TW200815880A

TW200815880A - Liquid crystal sealing agent, fabricating method for liquid crystal display panel by using thereof and liquid crystal display panel

Info

Publication number: TW200815880A
Application number: TW096128402A
Authority: TW
Inventors: Daiki Taneichi; Takahisa Miyawaki
Original assignee: Mitsui Chemicals Inc
Priority date: 2006-08-04
Filing date: 2007-08-02
Publication date: 2008-04-01
Also published as: JP5345393B2; JPWO2008016122A1; TWI453512B; KR101084487B1; CN101501560B; KR20090018172A; CN101501560A; WO2008016122A1

Abstract

This invention is related to a liquid crystal sealing agent suitable for being applied to a liquid crystal display panel. The liquid crystal sealing agent of the invention includes (1) an epoxy resin and an amine latent heat-curing agent; (2) at least one latent heat-curing agent having the melting point less than or equal to 150 DEG C and chosen from a group consisted of a dihydrazide, a modified imidazole, an amine adduct and a polyaminourea latent heat-curing agents; and (3) at least one latent heat-curing agent having the melting point more than or equal to 180 DEG C and chosen from a group consisting of a dihydrazide, a modified imidazole and a diamide latent heat-curing agents. The liquid crystal sealing agent has a fast curing rate and good moisture resistance. Besides, the reactivity at the low temperature range including a room temperature is low, so the viscosity stability could be maintained and the usable time is long. Therefore, when using the liquid crystal sealing agent to fabricate the liquid crystal display panel, the high productivity could be maintained and the liquid crystal display panel could be fabricated with high quality at the same time.

Description

200815880 九、發明說明：【發明所屬之技術領域】本毛明是有關於一種液晶密封劑、使面板的掣株十、足/夜晶顯不败]衣造方法及液晶顯示面板。【先前技術】近年來，液晶顯示面板由於具有薄型、雷工·/?态塋泣寸工里 m消f毛200815880 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a liquid crystal sealing agent, a panel for making a panel, a foot/night crystal, and a liquid crystal display panel. [Prior Art] In recent years, liquid crystal display panels have been thin, and have been smashed.

命早僅^點，而被廣泛用作以便攜式電話為代表的各種的顯示面板。液晶顯示面板是指具有在藉由液晶二曰^而貼合的兩塊基板之間封人有液晶的結構，藉由對施加電壓來控制液晶的配向，並藉由調節所透過的光的调製來顯示圖像的裝置。 =晶顯示面板主要利用液晶注入方式或液晶滴注方式或，4造。液晶注入方式是指，首先利用分配器或網版印刷於兩塊基板的其中任一塊上塗佈液晶密封劑， ^後藉由預固化(procure)處理（預乾燥）使液晶密封劑乾，。此時，在框架的一部分上預先設置作為液晶注入口的斗仅。其次，將兩塊基板對向重合後，藉由加熱壓合使基板彼此貼合。然後，在真空中從液晶注入口向空盒(ceU)内注入液晶，之後利用液晶密封劑等將液晶注入口封閉，從而衣造在基板間封入有液晶的液晶顯不面板。另一方面，所謂的液晶滴注方式包括以下製程。首先，在構成液晶顯示面板的兩塊基板的其中任一塊上塗佈液晶 i封劑’形成填充液晶的框狀#員不區域。其中，塗佈液晶密封劑的方法沒有特別限定，一般使用與上述液晶注入方 6 200815880 式相同的方法。其次，在形成的框内或另一塊基板上滴注適量的液晶，在液晶密封劑未固化的狀態下使兩塊基板在高真空中重合。然後，將重合的兩塊基板回復至大氣壓等，使基板彼此貼合後，使液晶密封劑固化，從而製造在基板間封入有液晶的液晶顯不面板。在上述液晶滴注方式中’ 向重合的基板之間照射紫外線等使液晶密封劑暫且固化後，通常藉由加熱來進行後固化。上述液晶注入方式中’向盒内注入液晶需要長時間’ Γ’ 同時為了使液晶密封劑固化，必需在120〜150°c的溫度範圍内加熱處理數小時，由於上述等原因而出現生產率低的問題。在這方面’當利用液晶滴注方式時’與液晶注入方式相比可以在短時間内封入液晶，因此生產率得到提高。因此，最近作為液晶顯示面板的製造方法，液晶滴注方式正成為主流。作為液晶顯示面板中使用的液晶密封劑，提出了以環氧樹脂作為主要成分的熱固化性液晶密封劑（以下，僅稱作熱固化性密封劑)(例如，參照日本特開2004-123909號公報）。但是，這種熱固化性密封劑，當將其用於製造液晶顯示面板時，因熱而導致黏度變低，由於上述等原因而出現 ^ 密封的配置容易錯位、且固化速度慢的問題。當在液晶滴注方式中使用固化速度慢的液晶密封劑時，有時單體等成分會缓慢地自未固化狀態的液晶密封劑中溶出或者滲出到液晶内。這種單體等成分溶出到液晶中的液晶顯示面板，即使施加電壓，也難以控制液晶的配向， 7 200815880 因此液晶顯示性低，並且出現顏色不均等問題。因〜提高液晶顯*面板的生產率和高品f化方面考慮 ^足供固化速度快的液晶密封劑。 ^ 王提The life is only a few points, and is widely used as various display panels typified by portable phones. The liquid crystal display panel has a structure in which liquid crystal is sealed between two substrates bonded by a liquid crystal, and the alignment of the liquid crystal is controlled by applying a voltage, and the adjustment of the transmitted light is adjusted. A device for displaying images. = Crystal display panel is mainly made by liquid crystal injection method or liquid crystal dropping method. The liquid crystal injection method is to first apply a liquid crystal sealing agent to any of the two substrates by a dispenser or screen printing, and then dry the liquid crystal sealing agent by a pre-curing (pre-drying). At this time, a bucket as a liquid crystal injection port is provided in advance on a part of the frame. Next, after the two substrates are opposed to each other, the substrates are bonded to each other by heat pressing. Then, liquid crystal is injected into the empty cell (ceU) from the liquid crystal injection port in a vacuum, and then the liquid crystal injection port is closed by a liquid crystal sealing agent or the like, thereby forming a liquid crystal display panel in which liquid crystal is sealed between the substrates. On the other hand, the so-called liquid crystal dropping method includes the following processes. First, a liquid crystal encapsulant is applied to any of the two substrates constituting the liquid crystal display panel to form a frame-like region in which the liquid crystal is filled. Here, the method of applying the liquid crystal sealing agent is not particularly limited, and the same method as the liquid crystal injection method of the above-mentioned liquid crystal injection method is generally used. Next, an appropriate amount of liquid crystal is dripped into the formed frame or another substrate, and the two substrates are superposed in a high vacuum in a state where the liquid crystal sealing agent is not cured. Then, the two substrates which have been superposed are returned to atmospheric pressure or the like, and after the substrates are bonded to each other, the liquid crystal sealing agent is cured to produce a liquid crystal display panel in which liquid crystal is sealed between the substrates. In the liquid crystal dropping method described above, after the liquid crystal sealing agent is temporarily cured by irradiating ultraviolet rays or the like between the superposed substrates, post-curing is usually performed by heating. In the above liquid crystal injection method, it takes a long time to inject liquid crystal into the cell. At the same time, in order to cure the liquid crystal sealing agent, it is necessary to heat-treat for several hours in a temperature range of 120 to 150 ° C, and productivity is low due to the above reasons. problem. In this respect, when the liquid crystal dropping method is used, the liquid crystal can be sealed in a short time as compared with the liquid crystal injection method, so that the productivity is improved. Therefore, recently, as a method of manufacturing a liquid crystal display panel, a liquid crystal dropping method is becoming mainstream. A thermosetting liquid crystal sealing agent containing an epoxy resin as a main component (hereinafter, simply referred to as a thermosetting sealing agent) has been proposed as a liquid crystal sealing agent used in a liquid crystal display panel (for example, refer to Japanese Patent Laid-Open No. 2004-123909) Bulletin). However, when such a thermosetting sealant is used for the production of a liquid crystal display panel, the viscosity is lowered due to heat, and the sealing arrangement is liable to be misaligned and the curing speed is slow due to the above-mentioned reasons. When a liquid crystal sealing agent having a slow curing speed is used in the liquid crystal dropping method, a component such as a monomer may be slowly eluted from the uncured liquid crystal sealing agent or ooze out into the liquid crystal. In such a liquid crystal display panel in which a monomer or the like is eluted into a liquid crystal, it is difficult to control the alignment of the liquid crystal even when a voltage is applied. 7 200815880 Therefore, the liquid crystal display property is low, and color unevenness occurs. Due to the improvement of the productivity and high quality of the liquid crystal display panel, it is sufficient for a liquid crystal sealing agent with a fast curing speed. ^ Wang Ti

U 因此，作為固化速度快的液晶密封劑，提出紫外線照射而固化的光固化性成分和藉由加熱而固化^ 固化性成分併用的液晶密封劑（例如，參照日本特= 2〇01-133794號公報、日本特開綱2·2·6號公報）、幵外，在日本特開2004-123909號公報、曰本牲= 2001-133794號公報和日本特開2〇〇2_214626號公報所: 出的液晶密封劑中，熱潛在性硬化劑使用熔點為= 1，3-雙(肼基羰乙基)-5-異丙基乙内醯脲(熔點12(Γ(：)。上、才、熱潛在性硬化劑，在一般的固化溫度12〇〜丨5〇它下迅逮、解，反應性高，因此預計液晶密封劑的固化速度會提高岫但是，低熔點的熱潛在性硬化劑，其水溶性較高，在使用了此種熱潛在性硬化劑的液晶密封劑中出現耐=性的問題。若在液晶顯示面板中使用上述擔心耐濕性的液晶密封劑，則有時固化後的液晶密封劑的黏合強度會變低，液日日顯不面板的顯不性會變差。另外，在液晶顯示面板的製造領域中，認為液晶密封劑的可使用時間的長度很重要。可使用時間是指可以滿意地使用液晶密封劑的時間。可以滿意地使用液晶密封劑，是指在基板上易於塗佈、可以塗佈液晶密封劑等。液晶密封劑的可使用時間隨液晶密封劑黏度的上升而變短。其原因在於，若液晶密封劑的黏度變高，則難以在基板上塗佈， 8 200815880 而且必需更換分配器等裝置中使用的液晶密封劑。因此，長液晶密賴的可使科間，優選鱗間穩定地保持黏度不變，即提高黏度穩定性。㈣但是’上述包括高反應性的熱潛纽魏_液晶密道7使在室溫附近的低溫範圍也容易進行固化反應， ί，/黏度上升。因而，树液晶密封_黏度穩定性邑、义低’可使用時間會變短。【發明内容】種固it Γ上述課題，本發明的第-目的在於提供一性的二：f耐濕性良好’而且長時間保持高黏度穩定目，阳饴封蜊。本發明的第二目的在於提供藉由使用上 =有優異特性及可使料間長的液晶密㈣，在古晶ί率!Γ夺Γ製造耐濕可靠性高的液晶顯示面板的：日日顯不面板的製造方法。叫低w狀U. As a liquid crystal sealing agent having a high curing speed, a photocurable component which is cured by ultraviolet irradiation and a liquid crystal sealing agent which is cured by heating and cured are proposed (for example, refer to Japanese Patent No. 2-01-133794). In the Japanese Unexamined Patent Publication No. 2004-123909, the Japanese Patent Publication No. 2001-133794, and the Japanese Patent Laid-Open Publication No. Hei. No. 2-214626: In the liquid crystal sealant, the thermal latent curing agent uses a melting point of = 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (melting point 12 (Γ(:). The thermal latent hardener has a high curing temperature of 12 〇 to 丨5 〇, and it is highly reactive. Therefore, the curing speed of the liquid crystal sealing agent is expected to increase. However, the low melting point thermal latent curing agent, The water-repellent property is high in the liquid crystal sealing agent using such a thermal latent curing agent. When the above-mentioned liquid crystal sealing agent which is concerned with moisture resistance is used in a liquid crystal display panel, it may be cured. The bonding strength of the liquid crystal sealing agent will become low, and the liquid will not be visible every day. In addition, in the field of manufacturing liquid crystal display panels, it is considered that the length of the usable time of the liquid crystal sealing agent is important. The usable time refers to the time during which the liquid crystal sealing agent can be satisfactorily used. The liquid crystal sealing agent is easy to apply on a substrate, and can be applied with a liquid crystal sealing agent, etc. The usable time of the liquid crystal sealing agent becomes shorter as the viscosity of the liquid crystal sealing agent increases. This is because the viscosity of the liquid crystal sealing agent is increased. When it is high, it is difficult to apply it on the substrate. 8 200815880 It is also necessary to replace the liquid crystal sealing agent used in the device such as a dispenser. Therefore, the long liquid crystal can be used to stabilize the viscosity between the sections, preferably the scale, that is, (4) However, the above-mentioned high-reactivity thermal latent _ liquid crystal dense channel 7 makes it easy to carry out the curing reaction at a low temperature range near room temperature, and the viscosity increases. Therefore, the tree liquid crystal seal _ viscosity The stability 邑, 义低' can be used for a short period of time. [Summary of the Invention] The first object of the present invention is to provide a singularity. f is good in moisture resistance' and maintains a high viscosity for a long time to stabilize the eyes, and the positive pressure is sealed. The second object of the present invention is to provide a liquid crystal dense (four) by using the upper = excellent characteristics and the length of the material, in the ancient crystal ί rate! Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ

U 人等反魏躲人研究，結果魏二=於1贼的熱潛在性硬化劑和嫁點大：完成了本ΪΓ魏侧，㈣_到解決，從而 == 劑本發包:的^ :等於_的第一熱潛二性硬化劑所組成的組群的-種或-種二 9 200815880 劑，上述(3)成分為選自二醯在性硬化劑所組成的組錄二醯胺系熱潛化劑。、#或種以上的熱潛在性硬八达⑺如⑴所述之液晶密封劑，其中上述⑵成八为為二醯肼系熱潛在性硬化劑。 77 口（對^3=]ί[2]所述之液晶贿劑，其中上述(3)成分相射於25 C的幻00 ml的溶解度小於等於2〇 g。风刀不 Ο [4]如[1]〜[3]中任一項所述之液晶密封劑，成分為下述通式(A)所示的化合物。，、中上述（) 【化1】U people and other anti-Wei hiding studies, the result Wei two = 1 thief's thermal latent hardener and marrying point: completed the Bian Wei side, (four) _ to solve, thus == agent hair package: ^ : equal The group consisting of the first thermal latent hardening agent, or the second kind, the above component (3) is selected from the group consisting of diterpenoids. A latent agent. (7) The liquid crystal sealing agent according to (1), wherein the above (2) is a diterpene thermal latent curing agent. 77 (referred to as ^3=] ί [2] liquid crystal bribe, wherein the above (3) component is incident on 25 C, the solubility of magic 00 ml is less than or equal to 2 〇 g. The wind knife is not Ο [4] The liquid crystal sealing agent according to any one of [1], wherein the component is a compound represented by the following formula (A).

其中，通式(A)中的R表示碳數大於等於8的亞烧基。 [5] 如[1]〜[4]中任一項所述之液晶密封劑，上述液晶密封劑為將上述⑴〜⑺成分均勻混合而得到的一液型液晶密封劑。 [6] 如[1]〜[5]中任〆項所述之液晶密封劑，其中在1〇〇重量份上述液晶密封劑中，上述(2)成分和(3)成分的總添加 ®為1〜25重量份。 [7] 如[1]〜[6]中任一項所述之液晶密封劑’當將上述(2) 200815880 成分的添加重量作為W1、將上述(3)成分的添加重量作為 W2 時，0.2$W2/(W1+W2)$0.8。 [8]如[1]〜[7]中任一項所述之液晶密封劑，其中相對於上述（1)成分的環氧當量，上述(2)成分和（3)成分的活性氫當量總計為0.3〜3.0。 • 另外，上述課題還藉由本發明的液晶顯示面板的製造、方法和由該方法得到的液晶顯示面板而得以解決。 [9卜紐晶顯不面板的製造方法，是將對向的兩塊基 , 板藉由液晶密封劑貼合在一起來製造液晶顯示面板，上述Among them, R in the formula (A) represents a calcined group having a carbon number of 8 or more. [5] The liquid crystal sealing agent according to any one of [1] to [4], wherein the liquid crystal sealing agent is a one-liquid type liquid crystal sealing agent obtained by uniformly mixing the components (1) to (7). [6] The liquid crystal sealing agent according to any one of [1] to [5] wherein, in the above liquid crystal sealing agent, the total addition of the above (2) component and (3) component is 1 to 25 parts by weight. [7] The liquid crystal sealing agent according to any one of [1] to [6], wherein when the weight of the component (2) 200815880 is W1 and the weight of the component (3) is W2, 0.2 $W2/(W1+W2)$0.8. The liquid crystal sealing agent according to any one of the above-mentioned (1), wherein the active hydrogen equivalents of the above (2) component and (3) component are total with respect to the epoxy equivalent of the component (1). It is 0.3 to 3.0. Further, the above problems are solved by the manufacture and method of the liquid crystal display panel of the present invention and the liquid crystal display panel obtained by the method. [9] The method for manufacturing a panel is to manufacture a liquid crystal display panel by bonding two substrates facing each other and a liquid crystal sealing agent together.

