molecule containing a glycidyl group and a (meth) acryl oxime (also known as a compound) Modified epoxy resin. Since the modified epoxy resin has both an epoxy group and a (meth) acrylonitrile group in the tree, it has excellent compatibility with the epoxy resin. Provide a uniform hardened material. The sealant of the present invention may contain a solvent, and the solvent may be any known solvent. Examples of the solvent include a ketone solvent such as cyclohexanone; a methyl alcohol-methyl carbitol; ), ethyl card rotation, I carbitol _ 赖; diethylene triol diacetic acid § |, alkoxydiethylene glycol monoacetate and other acetate solvent; and non-polar such as toluene, hexane In the case where the sealant of the present invention contains a solvent, it is preferred to form a seal pattern on one of the liquid crystal display substrates in a manufacturing process of the liquid crystal display panel at 50 ° C to 1 Torr. The liquid crystal sealing agent is temporarily subjected to a pre-hardening treatment at a temperature of 〇 ° C. The content of the solvent is preferably 20% or less, more preferably 10% or less, relative to the sealant. A sealant having a solvent content in this range makes the display characteristics of the liquid crystal display panel less likely to fall. The liquid crystal contamination of the sealant can be evaluated by manufacturing a liquid crystal display panel in accordance with the display state when the display panel is driven. If the liquid crystal is contaminated, the response of the liquid crystal of the display panel is poor and the display state is poor.

又，亦可於燒杯内將密封劑或作為此密封劑之主成分 的（甲基）丙烯酸酯化合物與液晶加熱混合，比較受到污染 的液晶與未受污染的液晶的NI點，以此來評價密封劑的 液晶污染性。 J 所謂NI點，是指液晶自向列相（nematic phase )向各 向同性相（isotropic phase)發生相轉變時的溫度。相轉變 溫度可使用示差熱分析裝置根據發熱峰之反曲點而測定。 △ NI點是「未受到污染的液晶的NI點」與「受污染的液 晶的NI點」之差。若將液晶污染性高的原料或密封劑與 液晶混合，則ΔΝΙ點的絕對值變大。相反，於原料或密封 劑的液晶污染性低時，ΔΝΙ點的絕對值變小。 本發明的化合物或含有該化合物的密封劑較好的是， 在進行下述試驗時，ANI點的絕對值小於0.8°C，更好的 37 20_3ll9 疋AMI點的絕對值小於04°c。試驗是以下述方式進行， I ’於處下對以1 : 10的重量比將本發明的化合物或 二有該化合物的密封劑與液晶混合*成的混合物加熱！小 哼’然後利用上述方法測定△ NI點。 2.密封劑的製備 f Ο 本發_密封_製備方法並無特別限定。密封劑可 用公知的方法將上•封劑_原料混合而獲得 法之例包括使用雙臂式製機、輥式混練機 ^ 卜磨混練機、以及行1式授拌機等公知的渴練 =。最後使用過濾器對經混合的密封劑進行過^= 後密封填充於玻璃瓶或聚乙烯製容器中，加: 0.液晶顯不面板的製造方法 明:密物侧顯示面板 限疋，以下，就較好的製造方法加以說明。 寸 的4=注=:板較好的是利用經由如下製程 密：=板:案製程’此第-基板具有由本發明的 的笨i)於上述密封圖案未魏的狀態下，向上述第-其祝 晶的製程； 枚靖向料二基板上滴注液 上述第-基板與上述第二基板 4)使上述密封劑硬化的製程。 的，以及 38 200903119 上述1 )〜3)製程可利用公知的方法而進行。上述4) 製程中，既可照射光使密封劑暫時硬化，然後如熱而行 後硬化，亦可僅藉由加熱使密封劑硬化。以此種J式製造 的液晶顯示面板，顯示不良少，具有良好的顯示特性。 [實施例] 根據實施例對本發明加以詳細說明，但本發明並未限 ，於此。又，以下所述的「％」、「份」分別指「猶％」、「重 量份」。 [實施例、比較例中所使用的材料等的製備] (1)(甲基）丙稀酸.酉旨化合物 (甲基)丙稀酸_化合物是由以下的合成例所合成。 [合成例1]曱基丙烯酸酯化合物（ Α1)的合成 以與專利文獻4的實施例1相同的方式，使〗，3,5_三(2_ 緩基乙基)異三聚氰酸g旨與曱基丙稀酸2_經乙醋反應，獲得 含有1，3,5-三[2-(2-曱基丙烯醯基乙氧基)叛基乙基]異三聚 氰酸酯的反應液。 L) 、 ，以飽和食鹽水清洗該反應液3次，然後濃縮氯仿相。 對所獲得的濃縮物途行梦膠管柱精製，單離⑶-却必 甲基丙婦醯基乙氧基)幾基乙基〕異三聚氰酸醋。此化合物 的純奴如T顿獅肌c分析㈣Λ。絲，由肌c 的峰面積比计异出此化合物的純度為。 [合成例2]丙烯酸酯化合物（Α2)的合成 使用丙烯酸2-經乙酯來代替甲基丙稀口酸2_經乙醋，除 *以外’以與合成例1相同的方式合成標記化合物。 39 200903119 [合成例3](曱基）丙烯酸酯混合物（A3)的合成 將/半量（莫耳換算）的甲基丙烯酸2-羥乙酯代替為 丙烯酸2-羥乙酯’除此以外，以與合成例1相同的方法獲 得標記混合物。 [合成例4](甲基）丙稀酸酯混合物（A4)的合成 使用丙烯酸4-經丁酯及甲基丙婦酸2-輕乙酯的混合物 (莫耳比1 : 1 )來代替甲基丙烯酸2-經乙酯，除此以外， 以與合成例1相同的方法獲得標記>'昆合物。所獲得的混合 Ψ % 物是上述化合物B1、化合物B2及化合物B3的混合物。 該混合物的1H-NMR的測定結果如下。測定是使用EX270 型核磁共振裝置（日本電子製造，270 MHz，CDC13，室溫） 而進行。又，測定該化合物的傅立葉變換紅外光譜（Fourier Transform Infrared Spectroscopy · FT-IR)，確認到源自異三 聚氰酸環的吸收峰。 H (a): 6.41 ppm (1.5H), H (b)： 5.83 ppm (1.5H), H (c, j): 6 ppm〜6.2 ppm (3H), H (d，g, i，m, n, p): 4 ppm〜4.5 ppm Ο (18H), H (e, f): 1.79 ppm (6H), H (h, o)： 2.68 ppm (6H), H (k): 5.60 ppm (1.5H), H (1): 1.95 ppm (4.5H) [化 24]Further, the sealant or the (meth) acrylate compound as a main component of the sealant may be heated and mixed with the liquid crystal in a beaker to compare the contaminated liquid crystal with the NI point of the uncontaminated liquid crystal. Liquid crystal contamination of the sealant. J The term "NI point" refers to the temperature at which a liquid crystal undergoes a phase transition from a nematic phase to an isotropic phase. The phase transition temperature can be determined using a differential thermal analysis device based on the inflection point of the exothermic peak. △ The NI point is the difference between the "NI point of uncontaminated liquid crystal" and the "NI point of contaminated liquid crystal". When a raw material or a sealant having a high liquid crystal contamination property is mixed with the liquid crystal, the absolute value of the ΔΝΙ point becomes large. On the contrary, when the liquid crystal contamination of the raw material or the sealant is low, the absolute value of the ΔΝΙ point becomes small. The compound of the present invention or the sealant containing the compound is preferably such that the absolute value of the ANI point is less than 0.8 ° C when the following test is carried out, and the absolute value of the 37 20_3ll 9 疋 AMI point is less than 04 ° C. The test was carried out by heating a mixture of the compound of the present invention or a sealant having the compound and a liquid crystal in a weight ratio of 1:10 at a ratio of 1: The small 哼' then uses the above method to determine the ΔNI point. 2. Preparation of Sealant f Ο The present invention is not particularly limited. The sealant can be obtained by mixing the upper sealant and the raw material by a known method, and includes a known method including a two-arm machine, a roll type kneading machine, a bucking machine, and a line type 1 mixer. . Finally, the mixed sealant is sealed and filled in a glass bottle or a polyethylene container by using a filter, and added: 0. The manufacturing method of the liquid crystal display panel is as follows: the density side display panel is limited, below, A description of a preferred manufacturing method will be given. 4 = Note =: The plate is preferably made by the following process: = plate: the process "this first substrate has the stupid i of the present invention" in the state in which the above-mentioned seal pattern is not inferior, to the above - The process of crystallizing the crystallizer; and the process of hardening the above-mentioned sealant by dropping the liquid on the first substrate and the second substrate 4). And 38 200903119 The above 1) to 3) processes can be carried out by a known method. In the above 4) process, the sealant may be temporarily hardened by irradiation of light, and then hardened as heat, or the sealant may be hardened only by heating. The liquid crystal display panel manufactured by such J type has less display defects and has good display characteristics. [Examples] The present invention will be described in detail based on examples, but the present invention is not limited thereto. In addition, "%" and "parts" described below refer to "%" and "weight", respectively. [Preparation of materials and the like used in the examples and the comparative examples] (1) (Methyl) acrylic acid. The compound (methyl) acrylic acid _ compound was synthesized by the following synthesis example. [Synthesis Example 1] Synthesis of thiol acrylate compound (Α1) In the same manner as in Example 1 of Patent Document 4, 1,3-, 3,5-tris(2-hydroxyethyl)isocyanuric acid was used. Reaction with mercaptopropionic acid 2_ via acetonitrile to obtain a reaction containing 1,3,5-tris[2-(2-mercaptopropenylethoxy) ethylethyl]isocyanate liquid. L), the reaction solution was washed three times with saturated brine, and then the chloroform phase was concentrated. The obtained concentrate is purified by a dream rubber tube, and is separated from (3)-but methyl propyl ethoxylated ethoxy) benzylethyl isomeric cyanuric acid. The pure slave of this compound is analyzed by T. lion muscle (4). The purity of the compound is determined by the peak area ratio of the muscle c. [Synthesis Example 2] Synthesis of acrylate compound (?2) A labeled compound was synthesized in the same manner as in Synthesis Example 1 except that 2-ethyl acrylate was used instead of methyl propyl benzoic acid. 39 200903119 [Synthesis Example 3] Synthesis of (fluorenyl) acrylate mixture (A3) / half amount (mole conversion) of 2-hydroxyethyl methacrylate was replaced by 2-hydroxyethyl acrylate' The labeling mixture was obtained in the same manner as in Synthesis Example 1. [Synthesis Example 4] Synthesis of (meth) acrylate mixture (A4) Instead of A, a mixture of 4-butyl acrylate and 2-light ethyl methacrylate (mole ratio 1: 1) was used. In the same manner as in Synthesis Example 1, except that the ethyl acrylate 2-ethyl ester was obtained, the mark > The obtained mixed oxime % is a mixture of the above compound B1, compound B2 and compound B3. The results of 1H-NMR measurement of this mixture were as follows. The measurement was carried out using an EX270 type nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., 270 MHz, CDC13, room temperature). Further, Fourier transform infrared spectroscopy (FT-IR) of the compound was measured, and an absorption peak derived from an isocyanuric acid ring was confirmed. H (a): 6.41 ppm (1.5H), H (b): 5.83 ppm (1.5H), H (c, j): 6 ppm~6.2 ppm (3H), H (d, g, i, m, n, p): 4 ppm~4.5 ppm Ο (18H), H (e, f): 1.79 ppm (6H), H (h, o): 2.68 ppm (6H), H (k): 5.60 ppm (1.5 H), H (1): 1.95 ppm (4.5H) [Chem. 24]

