TW201600588A - Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element - Google Patents

Sealant for one-drop filling process, vertically conductive material, and liquid crystal display element Download PDF

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TW201600588A
TW201600588A TW104116220A TW104116220A TW201600588A TW 201600588 A TW201600588 A TW 201600588A TW 104116220 A TW104116220 A TW 104116220A TW 104116220 A TW104116220 A TW 104116220A TW 201600588 A TW201600588 A TW 201600588A
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meth
liquid crystal
acrylate
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crystal dropping
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TWI682024B (en
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Inan IN
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Mathematical Physics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
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  • Macromonomer-Based Addition Polymer (AREA)
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Abstract

The present invention addresses the problem of providing a sealant for a one-drop filling process, which has a fast curing speed, excellent coating and adhesive properties, and can suppress liquid crystal pollution. The present invention also addresses the problem of providing a vertically conductive material and a liquid crystal display element that use said sealant for a one-drop filling process. The present invention is a sealant for a one-drop filling process, said sealant containing a curable resin and a thermal radical polymerization initiator, wherein the curable resin contains an at least trifunctional epoxy (meth)acrylate having at least three (meth)acryloyloxy groups in one molecule.

Description

液晶滴下法用密封劑、上下導通材料、及液晶顯示元件 Sealant for liquid crystal dropping method, upper and lower conductive materials, and liquid crystal display element

本發明係關於一種硬化速度較快、可抑制液晶污染、塗佈性及接著性優異之液晶滴下法用密封劑。又，本發明係關於一種使用該液晶滴下法用密封劑而成之上下導通材料及液晶顯示元件。 The present invention relates to a sealing compound for a liquid crystal dropping method which is fast in curing speed, can suppress liquid crystal contamination, and has excellent coatability and adhesion. Moreover, the present invention relates to an upper conductive material and a liquid crystal display element which are obtained by using the sealing compound for liquid crystal dropping methods.

近年來，作為液晶顯示元件之製造方法，就產距時間縮短、使用液晶量之最佳化之觀點而言，使用如專利文獻1、專利文獻2中所揭示之使用含有硬化性樹脂、光聚合起始劑、及熱硬化劑之光熱併用硬化型密封劑之稱為滴下法之液晶滴下方式。 In recent years, as a method of producing a liquid crystal display element, the use of a curable resin, photopolymerization as disclosed in Patent Document 1 and Patent Document 2 is used in view of shortening the production time and the use of the liquid crystal amount. A liquid crystal dropping method called a dropping method of a photoinitiator of a starter and a heat hardener and a hardening type sealant.

關於滴下法，首先於兩片附電極之透明基板之一者上，藉由滴塗而形成長方形狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴加至透明基板之框內整個面，立即重疊另一透明基板，對密封部照射紫外線等光而進行暫時硬化。其後，進行加熱而進行正式硬化，從而製作液晶顯示元件。藉由於減壓下進行基板之貼合，可以極高效率製造液晶顯示元件，目前該滴下法成為液晶顯示元件之製造方法之主流。 Regarding the dropping method, first, a rectangular sealing pattern is formed by one drop coating on one of the two transparent substrates with electrodes. Then, the liquid crystal droplets are dropped onto the entire surface of the transparent substrate in a state where the sealant is not cured, and the other transparent substrate is immediately superposed, and the sealing portion is temporarily hardened by irradiating light such as ultraviolet rays. Thereafter, the film was heated and subjected to main hardening to produce a liquid crystal display element. The liquid crystal display element can be manufactured with high efficiency by bonding the substrate under reduced pressure. At present, the dropping method is the mainstream of the manufacturing method of the liquid crystal display element.

且說，於行動電話、攜帶遊戲機等各種附液晶面板之行動機器普及之現代，裝置之小型化亦為業界最為追求之課題。作為小型化之方 法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下(以下，亦稱為窄邊緣設計)。 In addition, in the modernization of various mobile devices including mobile phones and mobile phones, such as mobile phones and mobile games, the miniaturization of devices is also the most sought after issue in the industry. As a miniaturized party The method includes a narrow edge of the liquid crystal display unit. For example, the position of the sealing portion is placed under a black matrix (hereinafter also referred to as a narrow edge design).

