TWI471351B - Sealing agent for liquid-crystal-one-drop-filling process and method for manufacturing liquid crystal display - Google Patents
Sealing agent for liquid-crystal-one-drop-filling process and method for manufacturing liquid crystal display Download PDFInfo
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本發明係關於藉助液晶滴注製程來製造液晶顯示器之方法,且尤其係關於其中藉由使用與光固化及熱固化組合使用之密封劑在基板外周形成主密封之製造方法。本發明亦係關於用於其之密封劑。The present invention relates to a method of manufacturing a liquid crystal display by means of a liquid crystal dropping process, and in particular to a manufacturing method in which a main seal is formed on the outer periphery of a substrate by using a sealant used in combination with photocuring and heat curing. The invention also relates to a sealant for use therewith.
在組裝尺寸相對較小之液晶顯示器(下文亦稱作LCD)之習用方法中,使兩個帶電極之透明基板以給定距離彼此對置,用密封劑將其周邊黏結起來以形成單元,自形成於該周邊之一部分處之液晶入口將液晶引入該單元中,及最後用密封劑密封液晶之入口來製造LCD。In a conventional method of assembling a liquid crystal display (hereinafter also referred to as LCD) having a relatively small size, two transparent substrates with electrodes are opposed to each other at a given distance, and a periphery thereof is bonded with a sealant to form a unit. The liquid crystal inlet formed at a portion of the periphery introduces liquid crystal into the unit, and finally the sealant seals the entrance of the liquid crystal to manufacture the LCD.
近年來,隨著大尺寸LCD的逐漸滲透,上述製造方法已造成了各種問題,例如,因液晶注射需要極長時間所致之低生產率。In recent years, with the gradual penetration of large-sized LCDs, the above-described manufacturing method has caused various problems, for example, low productivity due to the extremely long time required for liquid crystal injection.
前人已研究了稱作液晶滴注製程(ODF製程)之製造LCD之方法並將其作為製造大尺寸LCD之高效方法投入實際應用。在該製程中,首先在兩個帶電極之透明基板中之一個上藉助絲網印刷及諸如此類來形成矩形圖案密封。然後,將液晶微滴滴入透明基板上之密封框架中,但並不對密封劑實施固化。將另一透明基板放置其上,隨後固化密封劑以製造LCD。低壓層壓基板以便高效製造LCD。Previously, a method of manufacturing an LCD called a liquid crystal dropping process (ODF process) has been studied and put into practical use as an efficient method for manufacturing a large-sized LCD. In this process, a rectangular pattern seal is first formed by screen printing and the like on one of two transparent substrates with electrodes. Then, the liquid crystal droplets were dropped into the sealing frame on the transparent substrate, but the sealing agent was not cured. Another transparent substrate was placed thereon, and then the sealant was cured to manufacture an LCD. Low-voltage laminate substrates for efficient LCD manufacturing.
用於液晶滴注製程之密封劑通常係UV固化型或UV-熱組合固化型(JP-A-2001-133,794(專利文件1)、JP-A-2006-23,580(專利文件2)、JP-A-2006-23,581(專利文件3)、JP-A-2006-23,582(專利文件4)及諸如此類)。在UV-熱組合固化型之應用中,在將兩個基板彼此對置放置後,藉由短時間UV輻照將密封劑固化至不會發生移動之程度,隨後實施進一步加熱以熱固化該密封劑來達成最終強度,因此認為其可靠性較為有利。The sealant used in the liquid crystal dropping process is usually a UV curing type or a UV-thermal combination curing type (JP-A-2001-133, 794 (Patent Document 1), JP-A-2006-23, 580 (Patent Document 2), JP- A-2006-23,581 (Patent Document 3), JP-A-2006-23,582 (Patent Document 4), and the like. In the UV-thermal combination curing type application, after the two substrates are placed opposite each other, the sealant is cured to a degree that does not move by short-time UV irradiation, and then further heating is performed to thermally cure the seal. The agent is used to achieve the final strength, so it is considered to be more advantageous.
然而,UV固化型及UV-熱組合固化型密封劑含有光聚合起始劑。在UV輻照期間內未分解之殘餘光起始劑及由UV輻照所分解之材料接觸液晶材料會對液晶產生不利影響。前文所述之專利文件闡述了使用具有丙烯酸系基團之聚合起始劑可降低殘餘量(例如,專利文件2,第0022至0024段)。然而,人們認為光碎片化一定會產生分解材料,此乃因該分子含有光碎片化位點及丙烯酸系基團。However, the UV-curable and UV-thermal combination-curing sealants contain a photopolymerization initiator. The residual photoinitiator which is not decomposed during UV irradiation and the material which is decomposed by UV irradiation are in contact with the liquid crystal material, which adversely affects the liquid crystal. The patent documents described above state that the use of a polymerization initiator having an acrylic group can reduce the residual amount (for example, Patent Document 2, paragraphs 0022 to 0024). However, it is believed that photo-fragmentation must produce a decomposing material because the molecule contains a photo-fragmentation site and an acrylic group.
另一方面,已知包括馬來醯亞胺化合物之熱固性黏合劑及密封劑係無需使用光聚合起始劑之固化系統{參見,例如,WO 2003/082,940(專利文件5)、WO 2003/107,427(專利文件6)、JP-A-2005-532,678}。On the other hand, a thermosetting binder and a sealant comprising a maleic imine compound are known to be a curing system which does not require the use of a photopolymerization initiator (see, for example, WO 2003/082,940 (Patent Document 5), WO 2003/107,427 (Patent Document 6), JP-A-2005-532, 678}.
作為包括馬來醯亞胺化合物之組合物用於液晶應用中之申請案,JP-A-2002-338946(專利文件7)揭示了含(甲基)丙烯酸酯寡聚物及馬來醯亞胺衍生物之密封劑,且JP-A-2003-34708(專利文件8)揭示了含有環氧樹脂及含馬來醯亞胺之羧酸(maleimide-containing carboxylic acid)的樹脂組合物。然而,該等係用於形成具有「液晶入口」之空單元的密封劑,且未闡述液晶滴注製程(ODF製程)之應用。JP-A-2005-2015(專利文件9)已提出一種含馬來醯亞胺化合物之組合物,該化合物作為用於液晶滴注製程(ODF製程)之密封化合物具有衍生自雙酚-S之部分。另外,專利文件9已指出以下可能性,即,若將專利文件8之習用密封劑用作ODF製程之密封劑,則可能洗脫出馬來醯亞胺化合物及其他可聚合組份。JP-A-2002-338946 (Patent Document 7) discloses a (meth) acrylate-containing oligomer and a maleimide, as an application for a liquid crystal application, which comprises a composition of a maleimide compound. A sealant of a derivative, and JP-A-2003-34708 (Patent Document 8) discloses a resin composition containing an epoxy resin and a maleimide-containing carboxylic acid. However, these are used to form an encapsulant having an empty cell of "liquid crystal inlet", and the application of the liquid crystal dropping process (ODF process) is not explained. JP-A-2005-2015 (Patent Document 9) has proposed a composition containing a maleic imine compound which is derived from a bisphenol-S as a sealing compound for a liquid crystal dropping process (ODF process). section. Further, Patent Document 9 has pointed out the possibility that if the conventional sealant of Patent Document 8 is used as a sealant for the ODF process, the maleic imine compound and other polymerizable components may be eluted.