p ο n m 9 Jp ο n m 9 J

—CH2CH2COCH2CH2〇C、c_c/H—CH2CH2COCH2CH2〇C, c_c/H

0 CH, 、H I k i h g f e d 〇 a0 CH, , H I k i h g f e d 〇 a

—CH2CH2COCH2CH2CH2CH2OC、_ /H 0 h/C=C、h c b 40 200903119 [合成例5]丙烯酸酉旨化合物（A5)的合成 使用丙烯酸4-羥丁酯來代替甲基丙烯酸_2-羥乙酯，除 此以外，以與合成例1相同的方式獲得標記化合物。所獲 得的化合物是以上述式（B1)表示的化合物。根據HPLC 分析’計算出該化合物的純度為97.5面積％。 該化合物的1H-NMR的測定結果（條件與合成例4相 同）如下。又，測定該化合物的FT-IR，確認到源自異三 聚氰酸環的吸收峰。 H (a): 6.41 ppm (3H), H (b): 5.83 ppm (3H), H (c): 6.12 ppm (3H), H (d, g, i): 4 ppm〜4.4 ppm (18H), H (e, f): 1·79 ppm (12H), H (h): 2.66 ppm (6H) [化 25] i h g f e d 0 a-CH2CH2COCH2CH2CH2CH2OC, _ /H 0 h/C=C, hcb 40 200903119 [Synthesis Example 5] Synthesis of Acrylic Acid Compound (A5) Using 4-hydroxybutyl acrylate instead of _2-hydroxyethyl methacrylate Except that, a labeled compound was obtained in the same manner as in Synthesis Example 1. The compound obtained is a compound represented by the above formula (B1). The purity of the compound was calculated to be 97.5 area% based on HPLC analysis. The results of 1H-NMR measurement of this compound (conditions are the same as in Synthesis Example 4) are as follows. Further, the FT-IR of the compound was measured, and the absorption peak derived from the iso-cyanuric acid ring was confirmed. H (a): 6.41 ppm (3H), H (b): 5.83 ppm (3H), H (c): 6.12 ppm (3H), H (d, g, i): 4 ppm~4.4 ppm (18H) , H (e, f): 1.79 ppm (12H), H (h): 2.66 ppm (6H) [Chem. 25] ihgfed 0 a