方法包括：準備基板的製程，上述基板具有按照像素排列區域被上述[1]〜[8]所述之液晶密封劑包圍之方式形成的設有液晶注入口的框狀顯示區域；藉由上述液晶密封劑使兩塊基板重合後，進行加熱壓合使基板彼此貼合，從而名以及藉由加熱使存在於上晶密封劑固化的製程。 200815880 液晶聰_述之好，明’可以提供-種固化速度快且耐濕性良 “ 乂日寸間保持高黏度穩定性的液另 ==;種在r持高生產率的同時可以製造耐湯可 =ί: 的液晶顯示面板的製造方法。 Ο ϋ 易懂上ΐ和其他目的、特徵和優點能更明顯明如下。、+ #乂佳貫施例，並配合觸目式，作詳細說【實施方式】接下來，詳細說明本發明。在以下說明中，用「〜來Π職圍，但是本發明的「〜」包括臨界值。例如」， 10〜100」疋指大於等於10、小於等於丨⑻。於箄^^液30⑯封劑’包括：⑴環氧樹脂；⑺溶點小 =c：=：=：：r㈣；Μ⑽點大於等於 (1)環氧樹脂的ri=的環氧樹脂，是指分子内具有1個或1個以上的壞乳基的化合物。本發明的液晶密 ΐ=:=包括:雙紛A、雙W雙:二: 專所代表的方香族二S醇類以及將它們進行乙二醇、丙二醇、烧？二醇改性的二元醇類與環氧氣丙烧㈣cWorohydrin)反應而得到的芳香族多元縮水甘油㈣ 12 200815880 曱酴與甲’生得到的酴酸樹脂、聚烯二5二二一 ^所代表的聚賴與環氧氣丙烧反應而得 ===〜化合物;笨二甲輯脂的縮水樹脂其:=;=_:包型環氡The method includes: preparing a substrate, wherein the substrate has a frame-shaped display region provided with a liquid crystal injection port formed in a manner that the pixel arrangement region is surrounded by the liquid crystal sealing agent described in [1] to [8]; After the two substrates are superposed on each other, the sealing agent is heated and pressed to bond the substrates to each other, and the name and the process of curing the epitaxial sealant by heating are performed. 200815880 LCD Cong _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Can be = ί: The manufacturing method of the liquid crystal display panel. Ο 易 Easy to understand the upper and other purposes, features and advantages can be more clearly as follows., + #乂佳贯Example, and with the eye-catching style, detailed description [implementation Modes Next, the present invention will be described in detail. In the following description, "~" is used, but the "~" of the present invention includes a critical value. For example, "10 to 100" refers to greater than or equal to 10 and less than or equal to 丨 (8).箄箄 ^ ^ liquid 3016 sealant 'includes: (1) epoxy resin; (7) small melting point = c: =: =:: r (four); Μ (10) point is greater than or equal to (1) epoxy resin ri = epoxy resin, refers to A compound having one or more bad dairy groups in the molecule. The liquid crystal density of the present invention =: = includes: double A, double W double: two: the representative of the Fangxiang two S alcohols and their ethylene glycol, propylene glycol, burning? Aromatic polyglycidyl glycerol obtained by reaction of diol-modified diol with epoxide (4) cWorohydrin (12) 12 200815880 酴 and A's obtained by phthalic acid resin, polyene 2 522 The compound of poly lysate reacts with epoxidized gas to obtain ===~ compound; the shrinking resin of dimethyl ester grease is:=;=_: package type ring 氡

一一衣虱树脂、雙酚A型環氧樹脂、譬酿F 型壤氧樹脂、二笨齡曱燒型環氧樹脂、严 Ο Ο 樹脂、三雜型環氧樹脂、二環戊贿氧樹脂的丙稀酸類橡膠改性環氧樹脂。处衣乳使用，或者將多 1:::中’可以將上述環氧樹脂單獨 =法測定的軟 1000〜10000範圍内。^槎^仪、/、重置平均分子量是在性和擴散性低。封劑製造的液晶顯示面板顯示:種=乳樹脂的液晶密均分T量可以藉由例城膠滲透的重量平烯為標準進行測定。並且，曰/( )、以聚苯乙分子蒸舰等進料純度化、，優選使用利用 t相對於_重量份液氧樹月旨。選為5〜5G重量份，更優選為10〜的添加量優密封劑_性良好。但是，重讀。這樣的液晶則使液晶密封_化後，固化物:;苡重=方 13 200815880 面’若上述添加量超過50重量份，則液晶密封劑的耐熱性有時會降低。 [熱潛在性硬化劑] 所謂的熱潛在性硬化劑，是指維持通常的液晶密封劑在固化溫度下的反應速度不變，即使被混合到環氧樹脂 . 中，也可以使在室溫附近的低溫範圍内反應速度極低，同時藉由光或熱而呈現出與環氧基的反應活性的固化劑。含有上述熱潛在性硬化劑的液晶密封劑，其在塗佈、保存時 (: 的反應性低，因此黏度穩定性變高。在本發明的液晶密封劑中，併用熔點不同的兩種熱潛在性硬化劑，g卩(2)熔點小於等於15〇。〇的第一熱潛在性硬化背彳及(3)炫點大於等於的第二熱潛在性硬化劑。已知通#若液晶密封劑中包括熱潛在性硬化劑，則塗佈、保存％液晶密封劑的黏度穩定性變高。果然，像本發明這樣，，，熔點的第一熱潛在性硬化劑和在室溫附近反應性低的厂烙點的第二熱潛在性硬化劑併用時，在室溫附近的反應 G 生被抑制得更低，因此黏度穩定性變得極高。 . 美熱潛在性硬化劑，其藉由與環氧基反應或者促進環氧、、之間的來合，從而使環氧樹脂固化。但是，並不是所有潛在性硬化劑都與環氧基反應，還有一部分分散殘留化添、勿中。因此’在包括殘留於固化物中的熱潛在性硬水L勺區域中，若構成該區域的熱潛在性硬化劑是容易吸的物貝，則固化物本身也變得容易吸水，耐濕性有時會 14 200815880 相對於此，本發明的液晶密封劑，若將其在以通常的液晶滴注方式使用的固化溫度（120〜15(rc附近）下加熱，則低熔點的熱潛在性硬化劑參與反應，而高熔性硬化誠存在固化物巾，齡散於母财。上述高= 的熱潛在性硬化劑具有剛直的分子骨架，結晶性高。因此，在使本發明的液晶密封劑固化而得到的固化物中，分散、殘留有由高熔點的熱潛在性硬化劑構成的高疏水性區域， Ο u 所以固化物的耐濕性變得極高。另夕<卜，本發明的液晶密封劑製成一液型是有用的，同日了保，缺性南。所謂的—液型液晶密封劑，是指將環氧 f脂^要齡和熱潛在性硬化齡祕促進成分在使用 Γ頁ί 勻混合而成的液晶密封劑。所謂的保存穩定性卩使在至/皿附近保存液晶密封劑，也幾乎不進行 ==升t體=為將液晶密封劑在25t下保存5天時二广率小寺於保存前液晶密封劑的黏度的2倍。二)=小於等於15Gt的熱潛在性硬化劑等於tstir，料第—_在性硬化_「賴小於Yiyi resin, bisphenol A epoxy resin, brewing F type earth oxide resin, second aging epoxy resin, Yanqi 树脂 resin, tri-type epoxy resin, dicyclopentyl ethoxy resin Acrylic rubber modified epoxy resin. At the place where the latex is used, or will be more 1::: medium can be determined by the above epoxy resin alone = method of softness 1000~10000. ^槎^, /, reset average molecular weight is low in nature and diffusivity. The liquid crystal display panel manufactured by the sealant shows that the liquid crystal density of the seed=milk resin can be measured by the weight of the gelatin permeated by the gelatin. Further, 曰/( ) is purified by a feed such as a polyphenylene molecule vaporizer, and it is preferable to use t for a liquid oxygen tree. The amount of the sealant is preferably 5 to 5 parts by weight, more preferably 10% by weight. However, reread. In the case of such a liquid crystal, the liquid crystal is sealed and cured, and the cured product: 苡 weight = square 13 200815880 surface </ RTI> When the amount added is more than 50 parts by weight, the heat resistance of the liquid crystal sealing agent may be lowered. [Thermal latent curing agent] The so-called thermal latent curing agent means that the reaction rate of the usual liquid crystal sealing agent at the curing temperature is maintained, and even if it is mixed into the epoxy resin, it can be made near room temperature. In the low temperature range, the reaction rate is extremely low, and at the same time, a curing agent which reacts with an epoxy group by light or heat is exhibited. The liquid crystal sealing agent containing the above-mentioned thermal latent curing agent has high reactivity at the time of coating and storage (the reactivity is high, and in the liquid crystal sealing agent of the present invention, two kinds of heat potentials having different melting points are used in combination. Hardening agent, g卩(2) melting point is less than or equal to 15〇. The first thermal latent hardening backing of bismuth and (3) the second thermal latent hardening agent of greater than or equal to the bright point. Including a thermal latent hardener, the viscosity stability of the coating and preserving % liquid crystal sealing agent becomes high. Sure enough, like the present invention, the melting point of the first thermal latent curing agent and the low reactivity near room temperature When the second thermal latent hardener of the factory is used in combination, the reaction G is suppressed lower at room temperature, so the viscosity stability becomes extremely high. The heat latent hardener is used by The epoxy group reacts or promotes the bonding between the epoxy and the epoxy resin to cure the epoxy resin. However, not all of the latent curing agents react with the epoxy group, and some of the dispersion remains and is not added. Therefore 'including residues in the cured product In the hot potential hard water L spoon region, if the thermal latent curing agent constituting the region is a material that is easily absorbed, the cured product itself is easily absorbed, and the moisture resistance may be 14 200815880. When the liquid crystal sealing agent of the invention is heated at a curing temperature (about 120 to 15 (near rc)) which is used in a usual liquid crystal dropping method, a low-melting thermal latent curing agent participates in the reaction, and the high-melting hardening is performed. There is a cured material towel which is dispersed in the mother's money. The high latent heat-hardening agent has a rigid molecular skeleton and has high crystallinity. Therefore, in the cured product obtained by curing the liquid crystal sealing agent of the present invention, it is dispersed. A highly hydrophobic region composed of a high-melting point heat-hardening agent remains, so that the moisture resistance of the cured product becomes extremely high. Further, the liquid crystal sealing agent of the present invention is made into a one-liquid type. Useful, the same day, the lack of sex. The so-called liquid-liquid sealing agent refers to the liquid crystal obtained by mixing the epoxy resin and the thermal latent curing agent. Sealant. So-called preservation The stability of the liquid crystal sealant is kept in the vicinity of the / dish, and it is hardly carried out == l t body = the liquid crystal sealant is stored at 25t for 5 days, the viscosity of the liquid crystal sealant before the preservation of the 2nd wide temple Double) = 2 = less than or equal to 15Gt of thermal latent hardener equal to tstir, material first - _ in sexual hardening _ "Less is less

潛在性硬化劑」，是指熔點小於等於赋亚具有潛在熱固化性的化合物。今 L 潛在性硬化劑可:以;脲::熱潛在性硬化劑。上述熱熱潛在性；5f介制AA h 或者將多種組合使用。此種 I則定。 d 、★點可以利用公知的熔點測定裝置進行 200815880 上述1一 I耕'糸熱潛在性硬化劑，是指1分子内具有2 個酉&耕基並具有潛在性熱固化性的化合物。上述熱潛在性硬化劑的優選例子包括：有機酸二肼。上述有機酸二醯肼是指1分子内具有2個醯肼基的有機酸。優選用作本發明的(2)成分的有機酸二醯肼的例子包括：1,3-雙(肼基羰乙基)-5_異丙基乙内醯脲(熔點12〇。〇 ; valine 二醯肼(熔點 123〜125°C)。 • 市售的熔點小於等於150°C的有機酸二醯肼的例子包 C) 括：valine 二醯肼，即 AMICURE VDH(味之素 FINETECHNO(股）製，熔點 120。〇 ; 7，11-辛二烯-1,18-二碳醯肼，即AMICURE UDH(味之素FINETECHNO(股)製，熔點150°〇。上述咪唾系熱潛在性硬化劑，是指⑴向咪嗤中引入取代基等而得到的咪嗤衍生物或(ii)使咪嗤和能夠與該咪唑形成鹽的化合物反應而得到的π米吐改性物。上述(i)成分的例子包括：2-苯基咪唑，即CUREZOL Q 2PZ(四國化成(股）製，熔點137〜147T：) ; 2-甲基咪唑，即 • CUREZOL 2MZ_P(四國化成工業（股）製，熔點137〜 147°C) ; 1-氰乙基-2-苯基咪唑(四國化成工業（股)製，熔點 105〜lll°c)。上述咪唑衍生物可以以市售品而容易獲取。作為上述(ii)成分的化合物的例子包括：引入了喃嗤的樹脂。此種味唾改性物的例子包括：C11Z-CNS(四國化成工業（股)製，熔點143〜149Ό); 2PZ-OK(四國化成工業(股) 製，熔點 135°C) ; ADECAHARDNER EH4346S(熔點 16 200815880 125°C) ; ADECAHARDNER EH4347S(熔點 1〇5。〇 ; ADECAHARDNER EH4356S(熔點 110。〇(以上， ADEKA(股)製）。上述化合物可以以市售品而容易獲取。上述胺加成物系熱潛在性硬化劑，是指使具有潛在熱固化性並具有催化活性的胺系化合物和任意的化合物反應而得到的加成化合物。上述胺加成物系熱潛在性硬化劑藉 • 由熱使胺解離而活化。上述胺系化合物的例子包括：具有 • 第一級胺基、第二級胺基、第三級胺基的化合物。 Ο 優選用作本發明的（2)成分的胺加成物系熱潛在性硬化劑的例子包括：AMICURE PN-40(熔點11〇。〇和 AMICURE PN-23(熔點 100。〇 ; AMICURE PN-31(炼點"Positive hardener" means a compound having a melting point of less than or equal to that of a sub-thermally curable. Today L latent hardeners can be: urea;: thermal latent hardener. The above thermal potential; 5f mediates AA h or uses multiple combinations. This kind of I is fixed. The d and ★ points can be carried out by a known melting point measuring device. 200815880 The above-mentioned 1st I ploughing potential hardening agent refers to a compound having two 酉 & cultivating bases in one molecule and having latent thermosetting property. Preferable examples of the above thermal latent hardener include: an organic acid diterpene. The above organic acid dioxime means an organic acid having two mercapto groups in one molecule. Examples of the organic acid dihydrazine which is preferably used as the component (2) of the present invention include: 1,3-bis(decylcarbonylethyl)-5-isopropylethyl carbazide (melting point 12 〇. 〇; valine Dioxane (melting point 123~125°C). • Commercially available examples of organic acid diterpenes with a melting point of 150 ° C or less include C): valine dioxins, ie AMICURE VDH (Ajinomoto FINETECHNO) ), melting point 120. 〇; 7,11-octadiene-1,18-dicarbenium, ie AMICURE UDH (Ajinomoto FINETECHNO (shares), melting point 150 ° 〇. The sclerosing agent refers to (1) a hydrazine derivative obtained by introducing a substituent or the like into a quinone or (ii) a π-mute modified product obtained by reacting a quinone with a compound capable of forming a salt with the imidazole. Examples of the components of i) include: 2-phenylimidazole, that is, CUREZOL Q 2PZ (manufactured by Shikoku Chemical Co., Ltd., melting point: 137 to 147 T:); 2-methylimidazole, ie • CUREZOL 2MZ_P (Four countries chemical industry) ), melting point 137~ 147 ° C); 1-cyanoethyl-2-phenylimidazole (manufactured by Shikoku Chemical Industries, Ltd., melting point 105~lll °c). The above imidazole derivatives can be commercially available. Easy to obtain Examples of the compound of the above (ii) include: a resin to which a ruthenium has been introduced. Examples of such a taste modification include: C11Z-CNS (manufactured by Shikoku Kasei Kogyo Co., Ltd., melting point: 143 to 149 Å); 2PZ-OK (Four countries chemical industry (stock) system, melting point 135 ° C); ADECAHARDNER EH4346S (melting point 16 200815880 125 ° C); ADECAHARDNER EH4347S (melting point 1 〇 5. 〇; ADECAHARDNER EH4356S (melting point 110. 〇 (above, ADEKA (manufactured by ADEKA Co., Ltd.) The above compound can be easily obtained as a commercial product. The above amine addition product is a thermal latent curing agent, which means reacting an amine compound having a latent thermosetting property and catalytic activity with an arbitrary compound. And the obtained addition compound. The above amine addition product is a thermal latent curing agent which is activated by dissociation of the amine by heat. Examples of the above amine-based compound include: a first-order amine group, a second-stage amine group, A third-stage amine-based compound. An example of an amine-additive thermal latent hardener which is preferably used as the component (2) of the present invention includes: AMICURE PN-40 (melting point 11 〇. 〇 and AMICURE PN-23 ( Melting point 100. 〇; AMICURE PN-3 1 (refining point

115QC) ; AMICURE PN-H(熔點 115°C) ; AMICURE MY_24(熔點 120°C); AMICUREMY_H(熔點 130。〇(以上，味之素FINETECHNO(股)製）。上述聚胺系熱潛在性硬化劑，是指具有作為胺和環氧的反應物的聚合物結構，並顯示出具有催化活性的胺與任 G 意化合物形成穩定結構的潛在熱固化性的化合物。優選用 . 作本發明的（2)成分的聚胺系熱潛在性硬化劑的例子包括：ADECAHARDNER EH4357S(ADEKA(股)製，溶點 ^ • 〜83。〇。 ” 上述聚胺基脲系熱潛在性硬化劑是指使胺、纟尿#n 酉欠酉曰化合物反應而付到的具有服鍵的化合物。優選用作本發明的（2)成分的聚胺基脲系熱潛在性硬化劑的例子包括：fujicurefxe-iooo(富士化成工業(股)製，熔點12〇=) 17 200815880 1' 和FUJICURE FXE-1030(富士化成工業（股）製，熔點 140。〇、OMICURE 94(ICI JAPAN(股）製，熔點⑺二 129。〇。本發明中使用的（2)成分，特別優選為熔點大於等於 l〇〇°C。上述熱潛在性硬化劑，熱固化性非常良好，從而使液晶欲封劑的固化速度得以提高。若上述熔點溫度小於 100°c，則擔心在低溫範圍的反應性會變得高至必需程度以 ' 上，且黏度穩定性會變得極高。又 (Λ (3)熔點大於等於180°C的熱潛在性硬化劑在本發明中，用作第二熱潛在性硬化劑的「熔點大於專於180 C的熱潛在性硬化劑」，是指溶點大於等於並具有潛在熱固化性的化合物。上述第二熱潛在性硬化劑的優選例子包括：二酿耕系、味。坐系和二醯胺系熱潛在性硬化劑。使用了上述熱潛在性硬化劑的液晶密封劑，其在至溫下的黏度穩定性變得非常良好，因此可以在保持可使用時間長度的同時製造液晶顯示面板。上述熱潛在性硬化 ◎ 劑可以早獨使用，或者將多種組合使用。 • 其中，作為(3)成分優選二醯肼系熱潛在性硬化劑。上述二醯肼系熱潛在性硬化劑的例子包括；間苯二甲酸二醯肼(IDH，日本 nNECHEM(股)製，熔點 220。〇、1，3,5-三(2-肼基羰乙基)-異氰尿酸酯(HCIC，曰本FINECHEM(股)製，熔點197°〇。二醯肼系熱潛在性硬化劑中，作為(3)成分，優選有機酸—酿骄，優選下述通式(A)所示的化合物。本發明的有機 18 200815880 酸肼化的具有碳數大酸二醯肼是指將脂肪族二羧酸進行了於專於8的亞烧基的化合物。其中’脂肪族二竣酸的例子包括己二酸二酸拼(繩，日本FINECHEM(股)製，溶點18rc，相對於坑的水⑽AQURE PN-H (melting point 115 ° C); AMICURE MY_24 (melting point 120 ° C); AMICUREMY_H (melting point 130. 〇 (above, Ajinomoto FINETECHNO). The above polyamine thermal latent curing Agent, which refers to a polymer structure having a reactant as an amine and an epoxy, and exhibits a latent thermosetting compound in which a catalytically active amine forms a stable structure with a compound of any of G. It is preferably used as the present invention ( 2) Examples of the polyamine-based thermal latent curing agent of the composition include: ADECAHARDNER EH4357S (made by ADEKA Co., Ltd., melting point ^ • 83. 〇.) The above-mentioned polyaminourea-based thermal latent curing agent means an amine,纟 # #n 具有具有酉曰酉曰酉曰酉曰酉曰酉曰。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 fu fu fu Chemical industry (stock) system, melting point 12〇 =) 17 200815880 1' and FUJICURE FXE-1030 (Fuji Chemical Industry Co., Ltd., melting point 140. 〇, OMICURE 94 (ICI JAPAN (share) system, melting point (7) two 129. The component (2) used in the present invention is particularly preferably The point is greater than or equal to 10 ° C. The above thermal latent curing agent has very good thermal curability, so that the curing speed of the liquid crystal sealing agent is improved. If the melting point temperature is less than 100 ° C, the reaction in the low temperature range is feared. Sex will become high to the extent necessary, and the viscosity stability will become extremely high. (Λ (3) A thermal latent hardener having a melting point of 180 ° C or higher is used as the second heat in the present invention. The "melting potential of the latent hardener is greater than the thermal latent agent specific to 180 C." refers to a compound having a melting point greater than or equal to and having a latent thermosetting property. Preferred examples of the second thermal latent curing agent include: Tillage, taste, ketone and diamine thermal latent curing agent. Liquid crystal sealing agent using the above thermal latent curing agent, its viscosity stability to temperature is very good, so it can be maintained The liquid crystal display panel is manufactured at the same time as the length of time. The above-mentioned thermal latent curing agent may be used alone or in combination of a plurality of kinds. Among them, a diterpene thermal latent curing agent is preferable as the component (3). Examples of the above-mentioned diterpene thermal latent hardener include: diterpene isophthalate (IDH, manufactured by NNECHEM, Japan, melting point 220. 〇, 1,3,5-tris(2-mercaptocarbonyl) Base)-isocyanurate (HCIC, manufactured by F本FINECHEM Co., Ltd., melting point 197°〇. Among the diterpenoid thermal latent curing agents, as the component (3), organic acid is preferred. The compound represented by the formula (A). Organic 18 200815880 of the present invention The acid-dimerized diterpene having a carbon number is a compound in which an aliphatic dicarboxylic acid is subjected to a sub-alkyl group specific for 8. Examples of 'aliphatic dicaptanic acid include adipic acid diacid paste (rope, Japanese FINECHEM (share) system, melting point 18rc, water relative to the pit (10)