如上文所述,僅已知含特別馬來醯亞胺化合物且作為UV-熱組合固化型密封劑之密封劑,其適於ODF製程,且無需光聚合起始劑。As described above, only a sealant containing a special maleimide compound as a UV-heat combination curing type sealant is known, which is suitable for an ODF process, and does not require a photopolymerization initiator.
文件列表document list
專利文件1:JP-A-2001-133,794Patent Document 1: JP-A-2001-133, 794
專利文件2:JP-A-2006-23,580Patent Document 2: JP-A-2006-23, 580
專利文件3:JP-A-2006-23,581Patent Document 3: JP-A-2006-23, 581
專利文件4:JP-A-2006-23,582Patent Document 4: JP-A-2006-23,582
專利文件5:WO2003/082,940Patent Document 5: WO2003/082,940
專利文件6:WO2003/107,427Patent Document 6: WO2003/107,427
專利文件7:JP-2002-338946Patent Document 7: JP-2002-338946
專利文件8:JP-A-2003-34708Patent Document 8: JP-A-2003-34708
專利文件9:JP-A-2005-2015Patent Document 9: JP-A-2005-2015
本發明一個目的係提供藉助液晶滴注製程經由光-熱組合固化樹脂來製造LCD之方法,其不會對液晶產生不利影響且可製造具有優良的長期耐久性及高精度之LCD。An object of the present invention is to provide a method for manufacturing an LCD by photo-thermal combination curing of a resin by a liquid crystal dropping process which does not adversely affect liquid crystals and which can manufacture an LCD having excellent long-term durability and high precision.
本發明係關於下述條目。The present invention relates to the following items.
1.一種密封劑,其用於藉由液晶滴注製程來製造液晶顯示器,其中該密封劑至少包含馬來醯亞胺化合物且不含有光起始劑;且其中該密封劑可藉由光輻照暫時固化且可在該光輻照後藉由加熱固化至最終固化狀態。A sealant for manufacturing a liquid crystal display by a liquid crystal dropping process, wherein the sealant comprises at least a maleimide compound and does not contain a photoinitiator; and wherein the sealant can be irradiated by light It is temporarily cured and can be cured by heating to a final cured state after the irradiation of the light.
2.如上述條目1之密封劑,其另外包含環氧樹脂及潛在環氧硬化劑。2. The sealant of item 1 above, which additionally comprises an epoxy resin and a latent epoxy hardener.
3.如上述條目1或2中任一項之密封劑,其另外包含選自由填充劑、觸變劑及矽烷偶合劑組成之群的添加劑。3. The sealant according to any one of the above items 1 or 2, which further comprises an additive selected from the group consisting of a filler, a thixotropic agent and a decane coupling agent.
4.如上述條目2或3中任一項之密封劑,其中該環氧樹脂係選自由雙酚環氧樹脂、線性酚醛環氧樹脂及聯苯環氧樹脂組成之群。4. The sealant of any one of clauses 2 or 3, wherein the epoxy resin is selected from the group consisting of bisphenol epoxy resins, novolac epoxy resins, and biphenyl epoxy resins.
5.如上述條目2至4中任一項之密封劑,其中該潛在環氧硬化劑係選自有機酸二醯肼。5. The sealant of any of items 2 to 4 above, wherein the latent epoxy hardener is selected from the group consisting of diterpenoids.
6.如上述條目1至5中任一項之密封劑,其中該馬來醯亞胺化合物係選自由硬脂醯馬來醯亞胺、油基馬來醯亞胺、二十二烷基馬來醯亞胺及10,11-二辛基二十烷之1,20-雙馬來醯亞胺衍生物及其組合組成之群。The sealant according to any one of the above items 1 to 5, wherein the maleimide compound is selected from the group consisting of stearin, maleimide, oleyl maleimide, and behenyl A group consisting of quinone imine and 1,10-dimaleimide derivatives of 10,11-dioctylicocosane and combinations thereof.
7.一種藉助液晶滴注製程來製造液晶顯示器之方法,該液晶顯示器在第一基板與第二基板間具有液晶層,該方法包含下述步驟:7. A method of fabricating a liquid crystal display by means of a liquid crystal dropping process, the liquid crystal display having a liquid crystal layer between a first substrate and a second substrate, the method comprising the steps of:
(a)在該第一基板表面外周之密封區域上施加如上述條目1至6中任一項之密封劑;(a) applying a sealant according to any one of the above items 1 to 6 on a sealing region on the outer periphery of the surface of the first substrate;
(b)在由該第一基板表面之密封區域所包圍之中心區域上滴加液晶;(b) dropping liquid crystal on a central region surrounded by the sealing region of the surface of the first substrate;
(c)將該第二基板覆蓋於該第一基板上;(c) covering the second substrate on the first substrate;
(d)藉由光輻照該密封劑來實施暫時固定;及(d) performing temporary fixation by irradiating the sealant with light; and
(e)藉由加熱該密封劑來實施最終固定。(e) Final fixing is carried out by heating the sealant.
8.一種在第一基板與第二基板間具有液晶層之液晶顯示器,其中該液晶顯示器係藉由液晶滴注製程來製造,其中該液晶顯示器係藉由如上述條目1至6中任一項之密封劑的固化產物來進行密封。8. A liquid crystal display having a liquid crystal layer between a first substrate and a second substrate, wherein the liquid crystal display is manufactured by a liquid crystal dropping process, wherein the liquid crystal display is by any one of the above items 1 to 6 The cured product of the sealant is sealed.