然而，若藉由滴下法而製造窄邊緣設計之液晶顯示元件，則因黑矩陣而於密封部存在照射不到光之部位，故而有如下問題：未充分進行光照射，而產生不進行硬化之光硬化性樹脂之部分，於暫時硬化步驟後未硬化之光硬化性樹脂溶出，而導致液晶被污染。 However, when a liquid crystal display element having a narrow-edge design is produced by a dropping method, since there is a portion where the light is not irradiated to the sealing portion due to the black matrix, there is a problem in that light irradiation is not sufficiently performed, and hardening is not caused. The portion of the photocurable resin is eluted by the photocurable resin which is not cured after the temporary curing step, and the liquid crystal is contaminated.

因此，為了僅藉由熱而使密封劑硬化，研究有使用含有熱硬化性樹脂與熱硬化劑之密封劑之情況，但此種密封劑於硬化時耗時，因此有硬化中途之密封劑於液晶中溶出而使液晶受到污染，或液晶***至密封劑中之問題。 Therefore, in order to harden the sealant by heat alone, it has been studied to use a sealant containing a thermosetting resin and a heat hardener. However, such a sealant takes time to harden, so that the sealant in the middle of hardening is used. The problem that the liquid crystal is eluted to contaminate the liquid crystal or the liquid crystal is inserted into the sealant.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：日本特開2001-133794號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-133794

專利文獻2：國際公開第02/092718號 Patent Document 2: International Publication No. 02/092718

本發明之目的在於提供一種硬化速度較快、可抑制液晶污染、塗佈性及接著性優異之液晶滴下法用密封劑。又，本發明之目的在於提供一種使用該液晶滴下法用密封劑而成之上下導通材料及液晶顯示元件。 An object of the present invention is to provide a sealing compound for a liquid crystal dropping method which has a high curing rate and can suppress liquid crystal contamination, and has excellent coatability and adhesion. Moreover, an object of the present invention is to provide an upper conductive material and a liquid crystal display element which are obtained by using the sealing compound for liquid crystal dropping methods.

本發明係一種液晶滴下法用密封劑，含有硬化性樹脂與熱自由基聚合起始劑，並且上述硬化性樹脂含有於1分子中具有3個以上(甲基)丙烯醯氧基之3官能以上之環氧(甲基)丙烯酸酯。 The present invention is a sealing agent for a liquid crystal dropping method, comprising a curable resin and a thermal radical polymerization initiator, and the curable resin contains three or more functional groups having three or more (meth) acryloxy groups in one molecule. Epoxy (meth) acrylate.

以下，詳述本發明。 Hereinafter, the present invention will be described in detail.

本發明人發現：將於1分子中具有3個以上(甲基)丙烯醯氧基之3官能以上之環氧(甲基)丙烯酸酯作為硬化性樹脂與熱自由基聚合起始劑組合而調配，可獲得硬化速度較快、可抑制液晶污染、塗佈性及接著性優異之液晶滴下法用密封劑，從而完成本發明。 The present inventors have found that a trifunctional or higher epoxy (meth) acrylate having three or more (meth) acryloxy groups in one molecule is formulated as a curable resin in combination with a thermal radical polymerization initiator. The present invention can be obtained by obtaining a sealing agent for a liquid crystal dropping method which has a high curing speed, can suppress liquid crystal contamination, and has excellent coatability and adhesion.

本發明之液晶滴下法用密封劑含有硬化性樹脂。 The sealing compound for liquid crystal dropping methods of this invention contains a hardening resin.

上述硬化性樹脂含有於1分子中具有3個以上(甲基)丙烯醯氧基之3官能以上之環氧(甲基)丙烯酸酯。 The curable resin contains a trifunctional or higher epoxy (meth) acrylate having three or more (meth) acryloxy groups in one molecule.

藉由將上述3官能以上之環氧(甲基)丙烯酸酯與熱自由基聚合起始劑組合而使用，本發明之液晶滴下法用密封劑成為硬化速度較快，可抑制液晶污染，塗佈性及接著性優異者。 By using the above-mentioned trifunctional or higher epoxy (meth) acrylate in combination with a thermal radical polymerization initiator, the sealing agent for liquid crystal dropping method of the present invention has a high curing rate and can suppress liquid crystal contamination. Excellent sex and adhesion.