mi的溶解度為10 g)。使用了通式(A)所示的有機酸二酉篮耕的液晶密封劑，其耐水性良好。因此，上述液晶密封劑的 ^匕物，由於耐水性高，當用於液晶顯示面板時，即使在高濕下固化的液晶密封劑和基板的黏合強度也高，顯示出優異的耐濕可靠性的液晶顯示面板。【化2】The solubility of mi is 10 g). The liquid crystal sealing agent of the organic acid diterpene of the formula (A) was used, and the water resistance was good. Therefore, the liquid crystal sealing agent has high water resistance, and when used in a liquid crystal display panel, the liquid crystal sealing agent and the substrate which are cured under high humidity have high bonding strength, and exhibit excellent moisture resistance reliability. LCD panel. [Chemical 2]

• (A) 〇上述通式(A)中，R表示碳數大於等於8的亞烷基。 . 優選用作本發明的（3)成分的有機酸二醯肼的例子包 • 括：癸二酸二酿肼(SDH，日本fineCHEM(股）製，熔點 190 C，相對於25 C的水10Q mi為不溶）、十二垸二酸二醯• (A) 〇 In the above formula (A), R represents an alkylene group having a carbon number of 8 or more. An example of an organic acid diterpene which is preferably used as the component (3) of the present invention includes: azelaic acid di-n-doped (SDH, manufactured by Japan fineCHEM Co., Ltd., melting point 190 C, 10 Q relative to 25 C water) Mi is insoluble), dioxadiamine dioxime

肼(N-12,日本nNECHEM(股)製，熔點189°C，相對於25°C 的水100 ml為不溶）。上述味哇糸熱潛在性硬化劑與上述(2)成分中說明的定義相同，是指⑴向咪唑中引入了取代基等的咪唑衍生物 19 200815880 或(Η)使咪嗅和能夠與樹脂或咪π坐形成鹽的化合物反應而得到的咪唑改性物。其中，藉由增加分子量和強化構成樹脂骨架的分子的結合等而使熔點大於等於l8〇t的咪唑系化合物相當於(3)成分。上述咪唑系熱潛在性硬化劑中，上述(3)成分優選為作為⑴成分的咪唑衍生物。上述咪唾衍生物的例子包括：2,4-二胺基-6-[2’-乙基-4’·》曱基味唾_(ι’)]_乙基_s_三嗪。上述化合物可以以CUREZOL 2E4MZ-A(四國化成工業（股）製，熔 Ο 點215〜225°C)等市售品而獲取。本發明的二醯胺系熱潛在性硬化劑是指1分子内具有 2個醯胺基並具有潛在熱固化性的化合物。優選用作本發明的(3)成分的二醯胺系熱潛在性硬化劑的例子包括：雙氰胺(熔點209°C等）。其具體包括：AH_154(熔點2〇〇。〇、 AH-162(熔點200。〇(以上，味之素fiNETECHN〇(股)製），上述二醯胺系熱潛在性硬化劑可以以市售品而容易獲取。優送用作上述(3)成分的化合物可以單獨使用，或者將 Ο 夕種組合使用。除了上述P)成分以外，還可以使用對經基 •苯曱酸醯肼(PHBH，日本FINECHEM(股)製，熔點264。〇等醯肼類。並且，用作(3)成分的熱潛在性硬化劑，優選藉由水洗法、重結晶法等進行高純度化。另外，(3)成分優選為相對於25。〇的水1〇〇 -的溶解度小於等於2G g。特別優選為上述溶解度小於等於5 g。使用了上述(3)成分的液晶密封劑，其耐濕性變得良好，所以結果是液晶顯示面板的耐濕可靠性提高。其中，⑶成分 20 200815880肼 (N-12, manufactured by NNECHEM Co., Ltd., melting point 189 ° C, insoluble in 100 ml of water at 25 ° C). The above-mentioned taste-hardening agent is the same as defined in the above (2) component, and means (1) an imidazole derivative in which a substituent or the like is introduced into an imidazole, and the like. An imidazole modified product obtained by reacting a compound of a salt with a salt. Among them, an imidazole-based compound having a melting point of 18 〇t or more is equivalent to the component (3) by increasing the molecular weight and strengthening the bonding of molecules constituting the resin skeleton. In the above imidazole-based thermal latent curing agent, the component (3) is preferably an imidazole derivative as the component (1). Examples of the above-mentioned imino-salt derivatives include: 2,4-diamino-6-[2'-ethyl-4'." sulfhydryl-salt-(ι')]-ethyl-s-triazine. The above compound can be obtained by a commercial product such as CUREZOL 2E4MZ-A (manufactured by Shikoku Chemicals Co., Ltd., melting point: 215 to 225 ° C). The diamine-based thermal latent curing agent of the present invention refers to a compound having two guanamine groups in one molecule and having latent thermosetting properties. Examples of the diamine-based thermal latent curing agent which is preferably used as the component (3) of the present invention include dicyandiamide (melting point: 209 ° C, etc.). Specifically, it includes: AH_154 (melting point 2 〇〇. 〇, AH-162 (melting point 200. 〇 (above, Ajinomoto fiNETECHN 〇 (manufactured by the company)), the above diamine-based thermal latent curing agent can be commercially available It is easy to obtain. The compound which is used as the above component (3) can be used singly or in combination with the genus. In addition to the above P), hydrazine benzoate (PHBH, Japan) can also be used. FINECHEM (manufactured by FINECHEM), melting point 264, hydrazine, etc., and the thermal latent curing agent used as the component (3) is preferably purified by a water washing method, a recrystallization method, or the like. The component preferably has a solubility of 2 g g or less with respect to 25 〇. The solubility is preferably 5 g or less. The liquid crystal sealing agent using the component (3) has good moisture resistance. Therefore, the result is improved moisture resistance reliability of the liquid crystal display panel. Among them, (3) component 20 200815880

U 至=解度越接近於0 g，製備的液晶密封劑的賴性越得 =南。但是，若⑶成分的溶解度超過20 g，則液晶密封 1耐濕性劣化、降低，因此當將上述液晶密封劑用曰曰顯示面板時’液晶齡面板的耐濕可靠性有時會降低。 _為了提高液晶密封劑的耐濕性和固化速度，更優 ^酿肼系熱潛在性硬化劑併用作為⑺成分和(3)成分。迄今為止’作為液晶密封·賴潛在性硬化劑，已知有單^ =熱潛在性硬化劑。上述具有u_職作為官能團白: =肼系熱潛在性硬化劑，與二_系等多官能型熱潛在，硬化劑相比熔點低，且與其他樹脂的相溶性高，因此潛，固化性請。但是另-方面，錢了上賴潛在性硬化 =液晶密封_固化物，存在著交聯密度和_性低的但是，二醯肼系熱潛在性硬化劑具有2個醯肼基作 t官能基，所以其除了潛在固化性高以外，反應性也良好。因，，當將上述熱潛在性硬化劑用於液晶密封劑時，可得到又聯密度高，並且機械強度和耐水性也良好的固化物。旦在100重量份液晶密封劑中，（2)成分和(3)成分的總添和=優選為1〜25重量份，更優選為3〜2〇重量份。上述液曰曰费封劑耐濕性和黏度穩定性良好，因此可使用時間長曰另外’由於上述液晶密封劑耐濕性良好，當將其用於，晶顯示面板時，固化的液晶密封劑和基板的黏合強度回，可得到顯示性優異的液晶顯示面板。另一方面，若上泰加量超過25重量份，則黏度穩定性惡化；若上述總添加量小於1重量份，則有時固化不充分。 21 200815880 Ο υ 當將(2)成分的添加重量作為wi、將(3)成分的添加重量作為W2時，優選為0.2$W2/(W1+W2)‘0.8。更優選為 0.4$W2/(W1+W2)‘0.6。此時，當在液晶密封劑的製備中使用多種化合物作為(2)成分和(3)成分時，將各成分中所使用的化合物的總量視為Wl、W2。這種液晶密封劑黏度穩定性良好，所以可使用時間變長，當將這種液晶密封劑用於液晶顯示面板時，固化的液晶密封劑和基板的黏合強度高，可以得到顯示性和耐濕可靠性優異的液晶顯示面板。 s本發明的液晶密封劑，優選蝴於⑴成分的環氧當 I ’上述(2)成分和⑶成分的活性氫當量總計為〇 3〜3 〇。 ==技指_與(2)成分和(3)成分的環氧基反應的 —g H活性氫當量可以利用NMR等進行測定，也可以由具有該羥基的材料的投料量算出。 >適當地調整了上述活性氫當量的液晶密，氧樹脂和固化劑的反應性高。因桔 θ /、 < 則在短時_且充分蘭行固1此右·^晶賴劑固化，留。其中，若上述活性氫當量超過口/匕未固化部分不易殘封劑中殘留有大量的(2)成分，所 ^則固化的液晶密另-方面，若活性氫當量小於口，物㈣水性降低。順利，未固化部分殘留，無_ 2時固化進行得不如上所述，本發明中所于^刀的機械強度。點不同，但是均為具有胺基的胺在性硬化劑儘管熔了上述胺系熱潛在性硬化劑的液晶;；=性硬化劑。使用黏度穩定性極其良好，因此 =圳，其在室溫下的 W日守間長，可以優選用作 22 200815880 i 一液型液晶密封劑。其中，所謂的一液型液晶密封劑，是指預先將熱潛在性硬化劑等固化劑和環氧樹脂等作為被固化成分的主劑均勻混合，且保存時穩定性(保存穩定性）良好的液晶密封劑。U to = the closer the resolution is to 0 g, the more the liquid crystal sealant prepared is = south. However, when the solubility of the component (3) exceeds 20 g, the moisture resistance of the liquid crystal sealing material 1 is deteriorated and lowered. Therefore, when the liquid crystal sealing agent is used as a display panel, the moisture resistance reliability of the liquid crystal age panel may be lowered. _ In order to improve the moisture resistance and curing speed of the liquid crystal sealing agent, it is preferable to use a thermal latent curing agent as the (7) component and the (3) component. Heretofore, as a liquid crystal sealing and a latent curing agent, a single thermal latent curing agent has been known. The above has the u_ position as a functional group white: = lanthanide thermal latent curing agent, and polyfunctional heat potential such as bismuth system, the melting point is lower than the curing agent, and the compatibility with other resins is high, so the latent, curable property please. But on the other hand, the money is dependent on the latent hardening = liquid crystal sealing _ cured product, there is a low crosslink density and _ low, but the diterpene thermal latent curing agent has two thiol groups as t functional groups. Therefore, in addition to the high potential curability, the reactivity is also good. Therefore, when the above-mentioned thermal latent curing agent is used for the liquid crystal sealing agent, a cured product having a high bonding density and good mechanical strength and water resistance can be obtained. In 100 parts by weight of the liquid crystal sealing agent, the total addition of the components (2) and (3) is preferably 1 to 25 parts by weight, more preferably 3 to 2 parts by weight. The liquid helium sealant has good moisture resistance and viscosity stability, and therefore can be used for a long time. In addition, since the liquid crystal sealant has good moisture resistance, when used for a crystal display panel, the cured liquid crystal sealant When the adhesion strength to the substrate is returned, a liquid crystal display panel excellent in display property can be obtained. On the other hand, when the amount of the added amount exceeds 25 parts by weight, the viscosity stability is deteriorated; and when the total amount added is less than 1 part by weight, the curing may be insufficient. 21 200815880 Ο υ When the added weight of the component (2) is wi and the added weight of the component (3) is W2, it is preferably 0.2$W2/(W1+W2)'0.8. More preferably, it is 0.4$W2/(W1+W2)'0.6. At this time, when a plurality of compounds are used as the components (2) and (3) in the preparation of the liquid crystal sealing agent, the total amount of the compounds used in the respective components is regarded as W1 and W2. The liquid crystal sealing agent has good viscosity stability, so that the usable time is long. When the liquid crystal sealing agent is used for a liquid crystal display panel, the cured liquid crystal sealing agent and the substrate have high bonding strength, and displayability and moisture resistance can be obtained. A liquid crystal display panel with excellent reliability. s The liquid crystal sealing agent of the present invention preferably has an active hydrogen equivalent of 上述 3 to 3 〇 in the epoxy of the component (1), and the active hydrogen equivalents of the components (2) and (3). == Technical index The -g H active hydrogen equivalent which reacts with the epoxy group of the component (2) and the component (3) can be measured by NMR or the like, or can be calculated from the amount of the material having the hydroxyl group. > The liquid crystal density of the above active hydrogen equivalent is appropriately adjusted, and the reactivity of the oxygen resin and the curing agent is high. Because orange θ /, < then in a short time _ and full blue line solid 1 this right ^ ^ crystallizer solidified, stay. Wherein, if the active hydrogen equivalent exceeds a large amount of the (2) component remaining in the uncured portion of the mouth/匕 uncured portion, the cured liquid crystal is densely sealed, and if the active hydrogen equivalent is less than the mouth, the water content of the substance (4) is lowered. . Smooth, the uncured portion remains, and the curing does not proceed when _ 2 is not as described above, and the mechanical strength of the knives in the present invention. The points are different, but all of the amine-based amine-based hardeners melt the liquid crystal of the above-mentioned amine-based thermal latent curing agent; The viscosity stability is extremely good, so it is preferably used as a liquid crystal sealant for 22 200815880 i. In the above-mentioned one-liquid type liquid crystal sealing agent, a curing agent such as a thermal latent curing agent and an epoxy resin are uniformly mixed as a main component of a curing component, and stability (storage stability) during storage is good. Liquid crystal sealant.

u 另外，胺系熱潛在性硬化劑在加熱時，其中所具有的活性氫相對於下述(6)成分和（7)成分中的（甲基）丙烯酸酯基顯示出高親核加成性。由此，使用了胺系熱潛在性硬化劑的液晶密封劑，其熱固化性變高，故加熱時的固化速度極快。當在液晶顯示面板的製造中使用上述液晶密封劑時，即使在存在遮光區域的情況下，固化的進行也不會過度不足’其結果是得到顯示性良好的液晶顯示面板，同時縮短了固化時間，故生產率良好。本發明的液晶密封劑可以進一步包括：（4)填充劑 (filler)、（5)其他添加劑。包括⑴〜(5)成分的液晶密封劑優選用作熱固化性液晶密封劑。 (4)填充劑本么明的填充劑’是指藉由控制液晶密封劑的黏度和提高使液晶密封劑固化而得到的固化物的強度或者抑制線雜性來❹j提高液晶㈣觸齡可靠性等目的本發明中可以優選使用的填充劑可以使用公知的物吳’>又有特別限定。填充劑的例子包括：碳賴、碳酸鎮、石爪酉义鋇、硫酸鎂、㈣銘、⑨酸錯、氧化鐵、氧化欽化銘(恭土）、氧化鋅、二氧化石夕、欽酸斜、高嶺土、滑石 23 200815880 粉、石棉粉、石英 + 母、活性白土，潤土:氮：璃:：、破璃珠粒、絹雲作為本發明的埴㈣1乳化石夕等無機填充劑。可以在不指、W，* 了上述無機填充劑以外，還酸甲騎、=::触咖内，使用聚，基丙稀行共聚所得到的丑成合物的單體和其他單體進粒等g知的有機填ί劑。、福微粒、聚氨醋微粒、橡膠微Further, the amine-based thermal latent curing agent exhibits high nucleophilic addition to the (meth) acrylate group in the following components (6) and (7) when heated. . Thus, a liquid crystal sealing agent using an amine-based thermal latent curing agent has high heat curability, so that the curing speed at the time of heating is extremely fast. When the liquid crystal sealing agent is used in the production of a liquid crystal display panel, even in the case where a light-shielding region is present, the progress of curing is not excessively insufficient. As a result, a liquid crystal display panel having good display properties is obtained, and the curing time is shortened. Therefore, the productivity is good. The liquid crystal sealing agent of the present invention may further comprise: (4) a filler, and (5) other additives. The liquid crystal sealing agent comprising the components (1) to (5) is preferably used as a thermosetting liquid crystal sealing agent. (4) Filler The filler of the present invention means improving the liquid crystal (IV) contact age reliability by controlling the viscosity of the liquid crystal sealing agent and improving the strength of the cured product obtained by curing the liquid crystal sealing agent or suppressing the line impurity. The filler which can be preferably used in the present invention can be preferably used by using a known material. Examples of the filler include: carbon lanthanum, carbonic acid town, stone claw 酉钡, magnesium sulfate, (four) Ming, 9 acid wrong, iron oxide, oxidized Qin Huaming (Kongzan), zinc oxide, sulphur dioxide, sulphuric acid Oblique, kaolin, talc 23 200815880 Powder, asbestos powder, quartz + mother, activated clay, soil: nitrogen: glass::, glass beads, and yunyun as the inorganic filler of the 埴(4)1 emulsified stone eve of the present invention. In addition to the above-mentioned inorganic fillers, it is also possible to use granules and other monomers obtained by copolymerization of poly(acrylic) propylene in addition to the above-mentioned inorganic fillers. I know the organic filling agent. , fine particles, polyurethane granules, rubber micro