使用用於液晶滴注製程之本發明密封劑允許製造不會發生移動之LCD,同時可保持精準定位且不會對液晶產生不利影響。然後,所製造LCD在其密封區域中具有優良耐久性及可靠性。The use of the sealant of the present invention for a liquid crystal dropping process allows the manufacture of an LCD that does not move while maintaining precise positioning without adversely affecting the liquid crystal. Then, the manufactured LCD has excellent durability and reliability in its sealed region.
本發明製造方法通常包含下述步驟:The manufacturing method of the present invention generally comprises the following steps:
(a)在第一基板表面外周之密封區域上施加液體密封劑;(a) applying a liquid sealant on the sealing area on the outer periphery of the surface of the first substrate;
(b)在由該基板表面之密封區域所圍繞之中心區域上滴加液晶;(b) dropping a liquid crystal on a central region surrounded by a sealing region on the surface of the substrate;
(c)將該第二基板覆蓋於該第一基板上;(c) covering the second substrate on the first substrate;
(d)藉由光輻照該密封劑來實施暫時固定;及(d) performing temporary fixation by irradiating the sealant with light; and
(e)藉由加熱該密封劑來實施最終固定。(e) Final fixing is carried out by heating the sealant.
在本發明中所用之第一基板及第二基板一般係透明玻璃基板。通常,透明電極、主動矩陣元件(例如,TFT)、配向膜、彩色濾光器及諸如此類係在兩個基板之至少一個對置面上形成。該等構造可根據LCD之類型來進行修改。吾人相信本發明製造方法可用於任何類型之LCD。The first substrate and the second substrate used in the present invention are generally transparent glass substrates. Generally, a transparent electrode, an active matrix element (for example, a TFT), an alignment film, a color filter, and the like are formed on at least one opposing surface of two substrates. These configurations can be modified depending on the type of LCD. I believe that the manufacturing method of the present invention can be applied to any type of LCD.
在步驟(a)中,將密封劑施加於一個該等基板之第一基板表面(另一基板之對置面)之外周部分上以便沿框架形狀圍住基板周邊。如本文所述,沿框架形狀施加密封劑之部分稱作密封區域。此時,密封劑係流體以便其能夠及可能藉由已知方法(例如,絲網印刷及分配)來施加。In the step (a), a sealant is applied to the outer peripheral portion of the first substrate surface (opposing surface of the other substrate) of one of the substrates so as to surround the substrate periphery along the shape of the frame. As described herein, the portion of the sealant applied along the shape of the frame is referred to as a sealed region. At this point, the sealant is a fluid so that it can and can be applied by known methods (eg, screen printing and dispensing).
在步驟(b)中,隨後將液晶滴加至由第一基板表面上沿框架形狀之密封區域所包圍之中心區域上。該步驟較佳在低壓下實施。In the step (b), the liquid crystal is then dropped onto the central region surrounded by the sealing region of the frame shape on the surface of the first substrate. This step is preferably carried out at a low pressure.
在步驟(c)中,隨後將該第二基板放置於該第一基板上,並在步驟(d)中對其實施光輻照。藉由該光輻照,可暫時固化密封劑且其展示其強度處於藉由手工不會發生移動之程度,藉此可將該等兩個基板暫時固定。In step (c), the second substrate is then placed on the first substrate and subjected to light irradiation in step (d). By the irradiation of the light, the sealant can be temporarily cured and exhibiting its strength to such an extent that it does not move by hand, whereby the two substrates can be temporarily fixed.
在步驟(d)之光輻照中,可至少使密封劑曝光且不必輻照整個基板。通常,輻射時間較短較佳,例如,不長於5分鐘、較佳不長於3分鐘、更佳不長於1分鐘。In the light irradiation of step (d), at least the sealant may be exposed and it is not necessary to irradiate the entire substrate. Generally, the irradiation time is preferably shorter, for example, no longer than 5 minutes, preferably no longer than 3 minutes, and even more preferably no longer than 1 minute.
在步驟(e)中,加熱密封劑使得密封劑達成最終固化強度(最終固化),藉此可最終固定該等兩個基板。In step (e), the encapsulant is heated such that the encapsulant achieves a final cure strength (final cure) whereby the two substrates can be finally secured.
在步驟(e)中之熱固化通常根據加熱曲線來進行加熱,該加熱曲線包括較佳高達150℃、及更佳高達130℃之最大溫度。加熱時間可任意選擇,例如,不長於3小時、較佳不長於2小時、仍較佳不長於1.5小時(通常為1小時)。對加熱設備並無特別限制,且可為能夠在其內部容納經暫時固定之基板的加熱設備。The thermal curing in step (e) is typically carried out according to a heating profile comprising a maximum temperature of preferably up to 150 ° C, and more preferably up to 130 ° C. The heating time can be arbitrarily selected, for example, no longer than 3 hours, preferably no longer than 2 hours, still preferably no longer than 1.5 hours (usually 1 hour). The heating device is not particularly limited, and may be a heating device capable of accommodating a temporarily fixed substrate therein.
藉由上述製程,完成LCD面板之主要部分。Through the above process, the main part of the LCD panel is completed.
接下來,解釋擬用於本發明中之密封劑。該密封劑之特徵在於至少包含馬來醯亞胺化合物且不包含光起始劑。在本發明之一個較佳實施例中,密封劑另外包含熱固性樹脂,尤佳包含環氧樹脂及固化該環氧樹脂之潛在環氧硬化劑。密封劑可另外包含(甲基)丙烯酸酯化合物或可不另外包含該化合物。即便不含有(甲基)丙烯酸酯化合物,亦可達成滿意性質。Next, the sealant to be used in the present invention will be explained. The encapsulant is characterized by comprising at least a maleimide compound and no photoinitiator. In a preferred embodiment of the invention, the encapsulant additionally comprises a thermosetting resin, particularly preferably an epoxy resin and a latent epoxy hardener that cures the epoxy resin. The sealant may additionally contain a (meth) acrylate compound or may not additionally comprise the compound. Satisfactory properties can be achieved even without the (meth) acrylate compound.