再者，於本說明書中，上述「(甲基)丙烯醯氧基」意指丙烯醯氧基或甲基丙烯醯氧基，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，上述「環氧(甲基)丙烯酸酯」意指使環氧樹脂中之全部環氧基與(甲基)丙烯酸進行反應而成之化合物，上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸。 In the present specification, the above "(meth)acryloxy" means propylene methoxy or methacryloxy group, and the above "(meth) acrylate" means acrylate or methacrylic acid. The above-mentioned "epoxy (meth) acrylate" means a compound obtained by reacting all of the epoxy groups in the epoxy resin with (meth)acrylic acid, and the above "(meth)acrylic acid" means acrylic or a Acrylic acid.

上述3官能以上之環氧(甲基)丙烯酸酯之介電常數之較佳下限為3。藉由使上述介電常數為3以上，而成為難以於液晶中溶出者。上 述介電常數之更佳下限為4。又，上述介電常數越高越好，但實質上之上限為20。 A preferred lower limit of the dielectric constant of the above trifunctional or higher epoxy (meth) acrylate is 3. When the dielectric constant is 3 or more, it is difficult to dissolve in the liquid crystal. on A lower limit of the dielectric constant is 4. Further, the higher the dielectric constant, the better, but the upper limit is substantially 20.

再者，於本發明之液晶滴下法用密封劑含有兩種以上化合物作為上述3官能以上之環氧(甲基)丙烯酸酯之情形時，上述3官能以上之環氧(甲基)丙烯酸酯之介電常數可由作為上述3官能以上之環氧(甲基)丙烯酸酯所含有之各化合物之介電常數與上述3官能以上之環氧(甲基)丙烯酸酯中之重量分率而算出。 In the case where the sealing compound for liquid crystal dropping method of the present invention contains two or more kinds of compounds as the above-mentioned trifunctional or higher epoxy (meth) acrylate, the above-mentioned trifunctional or higher epoxy (meth) acrylate is used. The dielectric constant can be calculated from the dielectric constant of each compound contained in the above-described trifunctional or higher epoxy (meth) acrylate and the weight fraction of the above-described trifunctional or higher epoxy (meth) acrylate.

上述「介電常數」可藉由使用阻抗分析儀(例如Solartron公司製造，「1260型」等)於25℃、1MHz之條件下測定複介電常數而測定，以實數部分進行定義。 The above-mentioned "dielectric constant" can be measured by measuring the complex permittivity at 25 ° C and 1 MHz using an impedance analyzer (for example, "Model 1260" manufactured by Solartron Co., Ltd.), and is defined by a real part.

上述3官能以上之環氧(甲基)丙烯酸酯係於1分子中具有 至少1個-OH基、-NH-基、-NH2基等氫鍵性官能基。上述3官能以上之環氧(甲基)丙烯酸酯較佳為於1分子中具有3個以上氫鍵性官能基。 The trifunctional or higher epoxy (meth) acrylate has at least one hydrogen bond functional group such as an -OH group, a -NH- group or a -NH 2 group in one molecule. The trifunctional or higher epoxy (meth) acrylate preferably has three or more hydrogen bonding functional groups in one molecule.

就熱硬化反應速度之觀點而言，上述3官能以上之環氧(甲 基)丙烯酸酯較佳為具有分別具有1個(甲基)丙烯醯氧基之3條以上之分子鏈從1個碳原子分支而成之結構。 From the viewpoint of the heat hardening reaction rate, the above-mentioned trifunctional or higher epoxy (A) The acrylate is preferably one having three or more molecular chains each having one (meth) propylene fluorenyloxy group branched from one carbon atom.

又，關於上述3官能以上之環氧(甲基)丙烯酸酯所具有之反應性官能基，就抑制液晶污染之觀點而言，較佳為僅為(甲基)丙烯醯氧基。 In addition, the reactive functional group of the above-mentioned trifunctional or higher epoxy (meth) acrylate is preferably only a (meth) acryloxy group from the viewpoint of suppressing liquid crystal contamination.

再者，上述所謂「反應性官能基」，意指有助於硬化反應之聚合性之官能基。 In addition, the above-mentioned "reactive functional group" means a functional group which contributes to the polymerizability of a hardening reaction.