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J 考慮其持性方面性高等方而去、、、枝真充劑中，從UV透過充劑充劑’本發明的液晶密終_ 物質。魏娜_絲合劑等進行了接枝改性的狀等ΐίϋ的形狀沒有特別限定，可以是球狀、板狀、針選為小定形物中的任一種。填充劑的最大粒徑優於4於6 μηι，更優選為小於等於2 μιη。填充 1:::乂利用雷射衍射法進行測定。當在液晶顯Μ板的衣&去中使用包括上述粒徑的填充劑的，形成盒間距_gap)的尺寸穩定性非常良好^曰曰 J& ° 、在100重量份除填充劑之外的液晶密封劑中，填充劑、、加里優選為1〜40重量份，更優選為10〜30重量份的範圍辦填充劑的添加量進行如此調整的液晶密封劑，其在基板上的塗佈性良好。填充劑可以和光固化性樹脂併 24 200815880 用。如此地將填充劑和光固化性樹脂併用的液晶 ί請’並在短時間内固化。並且，t間距的ϊί 大致保持恒定，所以尺寸穩定性變得良好。）見度 (5)其他添加劑 ' 本發明的液晶密封劑中，根據需要可以包括本發明中優選使用的添加劑的例子包括:n =、石夕絲合劑㈣合劑、離子捕獲劑、、、離子起、概平劑、顏料、染料、可塑劑、消泡劑。上述、天Λ t、丨^、 > _可以單獨❹，或者料她合制。為==根據料可以包括在液晶密封劑中，也可以構^材顯示面板的基板上進行使用。印於構成液晶製備熱固化性密封劑時可以包括溶劑’以佈性或網版印刷性。此種溶劑優選相對於作 =I配塗氧樹脂的相容性良好，且沸點在140〜22〇。〇範），的環蝴於環氧基為惰性。上聽_例子包括：^、二而且 ^ 乙酸酯系溶劑。上述溶劑可以單獨使用，或者將、夕4系、 . 使用。一乂百將夕種組合 - 本發明的液晶密封劑除了包括上述成分（1 :L包括：（6)丙單體及/或甲基或它們的低聚物，·⑺i分子内具有至少各H1 文酉曰早體 =氧基和(甲基)丙烯酸酯基的(甲基)丙：亡 ^曰；以及⑻光自由基聚合起始劑。上述液晶氣以用作藉由光或熱進行固化的液晶密封劑^可以 25 200815880 (6)丙稀酸酯單體及/或曱基丙浠酸酯單體或它們的低聚物本發明中所使用的丙烯酸酯單體及/或甲基丙烯酸酉旨單體或它們的低聚物的例子包括以下物質，沒有特別限定。 Ο u 上述物質包括：聚乙二醇、丙二醇、聚丙二醇等的二丙稀酸酯及/或二曱基丙烯酸酯；三(2-羥乙基）異氰尿酸酯的二丙烯酸酯及/或二曱基丙烯酸酯；在1莫耳新戊二醇上加成4莫耳或4莫耳以上的環氧乙烷或環氧丙垸而得到的一元醇的二丙烯酸酯及/或二曱基丙烯酸酯；在1莫耳雙盼 A上加成2莫耳的環氧乙烷或環氧丙烷而得到的二元醇的二丙烯酸酯及/或二曱基丙烯酸酯；在1莫耳三羥甲基丙烷上加成3莫耳或3莫耳以上的環氧乙烷或環氧丙烷而得到的二元醇的二丙烯酸酯或三丙稀酸酯及/或二甲基丙烯酸酯或三甲基丙烯酸酯；在1莫耳雙酚A上加成4莫耳或= 莫耳以上的環氧乙烷或環氧丙烷而得到的二元醇的二^广酸酯及/或二曱基丙烯酸酯；三(2_羥乙基)異氰尿酸酯的：丙烯酸酯及/或二曱基丙烯酸酯；三羥甲基丙燒三丙烯酸酽及/或三曱基丙烯酸S旨或其低聚物；季戊四醇三㊅稀酸^ /或三甲基丙稀酸醋或其低聚物；二季戊四醇的多丙稀二及/或多曱基丙烯酸S旨；三(丙稀li氧乙基)異氰尿酸酉旨广曰内酯改性三（丙烯醯氧乙基)異氰尿酸酯；己内酯改性= 基丙烯醯氧乙基)異氰尿酸酯；烷基改性二季戊四醇:甲烯酸酯及/或多甲基丙烯酸酯；己内酷改性__查子:夕丙内稀酸機多曱基丙細旨;經基三工 26 200815880 酯及/或二甲基丙烯酸酯;已内酯改性羥基三曱基 —丙烯酸酯及7或二甲基丙烯酸_ ;環氧乙烧 ==丙烯_旨及/或二甲基丙烯勸旨；環氧乙烧改性烧 :基丙燒、季戊四醇的低聚丙稀_旨及/或低聚甲基丙稀酸 a曰0 物單體及/或〒基丙烯酸_或它們的低聚 Γ ϋ r I ! ： ^ 乳树月曰、伽A型環氧樹脂、物ρ型環氧樹脂、曱烷型環氧樹脂、三苯盼乙烧型 _ 樹r、n ,,, 轉樹脂、三苯㈣環氧錄娜、聯料縣氣等的所有衣乳基與（甲基）丙稀酸g旨反應 (甲基）丙稀酸s旨化的樹脂。㈣％ & Μ ^王上述丙烯酸醋單體及/或甲基丙婦低聚物可以單獨使用，或者將多餘合早體h們的、當液晶密封劑中包括⑹成分時，相對於成分，(1)環氧樹脂的添加量優選為2〇〜2旦：：用光或熱使上述液晶密封劑固化時， $里伤。虽利溫度(Tg)高的固化物。液晶密封劑的固^坡璃化轉變動態黏彈性測定裝置(DMA)進行測— 的丁§可以利用高純度化的物質。、 9由水洗法等進行了 (7)(曱基）丙烯酸酯改性環氣樹脂本發明的（曱基)丙烯酸g旨氧树月日疋指使環氧樹 200815880 脂和（f基）丙稀酸酯反應而得到的化合物。上述化合物的例子包括··（a)l分子内兼具（甲基）丙烯酸酯基和環i基的化合物；（b)(甲基）丙烯酸酯的聚合物分散在環氣 | 材中得到的化合物。 θ寺母上述(a)l分子内兼具（甲基）丙烯酸酯基和環氧基的化合物的例子包括··例如在鹼性催化劑存在下，使雙酚型产氧樹脂或酉分盤型環氧樹脂等環氧樹脂和（甲基 : η ϋ 基丙烯酸苯岐應而得到_旨。上述改性環氧脂骨架内兼具環氧基和（甲基）丙稀酸酉旨基，因此與液晶才封劑的⑴成分的相容性優異。因此，提供玻 (Tg)高且黏合性高的固化物。和文/皿度作為改性環氧樹脂的補_補㈣例子包括 =1=樹脂、苯嶋型環氧樹脂、雙環 =!環她旨、三苯晴型環氧樹脂、：ί =、兀31%氧树脂、三苯酉分型環氧樹脂、二乳树脂、聯苯型環龛料日匕_ kL 叹歸又館法、洗躲等二::性環氧樹脂優選利用分子蒸材4:=::=聚環氧樹脂等母醋改性的丙稀酸類橡膠改氧:减細咖㈣改性環氧樹脂可以使用公知S3 ^述丙稀酸類橡膠成的樹脂。市α 口口，也可以使用任意合 (8)光自由基聚合起始劑本^月的光自由基聚合起始劑是指藉由光產生自由基 200815880 的化合物。光自由基平括：苯偶姻系化合物起始劑沒有特別限制，其例子包 α-醯基祕類、苯偶^乙_類'二苯甲_貞啼_類、节基類、偶氮系化:類：苯偶_類、笨酸甲酸酿類、膦氧化物系化合物^機、=類、苯硫—化合物、醯基勿：使用作為光聚合起始 : 起始劑可以單獨❹，或者將多齡合^。述“合括上t光自由基聚合起始劑的液晶密封劑，由光固化來達到暫且固 =封士可以猎摔作掣程宏異、隹— 衣1^ /文日日顯示面板時的 = 易進仃。相對於⑽重量份液晶密封劑，⑻ 加量優選為⑽〜5重量份1光自由基聚人起峋的添加量大於等於_ t量份，則藉由光昭射二，短時間内固化。若上述添力賴等於 Ο 塗佈性良好’且藉由光照射可以得到均勻固 [液晶密封劑的製備方法] ^備本發明的液晶密封劑的方法沒有特別限定，可以 =t知的技術。混合液晶密封劑巾各成分的I置沒有特杆二:機其：子包括：雙臂式攪拌機、輥式混煉機、雙螺混混煉機、行星錢拌機，可以制公知的二煉钱械。將利用任一種方法進行了適當混合師提☆如除去^貝然後，進灯真空脫泡處理後， i輪^充到玻璃瓶或聚合物容器中，根據需要進行存儲、 29 200815880 妾下來，對本發明的液晶顯示面板的製造方法進行說明:上述本發明的液晶密封劑可以適用於液晶注入方式和液晶滴庄方式中的任一種方式。以下，依序對與液晶注入方式和液晶滴注方式相關的本發明之液晶顯示面板的製造方法進行說明。 [利用液晶注入方式製造液晶顯示面板的方法] 、明的利用液晶注入方式製造液晶顯示面板的方 r\ Ο 制、iL疋扣將對向的兩塊基板藉由液晶密封劑貼合在一起來夜_顯7^面板，該方法包括··⑴準備基板的製程，上具有按照像素排列區域被本發明之液晶、f /曰Ϊ成的設有液晶注入口的框狀顯示區域；⑺藉由上使兩塊基板重合後’進行加熱壓合，使基板在—起，從而在上述基板之間形成液晶盒的製 Ϊ(4 :用t述注入口向上述液晶盒内注入液晶的製程;以入口封ΗόίΓ用密封劑將上述注人有液晶之液晶盒的注入口封閉的製程。在（1)的製程中，準備於兩塊基板的其中液晶密封劑，並配置有框狀顯示區域的基板。其^上^ 框狀顯不區域中形成有注人液晶的注入口。 =明的液晶顯示面板中使用的兩塊基板的例子包有矩陣狀TFT的玻璃基板或形成有彩色濾光片、 :f+ #的基板。基板材質的例子包括：玻璃或聚碳酸醋、來對本二甲酸乙二醇酯、聚醚砜、PMMA等塑膠。可以在 i基板的表面设置：以氧化銦為代表的透明電極；以聚 30 200815880 醯亞胺等為代表的配向膜；以及其他無機質離子遮蔽膜等。液曰曰雄封劑優遥使用本發明的液晶密封劑。液晶穷、封劑不僅形成顯示區域等的框架，還用作將兩塊基板空出一 ^間隔地進行貼合的黏合劑。當利用液晶注入方式=造液晶顯示面板時，本發明的液晶密封劑中特別優選熱固化性密封劑。 Μ 於基板上塗佈液晶密封劑的方法沒有特別限定。該塗 :布方法，例子包括··網版印刷或利用分配^行塗佈^ 说明的疋，液晶密封劑可以塗佈於雙方基板的表面。主佈了液晶密封劑之後的基板，根據需要對其口化處理。預固化處理是指用於使液晶密封劑暫的 ^燥。顧化處理巾的加熱溫度域理日㈣#沒有^ 但是劑中溶㈣劑中包括溶劑時，優選將液晶密封二的至少95重量百分比(，除去J considers the high-performance side of the holding agent, and the medicinal charge of the present invention. The shape of the Wei Na _ silking agent or the like which has been subjected to graft modification or the like is not particularly limited, and may be any of a spherical shape, a plate shape, and a needle shape. The maximum particle diameter of the filler is preferably 4 to 6 μη, more preferably 2 μηη or less. Fill 1::: 乂 was measured by laser diffraction. When the filler including the above-mentioned particle diameter is used in the coating & removal of the liquid crystal display panel, the dimensional stability of the formation of the cell pitch _gap is very good. ^ J & °, in addition to the filler in 100 parts by weight In the liquid crystal sealing agent, the filler and the garnish are preferably 1 to 40 parts by weight, more preferably 10 to 30 parts by weight, in terms of the amount of the filler to be added, and the liquid crystal sealing agent thus adjusted is coated on the substrate. Good sex. The filler can be used with a photocurable resin. In this manner, the liquid crystal used in combination with the filler and the photocurable resin is cured and cured in a short time. Also, the 间距ί of the t pitch is kept substantially constant, so the dimensional stability becomes good. (5) Other Additives 'In the liquid crystal sealing agent of the present invention, examples of additives which are preferably used in the present invention, as needed, include: n =, shisha mixture (tetra) mixture, ion trapping agent, ion, , leveling agents, pigments, dyes, plasticizers, defoamers. The above, Tianzhu t, 丨^, > _ can be smashed alone, or she is expected to make it. The == material may be included in the liquid crystal sealant or may be used on the substrate of the display panel. The solvent can be included in the composition of the liquid crystal to prepare a thermosetting sealant. Such a solvent is preferably compatible with respect to the oxy-resin as a =I, and has a boiling point of 140 to 22 Torr. The ring is inert to the epoxy group. The above examples include: ^, two and ^ acetate solvent. The above solvent may be used singly or in the form of a sap. The liquid crystal sealing agent of the present invention comprises, in addition to the above components (1: L, including: (6) a propylene monomer and/or a methyl group or an oligomer thereof, (7) i having at least each H1 in the molecule.酉曰酉曰 = = oxy and (meth) acrylate-based (meth) acrylate: 曰曰以及; and (8) photoradical polymerization initiator. The above liquid crystal gas is used for curing by light or heat Liquid crystal sealing agent can be 25 200815880 (6) acrylate monomer and / or mercapto propyl phthalate monomer or their oligomers acrylate monomer and / or methacrylic acid used in the present invention Examples of the monomer or oligomer thereof include the following, and are not particularly limited. Ο u The above substances include diacrylates and/or dimercapto acrylates such as polyethylene glycol, propylene glycol, and polypropylene glycol. Di(2-hydroxyethyl)isocyanurate diacrylate and/or dimercaptoacrylate; addition of 4 moles or more than 4 moles of epoxy B to 1 mole of neopentyl glycol a diacrylate or a dimercapto acrylate of a monohydric alcohol obtained by alkane or epoxidizing propylene; adding 2 moles to 1 mole of double-hop A Diacrylate and/or dimercapto acrylate of diol obtained from ethylene oxide or propylene oxide of the ear; addition of 3 moles or more of 3 moles to 1 mole of trimethylolpropane Diacrylate or triacrylate and/or dimethacrylate or trimethacrylate of diol obtained by ethylene oxide or propylene oxide; addition 4 to 1 mol bisphenol A Diethyl or dimercapto acrylate of diol obtained by mole or = ethylene oxide or propylene oxide; tris(2-hydroxyethyl)isocyanurate Acrylate and / or dimercapto acrylate; trimethylol propyl triacrylate acrylate and / or tridecyl acrylate S or its oligomer; pentaerythritol trisuccinic acid / / trimethyl propylene Sour vinegar or its oligomer; dipentaerythritol polypropylene di- and/or poly-mercapto acrylic acid S; tris(propyl dioxyethyl)isocyanurate 曰曰曰曰改性改性 ( Ethyl)isocyanurate; caprolactone modification = propylene oxyethyl)isocyanurate; alkyl-modified dipentaerythritol: methacrylate and/or polymethacrylate; Cool modification __查子: 丙丙内稀酸机多曱基丙细旨; 经基三工26 200815880 Ester and / or dimethacrylate; lactone modified hydroxytridecyl-acrylate and 7 or dimethyl Acrylic acid _; Ethylene ethoxide == propylene _ and / or dimethyl propylene sensation; Ethylene ethoxide modified calcination: propyl propylene, pentaerythritol oligo propylene and / or oligomethyl propylene Acid a oxime monomer and / or methacrylic acid _ or their oligomeric Γ I r I ! : ^ Milk tree sorghum, gamma A epoxy resin, p-type epoxy resin, decane epoxy Resin, triphenyl acetonitrile type _ tree r, n,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Base) A resin for the purpose of acrylic acid. (4) % & Μ ^ Wang The above acrylic acrylate monomer and / or methyl propyl acrylate oligomer can be used alone, or the excess of the early body, when the liquid crystal sealant includes (6) component, relative to the composition, (1) The amount of the epoxy resin to be added is preferably 2 Å to 2 Å: When the liquid crystal sealing agent is cured by light or heat, it is injured. A cured product having a high temperature (Tg). The liquid crystal sealant is modified by a dynamic viscoelasticity measuring device (DMA) to measure high-purity substances. 9 (7) (fluorenyl) acrylate modified ring gas resin (7) (fluorenyl) acrylate modified ring gas resin (inventive) of the present invention, the purpose of the oxygen tree, the eucalyptus, the epoxy resin 200815880 grease and (f-based) propylene A compound obtained by reacting an acid ester. Examples of the above compound include (a) a compound having both a (meth) acrylate group and a ring i group in the molecule; (b) a polymer obtained by dispersing a polymer of (meth) acrylate in a ring gas material; Compound. Examples of the compound having the (meth) acrylate group and the epoxy group in the above (a) 1 molecule include: bisphenol type oxygen generating resin or bismuth disc type, for example, in the presence of a basic catalyst An epoxy resin such as an epoxy resin or a (methyl: η methacrylic acid benzoquinone) is obtained. The modified epoxy resin skeleton has both an epoxy group and a (meth) acrylate group. It is excellent in compatibility with the component (1) of the liquid crystal sealing agent. Therefore, it provides a cured product having high glass (Tg) and high adhesion, and the text/dishability as a supplementary epoxy resin (4) example includes =1= Resin, benzoquinone epoxy resin, double ring =! ring her, triphenylene type epoxy resin,: ί =, 兀31% oxygen resin, triphenylsulfonium type epoxy resin, dilacquer resin, biphenyl type龛龛匕 k k L 又又又又又又、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、、 : Fine coffee (4) Modified epoxy resin can be made of a resin known as S3 ^ acrylic acid rubber. City α mouth, you can also use any combination (8) photoradical The photo-radical polymerization initiator of the present invention refers to a compound which generates radicals by light 18815880. The photoradicals are exemplified: the benzoin-based compound initiator is not particularly limited, and examples thereof include α-醯秘秘、、、秘秘秘秘秘秘秘苯苯苯苯苯苯苯苯苯苯苯秘、、、、、、、、、、 : : : : : : : : : : : : : : : , =, benzene-sulfur-compound, sulfhydryl-based: use as a photopolymerization start: the initiator can be singly singly or multi-aged. "Liquid liquid crystal sealing with t-radical polymerization initiator Agent, by light curing to achieve temporary solid = seal can be hunted for the process of macro, 隹 - clothing 1 ^ / text display panel when the = Yi Jin 仃. Relative to (10) parts by weight of liquid crystal sealant, (8) plus The amount is preferably (10) to 5 parts by weight. The amount of the photoradical polyfluorene added is greater than or equal to _ t, and is cured in a short time by light exposure. If the above-mentioned addition force is equal to Ο good coating property' And a uniform solid can be obtained by light irradiation [Method for Preparing Liquid Crystal Sealant] Method for Preparing Liquid Crystal Sealant of the Present Invention There are special restrictions, which can be used to know the technology. The I liquid of the liquid crystal sealant towel has no special poles. The machine includes: a two-arm mixer, a roller mixer, a double screw mixer, and a planet. The money mixing machine can make a well-known two refining machinery. It will be properly mixed by any method. If you remove the shell, then after the vacuum defoaming process, the i wheel is filled into a glass bottle or a polymer container. In the liquid crystal display panel of the present invention, the liquid crystal sealing agent of the present invention can be applied to any one of a liquid crystal injection method and a liquid crystal dropping method. A method of manufacturing the liquid crystal display panel of the present invention related to the liquid crystal injection method and the liquid crystal dropping method will be described in order. [Method of manufacturing liquid crystal display panel by liquid crystal injection method] The liquid crystal display panel is manufactured by a liquid crystal injection method, and the iL snaps are bonded together by a liquid crystal sealing agent. a night-display panel, the method includes: (1) a process for preparing a substrate having a frame-shaped display region provided with a liquid crystal injection port formed by a liquid crystal of the present invention in accordance with a pixel arrangement region; (7) After the two substrates are superposed, the heating and pressing are performed to form the substrate, thereby forming a liquid crystal cell between the substrates (4: a process of injecting liquid crystal into the liquid crystal cell by using the injection port; In the process of (1), in the process of (1), a liquid crystal sealing agent is prepared on the two substrates, and a substrate having a frame-shaped display area is disposed. An injection port for injecting a liquid crystal is formed in the frame-shaped display area. An example of two substrates used in the liquid crystal display panel includes a glass substrate of a matrix TFT or a color filter. :f+ # Substrate. Examples of the material of the substrate include: glass or polycarbonate, and the plastic such as ethylene glycol dicarboxylate, polyether sulfone, PMMA, etc. It can be disposed on the surface of the i substrate: a transparent electrode typified by indium oxide; 30 200815880 An aligning film represented by sulfimine or the like; and other inorganic ion shielding films, etc. The liquid enamel sealing agent is preferably used in the liquid crystal sealing agent of the present invention. The liquid crystal poor and the sealing agent not only form a frame such as a display region but also The adhesive used for bonding the two substrates to each other at intervals is used. When the liquid crystal injection method is used to form a liquid crystal display panel, a thermosetting sealant is particularly preferable among the liquid crystal sealing agents of the present invention. The method of applying the liquid crystal sealing agent is not particularly limited. The coating method includes, for example, screen printing or coating by a dispensing method, and the liquid crystal sealing agent may be applied to the surfaces of both substrates. The substrate after the liquid crystal sealing agent is subjected to a mouth treatment as needed. The pre-curing treatment refers to temporarily drying the liquid crystal sealing agent. The heating temperature range of the treated towel is (4) #没有^ However, when the solvent is included in the solvent (four) agent, it is preferred to seal at least 95% by weight of the liquid crystal (of