—CH2CH2COCH2CH2CH2CH2〇f!i、 .H—CH2CH2COCH2CH2CH2CH2〇f!i, .H

° Η，、H C b [合成例6]丙稀酸酯混合物（A6)的合成 將一半量（莫耳換算）的丙稀酸4-經丁醋替換為丙稀 酸2-羥乙酯，除此以外，以與合成例5相同的方法獲得丙 烯酸酯混合物（A6)。該混合物的1H-NMR的測定結果（條 件與合成例4相同）如下。又，測定該混合物的FT-IR， 確認到源自異三聚氰酸環的吸收峰。 H (a，q): 6.3 ppm〜6.5 ppm (3H)，H (b，r): 5.75 ppm〜 5,95 ppm (3H), H (c，s): 6 pjpm〜6.25 ppm (3H)，H (d, g, i, t， u，w): 4 ppm〜4.6 ppm (18H), H (e, f): 1.79 ppm (6H)，H (h, 41 200903119 v): 2.55 ppm〜2.85 ppm (6H) (2)其他成分 使用以下成分。 環氧樹脂：鄰甲酚酚醛清漆型固態壤氧樹脂 (EOCN-1020-75 :曰本化藥製造） & 光自由基聚合起始劑：1-羥基-環已基、苯基_酮 (Irgacure 184 :汽巴精化製造） c 熱自由基聚合起始劑：1,1-偶氮雙(2，扣環己燒甲猜） (V-40 :和光純藥製造） & ^ 潛伏性環氧硬化劑：1,3-雙(肼基羧乙基)_5_異丙声,内 醯脲（Amicure VDH :味之素製造，熔點為]7〇。〇、 填充料：球狀二氧化石夕（Seafoster-S-3〇 :日本觸媒攀 造） ’ 添加劑：作為矽烷偶合劑的7〜縮水甘涵氧基二曱氧芦 矽烷（ΚΒΜ403 :信越化學工業製造） 土— 年土、 改質環氧樹脂：由下述合成例7所得的樹脂 〇 [合成例7] 8 於具備攪拌機、氣體導入管、溫度計、冷卻管的5〇〇 ml 四口燒瓶中，添加160 g的雙酚F型環氧樹脂（Epot〇te YDF-8170C .東都化成製造）、36 g的丙烯酸、及0.2 g的 • 三乙醇胺。其次，於乾燥空氣流下、於11(TC下將該些化 合物加熱攪拌5小時使之進行反應，獲得丙烯酸改質環氣 樹脂。以超純水清洗所獲得的樹脂12次。 [各種評價方法] 42 200903119 1) 原料以及液晶密封劑的液晶污染性評價測試 於1 ml的燒杯中準確稱量〇.〇3 g的（甲基)丙烯酸酯化 合物及 0.3 g 的液晶（MLC-11900-000 : MERCK 製造）， 於1.20°C下加熱1小時。加熱完畢後’比較受到污染的液 晶與未受污染的液晶的：ΝΊ點，計算.出ΔΝΙ點。於使用液 晶污染性低的原料或液晶密封劑的情形時’ △ NI點的絕對 值_變小。 對於（曱基)丙烯酸酯混合物以及利用下述方法所製備 的密封劑，亦分別以同樣的方式求出ΔΝΙ點。 2) 光硬化及熱硬化後的液晶顯示面板的顯示狀態測試 a)準備附有透明電極以及配向膜的40 mmx45 mm玻 璃基板（RT-DM88PIN : EHC 製造）。 於利用下述方法所製備的液晶密封劑中，添加混合1% 的5 μηι破璃纖維。將該密封劑填充於點膠機 (Shotmaster :武藏高科技製造）中，於上述基板上以線 寬為0.5 mm、線厚為5〇陣的線描繪出35 mmx4〇 mm的 框型密封圖案。 b ) ,¾而，使用點膠機，將與貼合後的面板内容量相當 的液晶材料（MLC-11900-000 : MERCK製造）精密滴注 至成對的玻璃基板上。進而，於9〇 Pa的減壓下將此兩片 基板疊合以將液晶密封。 c)使用牛尾電機（ushio)製造的紫外線照射裝置， =100 mW/crn2的紫外線照射照度，對上述已疊合的基板 照射2000 mj的照射能量而進行光硬化。光源是使用金屬 43 200903119 處素燈’累積光量的測定是使用具有300 nm〜390 nm的 測定波長範圍、且峰靈敏度波長為365 nm的紫外線累加 光里計（UVR-T35 : TOPCON 製造）。 d) 藉由紫外線進行光硬化之後，進一步於i2〇t下妒 熱60分鐘而進行後硬化。 e) 此後’於破璃基板的兩表面上貼附偏光膜。 使用直流電源裝置以5 V的施加電壓來驅動此液晶_ 示面板，評價顯示功能。具體而言，評價液晶密封劑附远 的液晶顯示功能是否自驅動初期開始正常工作。由於|貢# 異常是自密封劑附近朝向液晶顯示部而產生，故根據齅齐 異常區域之距離密封處的距離來進行判斷。於未觀測剎麟 示異常之情形時，即於上述距離幾乎為零之情形時，蔣麟 示特性判斷為良好（〇），於上述距離超過0.3 mm之情形 時，將顯示特性判斷為顯著差（X)。 3)熱硬化後的液晶顯示面板的液晶顯示狀態測試 以與上述a)〜b)相同的方式獲得已疊合的基板。 U f)繼而’於120°C下加熱60分鐘以進行後硬化。 此後，於玻璃基板的兩表面上貼附偏光膜。 使用直流電源裝置以5 V的施加電壓來驅動此液晶麟 示面板，評價顯示功能。具體評價方法與上述相同。 . 4)光硬化及熱硬化後的液晶密封劑接著強度測試 準備如下密封劑，即，在利用下述方法製備的液晶密 封劑中添加5 μπι的玻璃纖維作為間隔物而形成的密封 劑。繼而，將該密封劑以直徑為1 mm的圓狀絲網印刺於 Ο υ 200903119 25麵χ45麵、的厚5 _的無驗玻璃上，以十字形貼合成 對的相同破璃並加，固定。使用牛尾製造的紫外線照射裝 置X 0 mW/cm白勺务、外線照射照度對該玻璃照射〇 mJ的照射能量而進行光硬化。進而，此後於i2()t下進行 60分鐘後硬化，製作試驗片。 使用拉伸減驗機（M〇dd21〇 : intesc〇製造），以2 麵―的㈣速度對·得的試驗㈣定平面拉伸強 度此判疋方法為.於獲得大於等於1〇 的接著強度 之情形時，判定接著強度為良好（〇），於獲得小於1〇術 的接著強度之情形時，判定接著強度為不良（χ)。 5) 熱硬化後的液晶密封雜著強度測試 以與上述相同的方式，準備已以十字形貼 璃。繼而，於12〇。(：下對該破璃進行6〇分鐘加 作僅施以熱硬化而獲得的試驗片。以如 價所獲得的試驗片。 ]万式不汁 6) 黏度穩定性 將100重量份之液晶密封劑放入聚乙稀製容 ，於此狀態下於25t下保持5天，測猶時物中匕後二 密封劑的黏度。隨時間變化後的密封劑的黏度， 先測定的密封時的25°C黏度值設為100時的二：一、 於黏度的上升率小於等於2〇〇/0之情形時，將1 ^义示 俨盔*拉❿才將错存穩定性評 知為良好（〇），於上述上升率超過2〇%之 存穩定性評價為差（x> ^夺’將儲 [實施例1] 45 200903119 以混合機來預混合以下所示的材料，繼而以三輕研磨 機進行混練直至固體原料小於等於5 μιη為止。接著，以 孔徑為10 μιη的過濾器（MSP-10~E10S: ADVANTEC製造） 過濾此組合物，然後進行真空脫泡處理而獲得液晶密封劑 (P1)。 曱基丙稀酸酯化合物（由合成例1所獲得）35份 潛伏性環氧硬化劑 10份 ζ\ %•氧樹脂 5份 光自由基聚合起始劑 2份 填充料 15份 丙歸酸改質環氧樹脂（由合成例7所獲得）5份 石夕霞偶合劑 1份 利用上述方法，對所獲得的密封劑進行評價。 [實施例2] 使用合成例2中所獲得的化合物（Α2)來代替化合物 L) 圭)，除此以外，以與實施例1相同的方式獲得液晶密 ，Λ〗（Ρ2 )。利用上述方法，對所獲得的密封劑進行評價。 [實施例3] 、 (Α使用合成例3中所獲得的化合物（Α3)來代替化合物 封添,除此以外，以與實施例1相同的方式獲得液晶密 ^3)。利用上述方法，對所獲得的密封劑進行評價。 [貫施例4] (△if用合成例4中所獲得的混合物（Α4)來代替化合物 ，除此以外，以與實施例1相同的方式獲得液晶密 46 200903119 封劑（P4)。利用上述方法，對所獲得的密封劑進行評價。 [實施例5] 使用合成例5中所獲得的化合物（A5)來代替化合物 (A1)，除此以外，以與實施例1相同的方式獲得液晶密 封劑（P5)。利用上述方法，對所獲得的密封劑進行評價。 [實施例6] 使用將化合物（A1)與化合物（A5)以1 : 1的重量 . 比混合而成的混合物來代替化合物（A1 )，除此以外，以 ξ \ 與實施例1相同的方式獲得液晶密封劑（Ρ6)。利用上述 方法，對所獲得的密封劑進行評價。 [實施例7] 使用合成例6中所獲得的混合物（Α6)來代替化合物 (Α1)，除此以外，以與實施例1相同的方式獲得液晶密 封劑（Ρ7)。利用上述方法，對所獲得的密封劑進行評價。 [實施例8] 將一半量（重量換算）的化合物（Α1)代替為混合物 ◎ (Α6)，除此以外，以與實施例1相同的方式獲得液晶密 封劑（Ρ8)。利用上述方法，對所獲得的密封劑進行評價。 [實施例9〜實施例16] 使用作為熱自由基聚合起始劑的1,1-偶氮雙(2,4-環己 烷-1-甲腈)來代替作為光自由基聚合起始劑的1-羥基-環己 基-苯基-酮，除此以外，以與實施例1〜實施例8相同的方 式獲得液晶密封劑（Τ1)〜（Τ8)。利用上述方法，對所 獲得的密封劑進行評價。 47 200903119 [比較例1] 使用以上述式（1)表不的丙烯酸酯（Rl)來代替化合 物（A1) ’除此以外，以與實施例}相同的方式獲得液晶 密封劑（C1 )。 、上述丙烯酸酯化合物（R1)是依照專利文獻2的參考 例=及實施例而合成。相對於i 的u，5_三(2_羥乙基) 異三聚氰酸酯，使2.5 mol的卜己内酯開環加成而獲得 醇。進而使該醇與丙烯酸進行酯化反應而獲得含有 的反應混合物。接著氫氧化鈉水溶液清^ = 混合物，進而以超純水清洗，進行高純度化。 [比較例2] 使用以上述式（11 )表示的丙烤酸酯化合物（、李 代替化合物（A1)，除此以外，以與實施例1相同的方式 獲得液晶密封劑（C2)。 一八 上述丙烯酸酯化合物（R2)是依照專利文獻3的實施 例1而合成。相對於1 mol的三羥甲基丙烧，使3 m〇1的 己内酯開環加成而獲得醇。進而使該醇與丙烯酸進行醋化 反應而獲得含有目標物的反應混合物。接著，以1%氯氧 化納水溶液清洗該反應混合物’進而以超純水清洗，進行 高純度化。 [比較例3] 使用作為熱自由基聚合起始劑的U-偶氮雙(2,4-環己 烷-1-曱腈)來代替作為光自由基聚合起始劑的1-羥基_環己 基-笨基-酮，除此以外，以與比較例1相同的方式獲得液 48 200903119 晶密封劑（C3) [比較例4] 使时為熱自由絲合起始綱U-偶Ιι雙(2,4-環己 腈)來代替作為光自由基聚合起始劑的1-經基-環己 i密本二4除)此以外，以與比較例2相同的方式獲得液° Η,, HC b [Synthesis Example 6] Synthesis of acrylate mixture (A6) A half amount (mole-converted) of acrylic acid 4-substituted with butyl vinegar was changed to 2-hydroxyethyl acrylate. Except that, an acrylate mixture (A6) was obtained in the same manner as in Synthesis Example 5. The results of 1H-NMR measurement of the mixture (the same conditions as in Synthesis Example 4) were as follows. Further, the FT-IR of the mixture was measured, and the absorption peak derived from the iso-cyanuric acid ring was confirmed. H (a,q): 6.3 ppm~6.5 ppm (3H), H (b,r): 5.75 ppm~ 5,95 ppm (3H), H (c,s): 6 pjpm~6.25 ppm (3H), H (d, g, i, t, u, w): 4 ppm~4.6 ppm (18H), H (e, f): 1.79 ppm (6H), H (h, 41 200903119 v): 2.55 ppm~2.85 Ppm (6H) (2) The following ingredients are used for other ingredients. Epoxy Resin: o-cresol novolac type solid earth oxide resin (EOCN-1020-75: manufactured by Sakamoto Chemicals) & Photoradical polymerization initiator: 1-hydroxy-cyclohexyl, phenyl-ketone ( Irgacure 184: Ciba Specialty Chemicals) c Thermal Radical Polymerization Starter: 1,1-Azobis (2, Cyclohexanone) (V-40: manufactured by Wako Pure Chemical Industries) & ^ Latency Epoxy hardener: 1,3-bis(decyl carboxyethyl)_5_isopropyl sonic, uret urea (Amicure VDH: manufactured by Ajinomoto, melting point is 7 〇. 〇, filler: spherical dioxide Shi Xi (Seafoster-S-3〇: Nippon Catalyst Climbing) ' Additive: 7~shrinking sulphate oxydioxetane as a decane coupling agent (ΚΒΜ403: manufactured by Shin-Etsu Chemical Co., Ltd.) Epoxy resin: Resin oxime obtained in the following Synthesis Example 7 [Synthesis Example 7] 8 In a 5 〇〇ml four-necked flask equipped with a stirrer, a gas introduction tube, a thermometer, and a cooling tube, 160 g of bisphenol F was added. Type epoxy resin (Epot〇te YDF-8170C. manufactured by Tohto Kasei Co., Ltd.), 36 g of acrylic acid, and 0.2 g of • triethanolamine. Secondly, under a dry air flow, at 11 (TC) The compound was heated and stirred for 5 hours to carry out a reaction to obtain an acrylic modified ring-air resin. The obtained resin was washed 12 times with ultrapure water. [Various Evaluation Methods] 42 200903119 1) Liquid crystal of raw material and liquid crystal sealing agent Contamination evaluation test accurately weighed 3 g of (meth) acrylate compound and 0.3 g of liquid crystal (MLC-11900-000: manufactured by MERCK) in a 1 ml beaker, and heated at 1.20 ° C for 1 hour. After the heating is completed, 'Compared with the contaminated liquid crystal and the uncontaminated liquid crystal: ΝΊ, calculate the ΔΝΙ point. When using liquid crystal contamination low raw material or liquid crystal sealing agent' △ NI absolute value _ The ΔΝΙ point was also obtained in the same manner for the (fluorenyl) acrylate mixture and the sealant prepared by the following method. 2) Display state test of the liquid crystal display panel after photohardening and thermosetting a ) Prepare a 40 mm x 45 mm glass substrate (RT-DM88PIN: manufactured by EHC) with a transparent electrode and an alignment film. To the liquid crystal sealing agent prepared by the following method, 1% of 5 μηι broke glass fiber was added. The sealant was filled in a dispenser (Shotmaster: manufactured by Musashi Hi-Tech Co., Ltd.), and a frame seal pattern of 35 mm x 4 mm was drawn on the substrate with a line width of 0.5 mm and a line thickness of 5 lines. b), 3⁄4, using a dispenser, a liquid crystal material (MLC-11900-000: manufactured by MERCK) equivalent to the amount of the panel after bonding is precisely dispensed onto a pair of glass substrates. Further, the two substrates were laminated under reduced pressure of 9 〇 Pa to seal the liquid crystal. c) The ultraviolet irradiation illuminator manufactured by ushio, illuminating the ultraviolet illuminance of =100 mW/crn2, and irradiating the superposed substrate with an irradiation energy of 2000 mj to perform photohardening. The light source is made of metal 43 200903119 The lamp is used to measure the cumulative amount of light using an ultraviolet light accumulometer (UVR-T35: manufactured by TOPCON) having a wavelength range of 300 nm to 390 nm and a peak sensitivity wavelength of 365 nm. d) After photohardening by ultraviolet light, it is further post-hardened by heating at i2〇t for 60 minutes. e) Thereafter, a polarizing film is attached to both surfaces of the glass substrate. The liquid crystal display panel was driven with a voltage of 5 V using a DC power supply unit to evaluate the display function. Specifically, it is evaluated whether or not the liquid crystal display function of the liquid crystal sealing agent is far from the initial stage of driving. Since the | Gong # anomaly occurs from the vicinity of the sealant toward the liquid crystal display portion, the distance is determined based on the distance from the seal abnormal region. When the abnormality is not observed, that is, when the above distance is almost zero, Jiang Lin's characteristic is judged to be good (〇), and when the above distance exceeds 0.3 mm, the display characteristic is judged to be significantly worse (X). ). 3) Liquid crystal display state test of the liquid crystal display panel after thermosetting The laminated substrate was obtained in the same manner as the above a) to b). U f) was then heated at 120 ° C for 60 minutes for post-hardening. Thereafter, a polarizing film was attached to both surfaces of the glass substrate. This liquid crystal display panel was driven with a voltage of 5 V using a DC power supply device to evaluate the display function. The specific evaluation method is the same as described above. 4) Liquid crystal sealant after photohardening and heat hardening Next strength test A sealant prepared by adding a glass fiber of 5 μm as a spacer to a liquid crystal sealing agent prepared by the following method was prepared. Then, the sealant was printed on a circular screen with a diameter of 1 mm on the non-inspected glass of the thickness of 5 υ on the surface of the 03 υ 200903119 25 surface, and the same broken glass was added in a cross shape. fixed. The glass was irradiated with illuminating energy of 〇 mJ using an ultraviolet ray irradiation apparatus manufactured by oxtail, X 0 mW/cm, and external illuminance, and photohardening was performed. Further, thereafter, it was cured at i2 () t for 60 minutes, and then a test piece was produced. Using a tensile reduction tester (M〇dd21〇: manufactured by intesc〇), the test is performed at a speed of 2 planes (four). (4) The plane tensile strength is determined by the method of obtaining a joint strength of 1 大于 or more. In the case of the case, it is judged that the subsequent strength is good (〇), and when the subsequent strength of less than 1 〇 is obtained, it is determined that the subsequent strength is bad (χ). 5) Liquid crystal sealing hybrid strength test after heat hardening In the same manner as described above, a cross-shaped glass was prepared. Then, at 12 〇. (: The test piece obtained by applying only the heat hardening for 6 minutes is added to the test piece obtained by the heat hardening. The test piece obtained by the price. ] The type of the juice is not viscous 6) The viscosity stability is 100 parts by weight of the liquid crystal sealed The agent was placed in a polyethylene container, and in this state, it was kept at 25 t for 5 days, and the viscosity of the second sealant was measured. The viscosity of the sealant after changing with time, the first measurement of the 25 ° C viscosity value of the seal is set to 100 when the two: First, when the rate of increase of viscosity is less than or equal to 2 〇〇 / 0, will be 1 ^ The performance of the faulty stability is evaluated as good (〇), and the stability of the above-mentioned increase rate exceeding 2〇% is evaluated as poor (x> The material shown below was premixed with a mixer, and then kneaded by a three-light mill until the solid raw material was 5 μm or less. Then, it was filtered with a filter having a pore size of 10 μm (MSP-10~E10S: manufactured by ADVANTEC). This composition was then subjected to vacuum defoaming treatment to obtain a liquid crystal sealing agent (P1). Mercaptopropionate compound (obtained from Synthesis Example 1) 35 parts of latent epoxy hardener 10 parts ζ\%•oxy resin 5 parts of photoradical polymerization initiator 2 parts of filler 15 parts of agglomerated acid-modified epoxy resin (obtained from Synthesis Example 7) 5 parts of Shi Xixia coupling agent 1 part using the above method, the obtained sealant was subjected to the above method Evaluation Example 2 The compound obtained in Synthesis Example 2 was used. (Alpha] 2) instead of the compound L) Kyu), except that, in the same manner as in Example 1 to obtain liquid-tight, Lambda〗 (Ρ2). The obtained sealant was evaluated by the above method. [Example 3] (Liquid crystals were obtained in the same manner as in Example 1 except that the compound (Α3) obtained in Synthesis Example 3 was used instead of the compound. The obtained sealant was evaluated by the above method. [Example 4] A liquid crystal dense 46 200903119 sealant (P4) was obtained in the same manner as in Example 1 except that the mixture (Α4) obtained in Synthesis Example 4 was used instead of the compound. In the method, the obtained sealant was evaluated. [Example 5] A liquid crystal seal was obtained in the same manner as in Example 1 except that the compound (A5) obtained in Synthesis Example 5 was used instead of the compound (A1). Agent (P5) The obtained sealant was evaluated by the above method. [Example 6] A compound obtained by mixing the compound (A1) and the compound (A5) in a weight ratio of 1:1 was used instead of the compound. (A1), a liquid crystal sealing agent (Ρ6) was obtained in the same manner as in Example 1. The obtained sealant was evaluated by the above method. [Example 7] Using Synthesis Example 6 A liquid crystal sealing agent (Ρ7) was obtained in the same manner as in Example 1 except that the obtained mixture (Α6) was used instead of the compound (Α1). The obtained sealant was evaluated by the above method. ] half the amount (weight conversion) A liquid crystal sealing agent (Ρ8) was obtained in the same manner as in Example 1 except that the compound (Α1) was replaced by the mixture (Α6). The obtained sealant was evaluated by the above method. 9 to Example 16] 1,1-azobis(2,4-cyclohexane-1-carbonitrile) as a thermal radical polymerization initiator was used instead of 1- as a photoradical polymerization initiator Liquid crystal sealing agents (Τ1) to (Τ8) were obtained in the same manner as in the first to eighth embodiments except for the hydroxy-cyclohexyl-phenyl-ketone. The obtained sealant was evaluated by the above method. 47 200903119 [Comparative Example 1] A liquid crystal sealing agent (C1) was obtained in the same manner as in Example except that the acrylate (R1) represented by the above formula (1) was used instead of the compound (A1). The above acrylate compound (R1) is synthesized in accordance with Reference Example = and Examples of Patent Document 2. With respect to i, 5-tris(2-hydroxyethyl)isocyanate gives 2.5 mol. The caprolactone is subjected to ring-opening addition to obtain an alcohol, and the alcohol is further esterified with acrylic acid to obtain a counter-containing reaction. The mixture was washed with ultra-pure water and purified to obtain a high purity. [Comparative Example 2] A propionate compound represented by the above formula (11) was used (, a substitute compound of Li (A1) In addition, a liquid crystal sealing agent (C2) was obtained in the same manner as in Example 1. The above acrylate compound (R2) was synthesized in accordance with Example 1 of Patent Document 3. Relative to 1 mol of trishydroxyl Methylpropane was calcined to obtain an alcohol by ring-opening addition of caprolactone of 3 m〇1, and the alcohol was subjected to a acetification reaction with acrylic acid to obtain a reaction mixture containing the target. Subsequently, the reaction mixture was washed with a 1% aqueous sodium oxychloride solution, and further washed with ultrapure water to obtain high purity. [Comparative Example 3] U-azobis(2,4-cyclohexane-1-phthalonitrile) as a thermal radical polymerization initiator was used instead of 1-hydroxy-ring as a photoradical polymerization initiator In the same manner as in Comparative Example 1, a liquid 48 200903119 crystal sealant (C3) was obtained in the same manner as in Comparative Example 1. [Comparative Example 4] The time was a hot free-knit start-up U-even Ι double ( The liquid was obtained in the same manner as in Comparative Example 2 except that 2,4-cyclohexanecarbonitrile was used instead of 1-mono-cycloheximide as the photoradical polymerization initiator.