如本發明中所定義之「光起始劑」包括通常用於光聚合之光起始劑。馬來醯亞胺化合物並非意指光起始劑。「光起始劑」亦並不包括可在本發明中用作可選組份之普通(甲基)丙烯酸酯化合物。然而,「光起始劑」包括具有能夠產生除(甲基)丙烯酸酯基團外之基團部分的化合物,即便其具有(甲基)丙烯酸酯基團(即,(甲基)丙烯醯氧基)時亦如此。特定而言,如(例如)JP-A-2006-23580中所述,具有安息香(醚)結構與丙烯酸酯基團(丙烯醯氧基)之化合物係「光起始劑」。據推測,該化合物藉由在基團產生部位實施切割甚至可產生分解物。The "photoinitiator" as defined in the present invention includes a photoinitiator which is generally used for photopolymerization. The maleimide compound does not mean a photoinitiator. The "photoinitiator" also does not include ordinary (meth) acrylate compounds which can be used as optional components in the present invention. However, the "photoinitiator" includes a compound having a group moiety capable of generating a group other than a (meth) acrylate group even if it has a (meth) acrylate group (ie, (meth) propylene oxime) The same is true for the base. Specifically, a compound having a benzoin (ether) structure and an acrylate group (propylene oxy) is a "photoinitiator" as described in, for example, JP-A-2006-23580. It is speculated that the compound can even produce a decomposition product by performing cutting at the site where the group is generated.
在本發明中,馬來醯亞胺化合物具有藉由光輻照、尤其UV輻照起始聚合之功能且其自身可進行聚合。當(甲基)丙烯酸酯化合物存在時,馬來醯亞胺化合物亦具有聚合(共聚合)(甲基)丙烯酸酯化合物之功能。加熱時可最終固化在光輻照期間未反應之部分。In the present invention, the maleimide compound has a function of initiating polymerization by light irradiation, particularly UV irradiation, and it can be polymerized by itself. The maleimide compound also functions to polymerize (copolymerize) a (meth) acrylate compound when a (meth) acrylate compound is present. The portion that is not reacted during the irradiation of light can be finally cured upon heating.
馬來醯亞胺化合物在其分子中具有一或多個、較佳一或兩個以部分(I)表示之亞結構:
用於本發明中之馬來醯亞胺化合物並不具有衍生自雙酚-S(即,苯基-SO2 -苯基結構)之部分。The maleic imine compound used in the present invention does not have a moiety derived from bisphenol-S (i.e., a phenyl-SO 2 -phenyl structure).
馬來醯亞胺化合物在室溫下較佳為液體,且因此部分(I)鍵結至使馬來醯亞胺化合物為液體之基團上,例如,包含具有足夠長度及支鏈以使得馬來醯亞胺化合物為液體之具支鏈烷基、伸烷基、環氧烷、伸烷基羧基或伸烷基醯胺結構的有機基團。馬來醯亞胺化合物可包含一個、或兩個或多個亞結構(I)。具有兩個該等基團之化合物係雙馬來醯亞胺化合物。另外,若密封劑在與其他馬來醯亞胺化合物混合或與其他組份混合時變成液體,則即便馬來醯亞胺化合物不為液體,其亦可使用。The maleimide compound is preferably liquid at room temperature, and thus the moiety (I) is bonded to a group which renders the maleimide compound liquid, for example, comprising a sufficient length and a branch to make the horse The imine compound is a liquid organic group having a branched alkyl group, an alkylene group, an alkylene oxide group, an alkylene group carboxyl group or an alkylamine structure. The maleimide compound may comprise one or two or more substructures (I). A compound having two such groups is a bismaleimide compound. Further, if the sealant becomes a liquid when it is mixed with other maleidin compound or mixed with other components, it can be used even if the maleimide compound is not a liquid.
其中部分(I)鍵結至烷基或伸烷基(該等基團可包含雙鍵及飽和脂環)之馬來醯亞胺化合物包括下述化合物。The maleimide compound in which part (I) is bonded to an alkyl group or an alkyl group (the group may include a double bond and a saturated alicyclic ring) includes the following compounds.
其中部分(I)鍵結至具有伸烷氧化物結構之基團的馬來醯亞胺化合物包括以下化合物。The maleimide compound in which a part (I) is bonded to a group having an alkylene oxide structure includes the following compounds.
可用馬來醯亞胺化合物之其他實例包括下式化合物:
密封劑中馬來醯亞胺化合物之含量比率可介定在寬廣的範圍內,且馬來醯亞胺化合物在整個密封劑中可以0.1 wt%至100 wt%之比率存在。即使少量亦能使密封劑固化(暫時固化),且納入諸如(甲基)丙烯酸酯化合物等光可固化單體通常可降低該比率。馬來醯亞胺化合物之含量比率較佳不低於0.5 wt%、更佳不低於1 wt%。儘管其甚至在馬來醯亞胺化合物之含量比率為100 wt%時亦可固化,但該比率一般低於100 wt%,此乃因密封劑通常含有填充劑及諸如此類。當含有其他樹脂時,密封劑較佳含有不超過90 wt%之馬來醯亞胺化合物,例如,若含有諸如環氧樹脂等熱固性樹脂及/或諸如(甲基)丙烯酸酯等可光聚合樹脂時即如此。The content ratio of the maleimide compound in the sealant can be defined in a wide range, and the maleimide compound can be present in a ratio of 0.1 wt% to 100 wt% throughout the sealant. Even a small amount enables the sealant to be cured (temporarily cured), and the incorporation of a photocurable monomer such as a (meth) acrylate compound generally lowers the ratio. The content ratio of the maleimide compound is preferably not less than 0.5% by weight, more preferably not less than 1% by weight. Although it can be cured even when the content ratio of the maleimide compound is 100 wt%, the ratio is generally less than 100 wt% because the sealant usually contains a filler and the like. When other resins are contained, the sealant preferably contains not more than 90% by weight of the maleimide compound, for example, if it contains a thermosetting resin such as an epoxy resin and/or a photopolymerizable resin such as (meth) acrylate That's it.
就密封強度及諸如此類而言,除馬來醯亞胺化合物外,本發明密封劑較佳亦可包含熱固性樹脂,尤佳包含環氧樹脂。In terms of seal strength and the like, the sealant of the present invention may preferably comprise a thermosetting resin, particularly preferably an epoxy resin, in addition to the maleimide compound.
在密封劑中所包含之環氧樹脂較佳包含具有芳環作為主要組份之環氧樹脂,且其在環氧樹脂組份中具體而言為50%(基於重量)或更多、較佳70%或更多、及尤佳90%或更多,且甚至100%亦較佳。若需要,可含有無芳環之環氧樹脂。The epoxy resin contained in the sealant preferably contains an epoxy resin having an aromatic ring as a main component, and it is specifically 50% by weight or more, more preferably in the epoxy resin component. 70% or more, and particularly preferably 90% or more, and even 100% is also preferred. If necessary, it may contain an epoxy resin without an aromatic ring.