二SI:等於液晶密封劑中所含有的熱卿硬化夂，、、活度。脫溶劑化是指晶密封劑中除去。從上_ U ,4而將其自液力侧為:加二==優選的預固化處理的分鐘範二度為6〇〜11〇C’加熱時間在5〜6。預固化處理中，在不因埶而損〜加熱溫度大於等於11(rc，也可㈣=日此％，即使使劑化，但是有時固化會進行丁劑的脫溶狂度以上，盒間距的寬 31 200815880 度會叙生、交化。因此，預固化處理時的加熱條件根據構成液晶密封劑的各成分的種類等而適當確定。在(2)的工序中，將液晶密封劑被預乾燥的基板和另一塊基板重合且對準位置，之後進行加熱壓合。藉由加熱壓合使液晶密封劑固化，因此兩塊基板彼此藉由液晶密封劑而貼合在一起。此時，優選適當調整加熱壓合時的加壓條件專以使基板彼此貼合後的液晶密封劑的厚度為1 5〜 7·0 μιη範圍内的均勻厚度。將基板彼此之間加熱壓合時的加熱條件沒有特別限定。一般說來，若在1〇〇〜16CTC的溫度範圍内加熱〇.5二 24小時，則可以使液晶密封劑適當固化。加熱壓合兩塊基板時，可以使用單片熱壓機。單片熱壓機是指使每組兩塊基板黏合的熱壓機。上述單片熱壓^ 的例=包括：可以在真空下進行加熱的真空單片熱壓^或在大氣壓下藉由熱板進行強制加熱壓合的剛體單片熱厣機。 …、土利用單片熱壓機將兩塊基板貼合在一起時，首先，將重合的兩塊基板在100〜160。〇下加熱壓合2〜1〇分鐘乂右使其暫且黏合。其次，開放熱壓機的壓力，自熱题機中取出貼合在一起的兩塊基板。然後，在溫度大致保^恂定的加熱烘箱中使液晶密封劑完全固化。其中，加熱液^ 密封，的製程可以分兩段或兩段以上的多段來進行了^ 取代單片熱壓機，以多塊成批加熱壓合黏合方式顯示單元。 32 200815880 在(3)的製程中，自注入口向液晶盒内注入液晶。液晶可以根據盒的容積而適當確定，沒有特別限定。在(4)的製程中，利用封閉用密封劑將上述注入有液晶之液晶盒的注入口封閉。封閉用密封劑沒有特別限定，其例子包括：兩液固化型密封劑或紫外線固化型密封劑。 [利用液晶滴注方式製造液晶顯不面板的方法] 本發明的利用液晶滴注方式製造液晶顯示面板的方 • 法，是將對向的兩塊基板藉由液晶密封劑貼合在一起來製 ( k液B曰顯示面板，該方法包括：（10)準備基板的製程，上述基板具有按照像素排列區域被本發明的液晶密封劑包圍的方式形成的框狀顯示區域；（11)向未固化狀態的上述顯示區域内或另一塊基板上滴注液晶的製程；（12)將上述滴注有液晶的基板和另一塊基板在減壓下重合的製程；以及 (13)藉由加熱使存在於上述重合的兩塊基板間的上述液晶岔封劑固化的製程。在（10)的製程中，準備包括按照像素排列區域被本發〇明的液晶密封劑包圍的方式形成的框上的顯示區域的基 • t反W /、中所使用的基板和於基板上塗佈液晶密封劑的方法 #，有特別限定，可以和液晶注入方式中的相同。當利用液曰曰滴’主方式製造液晶顯示面板時，優選使用光和埶固化性密封劑。 /在（11)的製程中，向作為顯示區域的未固化狀態的框内，=一塊基板上滴注適量的液晶。上述液晶滴注通常在大氣壓下進行。此時，優選根據框的大小來調節液晶的滴 33 200815880 注量，將液晶存儲在框内。當如此操作向框内滴注液晶時，液晶的容量不會超過用貼合後的框和基板圍起的空各的容量。因此，不會對框施加過剩的壓力，所以形成框的穷封被破壞的可能性小。在（11)的製程中，滴注有液晶的另一塊基板是指與具有顯示區域的基板不同的基板。在向未配置密封的其板上滴注液晶的情況下，使基板彼此重合時，可以向能夠作為顯示區域的另一塊基板上的任意位置處滴注液晶。 Γ 在（12)的製程中，在減壓下使滴注有液晶的基板和另一塊基板重合。其中，基板彼此之間的重合可以使用真空貼合裝置等來進行，沒有特別限定。通常，在液晶滴注方式中，基板的重合在減壓下進行。在減壓下進行重合的理由在於利用氣壓差使基板彼此貼合。在（13)的製程中，使存在於重合的兩塊基板間的液晶密封劑固化。液晶密封劑的固化處理沒有特別限定，可以根據固化劑的種類而適當決定。當使用光固化性液晶密封〇劑時，進行紫外線等光照射；當使用熱固化性液晶密封劑時，適當進行加熱處理。在固化處理中，用於使液晶密封劑固化而照射的光的種類和照射時間或者加熱時的溫度和時間等固化處理條件，可以根據所使用的液晶密封劑的組成而適當選擇。例 t ’利用光使液晶密封劑固化時，固化條件可以是：於加壓下在i〇00〜18000 mJ的範圍内照射紫外線。當藉由加熱使液晶密封劑固化時，在未加壓狀態下將溫度設定在u〇 34 200815880 〜140c範圍内，只要加熱1小時，就可以使液晶密封劑充分固化。無論是液晶注入方式還是液晶滴注方式，藉由將本發明的液^密封劑和製造方法組合而製造的液晶顯示面板的耐濕可罪性良好。本發明中也包括這些液晶顯示面板。以下’列舉本發明的實施例和比較例，以更詳細地說明本發明。但是，本發明並不限於其中所示的方式。、首先，對本實施例和比較例中用於製備液晶密封劑的 ^ ；各成分進行說明。在以下的實施例和比較例中，適當選擇使用下述2種液晶密封劑（液晶密封劑a、b)。其中，液晶密封劑a作為熱固化性密封劑而發揮作用，液晶密封劑b 作為光和熱固化性密封劑而發揮作用。 (1) 環氧樹脂環氧樹脂使用鄰甲酚酚醛型固體環氧樹脂 (EOCN_1020_75，日本化藥(股)製，用環球法測得的軟化點為75°C，環氧當量為215 g/eq)。 (2) 熔點小於等於150°C的第一熱潛在性硬化劑作為第一熱潛在性硬化劑，適當使用以下4種熱潛在性硬化劑：⑻2-苯基咪唑(ADECAHARDNER EH4346S，Two SI: equal to the heat hardening enthalpy, and activity contained in the liquid crystal sealing agent. Desolvation is removed in the crystal sealant. From the upper _ U , 4, the self-hydraulic side is: plus two == preferred pre-curing treatment, the second-degree range is 6 〇 11 11 C, and the heating time is 5 to 6. In the pre-curing treatment, it is not damaged by 〜~ The heating temperature is 11 or more (rc, or (4) = 5% by day, even if it is made into a chemical agent, the curing may be performed by the de-dissolving madness of the butadiene agent. Therefore, the heating conditions at the time of the pre-curing treatment are appropriately determined depending on the type of each component constituting the liquid crystal sealing agent, etc. In the step (2), the liquid crystal sealing agent is preliminarily determined. The dried substrate and the other substrate are overlapped and aligned, and then heated and pressed. The liquid crystal sealing agent is cured by heat pressing, so that the two substrates are bonded together by the liquid crystal sealing agent. The pressure conditions at the time of heating and pressing are appropriately adjusted so that the thickness of the liquid crystal sealing agent after bonding the substrates to each other is a uniform thickness in the range of 15 to 7·0 μm. Heating conditions when the substrates are heated and pressed together In general, the liquid crystal sealing agent can be appropriately cured by heating it for 5 to 24 hours in a temperature range of 1 to 16 CTC. When heating and pressing two substrates, a single piece of hot pressing can be used. A single-sheet hot press is a hot press that bonds two sets of substrates. The above-mentioned single-piece hot press case includes: a vacuum monolithic hot press that can be heated under vacuum or heat at atmospheric pressure. The rigid-body single-plate heat-pressing machine for forcibly heating and pressing the plate. ... When the two substrates are bonded together by a single-plate hot press, first, the two substrates which are overlapped are placed at 100 to 160. After 2~1〇 minutes, the right side is temporarily bonded. Secondly, the pressure of the hot press is opened, and the two substrates that are attached together are taken out from the heat-fixing machine. Then, in a heating oven with a substantially constant temperature. The liquid crystal sealing agent is completely cured, wherein the heating liquid is sealed, and the process can be divided into two or more stages to replace the single-plate hot press, and the plurality of pieces of the heating and pressing bonding display unit are batch-wise. 32 200815880 In the process of (3), liquid crystal is injected into the liquid crystal cell from the injection port. The liquid crystal can be appropriately determined according to the volume of the cartridge, and is not particularly limited. In the process of (4), the above injection is performed by a sealing agent for sealing. Note with liquid crystal cell The sealing agent for sealing is not particularly limited, and examples thereof include a two-liquid curing type sealing agent or an ultraviolet curing type sealing agent. [Method of manufacturing liquid crystal display panel by liquid crystal dropping method] Liquid crystal dropping method of the present invention The method for manufacturing a liquid crystal display panel is to fabricate two substrates facing each other by a liquid crystal sealing agent (k liquid B 曰 display panel, the method comprising: (10) preparing a substrate, the substrate a frame-shaped display region formed in such a manner that a pixel arrangement region is surrounded by the liquid crystal sealing agent of the present invention; (11) a process of injecting liquid crystal into the display region in an uncured state or on another substrate; (12) a process in which a liquid crystal substrate and another substrate are superposed under reduced pressure; and (13) a process of curing the liquid crystal sealing agent existing between the two stacked substrates by heating. In the process of (10), preparation is made to include a substrate on the frame formed by the liquid crystal sealing agent surrounded by the pixel arrangement region, and the substrate used in the substrate and the substrate are used on the substrate. The method # of applying the liquid crystal sealing agent is particularly limited and can be the same as in the liquid crystal injection method. When a liquid crystal display panel is manufactured by a liquid helium drop method, it is preferred to use a light and a hydrazine curable sealant. / In the process of (11), an appropriate amount of liquid crystal is dripped onto a substrate in a frame which is an uncured state of the display region. The above liquid crystal instillation is usually carried out under atmospheric pressure. At this time, it is preferable to adjust the liquid crystal droplets according to the size of the frame. The liquid crystal is stored in the frame. When the liquid crystal is dripped into the frame in this manner, the capacity of the liquid crystal does not exceed the capacity of the space surrounded by the bonded frame and the substrate. Therefore, no excessive pressure is applied to the frame, so that the possibility that the formed envelope is broken is small. In the process of (11), the other substrate to which the liquid crystal is dropped refers to a substrate different from the substrate having the display region. In the case where the liquid crystal is dripped onto the plate on which the seal is not disposed, when the substrates are overlapped with each other, the liquid crystal can be dripped at an arbitrary position on the other substrate which can serve as the display region. Γ In the process of (12), the substrate on which the liquid crystal is dropped is superposed on the other substrate under reduced pressure. Here, the superposition of the substrates can be carried out by using a vacuum bonding apparatus or the like, and is not particularly limited. Generally, in the liquid crystal dropping method, the superposition of the substrates is performed under reduced pressure. The reason for the overlap under reduced pressure is that the substrates are bonded to each other by the difference in gas pressure. In the process of (13), the liquid crystal sealing agent existing between the two substrates which are superposed is cured. The curing treatment of the liquid crystal sealing agent is not particularly limited, and can be appropriately determined depending on the type of the curing agent. When a photocurable liquid crystal sealing agent is used, light irradiation such as ultraviolet rays is performed, and when a thermosetting liquid crystal sealing agent is used, heat treatment is appropriately performed. In the curing treatment, the curing treatment conditions such as the type of light used to cure the liquid crystal sealing agent and the irradiation time or the temperature and time during heating can be appropriately selected depending on the composition of the liquid crystal sealing agent to be used. In the case where the liquid crystal sealing agent is cured by light, the curing condition may be that ultraviolet rays are irradiated in a range of i 00 to 18000 mJ under pressure. When the liquid crystal sealing agent is cured by heating, the temperature is set in the range of u〇 34 200815880 to 140c in an unpressurized state, and the liquid crystal sealing agent can be sufficiently cured by heating for 1 hour. The liquid crystal display panel manufactured by combining the liquid sealing agent of the present invention and the production method is excellent in moisture resistance and sin resistance regardless of the liquid crystal injection method or the liquid crystal dropping method. These liquid crystal display panels are also included in the present invention. The invention will be described in more detail below by way of examples and comparative examples of the invention. However, the invention is not limited to the manner shown therein. First, the components used in the preparation of the liquid crystal sealing agent in the present embodiment and the comparative examples will be described. In the following examples and comparative examples, the following two kinds of liquid crystal sealing agents (liquid crystal sealing agents a, b) were appropriately selected and used. Among them, the liquid crystal sealing agent a functions as a thermosetting sealant, and the liquid crystal sealing agent b functions as light and a thermosetting sealant. (1) Epoxy resin epoxy resin is made of o-cresol novolac type solid epoxy resin (EOCN_1020_75, manufactured by Nippon Kayaku Co., Ltd.), the softening point measured by the ring and ball method is 75 ° C, and the epoxy equivalent is 215 g / Eq). (2) First thermal latent curing agent having a melting point of 150 ° C or less. As the first thermal latent curing agent, the following four thermal latent curing agents are suitably used: (8) 2-phenylimidazole (ADECAHARDNER EH4346S,

' ADEKA(股）製，熔點 125。〇 ·，（b)聚胺基脲系（FUJICURE FXE-1000，富士化成工業(股)製，熔點120°C) ; (c)胺加成物系（ADECAHARDNER EH4357S，ADEKA(股)製，熔點 78°C) ; (d)l，3-雙（肼基羰乙基）-5-異丙基乙内醯脲 (AMICURE VDH，味之素 FINETECHNO(股）製，熔點 35 200815880 120 C ’相對於251：的水100 ml的溶解度超過100 g)。 (3) 熔點大於等於的第二熱潛在性硬化劑作為第二熱潛在性硬化劑，適當使用以下5種熱潛在性硬化劑：⑻工醯胺系（ah- 154，味之素HNETECHNO(股) 製’熔點 200。〇 ; (b)味唑系（CUREZOL 2E4MZ-A，四國化成工業（股）製，熔點22〇t) ; (c)十二烷二酸二醯肼' ADEKA (share) system, melting point 125. 〇·, (b) Polyamine urea system (FUJICURE FXE-1000, manufactured by Fuji Chemical Industry Co., Ltd., melting point 120 ° C); (c) Amine addition system (ADECAHARDNER EH4357S, made by ADEKA) (d) l,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH, Ajinomoto FINETECHNO), melting point 35 200815880 120 C 'relative The solubility of 100 ml of water in 251: exceeds 100 g). (3) A second thermal latent curing agent with a melting point greater than or equal to the following two thermal latent curing agents: (8) Aminoguanidine (ah-154, Ajinomoto HNETECHNO) The system has a melting point of 200. 〇; (b) sulphurazole (CUREZOL 2E4MZ-A, manufactured by Shikoku Chemical Industry Co., Ltd., melting point 22〇t); (c) dodecanedioic acid dioxime