作為上述3官能以上之環氧(甲基)丙烯酸酯，具體而言， 例如可列舉：三羥甲基丙烷三環氧丙醚(甲基)丙烯酸酯、三羥甲基乙烷 三環氧丙醚(甲基)丙烯酸酯、甲烷三基三(環氧丙醚(甲基)丙烯酸酯)、(丙烷-1,2,3-三基)三(環氧丙醚(甲基)丙烯酸酯)、新戊四醇四環氧丙醚(甲基)丙烯酸酯、苯酚酚醛清漆型環氧(甲基)丙烯酸酯、萘系環氧丙烯酸酯等。其中，就接著性之觀點而言，上述3官能以上之環氧(甲基)丙烯酸酯較佳為不具有酚醛清漆結構，更佳為不具有芳香族環之脂肪族環氧(甲基)丙烯酸酯。進而，就可使硬化速度更快之方面而言，較佳為本發明之液晶滴下法用密封劑含有3官能環氧(甲基)丙烯酸酯及/或4官能環氧(甲基)丙烯酸酯作為上述3官能以上之環氧(甲基)丙烯酸酯，更佳為含有下述式(1)所表示之化合物。 The trifunctional or higher epoxy (meth) acrylate, specifically, For example, trimethylolpropane triglycidyl ether (meth) acrylate, trimethylol ethane Triglycidyl ether (meth) acrylate, methane trisyl tris (glycidyl ether (meth) acrylate), (propane -1,2,3-triyl) tris (glycidyl ether (methyl) ) acrylate), pentaerythritol tetraglycidyl ether (meth) acrylate, phenol novolac type epoxy (meth) acrylate, naphthalene epoxy acrylate, and the like. Among them, the above-mentioned trifunctional or higher epoxy (meth) acrylate preferably has no novolak structure, and more preferably an aliphatic epoxy (meth) acrylate having no aromatic ring. ester. Further, in terms of making the curing speed faster, it is preferred that the sealing compound for liquid crystal dropping method of the present invention contains a trifunctional epoxy (meth) acrylate and/or a tetrafunctional epoxy (meth) acrylate. The trifunctional or higher epoxy (meth) acrylate is more preferably a compound represented by the following formula (1).

式(1)中，R1為氫、碳數1~5之烷基、或下述式(2)所 表示之基，各R2分別獨立地為氫或甲基，l、m、及n分別獨立地為1~5之整數。 In the formula (1), R 1 is hydrogen, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (2), and each R 2 is independently hydrogen or methyl, and l, m, and n are each independently They are independently integers from 1 to 5.

式(2)中，R3為氫或甲基，k為1~5之整數。 In the formula (2), R 3 is hydrogen or a methyl group, and k is an integer of from 1 to 5.

作為上述3官能以上之環氧(甲基)丙烯酸酯，例如可列舉：藉由使於1分子中具有3個以上環氧基之3官能以上之環氧化合物與(甲 基)丙烯酸依據常法於鹼性觸媒之存在下進行反應而獲得者。 Examples of the above-mentioned trifunctional or higher epoxy (meth) acrylate include a trifunctional or higher epoxy compound having three or more epoxy groups in one molecule. Acrylic acid is obtained by reacting in the presence of a basic catalyst according to a conventional method.

作為上述3官能以上之環氧化合物，例如可列舉：三羥甲基 丙烷三環氧丙醚、三羥甲基乙烷三環氧丙醚、甲烷三基三(環氧丙醚)、(丙烷-1,2,3-三基)三(環氧丙醚)、新戊四醇四環氧丙醚、苯酚酚醛清漆型環氧樹脂、萘系環氧化合物等。 Examples of the above-mentioned trifunctional or higher epoxy compound include trimethylol group. Propane triglycidyl ether, trimethylolethane triglycidyl ether, methane tris-tris(glycidyl ether), (propane-1,2,3-triyl)tris(glycidyl ether), Pentaerythritol tetraglycidyl ether, phenol novolac type epoxy resin, naphthalene epoxy compound, and the like.