含芳環環氧樹脂包括雙酚型環氧樹脂,例如,雙酚-A型環氧樹脂、雙酚-F型環氧樹脂及雙酚-S型環氧樹脂;線性酚醛型環氧樹脂,例如,酚-線性酚醛型環氧樹脂及甲酚-線性酚醛型環氧樹脂;及聯苯型環氧樹脂,例如,由日本Epoxy Resin有限公司製造之產品名YX4000。含芳環環氧樹脂在其分子中一般具有一或多個環氧基,且可視情況選擇該樹脂之環氧等效物。The aromatic ring-containing epoxy resin includes a bisphenol type epoxy resin, for example, a bisphenol-A type epoxy resin, a bisphenol-F type epoxy resin, and a bisphenol-S type epoxy resin; a novolac type epoxy resin, For example, a phenol-phenolic novolac type epoxy resin and a cresol-phenolic novolac type epoxy resin; and a biphenyl type epoxy resin, for example, a product name YX4000 manufactured by Japan Epoxy Resin Co., Ltd. The aromatic ring-containing epoxy resin generally has one or more epoxy groups in its molecule, and an epoxy equivalent of the resin may be selected as appropriate.
不含芳環的環氧樹脂包括具有環氧基且在分子中具有環變形(例如,環氧環己烷結構及環氧環戊烷結構)的脂環環氧樹脂(例如,由下式(1)至(5)所表示之化合物):
環氧樹脂組份亦可包含其他已知稀釋劑。The epoxy resin component may also contain other known diluents.
擬用於本發明中之潛在環氧硬化劑在加熱時可固化環氧樹脂。潛在硬化劑可係一或多種適當地選自市售潛在硬化劑之潛在硬化劑,且潛在硬化劑之擬添加量較佳係在考量環氧樹脂之環氧等效物後進行適當地確定。The latent epoxy hardener to be used in the present invention cures the epoxy resin upon heating. The latent hardener may be one or more potential hardeners suitably selected from commercially available latent hardeners, and the amount of latent hardener to be added is preferably determined after considering the epoxy equivalent of the epoxy resin.
特定而言,擬較佳用於本發明中之潛在硬化劑較佳係熱固化型潛在硬化劑,且包括胺基化合物硬化劑、細粉型改質胺基及改質咪唑基潛在硬化劑。改質胺基及改質咪唑基潛在硬化劑包括芯-殼型硬化劑,其中胺化合物(或胺加合物)芯表面包覆有改質胺產物(表面加合及諸如此類)及母料型硬化劑的殼,該等母料型硬化劑係芯-殼型硬化劑與環氧樹脂之摻合物。In particular, the latent curing agent to be preferably used in the present invention is preferably a thermosetting latent curing agent, and includes an amine-based compound hardener, a fine powder-modified amino group, and a modified imidazole-based latent curing agent. Modified amine-based and modified imidazolium-based latent hardeners include core-shell type hardeners in which the amine compound (or amine adduct) core is coated with a modified amine product (surface addition and the like) and a masterbatch type A shell of a hardener, which is a blend of a core-shell type hardener and an epoxy resin.
胺基化合物硬化劑之實例包括芳族一級胺,例如二胺基二苯甲烷及二胺基二苯碸;咪唑,例如2-十七烷基咪唑、偏苯三酸1-氰乙基-2-十一烷基咪唑鎓、2,4-二胺基-6-[2-甲基咪唑基-(1)]-乙基-S-三嗪、氯化1-十二烷基-2-甲基-3-苄基咪唑鎓、2-苯基咪唑鎓異氰尿酸鹽、2-苯基-4-甲基-5-羥甲基咪唑;三氟化硼-胺錯合物;雙氰胺衍生物,例如雙氰胺、o-甲苯基雙胍及α-2,5-甲基雙胍;有機酸醯肼,例如碳醯肼、丁二酸二醯肼、己二酸二醯肼、癸二酸二醯肼、十二烷二酸二醯肼及間苯二甲酸二醯肼;及二胺基馬來腈及其衍生物;及三聚氰胺衍生物,例如三聚氰胺及二烯丙基三聚氰胺。Examples of the amine compound hardener include aromatic primary amines such as diaminodiphenylmethane and diaminodiphenyl hydrazine; imidazoles such as 2-heptadecylimidazole, trimellitic acid 1-cyanoethyl-2 -undecyl imidazolium, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-S-triazine, 1-dodecyl-2-chloride Methyl-3-benzylimidazolium, 2-phenylimidazolium isocyanurate, 2-phenyl-4-methyl-5-hydroxymethylimidazole; boron trifluoride-amine complex; dicyandiamide Amine derivatives such as dicyandiamide, o-methylphenyl biguanide and α-2,5-methyl biguanide; organic acid hydrazines such as carbonium, bismuth succinate, dioxane adipate, hydrazine Dioxalate dihydrate, dioxonium dodecanoate and dioxonium isophthalate; and diaminomaleonitrile and its derivatives; and melamine derivatives such as melamine and diallyl melamine.
改質胺基潛在硬化劑係藉由將胺化合物與環氧化合物、異氰酸鹽化合物或尿素化合物之固體反應產物精細粉末化而獲得。改質咪唑基潛在硬化劑係藉由將一般藉由咪唑化合物與環氧化合物之加合反應所獲得之固體反應產物精細粉末化而得到。The modified amine-based latent curing agent is obtained by finely pulverizing an amine compound with a solid reaction product of an epoxy compound, an isocyanate compound or a urea compound. The modified imidazole-based latent curing agent is obtained by finely pulverizing a solid reaction product generally obtained by an addition reaction of an imidazole compound and an epoxy compound.
代表性市售改質胺基潛在硬化劑包括(例如)「Adeca硬化劑EH-3615S」(ADEKA公司商標)、「Adeca硬化劑EH-4070S」(ADEKA公司商標)、「Adeca硬化劑EH-4357S」(ADEKA公司商標)、「Ajicure MY-24」(Ajinomoto公司商標)、「FujiCureFXE-1000」(Fuji Chemicals有限公司商標)、「FujiCureFXR-1036」(Fuji Chemicals有限公司商標)、Aradur 939(Huntsman Advanced Materials公司商標)及諸如此類。Representative commercially available modified amine-based latent curing agents include, for example, "Adeca hardener EH-3615S" (trademark of Adeka), "Adeca hardener EH-4070S" (trademark of Adeka), and "Adeca hardener EH-4357S" (Adeka brand), "Ajicure MY-24" (trademark of Ajinomoto), "FujiCureFXE-1000" (trademark of Fuji Chemicals Co., Ltd.), "FujiCureFXR-1036" (trademark of Fuji Chemicals Co., Ltd.), Aradur 939 (Huntsman Advanced) Materials company logo) and the like.