(N_l2 ’曰本FINECHEM(股)製，熔點189T：，相對於25°C 的水100 ml為不溶）；⑻癸二酸二醯肼，大塚化學(股) 製’熔點190。〇 ; (e)脂肪族二羧酸（ADH，曰本 FINECHEM(股）製，熔點181rc ;相對於25r的水丨⑽ml 的溶解度為10 g)。 (4) 填充劑作為填充劑，適當使用以下3種填充劑：（a)無定形氧化矽（MU-l2〇，信越化學工業（股）製）；⑻無定形礬土 (UA-5105，昭和電工（股）製）；（(〇無機球狀氧化矽 (SEAHOSTAR S_30，日本觸媒(股)製，平均—級粒徑〇.3 μιη，比表面積11 m2/g)。 (5) 其他添加劑作為其他添加劑，使用矽烷耦合劑(γ-縮水甘油氧基丙基三曱氧基石夕烧’ ΚΒΜ-403，信越化學工業(股)製）。 (6) 丙烯酸酯及/或曱基丙烯酸酯單體或它們的低聚物作為(6)成分，適當選擇使用雙酚Α型環氧基二曱基丙烯酸酷(3000M’共榮社化學(股)製)和雙齡A型環氧基丙稀酸酯(EB-3700，DAICEL-CYTEC(股)製）。 36 200815880 (7)(曱基)丙烯酸醋改性環氧樹脂作為（甲基）丙烯酸酉旨改性中得到的將環氧樹月旨進行了丙以下合靡改性環氧樹脂。欠知改性的丙烯酸類橡膠 [合成例1](N_l2 '曰本 FINECHEM (share) system, melting point 189T: 100 ml of water is insoluble in 25 ° C); (8) diterpene sebacate, Otsuka Chemical Co., Ltd.' melting point 190. (e) an aliphatic dicarboxylic acid (ADH, manufactured by Fenchem Fenchem Co., Ltd., melting point 181 rc; solubility of 10 g with respect to 25 r of hydrazine (10) ml). (4) Filler As a filler, the following three types of fillers are suitably used: (a) amorphous yttrium oxide (MU-l2〇, manufactured by Shin-Etsu Chemical Co., Ltd.); (8) amorphous alumina (UA-5105, Showa) (Electrical (stock) system); ((Inorganic spherical cerium oxide (SEAHOSTAR S_30, manufactured by Nippon Shokubai Co., Ltd., average-grade particle size 〇.3 μιη, specific surface area 11 m2/g). (5) Other additives As other additives, a decane coupling agent (γ-glycidoxypropyltrimethoxyxanthine ΚΒΜ-403, manufactured by Shin-Etsu Chemical Co., Ltd.) is used. (6) Acrylate and/or mercapto acrylate As the component (6), the bisphenol quinone type epoxy bis decyl acrylate (manufactured by 3000M 'Kyoeisha Chemical Co., Ltd.) and the two-age type A epoxy propylene are appropriately selected. Acid ester (EB-3700, manufactured by DAICEL-CYTEC Co., Ltd.) 36 200815880 (7) (Alkyl) acrylic vinegar modified epoxy resin as the (meth)acrylic acid modified in the epoxy resin tree It is intended to carry out a modified epoxy resin of the following C. Unknown modified acrylic rubber [Synthesis Example 1]

U 向具備攪拌機、導氣管、溫产四口燒瓶中裝人6GGg作為液二/⑼官的2_ ml 樹脂(E_C W柳，三為井脂的雙紛A型環氧二甲基乙醇胺和5〇g甲苯井稀酸、lg ς f ^ s尽隹軏“工氣流下於110°c加熱縣5小日r接下來，向該混合物中加人35Q g丙稀酸丁，20 g甲基丙烯酸縮水甘油酷、i g二乙稀基苯、1 g偶氮雙，甲基和2 g減雙異了腈，―邊向反應系統内U to a mixer, air tube, and a four-necked flask equipped with 6GGg as a liquid 2/(9) official 2_ml resin (E_C W Liu, three is a well-oiled double-type A-type epoxy dimethylethanolamine and 5〇 g toluene dilute acid, lg ς f ^ s exhausted "work gas flow at 110 ° c heating county 5 small days r next, add 35Q g butyl acrylate to the mixture, 20 g methacrylic acid shrinkage Glycerol cool, ig diethylene benzene, 1 g azo double, methyl and 2 g minus diiso nitrile, "lateral reaction system

V入氮，一邊使之在70°C下反應3小時，之後再在9〇°C 下反應1小時。最後，將製備的混合物於110°C的減壓下脫去甲笨，得到丙烯酸類橡膠改性環氧樹脂。 (8)光自由基聚合起始劑作為光自由基聚合起始劑，使用羥基環己基苯基酮 (IRGACURE 184，CIBA SPECIALTY CHEMICAL(股)製）。並且根據需要，使用丙二醇二乙酸_(D0WAN0L PGDA，DOW CHEMICAL(股)製)作為溶劑。除上述以外，熱潛在性硬化劑A適當使用單醯肼系熱潛在性硬化劑 (SMH，大塚化學(股)製，熔點148°C，相對於25°C的水100 ml的溶解度小於10 g)。在各實施例和比較例中，分別測定、評價以下各項， 37 200815880 評價液晶密封劑的特性。上述各項包括：（i)液晶密封劑的黏度穩定性；⑴)熱固化性密封劑的黏合強度；（iii)光和熱口化生*封劑的黏合強度；（iv)使用了熱固化性密封劑的液晶顯不面板的顯示性；以及汐)使用了光和熱固化性密封劑的液晶顯示面板的顯示性。各項測定的細節如下所示。其 • : ’⑴的液晶密封劑黏度穩定性的評價方法使用熱固化性始、封劑、光和熱固化性密封劑中任一種相同的方法。 (1)液晶密封劑的黏度穩定性 ( 使用E型黏度计測定25°C時液晶密封劑的黏度值。將用於黏度測定的液晶密封劑密封在聚乙烯製容器中，之後在25 C下保管5天。然後，經過預定期間後，使用e型黏度计測疋25 C時液晶密封劑的黏度值，以測定值為基準，以，封前的黏度值作為1〇〇,算出經過25t/5天後的黏度值。變化率。此時，按3個等級進行評價：若變化率小於 10=，則認為黏度穩定性極高（◎);若變化率大於等於 10%、小於15%，則認為黏度穩定性高（〇);若變化率超過 y 15%，則認為黏度穩定性差（X)。 (ii)熱固化性密封劑的黏合強度首先’將添加了 1 wt%的5μιη玻璃纖維的液晶密封劑在25 mmx45 mmx厚5 mm的無鹼玻璃上進行網版印刷二形成直徑為1 mm的圓形，在9(rc下預固化處理1〇分鐘。接下來，將與該基板成對的相同玻璃按十字交叉貼合後，用夾具固疋，利用烘箱在12〇。〇下加熱處理6〇分鐘。使用拉伸試驗機(Model 210，INTESCO(股)製），拉伸 38 200815880 速度為2 mm/分鐘，在與玻璃底而的試驗片，測定平面拉伸強度。Ιφ仃的方向上剝下作成的大小，按3個料評價黏合如根據平面拉伸強度於15 MPa時，認為黏合強度特別又古』’拉伸強度大於等於K)嫩、小於i遭a時，f ; ^強度大於等度小於10 MPa時，認為黏合強度^)強度向（〇);拉伸強 Γ ϋ 對利用與上述相同之方式製作的試 (pressure cooker test)後，按昭 | μ、+、上 ^ 力銷武％後的拉伸強度大於等於1Π =性_高_;當拉伸強度大於等:二為a= MP^，認為耐濕黏合可靠性高(〇);當拉伸強度小於7 MPa時，認為耐濕黏合可靠性低(χ)。、 (iii)光和熱固化性密封劑的黏合強度产首先，將添加了1wt%的5_玻璃纖維的液晶密封劑在25 mmx45 mmx厚5咖的無驗玻璃上進行網版印刷，形^直徑為1 mm的圓形，將成對的相同玻璃按十字交叉貼口。接下來，將該貼合的兩塊基板用夾具挾持以施加負荷時，，用紫外線照射裝置(USHI0電機(股)製），照射10〇 mW/cm㈣外線1作制用光使液晶密封劑固化的試驗片。此時’紫外線的照射能量為2000 mJ。使用供箱將作成的試驗片在氮環境中、120°C下加熱處理60分鐘。使用拉伸試驗機(M〇dd 21〇，INTESC〇(股)製） 39 200815880 測定作成的試驗片的平面拉伸強度。此時，利用與上述熱固化性逾封劍相同之方法進行平面拉伸強度的測定、測定結果的評價以及比較壓力鍋試驗前後的平面拉伸強度。 (iv)使用了熱固化性密封劑的液晶顯示面板的顯示性使用添加了 1 wt°/〇的5 μιη玻璃纖維的熱固化性密封劑，在具有透明電極和配向膜的4〇 mmx45 mm的玻璃基板(RT_DM88 PINEHC(股)製)上描繪線寬〇.5 mm、厚度5〇 μιη的35 mmx40 mm的框架。此時，在框上設置液晶注入口。使用分配器（SHOTMASTER，武藏 ENGINEERING 公司製）進行描繪。將描繪的熱固化性密封劑加熱乾燥1〇分鐘作為預固化處理，之後將成對的另一塊玻璃基板重合，之後將其用火具固疋，使用烘相在120 C下加熱處理60分鐘。接下來，自注入口向形成於兩塊基板之間的液晶盒中注入相當於貼合以後的盒内容量的液晶材料V was introduced into the nitrogen, and it was allowed to react at 70 ° C for 3 hours, and then reacted at 9 ° C for 1 hour. Finally, the prepared mixture was deodorized under reduced pressure at 110 ° C to obtain an acrylic rubber-modified epoxy resin. (8) Photoradical polymerization initiator As a photoradical polymerization initiator, hydroxycyclohexyl phenyl ketone (IRGACURE 184, manufactured by CIBA SPECIALTY CHEMICAL Co., Ltd.) was used. Further, if necessary, propylene glycol diacetate (D0WAN0L PGDA, manufactured by DOW CHEMICAL Co., Ltd.) was used as a solvent. In addition to the above, the thermal latent curing agent A suitably uses a monoterpene thermal latent curing agent (SMH, manufactured by Otsuka Chemical Co., Ltd., melting point 148 ° C, and solubility of 100 ml with respect to water at 25 ° C is less than 10 g. ). In each of the examples and comparative examples, the following were measured and evaluated, respectively, 37 200815880 Evaluation of characteristics of the liquid crystal sealing agent. The above items include: (i) viscosity stability of liquid crystal sealant; (1) adhesion strength of thermosetting sealant; (iii) bonding strength of light and hot mouthing * sealant; (iv) use of heat curing The liquid crystal display panel exhibits the display property of the liquid crystal display panel using the light and heat curable sealant. The details of each measurement are shown below. The method for evaluating the viscosity stability of the liquid crystal sealing agent of '(1) is the same as any one of the thermosetting starter, the sealant, the light, and the thermosetting sealant. (1) Viscosity stability of liquid crystal sealing agent (Measure the viscosity of liquid crystal sealing agent at 25 ° C using an E-type viscometer. Seal the liquid crystal sealing agent for viscosity measurement in a polyethylene container, then at 25 C After storage for 5 days, after a predetermined period of time, the viscosity value of the liquid crystal sealing agent at 25 C was measured using an e-type viscometer, and the viscosity value was taken as 1 〇〇 after the predetermined value, and 25 t/ was calculated. The viscosity value after 5 days. The rate of change. At this time, the evaluation is performed in three levels: if the rate of change is less than 10 =, the viscosity stability is considered to be extremely high (◎); if the rate of change is 10% or more, less than 15%, It is considered that the viscosity stability is high (〇); if the rate of change exceeds y 15%, the viscosity stability is considered to be poor (X). (ii) The adhesive strength of the heat-curable sealant Firstly, 1 wt% of 5 μιη glass fiber will be added. The liquid crystal sealant is screen-printed on a 25 mm x 45 mm x 5 mm thick alkali-free glass to form a circular shape with a diameter of 1 mm, and pre-cured for 1 minute at 9 (rc). Next, it will be formed with the substrate. After the same glass is pressed against the cross, it is fixed by a clamp and dried. The box was placed at 12 Torr. The underarm was heat treated for 6 minutes. Using a tensile tester (Model 210, manufactured by INTESCO Co., Ltd.), tensile test 38 200815880 at a speed of 2 mm/min, measured on a test piece with a glass bottom. The tensile strength of the plane is peeled off in the direction of Ιφ仃, and the adhesion is evaluated according to three materials. If the tensile strength is 15 MPa according to the plane, the bonding strength is considered to be particularly high. The tensile strength is greater than or equal to K). When less than i is a, f; ^ When the strength is greater than the isocraticity less than 10 MPa, the bonding strength is considered to be () strength (strength); tensile strength Γ ϋ After using the pressure cooker test prepared in the same manner as above According to Zhao | μ, +, upper ^ force after the strength of the tensile strength is greater than or equal to 1 Π = sex _ high _; when the tensile strength is greater than equal: two is a = MP ^, the reliability of the wet adhesion is considered high ( 〇); When the tensile strength is less than 7 MPa, the moisture-resistant adhesion reliability is considered to be low (χ). (iii) Bonding strength of light and heat-curable sealant First, a liquid crystal sealant to which 1 wt% of 5_glass fiber is added is screen-printed on a 25 mm x 45 mm x thick non-glass glass. A 1 mm diameter circle that pairs the same glass with a cross-over. Next, when the two bonded substrates are clamped by a jig to apply a load, the liquid crystal sealing agent is cured by irradiating a 10 〇mW/cm (four) outer line 1 with an ultraviolet ray irradiation device (manufactured by USHI0 Motor Co., Ltd.). Test piece. At this time, the irradiation energy of ultraviolet rays was 2000 mJ. The test piece prepared by the tank was heated in a nitrogen atmosphere at 120 ° C for 60 minutes. Using a tensile tester (M〇dd 21〇, manufactured by INTESC®) 39 200815880 The plane tensile strength of the prepared test piece was measured. At this time, the measurement of the plane tensile strength, the evaluation of the measurement results, and the comparison of the plane tensile strength before and after the pressure cooker test were carried out by the same method as the above-described thermosetting over-sealing sword. (iv) Displayability of a liquid crystal display panel using a thermosetting sealant Using a thermosetting sealant to which 5 wtm glass fibers of 1 wt/min were added, 4 mm x 45 mm with a transparent electrode and an alignment film A glass substrate (made by RT_DM88 PINEHC) was used to draw a 35 mm x 40 mm frame with a line width of 55 mm and a thickness of 5 μm. At this time, the liquid crystal injection port is set on the frame. The drawing is performed using a dispenser (SHOTMASTER, Musashi Engineering Co., Ltd.). The heat-curable sealant thus described was dried by heating for 1 minute as a pre-curing treatment, after which the other pair of glass substrates were superposed, and then they were fixed by a fire apparatus, and heat-treated at 120 C for 60 minutes using a baking phase. Next, a liquid crystal material corresponding to the amount of the contents of the cartridge after the bonding is injected into the liquid crystal cell formed between the two substrates from the injection port.

(mlc]i9〇(H)〇omerck(股)製），之後用密封劑(STRACT =〇NDES-302，三井化學(股)製)封閉上述注入口，作為液晶顯示面板。在所製作的液晶顯示面板的表面，於正面貼附偏振，、’並於背面貼附具有反射板的偏振板。然後，使用直流 =源I置對該液晶顯示面板施加5V的電壓，以驅動液晶心員示面板。此時，藉由目視觀察由液晶密封劑形成的密封 =近的液晶顯示功能從驅動初_始是否—直正常發二功能，根據以下所示的基準，#2個等級評價液晶顯^面板 40 200815880 的顯示性。情況;^ ί Γ顯不面板直到密封時一直發揮液晶顯示功能的内側偏離tr性良好(〇）；將從密封時附近開始直到向框的常差mm時未發揮顯示功能的情況視為顯示性非將上述液晶顯示面板在121t:、2大氣壓、濕度100% 2條件下進行40小時的壓力鍋試驗後，再按照相同的方法評價液晶顯示面板的顯示性，以比較研究壓力鋼試驗前後《的液晶顯示面板的顯示性。 (V)使用了光和熱固化性密封劑的液晶顯示面板的顯示性使用添加了 1 wt〇/。的5 μπι玻璃纖維的光和熱固化性密封劑，在具有透明電極和配向膜的4〇 mmx45 mm的玻璃基板(RT-DM88 PINEHC(股)製)上描繪線寬〇·5 mm、厚度50 μηι的35 mmx40 mm的框架。使用分配器 (SHOTMASTER，武藏 ENGINEERING(股)製）進行描繪。 U 接下來，使用分配器精密滴注相當於貼合以後的面板内容量的液晶材料(MLC-11900-000，MERCK(股）製）。接著，在90 Pa的減壓下將兩塊玻璃基板對向重合後，施加負荷、固定，再使用紫外線照射裝置(USHIO電機(股)製），照射100 mW/cm2的紫外線，使液晶密封劑固化。此時，紫外線的照射能量為2000 mJ。光源使用金屬鹵化物燈，累計光量的測定中使用具有300〜390 nm的測定波長範圍及峰值靈敏度波長為365 nm的紫外線累計光量計 41 200815880 (UVR-T35 TOPCON(股）製）。利用光使液晶密封劑固化後，再在120°C下加熱60分鐘，使液晶密封劑固化。(mlc) i9 (H) 〇omerck (manufactured by KK), and then the above-mentioned injection port was sealed with a sealant (STRACT = 〇NDES-302, manufactured by Mitsui Chemicals Co., Ltd.) as a liquid crystal display panel. On the surface of the produced liquid crystal display panel, a polarizing plate was attached to the front surface, and a polarizing plate having a reflecting plate was attached to the back surface. Then, a voltage of 5 V was applied to the liquid crystal display panel using DC = Source I to drive the liquid crystal panel. At this time, by visually observing the seal formed by the liquid crystal sealing agent = the near liquid crystal display function from the start of the drive - whether or not the normal function is normal, the liquid crystal display panel 40 is evaluated according to the following criteria. The displayability of 200815880. Case; ^ ί Γ 面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板面板直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到直到The liquid crystal display panel was subjected to a pressure cooker test under conditions of 121 t:, 2 atm, and humidity of 100% 2 for 40 hours, and then the display properties of the liquid crystal display panel were evaluated in the same manner to compare the liquid crystals before and after the pressure steel test. Display panel display. (V) Displayability of a liquid crystal display panel using a light and heat curable sealant The use of 1 wt〇/ was added. Light and heat-curable sealant of 5 μπι glass fiber, line width 〇·5 mm, thickness 50 on a 4〇mmx45 mm glass substrate (made by RT-DM88 PINEHC) with transparent electrode and alignment film Μηι's 35 mm x 40 mm frame. The drawing is performed using a dispenser (SHOTMASTER, Musashi Engineering Co., Ltd.). U Next, a liquid crystal material (MLC-11900-000, manufactured by MERCK Co., Ltd.) equivalent to the amount of the panel after bonding is precisely dispensed using a dispenser. Then, after the two glass substrates were superposed on each other under a reduced pressure of 90 Pa, the load was applied and fixed, and an ultraviolet ray irradiation apparatus (manufactured by USHIO Motor Co., Ltd.) was used to irradiate ultraviolet rays of 100 mW/cm 2 to form a liquid crystal sealing agent. Cured. At this time, the ultraviolet ray irradiation energy was 2000 mJ. A metal halide lamp was used as the light source, and an ultraviolet cumulative light meter having a measurement wavelength range of 300 to 390 nm and a peak sensitivity wavelength of 365 nm was used for the measurement of the integrated light amount. 41 200815880 (manufactured by UVR-T35 TOPCON Co., Ltd.). After the liquid crystal sealing agent was cured by light, it was further heated at 120 ° C for 60 minutes to cure the liquid crystal sealing agent.