上述硬化性樹脂100重量份中之上述3官能以上之環氧(甲 基)丙烯酸酯之含量之較佳下限為2重量份，較佳上限為30重量份。若上述3官能以上之環氧(甲基)丙烯酸酯之含量未達2重量份，則有無法充分發揮出加快硬化速度而抑制液晶污染之效果之情況。若上述3官能以上之環氧(甲基)丙烯酸酯之含量超過30重量份，則有於所獲得之液晶顯示元件暴露於高溫高濕環境下之情形時產生顯示不均之情況。上述3官能以上之環氧(甲基)丙烯酸酯之含量之更佳下限為4重量份，更佳上限為15重量份。 The above-mentioned trifunctional or higher epoxy resin in 100 parts by weight of the curable resin A preferred lower limit of the content of the acrylate is 2 parts by weight, and a preferred upper limit is 30 parts by weight. When the content of the above-mentioned trifunctional or higher epoxy (meth) acrylate is less than 2 parts by weight, the effect of increasing the curing rate and suppressing the liquid crystal contamination may not be sufficiently exhibited. When the content of the above-mentioned trifunctional or higher epoxy (meth) acrylate exceeds 30 parts by weight, display unevenness may occur when the obtained liquid crystal display element is exposed to a high-temperature and high-humidity environment. A more preferred lower limit of the content of the above-mentioned trifunctional or higher epoxy (meth) acrylate is 4 parts by weight, and a more preferred upper limit is 15 parts by weight.

上述硬化性樹脂亦可於不阻礙本發明之目的之範圍內，除上 述3官能以上之環氧(甲基)丙烯酸酯以外，亦含有其他硬化性樹脂。 The above curable resin may be included in the range which does not hinder the object of the present invention. In addition to the trifunctional or higher epoxy (meth) acrylate, other curable resins are also included.

作為上述其他硬化性樹脂，例如可列舉：3官能以上之環氧(甲基)丙烯酸酯以外之其他(甲基)丙烯酸化合物、或環氧化合物等。 Examples of the other curable resin include a (meth)acrylic compound other than a trifunctional or higher epoxy (meth)acrylate, or an epoxy compound.

再者，於本說明書中，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯氧基之化合物。 In the present specification, the above "(meth)acrylic compound" means a compound having a (meth)acryloxy group.

作為上述其他(甲基)丙烯酸化合物，例如可列舉：2官能 以下之環氧(甲基)丙烯酸酯、藉由使具有羥基之化合物與(甲基)丙烯酸進行反應所獲得之酯化合物、藉由使具有羥基之(甲基)丙烯酸衍生物 與異氰酸酯化合物進行反應所獲得之(甲基)丙烯酸胺酯等。其中，就提高接著性之觀點或抑制液晶污染之觀點而言，較佳為2官能以下之環氧(甲基)丙烯酸酯。 As the other (meth)acrylic compound, for example, a bifunctional one can be mentioned. The following epoxy (meth) acrylate, an ester compound obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid, by using a (meth)acrylic acid derivative having a hydroxyl group The (meth)acrylic acid amine ester obtained by the reaction with an isocyanate compound. Among them, from the viewpoint of improving adhesion or suppressing liquid crystal contamination, an epoxy (meth) acrylate having two or less functional groups is preferable.

作為上述2官能以下之環氧(甲基)丙烯酸酯，例如可列舉： 藉由使2官能以下之環氧化合物與(甲基)丙烯酸依據常法於鹼性觸媒之存在下進行反應所獲得者等。 Examples of the above-mentioned bifunctional or lower epoxy (meth) acrylate include, for example: A compound obtained by reacting a bifunctional or less epoxy compound with (meth)acrylic acid in the presence of a basic catalyst according to a usual method.

作為上述2官能以下之環氧化合物，例如可列舉：雙酚A 型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、2,2'-二烯丙基雙酚A型環氧樹脂、氫化雙酚型環氧樹脂、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、二環戊二烯酚醛清漆型環氧樹脂、聯苯酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、環氧丙胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、環氧丙酯化合物、雙酚A型環硫樹脂等中之於1分子中具有2個以下環氧基者。 Examples of the above-mentioned bifunctional or lower epoxy compound include bisphenol A. Epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, 2,2'-diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide plus Bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, Naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type Epoxy resin, epoxy propylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin, etc. 2 or less epoxy groups.