以如上方式對化合物（混合物）測定ΔΝΙ 結果示於表1中。 點。將測定 [表1]The ΔΝΙ was measured for the compound (mixture) in the above manner. The results are shown in Table 1. point. Will be measured [Table 1]

樣品 ΔΝΙ ^ *' --- (°〇 甲基丙烯酸酯（A1) 0.10 〜 丙烯酸酯（A2) 0.20 ' (甲基)丙烯酸酯（A3) 0.20 〜 施 (曱基）丙烯酸酯（A4) ---- 0.15 用 丙烯酸酯（A5) 0.20 〜 A1與A5的1 : 1混合物 0.15 〜 ——. 丙烯酸酯（A6) 0.20 ^ 比 丙烯酸酯（R1) 1.10 〜 較 丙烯酸酯（R2) 1.40 用 — 丙烯酸酯（R3) υ 1.30 ^两烯酸酯（R3)為下所示的化合物。 [化 26]Sample ΔΝΙ ^ *' --- (°〇methacrylate (A1) 0.10 〜 acrylate (A2) 0.20 '(meth) acrylate (A3) 0.20 ~ Shi (meth) acrylate (A4) -- -- 0.15 with acrylate (A5) 0.20 ~ A1 and A5 1:1 mixture 0.15 ~ --. Acrylate (A6) 0.20 ^ than acrylate (R1) 1.10 ~ acrylate (R2) 1.40 with - acrylate (R3) υ 1.30 ^ enoate (R3) is a compound shown below.