代表性市售改質咪唑基潛在硬化劑包括「Adeca硬化劑EH-3293S」(ADEKA公司商標)、「Adeca硬化劑EH-4344S」(ADEKA公司商標)、「Ajicure PN-23」(Ajinomoto公司商標)、「Cureduct P-505」(Shikoku Chemicals公司商標)及「Sanmide LH-210」(Air Products and Chemicals公司商標)。Representative commercially available modified imidazolium-based latent curing agents include "Adeca hardener EH-3293S" (trademark of ADEKA), "Adeca hardener EH-4344S" (trademark of ADEKA), and "Ajicure PN-23" (trademark of Ajinomoto) ), "Cureduct P-505" (trademark of Shikoku Chemicals Co., Ltd.) and "Sanmide LH-210" (trademark of Air Products and Chemicals).
此外,芯-殼型硬化劑係彼等其中胺化合物(或胺加合物)芯表面進一步經(例如)酸化合物(例如羧酸化合物及磺酸化合物)、異氰酸鹽化合物及環氧化合物處理而在其表面上形成改質產物(加合物或諸如此類)殼者。此外,母料型硬化劑係芯-殼型硬化劑與環氧樹脂之摻合物。Further, the core-shell type hardener is one in which the amine compound (or amine adduct) core surface is further subjected to, for example, an acid compound (for example, a carboxylic acid compound and a sulfonic acid compound), an isocyanate compound, and an epoxy compound. The treatment forms a modified product (adduct or the like) on the surface thereof. Further, the masterbatch type hardener is a blend of a core-shell type hardener and an epoxy resin.
市售母料型硬化劑包括(例如)「Novacure HX-3722」(Asahi Kasei Epoxy公司商標)、「Novacure HX-3742」(Asahi Kasei Epoxy公司商標)、「Novacure HX-3613」(Asahi Kasei Epoxy公司商標)及諸如此類。Commercially available masterbatch type hardeners include, for example, "Novacure HX-3722" (trademark of Asahi Kasei Epoxy Co., Ltd.), "Novacure HX-3742" (trademark of Asahi Kasei Epoxy Co., Ltd.), and "Novacure HX-3613" (Asahi Kasei Epoxy Co., Ltd.) Trademarks) and the like.
在本發明中之上述潛在硬化劑中,有機酸醯肼係尤佳者。有機酸醯肼可藉由考量溶點及諸如此類來進行任意選擇。Among the above-mentioned latent hardeners in the present invention, an organic acid lanthanum is preferred. The organic acid bismuth can be arbitrarily selected by considering the melting point and the like.
環氧樹脂與潛在硬化劑之比率可端視潛在硬化劑之種類而加以適當地選擇。舉例而言,對於100重量份數環氧樹脂而言,潛在硬化劑之量係0.5至500重量份數,較佳為2至200重量份數。The ratio of epoxy resin to latent hardener can be suitably selected depending on the type of latent hardener. For example, for 100 parts by weight of the epoxy resin, the amount of the latent hardener is from 0.5 to 500 parts by weight, preferably from 2 to 200 parts by weight.
環氧樹脂之含量比率可任意設定,例如,佔密封劑總重量之0-98 wt%、較佳10-90 wt%。以重量比率計,環氧樹脂與馬來醯亞胺化合物之比率係0至980倍、較佳0.1至約100倍。The content ratio of the epoxy resin can be arbitrarily set, for example, from 0 to 98% by weight, preferably from 10 to 90% by weight based on the total weight of the sealant. The ratio of the epoxy resin to the maleimide compound is from 0 to 980 times, preferably from 0.1 to about 100 times, by weight.
本發明密封劑可另外視情況包含可光聚合組份,例如(甲基)丙烯酸酯化合物及/或乙烯基醚化合物。然而,密封劑不含有該等化合物亦極佳。The sealant of the present invention may optionally contain a photopolymerizable component such as a (meth) acrylate compound and/or a vinyl ether compound. However, it is also preferred that the sealant does not contain such compounds.
特定而言,(甲基)丙烯酸酯包括(例如)甲基丙烯酸甲酯、甲基丙烯酸丙烯酸四氫糠基酯、甲基丙烯酸苯甲酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸2-羥乙基酯、縮水甘油醚(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、異戊四醇三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯及諸如此類。此處,如通常所使用,「(甲基)丙烯酸酯」表示甲基丙烯酸酯及丙烯酸酯二者。In particular, (meth) acrylates include, for example, methyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, isodecyl (meth)acrylate, (methyl) 2-hydroxyethyl acrylate, glycidyl ether (meth) acrylate, (poly)ethylene glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6 - hexanediol dimethacrylate, trimethylolpropane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, glycerol di(meth) acrylate, and the like. Here, as used conventionally, "(meth)acrylate" means both a methacrylate and an acrylate.
另外,環氧(甲基)丙烯酸酯較佳亦係作為丙烯酸酯化合物,且舉例而言,包括衍生自環氧樹脂(例如,雙酚-A型環氧樹脂)及丙二醇二縮水甘油醚之環氧(甲基)丙烯酸酯及(甲基)丙烯酸。Further, the epoxy (meth) acrylate is preferably also used as an acrylate compound, and includes, for example, a ring derived from an epoxy resin (for example, bisphenol-A type epoxy resin) and propylene glycol diglycidyl ether. Oxy (meth) acrylate and (meth) acrylic acid.
可光聚合組份(例如(甲基)丙烯酸酯化合物及/或乙烯基醚化合物)之摻和比率可任意設定,較佳佔密封劑總重量的不超過90 wt%、更佳不超過70 wt%。當含有該組份時,其較佳含有(例如)不低於3 wt%。另外,以重量比率計,該等可光聚合組份與馬來醯亞胺化合物之比率係0至900倍、較佳不超過100倍、更佳不超過20倍。當含有該組份時,以與馬來醯亞胺化合物之重量比率計,其較佳含有不低於0.1倍。然而,在本發明較佳態樣中,密封劑包含馬來醯亞胺化合物及較佳環氧樹脂,且極佳不含有其他可光聚合組份,例如(甲基)丙烯酸酯化合物及/或乙烯基醚化合物。The blending ratio of the photopolymerizable component (for example, a (meth) acrylate compound and/or a vinyl ether compound) can be arbitrarily set, preferably not more than 90% by weight, more preferably not more than 70% by weight based on the total weight of the sealant. %. When the component is contained, it preferably contains, for example, not less than 3% by weight. Further, the ratio of the photopolymerizable component to the maleimide compound is 0 to 900 times, preferably not more than 100 times, more preferably not more than 20 times by weight. When the component is contained, it preferably contains not less than 0.1 times by weight based on the weight ratio of the maleimide compound. However, in a preferred aspect of the invention, the sealant comprises a maleic imide compound and preferably an epoxy resin, and preferably does not contain other photopolymerizable components, such as (meth)acrylate compounds and/or Vinyl ether compound.