於本發明之液晶滴下法用密封劑含有上述2官能以下之環 氧(甲基)丙烯酸酯之情形時，上述3官能以上之環氧(甲基)丙烯酸酯與上述2官能以下之環氧(甲基)丙烯酸酯之含有比率以重量比計較佳為3官能以上之環氧(甲基)丙烯酸酯：2官能以下之環氧(甲基)丙烯酸酯=1：2~1：45。藉由使上述3官能以上之環氧(甲基)丙烯酸酯與上述2官能以下之環氧(甲基)丙烯酸酯之含有比率為該範圍，所獲得之液晶滴下法用密封劑成為尤其於塗佈性或接著性方面優異且抑制液晶污染之效果優 異者。上述3官能以上之環氧(甲基)丙烯酸酯與上述2官能以下之環氧(甲基)丙烯酸酯之含有比率更佳為3官能以上之環氧(甲基)丙烯酸酯：2官能以下之環氧(甲基)丙烯酸酯=1：2.5~1：11。 The sealing agent for liquid crystal dropping method of the present invention contains the above-mentioned ring of 2 or less functional groups In the case of the oxygen (meth) acrylate, the content ratio of the above-mentioned trifunctional or higher epoxy (meth) acrylate to the above bifunctional or lower epoxy (meth) acrylate is preferably 3 or more by weight. Epoxy (meth) acrylate: 2-functional or less epoxy (meth) acrylate = 1:2 to 1:45. When the content ratio of the above-described trifunctional or higher epoxy (meth) acrylate to the above bifunctional or lower epoxy (meth) acrylate is within this range, the obtained liquid crystal dropping method sealant is particularly coated. Excellent in cloth or adhesion and excellent in suppressing liquid crystal contamination Different. The content ratio of the above-mentioned trifunctional or higher epoxy (meth) acrylate to the above-mentioned bifunctional or less epoxy (meth) acrylate is preferably a trifunctional or higher epoxy (meth) acrylate: 2 or less Epoxy (meth) acrylate = 1:2.5 ~ 1:11.

作為上述酯化合物中之單官能者，例如可列舉：(甲基)丙 烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸雙環戊烯基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、醯亞胺(甲基)丙烯酸酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、琥珀酸2-(甲基)丙烯醯氧基乙酯、六氫鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯2-羥基丙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸環氧丙酯等。 As the monofunctional one of the above ester compounds, for example, (meth) propyl Methyl enoate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( 2-ethylhexyl methacrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) ) lauryl acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl) Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, (meth)acrylic acid 2 -phenoxyethyl ester, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy Polyethylene glycol (meth) acrylate, (meth) acrylate Anthracene ester, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, ( Methyl)acrylic acid 1H,1H,5H-octafluoropentyl ester, quinone imine (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , 2-(methyl) propylene methoxyethyl succinate, 2-(methyl) propylene methoxyethyl hexaphthalate, 2-(methyl) propylene oxy oxy phthalate Ester 2-hydroxypropyl ester, 2-(methyl) propylene methoxyethyl phosphate, glycidyl (meth) acrylate, and the like.

又，作為上述酯化合物中之2官能者，例如可列舉：1,3- 丁二醇二(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、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷加成雙酚A二(甲基)丙烯酸酯、環氧丙烷加成雙酚A二(甲基)丙烯酸酯、環氧乙烷加成雙酚F二(甲基)丙烯酸酯、二羥甲基二環戊二烯基二(甲基)丙烯酸酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。 Moreover, as a bifunctional one of the above ester compounds, for example, 1,3- Butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di Methyl) acrylate, 1,10-nonanediol di(meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol bis ( Methyl) acrylate, polyethylene glycol di(meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth) acrylate, dipropylene glycol di(meth) acrylate Ester, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, Propylene oxide addition bisphenol A di(meth) acrylate, ethylene oxide addition bisphenol F di(meth) acrylate, dimethylol dicyclopentadienyl di(meth) acrylate Ethylene oxide modified di(meth)acrylate isocyanurate, 2-hydroxy-3-(methyl)propenyloxypropyl (meth)acrylate, carbonate diol di(methyl) Acrylate, polyether diol di(meth) acrylate, polyester diol di(meth) acrylate, poly Ester diol di (meth) acrylate, polybutadiene diol di (meth) acrylate.