49 200903119 東亞合成股份有H製造AmnixM315 對以如上方式製備的密封劑測定△N 示於表2中。 I點。將測定結果 [表2] 樣品 _查封劑（P1) _ V ^ J Ιο.ίο _密封劑（P2) ρ.ιο _堯鼓翌(P3) (0.20 _密封劑（P4) |〇. 15 _密封劑（P5) 0.20 (P6) 0.15 _密封劑（Ρ8) Jf封劑(T149 200903119 East Asia Synthetic Co., Ltd. manufactured by Amnix M315. The sealant prepared by the above method was measured as ΔN shown in Table 2. I point. The measurement result will be [Table 2] Sample _ Sealing Agent (P1) _ V ^ J Ιο. ίο _ Sealant (P2) ρ.ιο _ 尧 Drumstick (P3) (0.20 _Sealant (P4) | 〇. 15 _ Sealant (P5) 0.20 (P6) 0.15 _Sealant (Ρ8) Jf Sealant (T1

C 實施例L 實施侈 實施例3_ 實施例_ 4 實施ί歹1 .實施你[6 貫施例_ if 封劑（T2 ) 〇.1〇 ΐϋ 劑（T3 0.10 t^ij3C Example L Implementation Example 3_ Example _ 4 Implementation 歹 . 1. Implementation of your [6 application _ if sealant (T2) 〇.1〇 ΐϋ agent (T3 0.10 t^ij3

.實施例_ 實施例9 [_實施例Jjj ί實施例11 〇 對以如上方式製 強度以及黏度穩定性 表示P1〜P8以及ci 備的密封劑評價液晶顯示狀態、接著 ’將評價結果示於表3、表4中。表3 、C2經光硬化及熱硬化後的密封劑性 50 200903119 ZO^OJpil 能，表4表示T1〜T8以及C3、C4經熱硬化後的密封劑 性能。 [表3]Example _ Example 9 [Example Jjj 实施 Example 11 评价 The liquid crystal display state was evaluated for the sealant having P1 to P8 and ci prepared by the strength and viscosity stability as described above, and then the evaluation results are shown in the table. 3. Table 4. Table 3, Sealing properties of C2 after photohardening and heat hardening 50 200903119 ZO^OJpil Yes, Table 4 shows the sealant properties of T1 to T8 and C3 and C4 after heat curing. [table 3]

液晶顯不 狀態測試 接著強度 測試 PCT (40 h)接 著強度測試 黏度穩定 性 測試 光硬化及熱硬化 光硬化及熱硬化 光硬化及熱硬 化 未硬化 密封 劑 結果 判定 結果 (MPa) 判定 結果 判定 結果 (%) 判 定 實 施 例 1 P1 未產生顯 示不良 〇 12 〇 — — 108 〇 2 P2 未產生顯 示不良 〇 22 〇 — — 105 〇 a D 卜3 未產生顯 示不良 0 18 〇 — — 106 〇 4 P4 未產生顯 示不良 〇 20 〇 17 〇 107 〇 5 P5 未產生顯 示不良 〇 27 〇 13 〇 105 〇 6 P6 未產生顯 示不良 〇 28 〇 15 〇 106 〇 7 P7 未產生顯 示不良 〇 25 〇 15 〇 106 〇 8 P8 未產生顯 示不良 〇 17 〇 15 〇 106 〇 b匕 較 例 1 C1 0.8 mm 的 顯不不良 X 18 〇 — — 106 〇 2 C2 0.9 mm 的 顯示不良 X 20 〇 — — 105 〇 51 200903119 [表4]Liquid crystal display state test followed by strength test PCT (40 h) followed by strength test viscosity stability test photohardening and thermosetting photohardening and thermosetting photohardening and thermosetting unhardened sealant result judgment result (MPa) judgment result judgment result ( %) Judgment Example 1 P1 does not produce display defect 〇12 〇—108 〇2 P2 No display defect 〇22 〇— 105 〇a D Bu 3 No display defect 0 18 〇 — — 106 〇4 P4 Not generated Poor display 〇20 〇17 〇107 〇5 P5 No display defect 〇27 〇13 〇105 〇6 P6 No display defect 〇28 〇15 〇106 〇7 P7 No display defect 〇25 〇15 〇106 〇8 P8 No display defect 〇17 〇15 〇106 〇b匕Comparative example 1 C1 0.8 mm unfavorable X 18 〇—106 〇2 C2 0.9 mm display poor X 20 〇— 105 〇51 200903119 [Table 4]