密封劑可另外包含添加劑、樹脂組份及諸如此類以改良或改變諸如流動性、施加性質、防腐性質、固化性質及固化後物理性質等性質。The sealant may additionally contain additives, resin components, and the like to improve or change properties such as fluidity, application properties, corrosion resistance properties, curing properties, and physical properties after curing.
可含於該組合物中之組份視需要可包括(例如)有機或無機填充劑、觸變劑、矽烷偶合劑、稀釋劑、改質劑、著色劑(例如顏料及染料)、表面活性劑、防腐劑-穩定劑、增塑劑、潤滑劑、消泡劑、調平劑及諸如此類;然而並不僅限於該等組份。具體而言,該組合物較佳包含選自由填充劑、觸變劑及矽烷偶合劑組成之群的添加劑。The components which may be contained in the composition may include, for example, organic or inorganic fillers, thixotropic agents, decane coupling agents, diluents, modifiers, colorants (for example, pigments and dyes), and surfactants. Preservatives - stabilizers, plasticizers, lubricants, defoamers, leveling agents, and the like; however, are not limited to such components. Specifically, the composition preferably comprises an additive selected from the group consisting of a filler, a thixotropic agent, and a decane coupling agent.
填充劑包括(無特別限制)(例如)無機填充劑,例如氧化矽、矽藻土、氧化鋁、氧化鋅、氧化鐵、氧化鎂,氧化錫、氧化鈦、氫氧化鎂、氫氧化鋁、碳酸鎂、硫酸鋇、石膏、矽酸鈣、滑石粉、玻璃珠、絹雲母粉活化白土、膨潤土(bentonite)、氮化鋁、氮化矽及諸如此類。The filler includes (without particular limitation), for example, an inorganic filler such as cerium oxide, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, carbonic acid Magnesium, barium sulfate, gypsum, calcium citrate, talc, glass beads, sericite-activated clay, bentonite, aluminum nitride, tantalum nitride, and the like.
觸變劑包括(無特別限制)(例如)滑石粉、細顆粒氧化矽、經超細表面處理之碳酸鈣、細氧化鋁、板狀氧化鋁;層狀化合物,例如蒙脫石(montmorillonite);針狀化合物,例如硼酸鋁晶須及諸如此類。其中滑石粉、細氧化矽、細氧化鋁及諸如此類係較佳者。The thixotropic agent includes (without particular limitation) (for example) talc, fine particle cerium oxide, ultrafine surface treated calcium carbonate, fine alumina, platy alumina; layered compound such as montmorillonite; Needle-like compounds such as aluminum borate whiskers and the like. Among them, talc, fine cerium oxide, fine alumina, and the like are preferred.
矽烷偶合劑包括但不特別限制於γ-胺基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、SH6062、SZ6030(主要由Toray-Dow Corning Silicone公司製造)、KBE903、KBM803(主要由Shin-Etsu Silicone公司製造)及諸如此類。The decane coupling agent includes, but is not particularly limited to, γ-aminopropyltriethoxydecane, γ-mercaptopropyltrimethoxydecane, γ-methacryloxypropyltrimethoxydecane, γ-glycidol Oxypropyltrimethoxydecane, SH6062, SZ6030 (mainly manufactured by Toray-Dow Corning Silicone Co., Ltd.), KBE903, KBM803 (mainly manufactured by Shin-Etsu Silicone Co., Ltd.), and the like.
上文所獲得之本發明密封劑可經由不高於5,000 mJ/cm2 、較佳不高於2,000 mJ/cm2 UV輻照能之光輻照而暫時固化,隨後經由加熱進行最後固化。因此,本發明密封劑可適於藉助液晶滴注製程來製造液晶顯示器。The sealant of the present invention obtained above can be temporarily cured by irradiation of light having a UV irradiation energy of not more than 5,000 mJ/cm 2 , preferably not more than 2,000 mJ/cm 2 , followed by final curing by heating. Therefore, the sealant of the present invention can be adapted to manufacture a liquid crystal display by means of a liquid crystal dropping process.
此外,本發明密封劑在施加溫度、較佳環境溫度(工作環境溫度)下係液體,而擬調配材料、尤其所有樹脂材料未必係液體。Further, the sealant of the present invention is a liquid at an application temperature, preferably an ambient temperature (working ambient temperature), and the material to be formulated, especially all resin materials, is not necessarily a liquid.
如上所述,本發明密封劑對液晶造成污染的可能性很小,此乃因密封劑不含有光起始劑,從而不會產生分解材料或諸如此類。如工作實例中所展示,分解材料及諸如此類之產生可使用在固化時自密封劑所產生氣體(脫氣)之量來進行評價。As described above, the sealant of the present invention is less likely to cause contamination of the liquid crystal because the sealant does not contain a photoinitiator, so that no decomposition material or the like is produced. As shown in the working examples, the decomposition material and the like can be evaluated using the amount of gas (degassing) generated from the sealant at the time of curing.
擬用於本發明中之密封劑亦可用於除液晶滴注製程外之其他應用中,其中需要實施無移動之精確組裝。The sealant to be used in the present invention can also be used in other applications than the liquid crystal dropping process, in which accurate assembly without movement is required.
<密封性質之評價><Evaluation of sealing properties>
藉助三輥磨機來充分混合在表1中所展示之材料,並將1 wt% 5 μm隔離物進一步混合以給出實例1至4及比較實例1至3之密封劑。藉由分配器將2 mg所得密封劑沿框架形狀施加在2 cm×7 cm尺寸之玻璃基板周邊。將約7 mg液晶材料滴加在玻璃基板中心周圍,並使其在真空中完全脫氣。覆蓋另一玻璃基板並調整其位置。將兩塊經密封基板放置於UV輻照設備(100 mW/cm2 )中並經UV輻照10秒。在UV輻照後,施加外力以證實玻璃基板是否移動並評價UV輻照所達成暫時固定之品質。已證實在本發明之實例中可達成良好固定。The materials shown in Table 1 were thoroughly mixed by means of a three-roll mill, and 1 wt% of 5 μm spacers were further mixed to give the sealants of Examples 1 to 4 and Comparative Examples 1 to 3. 2 mg of the obtained sealant was applied to the periphery of the glass substrate of 2 cm × 7 cm size by a dispenser in the shape of a frame. Approximately 7 mg of liquid crystal material was dropped around the center of the glass substrate and allowed to completely degas in a vacuum. Cover another glass substrate and adjust its position. The two sealed substrates were placed in a UV irradiation apparatus (100 mW/cm 2 ) and irradiated with UV for 10 seconds. After the UV irradiation, an external force was applied to confirm whether the glass substrate was moved and the quality of the temporary fixation achieved by the UV irradiation was evaluated. It has been confirmed that good fixation can be achieved in the examples of the present invention.