在貼合的兩塊基板的兩面分別貼附偏向臈，作為液晶顯示面板。使用直流電源裝置對該液晶顯示面板施加的電壓，以驅動液晶顯示面板。此時，藉由目視觀察由液晶密封劑形成的密封附近的液晶顯示功能是否從驅動初期，始一直正常發揮功能，根據預定的基準，按2個等級評價液晶顯示面㈣顯示性。其中，評價液晶顯示面板的顯不性的基準與上述熱固化性密封劑的相同，故省略了詳細的說明。 ' 1上述液晶顯示面板在12rc、2大氣壓、濕度纖價、=曰:進的壓力鋼試驗，並利用相同的方法評仞液曰曰如面板的顯示性，以比較液晶顯示面板的顯示性。刖後的 =且1總對各液晶_翁下基準，按3個等級綜合評價 ^貝、4根據以各評價結果f，當黏度穩定性特性。其中，顯示性全部或其中任—項^J、液晶顯不面板的始、封劑的特性良好(〇);各評义（〇)¥，涊為液晶合性、液晶顯示面板的料中’當黏度敎性、黏口 ® 士，貝性中任一項今乂 π、廿立，，、要有1項存在“χ，，時，都、7人不滿思，即， 4液晶密封劑的特性差（χ)。 42 200815880 [實施例1] 將作為（1)成分的25重量份鄰甲酚酚醛環氧樹脂 (EOCN-1020-75，曰本化藥（股）製）加熱溶解於作為溶劑的 15重量份丙二醇二乙酸酯（DOWANOL PGDA，DOW CHEMICAL(股）製）中。再加入20重量份下述合成例1的丙烯酸類橡膠改性環氧樹脂、作為(2)成分的9重量份1，3-雙(肼基羰乙基)-5-異丙基乙内醯脲(AMICURE VDH-J，味 • 之素FINETECHNO(股)製）、作為(3)成分的4重量份十二 Γ 烷二酸二醯肼(N-12,日本FINECHEM公司製)和2重量份 2,4-二胺基_6-[2’_乙基-4’·甲基咪唾基_(1’)]_乙基_s_三嗓 (CUREZOL 2E4MZ-A，四國化成工業(股)製）、作為(4)成分的2重量份無定形氧化矽(MU120，信越化學工業(股)製）和13重量份無定形礬土(UA-5105，昭和電工製）、作為(5) 成分的5重量份縮水甘油氧丙基三甲氧基矽烷 (ΚΒΜ403，信越化學工業(股)製），在混合器中進行預混。再使用三輥式混煉機進行混煉，直至固體原料小於等於5 υ μπι，之後對混合物進行真空脫泡處理，製備熱固化性密封劑。 [實施例2] 除了（3)成分使用4重量份癸二酸二醯肼(SDH)以外，利用與實施例1完全相同之方式製備液晶密封劑。 [實施例3] 除了 Ρ)成分的添加量為2重量份，（3)成分未使用2,4_ 二胺基_6-[2’-乙基_4、曱基咪唑基乙基小三嗓 43 200815880 (CUREZOL 2E4MZ_A)，且十二烷二酸二醯肼(队12)為 13 重量份以外，利用與實施例1完全相同之方式製備液晶密封劑。 [實施例4] 除了（2)成分的添加量為13重量份，（3)成分未使用2,4_ 二胺基_6-[2’-乙基_4’-甲基咪唑基_(ι，)]_乙基_s_三嗪 (CUREZOL 2E4MZ-A)，且十二烷二酸二醯肼(N-12)為 2 重量份以外，利用與實施例1完全相同之方式製備液晶密封 C) 劑。 [實施例5] 除了（2)成分使用9重量份2-苯基咪唑 (ADECAHARDNER EH-4346S)，(3)成分未使用 2,4-二胺基乙基_4、曱基咪唑基-(1，)]乙基+三嗪（CUREZOL 2E4MZ-A)，且十二烷二酸二醯肼(N-12)為6重量份以外，利用與實施例1完全相同之方式製備液晶密封劑。 [實施例6]A polarizing plate is attached to both surfaces of the two bonded substrates as a liquid crystal display panel. A voltage applied to the liquid crystal display panel by a DC power supply device is used to drive the liquid crystal display panel. At this time, it is visually observed whether or not the liquid crystal display function in the vicinity of the seal formed by the liquid crystal sealing agent functions normally from the initial stage of driving, and the liquid crystal display surface (4) is evaluated in two levels based on a predetermined standard. Here, the criteria for evaluating the visibility of the liquid crystal display panel are the same as those of the above-described thermosetting sealant, and thus detailed description thereof will be omitted. '1 The above liquid crystal display panel was tested at 12 rc, 2 atm, humidity, and 曰: incoming pressure steel, and the same method was used to evaluate the visibility of the liquid such as the panel to compare the display properties of the liquid crystal display panel. After the = = and 1 total for each liquid crystal _ 翁 lower reference, according to the three levels of comprehensive evaluation ^ Bay, 4 according to each evaluation result f, when the viscosity stability characteristics. Among them, all or all of the display properties, the characteristics of the liquid crystal display panel, and the sealing agent are good (〇); each evaluation (〇) ¥, 涊 is the liquid crystal consistency, the liquid crystal display panel material When the viscosity is 敎、, 粘 ® , , , , , , , , , , , , , , , , 任廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿廿In the case of the component (1), 25 parts by weight of o-cresol novolac epoxy resin (EOCN-1020-75, manufactured by Sakamoto Chemical Co., Ltd.) was dissolved and dissolved in the mixture as a component (1). 15 parts by weight of propylene glycol diacetate (manufactured by DOWANOL PGDA, manufactured by DOW CHEMICAL Co., Ltd.), and 20 parts by weight of the acrylic rubber-modified epoxy resin of the following Synthesis Example 1 as a component (2) 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH-J, manufactured by FINETECHNO), and 4 parts by weight of the component (3) Dioxonium dodecanoate (N-12, manufactured by FINECHEM, Japan) and 2 parts by weight of 2,4-diamino-6-[2'-ethyl-4'.methylimidyl-( 1')]_Ethyl_s_Sancha (CUREZOL 2 E4MZ-A, manufactured by Shikoku Chemicals Co., Ltd.), 2 parts by weight of amorphous cerium oxide (MU120, manufactured by Shin-Etsu Chemical Co., Ltd.) and 13 parts by weight of amorphous alumina (UA-5105) as component (4) 5 parts by weight of glycidyloxypropyltrimethoxydecane (ΚΒΜ403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a component (5), premixed in a mixer, and then mixed in a three-roller type. The mixture was kneaded until the solid raw material was 5 υ μπι or less, and then the mixture was subjected to vacuum defoaming treatment to prepare a thermosetting sealant. [Example 2] In addition to the component (3), 4 parts by weight of bismuth sebacate was used. A liquid crystal sealing agent was prepared in the same manner as in Example 1 except for 肼 (SDH). [Example 3] The addition amount of the component (2) was 2 parts by weight, and the component (3) was not used 2,4-diamino group _ 6-[2'-ethyl_4, decyl imidazolylethyl small triterpene 43 200815880 (CUREZOL 2E4MZ_A), and the dodecanedioic acid dioxane (team 12) was 13 parts by weight, and was used in the same manner as in Example 1. A liquid crystal sealing agent was prepared in exactly the same manner. [Example 4] The addition amount of the component (2) was 13 parts by weight, 3) the component does not use 2,4-diamino- 6-[2'-ethyl-4'-methylimidazolyl-(I)-ethyl-s-triazine (CUREZOL 2E4MZ-A), and A liquid crystal sealing C) agent was prepared in exactly the same manner as in Example 1 except that dioxane (N-12) was used in an amount of 2 parts by weight. [Example 5] In addition to the component (2), 9 parts by weight of 2-phenylimidazole (ADECAHARDNER EH-4346S) was used, and the component (3) was not used with 2,4-diaminoethyl-4, decyl imidazolyl-( A liquid crystal sealing agent was prepared in the same manner as in Example 1 except that 1,) ethyl group + triazine (CUREZOL 2E4MZ-A) and 6 parts by weight of dioxane (N-12) dodecanedioic acid were used. [Embodiment 6]

Q 除了⑺成分使用9重量份聚胺基脲系（FUJICURE FXE-1000)，（3)成分未使用2,4-二胺基-6_[2’-乙基-4，-曱基咪唑基-(1，)]-乙基-s-三嗪(CUREZOL 2E4MZ_A)，且十二烷二酸二醯肼(N-12)為6重量份以外，利用與實施例1完全相同之方式製備液晶密封劑。 [實施例7] 除了（2)成分使用9重量份胺加成物系 (ADECAHARDNER EH-4357S)，（3)成分未使用 2,4-二胺基 44 200815880 x y / ριι 各[2，-乙基-4，-甲基咪嗤基_(1，)]_乙基+三嗪（curez〇l 2E4MZ-A)，且十二烷二酸二醯肼(n_12)為6重量份以外，利用與實施例1完全相同之方式製備液晶密封劑。 [實施例8] 除了（2)成分的添加量為6重量份，（3)成分使用9重量 • 份脂肪族二羧酸(ADH)以外，利用與實施例！完全相同之方式製備液晶密封劑。 - [實施例9] ( 將作為⑴成分的15重量份鄰曱酚盼盤環氧樹脂 (EOCN-1020-75，日本化藥(股)製)加熱溶解於3〇重量份雙酚A型環氧二曱基丙烯酸酯（環氧基酯3〇〇〇m，共榮社化學(股)製）中，形成均勻溶液。接下來，將上述混合溶液冷部後，加入20重量份雙酚A型環氧丙稀酸酯(EB3700， DAICEL-CYTEC(股)製）、作為(8)光自由基聚合起始劑的2 重量份1-經基環己基苯基酮（IRGACURE184，CIBA SPECIALTY CHEMICALS(股)製）、作為⑺成分的6重量Q In addition to the (7) component, 9 parts by weight of the polyaminourea system (FUJICURE FXE-1000) is used, and the component (3) is not used with 2,4-diamino-6-[2'-ethyl-4,-mercaptoimidazolyl- A liquid crystal sealing film was prepared in exactly the same manner as in Example 1 except that (1,)]-ethyl-s-triazine (CUREZOL 2E4MZ_A) and 6 parts by weight of dioxonium dodecanoate (N-12) were used. Agent. [Example 7] In addition to the component (2), 9 parts by weight of an amine adduct system (ADECAHARDNER EH-4357S) was used, and the component (3) was not used with 2,4-diamino group 44 200815880 xy / ριι each [2, - B Use of 4,-methylmercapto-(1,)]-ethyl+triazine (curez〇l 2E4MZ-A), and dioxonium dodecanoate (n_12) is 6 parts by weight A liquid crystal sealing agent was prepared in exactly the same manner as in Example 1. [Example 8] The use of the component (2) was 6 parts by weight, and the component (3) was used in an amount of 9 parts by weight or more of the aliphatic dicarboxylic acid (ADH). The liquid crystal encapsulant was prepared in exactly the same manner. - [Example 9] (15 parts by weight of o-nonylphenol-pan epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd.) as the component (1) was heated and dissolved in 3 parts by weight of bisphenol A type ring. A homogeneous solution was formed in oxydimercapto acrylate (epoxy ester 3 〇〇〇m, manufactured by Kyoeisha Chemical Co., Ltd.). Next, after the above mixed solution was cooled, 20 parts by weight of bisphenol A was added. Type epoxy acrylate (EB3700, manufactured by DAICEL-CYTEC Co., Ltd.), 2 parts by weight of (8) photoradical polymerization initiator, 1-fluorocyclohexyl phenyl ketone (IRGACURE 184, CIBA SPECIALTY CHEMICALS ( Share)), as the weight of (7)