液晶顯不 狀態測試 接著強度 測試 PCT (40 h) 接著強度測試 黏度穩定 性 測試 熱硬化 熱硬化 熱硬化 未硬化 密 封 劑 結果 判定 結果 (MPa) 判定 結果 判 定 結果 (%) 判 定 ;^ [ 施 例 9 T1 未產生顯 示不良 〇 14 〇 — — 107 〇 10 T2 未產生顯 示不良 〇 24 〇 — — 104 〇 11 T3 未產生顯 示不良 〇 18 〇 — ~ 105 〇 12 T4 未產生顯 示不良 。 21 ° 17 G 107 0 13 T5 未產生顯 示不良 〇 29 〇 13 〇 105 〇 14 T6 未產生顯 示不良 〇 28 〇 15 〇 107 〇 15 T7 未產生顯 示不良 〇 27 〇 15 〇 105 〇 16 T8 未產生顯 示不良 〇 19 〇 15 〇 106 〇 比 3 C3 】.l imn的 顯示不良 X 18 〇 — — 106 〇 較 例 4 C4 1.4 mm 的 顯示不良 X 21 0 - — 106 〇 52 200903119 [實施例17]高純度化合物的合成 於具備攪拌機、溫度計、滴液漏斗、以及冷卻技、蠢 瓶内，添加188.3§(〇.47!11〇1，1^〇：純度為98〇/^。的^1的繞 三(氯甲醯基乙基)異三聚氰酸酯及732 g的曱茨，獾⑺，3’5· ' 、Ί 液。繼而’一邊擾拌此懸浮液一邊滴加將203 3 W 1 /11、’ sv i.41 in0i \ 的丙烯酸4·輕丁酯、111.4 g (1.41 mol)的ο比变、以及 g的曱苯均勻混合而成的溶液。滴加是於室温下進2 32 (、 時。一邊用溫度計測定懸浮液的液溫一邊滴加溶液，猡头 λ 滴加時懸浮液的液溫上升至35°C。 件° 使已滴加了全部溶液的懸浮液於室溫下熟化5小時 自滴加溶液起至進行熟化之期間，反應混合物為含有白色 結晶的漿料液。此漿料液含有溶劑、溶解於該溶劑中的目 標化合物 '不溶於溶劑中的°比啶鹽酸鹽的析出物、及不、容 於溶劑中的原料1,3,5-三（氯曱醯基乙基)異三聚氰酸醋。熟 化結束時，反應混合物中幾乎不存在未溶解的 曱醯基乙基)異三聚氰酸酯。使用過濾器（桐山製作所製 Ο 造，Νο·5Α )對該熟化後的反應混合物進行抽氣過液，自 反應混合物中除去吡啶鹽酸鹽。又，以300 g的甲苯清洗 所回收的吡啶鹽酸鹽，回收該甲苯幷混合至方才所獲得的 濾液中。 繼而，於2200 g的將吡啶鹽酸鹽除去後的反應混合物 中’添加600 g的1 wt%氫氧化鈉水溶液，然後振盪並靜 置一定時間。反應混合物與氫氧化鈉水溶液的混合物（以 下稱為「清洗時的混合物」）自靜置起經過10分鐘後分液 53 200903119 笨相。清洗時的混合物是由透明的甲苯相及透 明確7。目構成，不存在乳化相（emulsion phase)，界面 Λ入洗時的混合物巾除去水相之後，於甲苯相中再次 門a八、y §的1 Wt/°氳氧化鈉水溶液，振盈並靜置一定時 然後，自該清洗時的混合物巾除去水相之後， ^ _/了Μ 樹的],3_赚基） 的入旦έ士 Γ 基>5-(2_缓基乙基）異三聚氰酸酯 =二^ 除去溶劑，此化合物在甲苯相中的 後^定::?1导!_相_添加_g的純水，錄 ^置-心間，再次分液。自靜置起經過】G分鐘之 確認分液1測觀察甲苯相與純水的混合物（以下稱為 清洗時的混合物」），結果確認，甲苯相與水相的界面明 不存在乳化相。 ϋ 此後，於自水清洗時的混合物巾除去水相而獲得 苯相中，再次加入600 g的純水，振錢靜置—定 分液，反覆進行6次此操作。第6次操作結束後 _ 獲得的曱苯相中的丙烯酸4-羥丁酯的含量，結果含旦 0.01%。又，第6次操作時所獲得的水相㈤導^度3為里ο: ⑽/⑽。由此可確認’透過上述一系列的清洗操^、可白 甲苯相中充分去除離子性雜質。 自 於最終獲得的曱笨相中，添加〇 g的作為聚合 制劑的吩噻嗪（Phenothiazine )。使用將浴溫保持為美:口 54 2〇〇9〇3i|9 定在50〇C的蒸發器，於減壓下濃、縮 的1,3,5-三[(4_丙烯醯基丁氧基德基切液，獲得293 § 藉由HPLC分析而測定所製造的^異_二聚氰酸酯。 丁氧基)縣乙基]異三聚氰酸酉旨的純声，三队丙稀醯基 標物相對於原料3,5_三(氯甲醯基二、，果為㈣。目 產率為78%，產率高。又，以下=、)異三聚氰酸酯的 ::酸醋化合物中的離子性雜 二所=(甲基) 電度為UMS/cm。可確認，此化 知^果水相的導 少至可用於$曰—口物中離子性雜質已減 〜用於，夜a曰岔封劑此類電子設備中的水平。 [貫施例18] nf用等里（莫耳換异）的甲基丙稀酸2·趣乙酯來代替 經丁，’除此以外，以與實施例17完全相同的 7取，曰成1，3,5-三[(2-曱基丙烯醯基乙氧基)羰基乙基]里 酉旨。結果，所獲得的u，5_三[(2_甲基丙稀酿基乙 虱基基乙基]異三聚氰酸酯為267 g。Liquid crystal display state test followed by strength test PCT (40 h) Next strength test viscosity stability test heat hardening heat hardening heat hardening unhardened sealant result judgment result (MPa) judgment result judgment result (%) judgment; ^ [Example 9 T1 does not produce display defect 〇14 〇— 107 〇10 T2 No display defect 〇24 〇— 104 〇11 T3 No display defect 〇18 〇—~ 105 〇12 T4 No display defect. 21 ° 17 G 107 0 13 T5 No display error 〇29 〇13 〇105 〇14 T6 No display error 〇28 〇15 〇107 〇15 T7 No display error 〇27 〇15 〇105 〇16 T8 No display Poor 〇19 〇15 〇106 〇Comparative 3 C3 】.l imn display poor X 18 〇- 106 〇Comparative example 4 C4 1.4 mm poor display X 21 0 - — 106 〇52 200903119 [Example 17] High purity The compound is synthesized in a blender, a thermometer, a dropping funnel, and a cooling technique, and a stupid bottle is added. 188.3§(〇.47!11〇1,1^〇: purity of 98〇/^. (Chloromethylidene ethyl) iso-isocyanate and 732 g of hydrazine, hydrazine (7), 3'5·', hydrazine. Then 'while disturbing this suspension while dropping 203 3 W 1 / 11. A solution of 'sv i.41 in0i \ of acrylic acid 4 · light butyl ester, 111.4 g (1.41 mol) of ο ratio change, and g of terpene. The addition is 2 32 at room temperature ( While measuring the liquid temperature of the suspension with a thermometer, the solution is added dropwise, and the temperature of the suspension rises to 35 ° C when the taro λ is added dropwise. The suspension in which the entire solution has been added is aged at room temperature for 5 hours from the dropwise addition of the solution to the aging, and the reaction mixture is a slurry containing white crystals. The slurry contains a solvent and is dissolved in The target compound in the solvent is insoluble in the solvent, the precipitate of the pyridine hydrochloride, and the raw material which is not contained in the solvent, 1,3,5-tris(chloromethylethyl)isocyanide Sour vinegar. At the end of the aging, almost no undissolved mercaptoethyl)isomeric cyanurate was present in the reaction mixture. The cured reaction mixture was prepared using a filter (manufactured by Kirsaiyama Seisakusho Co., Ltd., Νο·5Α). The pulverized liquid was removed from the reaction mixture, and the recovered pyridine hydrochloride was washed with 300 g of toluene, and the toluene was recovered and mixed into the filtrate obtained. Then, at 2200 g. Add 600 g of a 1 wt% aqueous sodium hydroxide solution to the reaction mixture after removing the pyridine hydrochloride, and then shake and let stand for a certain period of time. The mixture of the reaction mixture and the aqueous sodium hydroxide solution (hereinafter referred to as "cleaning" mixture ") After 10 minutes from the standstill, the liquid separation 53 200903119 is stupid. The mixture during the cleaning is composed of a transparent toluene phase and a transparent phase. There is no emulsion phase, and the interface is washed. After the mixture towel is removed from the aqueous phase, the aqueous solution of 1 Wt/° 氲 sodium oxide in the toluene phase is again gated, y §, shaken and allowed to stand for a certain period of time, then, after removing the aqueous phase from the mixture of the cleaning, ^ _ / Μ 的 的 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 After the ^ set::? 1 lead! _ phase _ add _g of pure water, record ^ set - heart, again liquid. After the completion of the lapse of the G-minute, it was confirmed that the mixture of the toluene phase and the pure water (hereinafter referred to as the mixture at the time of washing) was observed by the liquid separation test. As a result, it was confirmed that the emulsified phase was not present at the interface between the toluene phase and the aqueous phase. ϋ Thereafter, the aqueous phase of the mixture was removed from the water to obtain a benzene phase, 600 g of pure water was again added, and the reaction was allowed to stand still, and the operation was repeated 6 times. After the end of the sixth operation, the content of 4-hydroxybutyl acrylate in the indole phase obtained was _ 0.01%. Further, the water phase (five) obtained in the sixth operation is 3 degrees ο: (10) / (10). From this, it was confirmed that the ionic impurities were sufficiently removed by the above-described series of cleaning operations and the white toluene phase. From the finally obtained stupid phase, phenothiazine (Phenothiazine) was added as a polymerization preparation. Use to keep the bath temperature beautiful: mouth 54 2〇〇9〇3i|9 set at 50 ° C evaporator, concentrated, reduced 1,3,5-three [(4_ acrylonitrile) under reduced pressure Oxygen-based cleavage solution, 293 § Measured by HPLC analysis to determine the produced iso-di-polycyanate. Butoxy) county ethyl] isocyanuric acid 酉 pure sound, three teams of C The dilute base standard is relative to the raw material 3,5_3 (chloroformyl group II, and the fruit is (4). The objective yield is 78%, and the yield is high. Further, the following =,) isocyanurate: : Ionic heteropoly in acid vinegar compound = (methyl) The electrical quantity is UMS/cm. It can be confirmed that the clarification of the aqueous phase is such that the ionic impurities in the sputum are reduced to the level used in such electronic devices. [Example 18] nf was replaced by a methacrylic acid 2 oxime in the same manner as in the above, except that the same procedure as in Example 17 was carried out. 1,3,5-Tris[(2-mercaptopropenylethoxy)carbonylethyl]. As a result, the obtained u,5_tri[(2-methylpropenylethenylethyl)isocyanate was 267 g.

C 妒A f ^ HPLC分析而測定所獲得的1，3,5-三阶甲基丙烯 ^2。/氣基)裁基乙基]異三聚氮酸醋的純度，結果該純度 相耕於°1^又’―利用與實施例17才目同的方法來計算目標物 產率為二(氣甲酿基乙基)異三聚氰酸酿的產率，結果 ㈣所獲得的（甲基)丙稀酸酯化合物中的離子性雜 結果水相的導電度為U W可確認， =雜貝已減少至可用於液晶密封劑此類電子設備中的 55 200903119 本發明中的HPLC分析以及離子性雜質重量的測定是 以如下方式進行。 [HPLC分析] • HPLC 管柱：YMC-Pack ODS-A A-312 150 mmx 6.0 mm I.D.S-5 μπι, 12 nm .洗脫液··乙腈/0.1 wt%麟酸水= 65/35 (體積比） .流量：1 ml/min .UV檢測器波長：2ΐ〇ηηι .注入量：20 μΐ ’注入樣品：將〇.〇】g (換算為未含有溶劑）稀釋於 50 ml的乙腈中 例如，〗，3,5-三[(4-丙烯醯基丁氧基）羰基乙基」！異三聚 氰酸酯的純度，是將由HPLC分析所測定的H5-三[(4-丙 烯醯基丁氧基）羰基乙基]異三聚氰酸酯的峰面積設為 ml、將除此以外的雜質的總峰面積設為m2時，以{ml/ (ml+m2)} χίοο 來計算。 [離子性雜質重量的測定方法] (甲基）丙烯酸酯化合物中的離子性雜質重量是以如下 所示的導電度來評價。 導電度的測定方法：取用作為測定對象的反應混合物 以及所製造的（曱基）丙烯酸酯化合物3 g，於其中混合30 g 甲苯以及3G g超純水。超純水是使用剛進㈣製之後的超The obtained 1,3,5-tri-order methyl propylene ^2 was determined by C 妒A f ^ HPLC analysis. / gas base) cleavage of ethyl hexamethacrylate vinegar, the purity of which is ploughed in ° 1 ^ ' ― using the same method as in Example 17 to calculate the target yield of two (air armor The yield of the brewing ethyl) isomeric cyanuric acid, the result of (4) the ionic heterojunction in the (meth) acrylate compound obtained. The conductivity of the aqueous phase is UW, and the number of miscellaneous shells has been reduced. 55 to 200903119, which can be used in an electronic device such as a liquid crystal sealing agent, HPLC analysis and measurement of the weight of ionic impurities in the present invention are carried out in the following manner. [HPLC analysis] • HPLC Column: YMC-Pack ODS-A A-312 150 mm x 6.0 mm IDS-5 μπι, 12 nm. Eluent··acetonitrile/0.1 wt% linalic acid= 65/35 (volume ratio) Flow rate: 1 ml/min . UV detector wavelength: 2ΐ〇ηηι. Injection volume: 20 μΐ 'Injection sample: dilute 〇.〇】g (converted to not containing solvent) in 50 ml of acetonitrile, for example, , 3,5-tris[(4-propenylfluorenyloxy)carbonylethyl"! The purity of the isomeric cyanurate is determined by HPLC analysis, and the peak area of H5-tris[(4-propenylbutoxy)ethyl)isocyanate is set to ml. When the total peak area of the other impurities is m2, it is calculated as {ml/ (ml+m2)} χίοο. [Method for Measuring Ion Impurity Weight] The weight of the ionic impurities in the (meth) acrylate compound was evaluated by the conductivity shown below. Method for measuring conductivity: 3 g of the reaction mixture to be measured and 3 g of the (meth) acrylate compound produced were mixed, and 30 g of toluene and 3 g of ultrapure water were mixed therein. Ultrapure water is super after the use of the new (four) system