另外,在UV輻照後,將玻璃基板置於120℃烘箱中保持1小時以完成模擬液晶單元之製造。目測檢查所完成液晶單元以證實液晶單元之條件(存在破裂及諸如此類)、密封形式之維持及諸如此類。已證實在本發明實例中可達成密封之良好條件。表1一同展示實例1至4及比較實例1至3之密封劑之結果。Further, after UV irradiation, the glass substrate was placed in an oven at 120 ° C for 1 hour to complete the manufacture of the dummy liquid crystal cell. The completed liquid crystal cell is visually inspected to confirm the conditions of the liquid crystal cell (there are cracks and the like), the maintenance of the sealed form, and the like. Good conditions for sealing have been demonstrated in the examples of the invention. Table 1 shows the results of the sealants of Examples 1 to 4 and Comparative Examples 1 to 3 together.
<脫氣產生之評價><Evaluation of degassing generation>
將100 mg工作實例及比較實例之密封劑量測至玻璃瓶中並蓋緊其瓶蓋,之後用100 mW/cm2 UV輻照輻照30秒,該瓶被放置在由JEOL有限公司製造之氣相層析質譜分析儀JMS-AM II 120中,並在120℃下加熱1小時。自動收集所產生氣體並對其實施數量分析。The sealed doses of 100 mg working examples and comparative examples were measured in glass vials and capped, and then irradiated with 100 mW/cm 2 UV irradiation for 30 seconds, the bottles were placed in JEOL Co., Ltd. The gas chromatography mass spectrometer JMS-AM II 120 was heated at 120 ° C for 1 hour. The generated gas is automatically collected and subjected to quantitative analysis.
表1展示結果。Table 1 shows the results.
在該表中:In the table:
-摻合數值係以wt%計,- the blending values are in wt%,
-ZX-1059:由Tohto Kasei有限公司製造之摻和有雙酚-A型及-F型之環氧樹脂,-ZX-1059: Made of Tohto Kasei Co., Ltd. blended with bisphenol-A and -F epoxy resins,
-EP828US:由日本Epoxy Resins有限公司製造之雙酚-A型環氧樹脂,-EP828US: bisphenol-A epoxy resin manufactured by Epoxy Resins Co., Ltd., Japan.
-X-BMI:由Henkel公司製造之雙馬來醯亞胺樹脂,-X-BMI: a bismaleimide resin manufactured by Henkel Corporation,
-Lumicure MIA-200:由DIC公司製造之雙馬來醯亞胺樹脂,-Lumicure MIA-200: Bismaleimide resin manufactured by DIC Corporation,
-Ajicure VDH-J:由Ajinomoto Fine-Techno公司製造之1,3-雙(肼基羰乙基)-異丙基乙內醯脲,二醯肼基環氧硬化劑,及-Ajicure VDH-J: 1,3-bis(decylcarbonylethyl)-isopropylhydantoin, a dimercapto epoxy curing agent manufactured by Ajinomoto Fine-Techno Co., Ltd., and
-Uvacure 1561:由Cytek Surface Specialties製造之環氧丙烯酸酯;雙酚-A型環氧樹脂之丙烯酸酯。- Uvacure 1561: epoxy acrylate manufactured by Cytek Surface Specialties; acrylate of bisphenol-A epoxy resin.
自表1顯而易見,各實例之密封劑並不產生氣體且UV輻照後之固定及最終密封係令人滿意的。此外,如實例1及2中所展示,甚至不含有除馬來醯亞胺化合物外之可光聚合組份(例如(甲基)丙烯酸酯)之密封劑在UV輻照後亦可產生良好固定。It is apparent from Table 1 that the sealants of the examples do not produce gas and the fixation and final sealing after UV irradiation are satisfactory. Further, as shown in Examples 1 and 2, even a sealant which does not contain a photopolymerizable component other than the maleimide compound (for example, (meth) acrylate) can be well fixed after UV irradiation. .
自上文顯而易見,可進行眾多種修改,此並不背離本發明之精神及範圍。因此,本文所闡釋之實施例係作為實例,且其並不限制在申請專利範圍中所闡述之本發明範圍。Numerous modifications may be made without departing from the spirit and scope of the invention. Therefore, the embodiments illustrated herein are by way of example, and are not intended to limit the scope of the invention as claimed.
使用用於液晶滴注製程之本發明密封劑允許製造不會發生移動之LCD,同時可保持精准定位且不會對液晶產生不利影響。所製造LCD在其密封區域中具有優良耐久性及可靠性。因此,本發明可用作擬用於製造LCD之方法中之密封劑。The use of the sealant of the present invention for a liquid crystal dropping process allows the manufacture of an LCD that does not move while maintaining precise positioning without adversely affecting the liquid crystal. The manufactured LCD has excellent durability and reliability in its sealed area. Accordingly, the present invention can be used as a sealant in a method for fabricating an LCD.
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CN106062075B (en) * | 2014-02-19 | 2019-11-01 | 汉高股份有限及两合公司 | Curable resin composition for encapsulated liquid crystals |
JP2015215514A (en) * | 2014-05-12 | 2015-12-03 | 協立化学産業株式会社 | Sealant for liquid crystal display |
WO2017008244A1 (en) * | 2015-07-14 | 2017-01-19 | Henkel IP & Holding GmbH | Curable compositions for one drop fill sealant application |
WO2017061303A1 (en) * | 2015-10-09 | 2017-04-13 | 積水化学工業株式会社 | Sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element |
WO2018062164A1 (en) * | 2016-09-29 | 2018-04-05 | 積水化学工業株式会社 | Sealing agent for liquid crystal display device, vertical conduction material, and liquid crystal display device |
KR20190055015A (en) * | 2016-09-29 | 2019-05-22 | 세키스이가가쿠 고교가부시키가이샤 | A sealing agent for a liquid crystal display element, an upper and lower conductive material, and a liquid crystal display element |
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