〇份！，3_雙（肼基羰乙基>5-異丙基乙内醯脲（AMICURE • VDH_J，味之素FINETECHNO(股)製）、作為(3)成分的2 重量份味唑系（CUREZOL 2Ε4ΜΖ·A，四國化成工業(股)製) 和4重量份十二烷二酸二醯肼(N-12,日本FINECHEM(股) 製）、作為(4)成分的20重量份球狀氧化矽(SEAHOSTAR S-3^0 ’日本觸媒(股)製）、作為(5)成分的1重量份丫_縮水甘油氧丙基三甲氧基矽烷(KBM403，信越化學工業(股)製），用混合裔進行預混。再用三輥式混煉機進行混煉，直至固 45 200815880 體原料小於等於5 μπι，用網孔為10 μπι的過濾器 (MSP-10-E10S，ADVANTEC(股）製）過濾後，對混合物進行真空脫泡處理，製備光和熱固化性密封劑。 [實施例10] 除了（3)成分使用4重量份癸二酸二醯肼(SDH)代替十二烷二酸二醯肼(Ν-12)以外，利用與實施例9完全相同之 _ 方式製備液晶密封劑。 ' [實施例11] 〇除了（2)成分的添加量為2重量份，（3)成分使用10重量份十二烷二酸二醯肼(Ν-12，日本FINECHEM(股）製）以外，利用與實施例9完全相同之方式製備液晶密封劑。 [實施例12] 除了（2)成分的添加量為10重量份，（3)成分使用2重量份十二烷二酸二醯肼(Ν-12)以外，利用與實施例9完全相同之方式製備液晶密封劑。 [實施例13] Q 除了（2)成分使用6重量份2-苯基咪唑 (ADECAHARDNEREH4346S)，（3)成分使用 6 重量份十二烷二酸二醯肼(N-12)以外，利用與實施例9完全相同之方 ' 式製備液晶密封劑。 [實施例H] 除了（2)成分使用6重量份聚胺基脲系（fujiCURE FXE-1000)，（3)成分使用6重量份十二烷二酸二醯肼(N-12) 以外，利用與實施例9完全相同之方式製備液晶密封劑。 46 200815880 [實施例15] 除了（2)成分使用6重量份胺加成物系 (ADECAHARDNEREH4357S)和 6 重量份十二烷二酸二醯肼(N-12，日本FINECHEM(股)製）以外，利用與實施例9 完全相同之方式製備液晶密封劑。 [實施例16] 除了（2)成分使用6重量份1,3-雙(肼基羰乙基)冬異丙 ' 基乙内醯脲(AMICURE VDH)，（3)成分使用5重量份二醯 D 胺系（AH-154)和6重量份脂肪族二羧酸(ADH)以外，利用與實施例9完全相同之方式製備液晶密封劑。 [比較例1] 除了未使用（3)成分，且(2)成分使用15重量份1,3-雙 (肼基羰乙基)-5-異丙基乙内醯脲(AMICURE VDH)以夕卜，利用與實施例1完全相同之方式製備液晶密封劑。 [比較例2] 除了未使用（2)成分，且(3)成分使用15重量份(d)癸二 y 酸二醯肼(SDH)以外，利用與實施例1完全相同之方式製備液晶密封劑。 [比較例3] 除了（2)成分使用9重量份單醯肼系熱潛在性硬化劑 (SMH)，(3)成分使用2重量份咪唑系（〇JREZOL2E4MZ_A) 和4重量份十二烷二酸二醯肼(N-12)以外，利用與實施例1 完全相同之方式製備液晶密封劑。 47 200815880 i y / pn [比較例4] 除了未使用（3)成分，且(2)成分的添加量為12重量份以外，利用與實施例9完全相同之方式製備液晶密封劑。 [比較例5] 除了未使用（2)成分，且(3)成分使用12重量份癸二酸二醯肼(SDH)，並且作為(4)成分的填充劑的添加量為2重量份，（5)成分的添加量為5重量份，（6)成分中使用20重量份環氧二甲基丙烯酸酯和15重量份環氧丙烯酸酯以外，利用與實施例9完全相同之方式製備液晶密封劑。 [比較例6] 除了（2)成分使用6重量份單酸肼系熱潛在性硬化劑 (SMH)，（3)成分使用2重量份咪唑系（CUREZOL2E4MZ-A) 和4重量份十二烷二酸二醯肼(N-12)，並且(4)成分的添加量為2重量份’（5)成分的添加量為5重量份，（6)成分中使用20重量份環氧二曱基丙烯酸酯和15重量份環氧丙烯酸酯以外，利用與實施例9完全相同之方式製備液晶密封劑。各實施例和比較例中使用的液晶密封劑的成分、添加量及各評價結果彙總在表1〜表3中。 48 200815880 [表i] 組成成分溶解度實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 實施例 8 (1) 環氧樹脂 — 25 25 25 25 25 25 25 25 (2) 第一熱潛在性硬化劑 ⑻ 不溶 — — — — 9 — — — (b) 不溶 — — — — — 9 — — (〇) 不溶 9 — ⑹ >100 9 9 2 13 — — — 6 (3) 第二熱潛在性硬化劑 ⑻ 不溶 (b) 不溶 2 2 (c) 不溶 4 — 13 2 6 6 6 — ⑷ 不溶 — 4 — — — — — — 10 — — — — — — — 9 (4) 填充劑 (a) 2 2 2 2 2 2 2 2 (b) 13 13 13 13 13 13 13 13 (5) 其他添加劑 5 5 5 5 5 5 5 5 ⑺ 丙烯酸類橡膠改性環氧樹脂 20 20 20 20 20 20 20 20 溶劑 15 15 15 15 15 15 15 15 (2)成分和(3)成分的摻合比 0.6 0.6 0.9 0,1 0,4 0.4 0.4 0.6 評價 ⑴黏度穩定性〇〇 ◎ 〇 ◎ 〇〇 ◎ (ii)黏合強度初期 ◎ ◎ 〇〇〇〇 ◎ 〇吸濕後 ◎ ◎ 〇 X 〇〇 ◎ X (IV)顯示性初期〇〇〇〇〇〇〇〇吸濕後〇〇 Δ 〇〇〇〇 Δ 綜合評價 ◎ ◎ 〇〇 ◎ ◎ ◎ 〇 ϋ 49 200815880 [表2] 組成成分溶解度實施例實施例10 實施例11 實施例12 實施例13 實施例14 實施例15 實施例16 ⑴ 環氧樹脂 5 11 5 r*- 5 Ί1 5 11 5 11 5 τ 5 11 (2) 第一熱潛在性硬化劑 ⑻ (b) (c) ⑷ 不溶不溶不溶 >100 6 6 2 ο 11 (3) 第二熱潛在性硬化劑 ⑻ (b) ⑷ ⑹ ⑹ 不溶不溶不溶不溶 10 ο 11 6 (4) 填充劑 (c) ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 (5) 其他添加劑 (6) 環氧二甲基丙烯酸酯 ο 3 ο 3 ο 3 ο 3 ο 3 ο 3 環氧丙烯酸酯 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 (8) 光自由基聚合起始劑 (2)成分和(3)成分的摻合比 ⑴黏度穩定性 ◎ ◎ ◎ 評價 (iii)黏合強度初期吸濕後 ◎ ◎ ◎ ◎ ◎ ◎ (v)顯示性綜合評價初期吸濕後 Δ Δ ◎ ◎ 〇 ◎ ◎ ◎ 〇 Ο 50 200815880 [表3] 組成成分溶解度 ⑴ 樹脂第不溶比較例 1 比較例 "2? 比較例比較例4 比較例5 比較例 (2) 熱潛在性硬化劑 (b) (c) (d) 不溶不溶 >100 15 (3) ia)_ (b) 不溶不溶 2 11 〇 (c) 2 11 第二熱潛在性硬化劑 (d) (e) 熱潛在性H匕#| A 不溶不溶 10 15〇! , 3_bis(decylcarbonylethyl)5-isopropylethyl carbazide (AMICURE • VDH_J, manufactured by Ajinomoto FINETECHNO Co., Ltd.), and 2 parts by weight of the oxazoline (CUREZOL) as the component (3) 2Ε4ΜΖ·A, Shikoku Chemical Industry Co., Ltd.) and 4 parts by weight of dioxonium dodecanoate (N-12, manufactured by Japan FINECHEM Co., Ltd.), 20 parts by weight of spherical component (4)矽 (SEAHOSTAR S-3^0 'Nippon Catalyst Co., Ltd.), 1 part by weight of (_glycidoxypropyltrimethoxy decane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) as component (5), Premixed with a mixed-use, and then mixed with a three-roller mixer until the solid 45 200815880 body material is less than or equal to 5 μπι, using a filter with a mesh size of 10 μm (MSP-10-E10S, ADVANTEC) After filtration, the mixture was subjected to vacuum defoaming treatment to prepare a light and heat-curable sealant. [Example 10] In addition to the component (3), 4 parts by weight of dioxonium sebacate (SDH) was used instead of dodecane two. A liquid crystal sealing agent was prepared in the same manner as in Example 9 except for acid diterpene (Ν-12). [Example 11] The addition amount of the component (2) was 2 weights. In the component (3), a liquid crystal sealing agent was prepared in the same manner as in Example 9 except that 10 parts by weight of dioxonium dodecanoate (manufactured by Nippon FINECHEM Co., Ltd.) was used. A liquid crystal sealing agent was prepared in the same manner as in Example 9 except that the amount of the component (2) was 10 parts by weight, and the component (3) was used in an amount of 2 parts by weight of dioxonium didecanoate (Ν-12). [Example 13] Q In addition to the component (2), 6 parts by weight of 2-phenylimidazole (ADECAHARDNEREH 4346S) was used, and the component (3) was used in an amount of 6 parts by weight of dioxonium dicarboxylate (N-12). The liquid crystal sealing agent was prepared in the same manner as in Example 9. [Example H] In addition to the component (2), 6 parts by weight of polyamine urea system (fujiCURE FXE-1000) was used, and the component (3) was used in an amount of 6 parts by weight. A liquid crystal sealing agent was prepared in the same manner as in Example 9 except for the dioxane (N-12). 46 200815880 [Example 15] In addition to the component (2), 6 parts by weight of an amine adduct system (ADECAHARDNEREH4357S) was used. And 6 parts by weight of dioxonium dodecanoate (N-12, manufactured by Japan FINECHEM Co., Ltd.) Example 9 A liquid crystal sealing agent was prepared in exactly the same manner. [Example 16] In addition to the component (2), 6 parts by weight of 1,3-bis(decylcarbonylethyl)-when-isopropyl-ethyl carbazide (AMICURE VDH) was used. (3) A liquid crystal sealing agent was prepared in the same manner as in Example 9 except that 5 parts by weight of a diterpene D amine system (AH-154) and 6 parts by weight of an aliphatic dicarboxylic acid (ADH) were used. [Comparative Example 1] Except that the component (3) was not used, and (2) component was used in an amount of 15 parts by weight of 1,3-bis(decylcarbonylethyl)-5-isopropylhydantoin (AMICURE VDH) A liquid crystal sealing agent was prepared in exactly the same manner as in Example 1. [Comparative Example 2] A liquid crystal sealing agent was prepared in the same manner as in Example 1 except that the component (2) was not used, and (3) component was used in an amount of 15 parts by weight of (d) dinonyl ruthenium dioxime (SDH). . [Comparative Example 3] In addition to the component (2), 9 parts by weight of a monoterpene thermal latent curing agent (SMH) was used, and the component (3) was used in an amount of 2 parts by weight of an imidazole system (〇JREZOL 2E4MZ_A) and 4 parts by weight of dodecanedioic acid. A liquid crystal sealing agent was prepared in the same manner as in Example 1 except for the second layer (N-12). 47 200815880 i y / pn [Comparative Example 4] A liquid crystal sealing agent was prepared in the same manner as in Example 9 except that the component (3) was not used and the amount of the component (2) added was 12 parts by weight. [Comparative Example 5] The component (2) was used, and 12 parts by weight of diterpene sebacate (SDH) was used as the component (3), and the amount of the filler as the component (4) was 2 parts by weight ( 5) A liquid crystal sealing agent was prepared in the same manner as in Example 9 except that the component was added in an amount of 5 parts by weight, and 20 parts by weight of epoxy dimethacrylate and 15 parts by weight of epoxy acrylate were used in the component (6). . [Comparative Example 6] In the case of the component (2), 6 parts by weight of a barium-based thermal latent curing agent (SMH) was used, and the component (3) was used in an amount of 2 parts by weight of an imidazole-based (CUREZOL 2E4MZ-A) and 4 parts by weight of dodecane. Dioxonium (N-12), and the amount of the component (4) added is 2 parts by weight 'the amount of the component (5) is 5 parts by weight, and 20 parts by weight of the component (6) is epoxy bisacrylic acid. A liquid crystal sealing agent was prepared in the same manner as in Example 9 except for the ester and 15 parts by weight of the epoxy acrylate. The components, the amounts of addition, and the respective evaluation results of the liquid crystal sealing agent used in each of the examples and the comparative examples are summarized in Tables 1 to 3. 48 200815880 [Table i] Composition Solubility Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 (1) Epoxy resin - 25 25 25 25 25 25 25 25 (2 ) The first thermal latent hardener (8) Insoluble — — — 9 — — — (b) Insoluble — — — — — 9 — — (〇) Insoluble 9 — (6) >100 9 9 2 13 — — — 6 (3 ) Second thermal latent hardener (8) Insoluble (b) Insoluble 2 2 (c) Insoluble 4 — 13 2 6 6 6 — (4) Insoluble — 4 — — — — — — 10 — — — — — — — 9 (4) Filler (a) 2 2 2 2 2 2 2 2 (b) 13 13 13 13 13 13 13 13 (5) Other additives 5 5 5 5 5 5 5 5 (7) Acrylic rubber modified epoxy resin 20 20 20 20 20 20 20 20 Solvent 15 15 15 15 15 15 15 15 (2) Mixing ratio of component (3) and component (3) 0.6 0.6 0.9 0,1 0,4 0.4 0.4 0.6 Evaluation (1) Viscosity stability 〇〇◎ 〇◎ 〇〇 ◎ (ii) Initial strength of bonding ◎ ◎ 〇〇〇〇 ◎ 〇 After moisture absorption ◎ ◎ 〇X 〇〇◎ X (IV) display 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 Δ 综合综合 ◎ ◎ 〇ϋ 49 200815880 [Table 2] Composition Solubility Example Example 10 Example 11 Implementation Example 12 Example 13 Example 14 Example 15 Example 16 (1) Epoxy resin 5 11 5 r*- 5 Ί1 5 11 5 11 5 τ 5 11 (2) First thermal latent curing agent (8) (b) (c (4) Insoluble, insoluble, insoluble >100 6 6 2 ο 11 (3) Second thermal latent curing agent (8) (b) (4) (6) (6) Insoluble, insoluble, insoluble, insoluble 10 ο 11 6 (4) Filler (c) ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 (5) Other Additives (6) Epoxy Dimethacrylate ο 3 ο 3 ο 3 ο 3 ο 3 ο 3 Epoxy Acrylate ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 ο 2 (8) Blending ratio of the photoradical polymerization initiator (2) component and (3) component (1) Viscosity stability ◎ ◎ Evaluation (iii) Adhesive strength at the initial stage of moisture absorption ◎ ◎ ◎ ◎ ◎ ◎ (v) Displayability comprehensive evaluation Initial moisture absorption Δ Δ ◎ ◎ 〇 ◎ ◎ ◎ 〇Ο 50 200815880 [Table 3] Composition solubility (1) Tree Insoluble Comparative Example 1 Comparative Example "2? Comparative Example Comparative Example 4 Comparative Example 5 Comparative Example (2) Thermal latent curing agent (b) (c) (d) Insoluble and insoluble > 100 15 (3) ia) (b) Insoluble and insoluble 2 11 〇(c) 2 11 Second thermal latent hardener (d) (e) Thermal latent H匕#| A Insoluble and insoluble 10 15

3 1X ο 2 5 11 5 11 改性環氧樹脂3 1X ο 2 5 11 5 11 Modified epoxy resin

20 取成分的摻合比20 Take the blending ratio of ingredients

◎ 由表1、表2明確癌認：使用了本申請發明的實施你〜16的液晶密封劑的上述黏度穩定性、黏合強度及使用述液sa禮封劑製造的液晶顯示面板的顯示性非常優異。另一方面，當以一種熱潛在性硬化劑和環氧樹脂作構成成分的液晶密封劑的情況下，由表3所示的各比較/ 51 200815880 的結果可知··與各實施例相比，黏度穩定性、黏合強度以及液晶顯示面板的顯示性變差。當熱潛在性硬化劑使用單驢肼系化合物時，確認黏度穩定性等諸特性變差。由以上結果可知：在醯肼化合物中，非單醯肼系而是二醯肼系熱潛在性硬化劑適合於液晶密封劑。 ' 、本發明的液晶密封劑，由於使用了熔點不同的2種熱 • 潛在性硬化劑，因此固化速度快，且耐濕性變高。另外， f ' 可，，間保持高黏度穩定性，故可使用時間長。若將上述液晶密封劑用於液晶顯示面板，則固化的液晶密封劑和基 =的黏合強度變高，因此可以得到耐濕可靠性高且顯示性 ^的液晶顯示面板。所以，本發明的液晶密封劑，即使白勺為包括液晶顯示面板的各種光學裝置的黏合劑也是有用雖然本發明已以較佳實施例揭限定本發明，任何孰習此減去* …、其嚴非用以，當可作些許之更動與潤飾，因神 C ^#視_之”專騎界定者轉。“之保護 • 【圖式簡單說明】百乃半【主要元件符號說明】 on 52◎ It is clear from Tables 1 and 2 that the above-mentioned viscosity stability, adhesion strength, and displayability of a liquid crystal display panel manufactured using the liquid sa sealing agent using the liquid crystal sealing agent of the invention of the present invention are very Excellent. On the other hand, in the case of a liquid crystal sealing agent containing a thermal latent curing agent and an epoxy resin as constituent components, it is known from the results of the comparisons shown in Table 3 / 51 200815880 that compared with the respective examples, Viscosity stability, adhesive strength, and displayability of the liquid crystal display panel deteriorate. When a monoterpene compound is used as the thermal latent curing agent, it is confirmed that the properties such as viscosity stability are deteriorated. From the above results, it is understood that among the antimony compounds, a non-monoterpene system is a diterpene thermal latent curing agent suitable for a liquid crystal sealing agent. In the liquid crystal sealing agent of the present invention, since two kinds of thermal latent curing agents having different melting points are used, the curing speed is high and the moisture resistance is high. In addition, f ' can, and maintain high viscosity stability, so it can be used for a long time. When the liquid crystal sealing agent is used for a liquid crystal display panel, the cured liquid crystal sealing agent and the base have a high bonding strength, so that a liquid crystal display panel having high moisture resistance reliability and display property can be obtained. Therefore, the liquid crystal sealing agent of the present invention is useful even if it is a binder of various optical devices including a liquid crystal display panel. Although the present invention has been limited to the present invention by a preferred embodiment, any of the above-mentioned subtraction is ... Strictly used, when you can make some changes and refinements, because God C ^ #视_ _ "Special rider defines the turn. "Protection • [Simple diagram] Bai Naiqi [main symbol description] on 52

Claims

200815880 十、申請專利範圍： L一種液晶密封劑，包括： (1) 環氧樹脂； (2) 熔點小於等於15(rc (物大於等於峨的=潛在性硬化劑；以及上峨分為選自二酸肼弟二::在性侧^ 聚胺系和聚胺美脇备勒概未唑糸、胺加成物系、 Γ u 或-種以上^ w。、"曰在十硬化劑所組成的組群的一種乂禋以上的熱潛在性硬化劑， τ ^ 上述(3)成分為選自二醯肼系、* 在性硬化_組成的組群的 ^糸和—_系熱潛化劑。次—種以上的熱潛在性硬 2.如申請專利範圍第丨項所述述，分和上述⑺成分為二_系熱夜; ㈣專魏圍第1項所述之液晶密封劑述(3)成分相對於25它的水100ml的溶解度小其中上、4.如申料利範圍帛丨韻述之液晶=於2〇g。述(3)成分為下述通式(A)所示的化合物· θ 其中上【化1】200815880 X. Patent application scope: L A liquid crystal sealant, including: (1) epoxy resin; (2) melting point less than or equal to 15 (rc (more than or equal to 峨 = latent hardener; and upper sputum is selected from Diacid diterpenoid II:: On the sexual side ^ Polyamines and polyamines Mi's preservatives are not oxazolidine, amine addition systems, Γ u or - more than ^ w., " 曰 in ten hardeners a group of thermal latent hardeners of 乂禋 or more, τ ^ The above components (3) are selected from the group consisting of diterpenoids, * in the group of hardening _ composition, and - _ system thermal latentization The thermal potential of the above-mentioned sub-species is hard. 2. As described in the scope of the patent application, the sub-component (7) is the second-class hot night; (4) The liquid crystal sealing agent described in the first paragraph of Weiwei (3) The solubility of the component relative to 25 of its water 100 ml is small, and the upper part is 4. The liquid crystal of the rhyme is as follows: (2) The composition is the following general formula (A) Compound θ shown therein

53 200815880 '、中，上述通式(A)中的R表示碳數大於等於δ的亞烷晶穷^利喊第1賴述之液晶密封劑，上述液液:密^將上述⑴〜⑺成分均勻混合而柳^53 200815880 ', wherein R in the above formula (A) represents an alkylene oxide having a carbon number of δ or more, and the liquid crystal sealing agent of the first embodiment is used, and the liquid liquid: the above components (1) to (7) Evenly mixed and willow ^

成分的^/^上；4液晶密封劑，上述(2)成分和上述⑶ 」、心添加置為1〜25重量份。述⑵料鄉㈣1 _述之液晶密_，當將上作為^ 1重量作為W1、將上述(3)成分的添加重量乍為 W2 時，〇mW2/(w1+W2)^〇.8。對:二=二第丄項所上述r液晶密封劑’其中相的活性氮當量總 9丄-種液晶顯示面板的製造方法，是將對向的兩塊基板錯由液晶密封劑貼合在—起來製造液晶顯示面板，上述方法包括： > fJl述基板的製程，上述基板包括按照像素排列區 V被如中4專利範圍第1項所述之液晶密封劑包圍的方式形成—的設有液晶的注人口的框狀的顯示區域；曰藉由上述液晶密封舰上述兩塊基板重合後，進行加 …匕&使上述基板彼此貼合，從而在上述兩塊基板之間形成液晶盒的製程；自上述注人口向上述液晶盒内注人液晶的製程；以及 54 200815880 利用封閉用密封劑注入口封閉的製程。八頁，夜曰曰的上述液晶盒的上述板藉由液晶_ ί 3對向的兩塊基方法包括：衣以’夜日日顯示面板，上述準備上述基板的製程，上域被如申請專利範圍第1項所述之液晶密:劑形成的框狀的顯示區域；了剎匕回的方式向未固化狀態的上述顯示區域内或另—塊上述美滴注液晶的製程； i 將滴注有液晶的上述基板和另一塊上述基板在減壓下重合的製程；以及 i 藉由加熱使存在於重合的上述兩塊基板之間的上述液晶密封劑固化的製程。 11·一種液晶顯示面板，是利用如申請專利範圍第9項或第10項所述之液晶顯示面板的製造方法得到的。 55 200815880 七、指定代表圖： (一）本案指定代表圖為：無。 (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： ^ 益〇4 liquid crystal sealing agent, the above component (2) and the above (3)", and the core addition is set to 1 to 25 parts by weight. In the case of (2) material town (4) 1 _ described liquid crystal density _, when the weight of ^1 is W1 and the weight of the above component (3) is W2, 〇mW2/(w1+W2)^〇.8. For the second liquid crystal sealing agent of the above-mentioned r liquid crystal sealing agent, the active nitrogen equivalent of the phase is 9 丄 - the liquid crystal display panel manufacturing method is that the two opposing substrates are misaligned by the liquid crystal sealing agent - The method for manufacturing a liquid crystal display panel, the method comprising: > fJ1 describing a substrate process, wherein the substrate comprises a liquid crystal encapsulant formed according to the pixel arrangement region V, which is surrounded by the liquid crystal sealing agent according to the first item of the fourth patent scope. a frame-shaped display area of the population; 重 by superimposing the two substrates on the liquid crystal sealing ship, and then bonding the substrates to each other to form a liquid crystal cell between the two substrates The process of injecting liquid crystal into the above liquid crystal cell from the above-mentioned injection population; and 54 200815880 a process closed by a sealing agent injection port. Eight pages, the two base methods of the above-mentioned board of the above-mentioned liquid crystal cell by the liquid crystal _ ί 3 include: the clothing is a 'night day display panel, the above-mentioned preparation process of the above-mentioned substrate, and the upper domain is patented. The liquid crystal density according to the first item: the frame-shaped display area formed by the agent; the method of braking the way back to the display area in the uncured state or the other process of the above-mentioned beauty dripping liquid crystal; i will drip a process in which the substrate of the liquid crystal and the other substrate are superposed under reduced pressure; and a process of curing the liquid crystal sealing agent existing between the two substrates which are overlapped by heating. A liquid crystal display panel obtained by the method of manufacturing a liquid crystal display panel according to claim 9 or 10. 55 200815880 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (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 * ^ Yi Yi