純水。接著’振盪此混合社後靜置，分液為有機相與水 相。繼而’使用導電度測定計（DKK. t〇a CC)Rp()RATIC)N 56 200903119 ，="^祖211>)，來咐取自混合液中的水相 的導電度bS/cm)。 [參考例1] 於具備攪拌機、溫度計、滴液漏斗'以 瓶中，加入1227 g的氯仿、203 g ( j % 今吕的燒 酸緒乙酉旨、以及n3.4ga43mQl)的_ = 備均匈的混合物。將i 88.3 g ( 0.47 _ )的i 3 ^而: 甲醯基乙基)幾基乙基異三聚氰酸墙一邊進行冷’卻 50分鐘添加至上述混合物中。其間， 合物的液溫，結果液溫自25t:上升^咖度计測疋反應混 將以此種方式獲得的溶液於65。 反應混合物直至熟化後的反應混合小時。冷卻Pure water. Then, the mixture was shaken and allowed to stand, and the liquid phase was separated into an organic phase and an aqueous phase. Then, using a conductivity meter (DKK. t〇a CC) Rp()RATIC)N 56 200903119 , ="^祖211>), to extract the conductivity of the aqueous phase from the mixed liquid bS/cm) . [Reference Example 1] In a bottle equipped with a stirrer, a thermometer, and a dropping funnel, 1227 g of chloroform, 203 g (j % of the yoghurt, and n3.4ga43mQl) were added. mixture. i 88.3 g (0.47 _) of i 3 ^ and: mercaptoethyl) benzyl ethyl isocyanuric acid wall was added to the above mixture while being cooled for 50 minutes. In the meantime, the liquid temperature of the compound, as a result, the liquid temperature was increased from 25t: the rise was measured by the calorie measurement. The solution obtained in this manner was at 65. The reaction mixture is allowed to mix until the reaction after aging. cool down

CJ 為止，，、'、後加人淑g的飽和食鹽水並靜置 分液為作為有機相的氯仿相與水相，但:^ 且氯仿相與水相的界面處存在乳化相等，、分液性差。濁， 仿相==物!去除水相，於藉此所獲得的氯 定時間。靜置後，氯仿相形成較 賴後靜置 與氯仿相。分液後納 “爾面而分液為水相 η%氫氧化鋼溶液再次、生·Γ fr 588 g的 m 5n〇 _ π洗。此後，以如上所述的方式 g的飽和食鹽水對氯仿相反覆清洗5次。 然後’藉由通常的方法自氯仿相中單離出(甲基)丙烯 57 2〇〇9〇3119 2化合物。利用上文已述的方法來評償此化合物中所含 黑子性雜質，結果水相的導電度為265 pS/cm。由該結 曰I確認，該化合物所含有的離子性雜質達到不適用於液 曰曰费封劑此類電子設備中的水平。 然而’以此種方式獲得的（甲基)丙稀酸酯化合物，夢 由石夕勝管柱精製，可將軒性雜質減少至可義於液晶^ 封劑等電子設備中的水平。 由以上内容表明，本發明的化合物於室溫下為液狀， 且使用此化合物的液晶密封劑具有極低的液晶污染性，尤 其可優異地用作液晶滴注方式用的密封_料以及液晶穷 封劑。 山 [產業上的可利用性]CJ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Poor liquidity. Turbid, imitation = = matter! Remove the aqueous phase and use this to obtain the chlorine time. After standing, the chloroform phase formed and remained stationary with the chloroform phase. After the liquid separation, the liquid phase is divided into the water phase η% hydroxide steel solution again, the raw Γ 588 g m 5n〇_ π washing. Thereafter, the saturated brine of the g as described above is used for the chloroform phase. The washing was repeated 5 times. Then, the (methyl)propene 57 2〇〇9〇3119 2 compound was isolated from the chloroform phase by a usual method. The method described above was used to evaluate the black spots contained in the compound. As a result of the impurity, the conductivity of the aqueous phase was 265 pS/cm. It was confirmed by the crucible I that the ionic impurities contained in the compound reached a level which was not suitable for use in such electronic devices as liquid helium sealants. The (meth) acrylate compound obtained in this way, which is refined by Shi Xisheng pipe column, can reduce the enamel impurities to the level of electronic devices such as liquid crystal sealing agents. The compound of the present invention is liquid at room temperature, and the liquid crystal sealing agent using the compound has extremely low liquid crystal contamination property, and is particularly excellent as a sealing material for a liquid crystal dropping method and a liquid crystal depressant. Mountain [industrial availability]

旅據本發明，可提供一種液晶污染性極低的液晶密封 ，。本發明的密封劑尤其適用於液晶滴注方式，有效製造 頌不性良好的液晶顯示面板。又，本發明的化合物由於離 子性雜質極少，為高純度，故亦可用作液晶密封劑以外的 電子材料用接著劑、或上漿劑（sizing agent)。 本申请案疋基於2007年7月6曰提出申請的曰本專利 申5月號JP2007-179096、2007年7月6日提出申請的曰本 專利申請號JP2007-179097、2007年8月7日提出申請的 曰本專利申請號JP2007-205896以及2008年6月2日提出 申請的日本專利申請號JP2008-145021，並主張該些申請 案的優先權。該些申請案的說明書以及圖式所揭示的内容 均援用於本案說明書中。 58 200903119 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何所屬技術領域中具有通常知識者，在不 脫離本發明之精神和範圍内，當可作些許之更動與潤飾， 因此本發明之保護範圍當視後附之申請專利範圍所界定者 為準。 【圖式簡單說明】 無 【主要元件符號說明】 無 59According to the present invention, it is possible to provide a liquid crystal sealing having extremely low liquid crystal contamination. The sealant of the present invention is particularly suitable for use in a liquid crystal dropping method, and is effective in producing a liquid crystal display panel which is highly defective. Further, since the compound of the present invention has extremely low ionic impurities and is highly pure, it can be used as an adhesive for electronic materials other than a liquid crystal sealing agent or a sizing agent. This application is based on the patent application No. JP2007-179096 filed on July 6, 2007, and the patent application number JP2007-179097 filed on July 6, 2007, and filed on August 7, 2007. Japanese Patent Application No. JP2007-205896, filed on Jun. 2, 2008, filed on Jun. The descriptions of the applications and the contents disclosed in the drawings are used in the present specification. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims. [Simple diagram description] None [Main component symbol description] None 59

Claims (1)

200903119 申請專利範圍： 1.-種液晶密封劑，其含有以下 基)丙烯酸酯化合物， 、式（I )表示的（甲 [化1] 〇 0 || || H2c=c—C - 〇—Z—0-C' k 〇 、N ：CHn O' 人丨人, N i A. 0 c-o-y-〇~c-c=ch2 0 I r2 ύ r 二i自獨立為碳數為2或3的亞烧基， R]〜R3各自獨立為氣原子或甲基，χ〜 為2〜4的亞烧基]。 曰㈣為石厌數 2‘如申請專利範圍第！項所述之液 述通式（I )中的A為亞乙基。 ，、’所 、、3.如申請專利範圍第1項所述之液晶密封劑；其中所 述（甲基)丙烯酸酯化合物是選自以下式（B1 )、式1 式（B3)以及式（E1)表示的化合物族群中的 以上化合物的混合物，且所述混合物中咖基的 LEt基的數量之比為70 : 30〜30 : 70， 、 LBu、 LBu LBu. [化2] 0200903119 Patent application scope: 1. A liquid crystal sealing agent containing the following acrylate compound, represented by the formula (I) (A[1] 〇0 || || H2c=c-C - 〇-Z —0-C' k 〇, N :CHn O' 人丨人, N i A. 0 coy-〇~cc=ch2 0 I r2 ύ r The second i is independently a sub-alkyl group having a carbon number of 2 or 3. R]~R3 are each independently a gas atom or a methyl group, and χ~ is a sub-alkyl group of 2 to 4.] 曰(4) is a stone-penetration number 2' as described in the patent scope of the item (I) The liquid crystal sealing agent of the above-mentioned item (1), wherein the (meth) acrylate compound is selected from the following formula (B1), A mixture of the above compounds in the compound group represented by the formula (B3) and the formula (E1), and the ratio of the number of LEt groups in the mixture is 70: 30 to 30: 70, LBu, LBu LBu. [化2] 0 NT I A LBu LBu LEt' Ό O. ΟNT I A LBu LBu LEt' Ό O. Ο NT I A I LEt 义/LBu LEt \ 〇 、0 0. ΟNT I A I LEt /LBu LEt \ 〇 , 0 0. Ο NT I A I LEt ,A...A-LEt 、0NT I A I LEt , A...A-LEt , 0 NT I A I LEt (B1) (B2) (B3; (E1) [式（Bl)〜式（El)中，a各自獨立為碳數為2或3 的亞烷基，LBu為以下式（LBu)表示的基團，LEt為以 60 200903119 下式（LEt)表示的基團]， [化3] 〇 -“-ch2CH2CH2CH2J_ H (hBU) [化4] 〇 一“H〇l?=CH2 ^ (LEt) ° ▼ — u犯阁罘1項, =晶密封劑更包括環氧樹脂 性％氧硬彳b#Ux及填充料。 由基聚合起始劑、潛伏 .申请專利範圍第1項戶斤述之液晶密封 :旦您 >±4· .*· / ' . Α . 、、5.如申请專利範圍第4項所述之液晶密封劑，其中相 〇〇重里h之所述（甲基)丙稀酸酯化合物，含有5重 里知60重里份之所述環氧樹脂、0.1重量份〜1〇重量份 之所述自由基聚合起始劑、5重量份〜40重量份之所述纸 伏性環氧硬化劑以及1G重量份〜5〇重量份之所述填充料θ。 6.—種（甲基）兩烯酸酯化合物的製造方法，其是製造如NT IAI LEt (B1) (B2) (B3; (E1) [In the formula (Bl) to (El), a is independently an alkylene group having 2 or 3 carbon atoms, and LBu is represented by the following formula (LBu)) The group, LEt is a group represented by the following formula (LEt) of 60 200903119], [Chemical 3] 〇-"-ch2CH2CH2CH2J_H (hBU) [化4] 〇一"H〇l?=CH2 ^ (LEt) ° ▼ — u 罘 罘 1 item, = crystal sealant further includes epoxy resin% oxygen hard 彳b#Ux and filler. Based on the base polymerization initiator, latent. Patent application scope Liquid crystal sealing: a liquid crystal sealing agent as described in claim 4, wherein the liquid crystal sealing agent described in claim 4, wherein the (meth) C is the same as that of the liquid a dilute ester compound containing 5 parts by weight of the epoxy resin in an amount of 60 parts by weight, 0.1 part by weight of the above-mentioned radical polymerization initiator, and 5 parts by weight to 40 parts by weight of the paper voltamability An epoxy hardener and 1 G parts by weight to 5 parts by weight of the filler θ. 6. A method for producing a (meth) dianoate compound, which is manufactured as 申請專利範圍第1項所述之（曱基）丙烯酸酯化合物的方 法，包括： 於三級胺的存在下，使下述通式（Im)所示的化合物 與下述通式（Llm)所示的化合物、下述通式（L2m)所 不的化合物及下述通式（L3m)所示的化合物在非鹵溶劑 中進行醋化反應，且使所述反應中所生成的齒化氫析出作 為胺鹽的製程； 於所述反應後對所獲得的反應混合物進行過濾的製 程； 61 200903119 、θ以鹼水溶液清洗藉由所述過濾而將所述胺鹽除去的反 應此合物，然後分液而獲得有機相的製程；以及 以純水清洗所述有機相的製程； [化5] 丨丨 〇Ha〆、、义 • k〆、 人 、Hal〇 〇=( 、Halo 、 (Im) 的亞烷基，Halo [弋（Im)中，a表示碳數為2或 表示鹵原子]， [化61 〇 H〇-x-〇-c-〇: CH, Ri Lim [化7] ο h〇-y-〇-6-c=ch2 r2 [化8] (L2m ) o ho~z-〇-c-c=ch2 r3 (L3m ) [式（Llm)〜式（L3m)中 原子或甲基，X〜Z各自獨立 3各自=二:虱 7.如申請專剎 反數為2〜4的亞烷基]。 物的製造方法，其中 、、= 斤述之（甲基）丙烯酸酯化合 或甲基異丁基鋼。、心〜谷劑為芳香族烴、乙酸乙酉旨 δ·如申請專利範圍第6項所逑之(甲基)丙烯酸合 62 200903119 物的製造方法，其中所述三級胺為°比°定、三乙胺或二甲夷 苯胺。 土 9.一種（曱基)丙烯酸酯化合物，以下述通式（B)所表 示， [化9] X2-〇-C- ch2chThe method of claim 1, wherein the compound represented by the following formula (Im) and the following formula (Llm) are used in the presence of a tertiary amine; The compound shown, the compound represented by the following formula (L2m), and the compound represented by the following formula (L3m) are subjected to a acetalization reaction in a non-halogen solvent, and the hydrogenated hydrogen generated in the reaction is precipitated. a process as an amine salt; a process for filtering the obtained reaction mixture after the reaction; 61 200903119, θ is washed with an aqueous alkali solution to remove the amine salt by the filtration, and then divided into a process for obtaining an organic phase from a liquid; and a process for washing the organic phase with pure water; [Chemical 5] 丨丨〇Ha〆, 义• k〆, human, Hal〇〇=(, Halo, (Im) Alkylene, Halo [in (Im), a represents a carbon number of 2 or represents a halogen atom], [Chemical 61 〇H〇-x-〇-c-〇: CH, Ri Lim [化7] ο h〇 -y-〇-6-c=ch2 r2 [L.8] (L2m) o ho~z-〇-cc=ch2 r3 (L3m ) [Formula (Llm)~式(L3m)) Or methyl, X~Z are each independently 3 = two: 虱 7. For example, an alkylene group having an inverse of 2 to 4 is applied. The method for producing the substance, wherein, = jin (meth)acrylic acid Ethyl ester or methyl isobutyl steel, and the core to the granules are aromatic hydrocarbons, acetic acid yttrium δ, and the method for producing (meth) acrylate 62 200903119 according to claim 6 of the patent application, wherein The tertiary amine is a ratio of triethylamine or aniline. Soil 9. A (mercapto) acrylate compound, represented by the following formula (B), [Chemical 9] X2-〇-C - ch2ch ch2ch2-c-0-xr0|〒=cH2 Ri Z r2 H2C=C-C-〇_ B ch2ch2—c-〇-x2-〇-c-c=ch 0 4 2 [式（B)中，x]表示碳數為3或4的亞烷基，X2各自 獨立表示碳數為2〜4的亞烷基，R!表示氫原子或甲基， R2各自獨立表示氫原子或甲基]。 土 10.如申請專利範圍第9項所述之（曱基）玲烯酸酯化合 物，其中所述通式（B)中的X〗為亞丁基，R】為氯原子°， 且X2為亞丁基或亞乙基。 Π.如申請專利範圍第9項所述之（曱基）丙烯酸酯化人 物，其中所述通式（B)中的Xl以及&為亞丁基，且Ri 及R2為氫原子。 12. —種液晶顯示面板的製造方法，包括·· 準備第一基板的製程，所述第一基板具有由申請專利 範圍第1項所述之液晶密封劑所形成的密封圖案； 於所述密封圖案未硬化的狀態下，向所述第一基板的 密封圖案框内或舆所述第一基板相對向的第二基板上，滴 注液晶的製程； 將所述第一基板與所述第二基板疊合的製程；以及 63 200903119Ch2ch2-c-0-xr0|〒=cH2 Ri Z r2 H2C=CC-〇_ B ch2ch2—c-〇-x2-〇-cc=ch 0 4 2 [in the formula (B), x] represents the carbon number The alkylene group of 3 or 4, X2 each independently represents an alkylene group having 2 to 4 carbon atoms, R! represents a hydrogen atom or a methyl group, and R2 each independently represents a hydrogen atom or a methyl group]. 10. The (fluorenyl) phthalate compound according to claim 9, wherein X in the formula (B) is a butylene group, R is a chlorine atom, and X2 is a butylene. Base or ethylene. The (mercapto) acrylated human body according to claim 9, wherein X1 and & in the formula (B) are a butylene group, and Ri and R2 are a hydrogen atom. 12. A method of manufacturing a liquid crystal display panel, comprising: a process for preparing a first substrate, wherein the first substrate has a sealing pattern formed by the liquid crystal sealing agent according to claim 1; a process of injecting a liquid crystal into a seal pattern frame of the first substrate or a second substrate facing the first substrate in a state where the pattern is not hardened; and the first substrate and the second substrate are Process for superimposing substrates; and 63 200903119 使所述液晶密封劑硬化的製程。 13.—種液晶顯示面板，是藉由如申請專利範圍第12 項所述之液晶顯示面板的製造方法而獲得。 64 200903119 七、 指定代表圖·· (一) 本案指定代表圖為：無指定代表圖。 (二) 本代表圖之元件符號簡單說明··無。 八、 本案若有化學式時，請揭示最能顯示發明特徵的化 學式z 〇 〇 II !1 h2c=c—C—〇一ζ—〇一ό- k 〇 〇o人人。 〇 人 〇 、 il C-〇-Y-〇-C-C=CHnA process for hardening the liquid crystal sealing agent. A liquid crystal display panel obtained by the method of manufacturing a liquid crystal display panel according to claim 12 of the patent application. 64 200903119 VII. Designation of Representative Representatives (1) The representative representative of the case is: no designated representative map. (2) A brief description of the component symbols of this representative figure·· None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention. z 〇 ! II !1 h2c=c-C—〇一ζ—〇一ό- k 〇 〇o Everyone. 〇人 〇 , il C-〇-Y-〇-C-C=CHn