又，作為上述酯化合物中之3官能以上者，例如可列舉：三 羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、環氧丙烷加成三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、環氧乙烷加成異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、環氧丙烷加成甘油三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、磷酸三(甲基)丙烯醯氧基乙酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等。 Further, as the trifunctional or higher of the above ester compounds, for example, three Hydroxymethylpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, Lactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition tris(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(methyl)propenyloxyethyl phosphate, di(trimethylolpropane)tetra(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

使具有羥基之(甲基)丙烯酸衍生物與上述異氰酸酯化合物 進行反應所獲得之(甲基)丙烯酸胺基甲酸酯例如可藉由相對於具有2個異氰酸酯基之化合物1當量，使具有羥基之(甲基)丙烯酸衍生物2當量於觸媒量之錫系化合物存在下進行反應而獲得。 A (meth)acrylic acid derivative having a hydroxyl group and the above isocyanate compound The (meth)acrylic acid urethane obtained by carrying out the reaction can, for example, be a tin (meth)acrylic acid derivative having a hydroxyl group of 2 equivalents to the amount of the catalyst by 1 equivalent of the compound having 2 isocyanate groups. It is obtained by carrying out a reaction in the presence of a compound.

作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合 物，例如可列舉：異佛酮二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯(MDI)、氫化MDI、聚MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯(XDI)、氫化XDI、離胺酸二異氰酸酯、三苯基甲烷三異氰酸酯、硫代磷酸三(異氰酸基苯基)酯、四甲基二甲苯二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Isocyanate compounding as a raw material of the above (meth)acrylic acid amine ester Examples of the substance include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane- 4,4'-diisocyanate (MDI), hydrogenated MDI, poly MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, benzodimethyl diisocyanate (XDI), hydrogenated XDI, Ammonic acid diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,11-undecane triisocyanate, and the like.

又，作為成為藉由使具有羥基之(甲基)丙烯酸衍生物與上 述異氰酸酯進行反應所獲得之(甲基)丙烯酸胺酯之原料的異氰酸酯化合物，亦可使用藉由乙二醇、甘油、山梨糖醇、三羥甲基丙烷、(聚)丙二醇、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等多元醇與過量之異氰酸酯化合物之反應所獲得之經鏈延長之異氰酸酯化合物。 Further, by using a (meth)acrylic acid derivative having a hydroxyl group and The isocyanate compound of the raw material of the (meth)acrylic acid amide obtained by the reaction of the isocyanate may also be used by ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate diol. A chain extended isocyanate compound obtained by reacting a polyhydric alcohol such as a polyether diol, a polyester diol or a polycaprolactone diol with an excess of an isocyanate compound.

作為成為上述(甲基)丙烯酸胺酯之原料之具有羥基之(甲 基)丙烯酸衍生物，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基丁酯等單(甲基)丙烯酸羥基烷基酯，或乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、聚乙二醇等二元醇之單(甲基)丙烯酸酯，三羥甲基乙烷、三羥甲基丙烷、甘油等三元醇之單(甲基)丙烯酸酯或二(甲 基)丙烯酸酯，雙酚A型環氧丙烯酸酯等環氧丙烯酸酯等。 As a raw material of the above (meth)acrylic acid amide, having a hydroxyl group (A) Examples of the acrylic acid derivative include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-(meth)acrylate. a hydroxyalkyl mono(meth)acrylate such as hydroxybutyl ester, or ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Mono (meth) acrylate of a monohydric alcohol, mono (meth) acrylate or di(a) of a trihydric alcohol such as trimethylolethane, trimethylolpropane or glycerol Epoxy acrylate such as acrylate, bisphenol A epoxy acrylate or the like.

作為上述(甲基)丙烯酸胺酯中所市售者，例如可列舉：M -1100、M-1200、M-1210、M-1600(均為東亞合成公司製造)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220(均為Daicel Allnex公司製造)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、Artresin UN-1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均為根上工業公司製造)、U-122P、U-108A、U-340P、U-4HA、U-6HA、U-324A、U-15HA、UA-5201P、UA-W2A、U-1084A、U-6LPA、U-2HA、U-2PHA、UA-4100、UA-7100、UA-4200、UA-4400、UA-340P、U-3HA、UA-7200、U-2061BA、U-10H、U-122A、U-340A、U-108、U-6H、UA-4000(均為新中村化學工業公司製造)、AH-600、AT-600、UA-306H、Al-600、UA-101T、UA-101I、UA-306T、UA-306I(均為共榮社化學公司製造)等。 As a commercially available product of the above (meth)acrylic acid amide, for example, M -1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700 , EBECRYL220, EBECRYL2220 (all manufactured by Daicel Allnex), Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, Artresin UN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH -500B (all manufactured by Gensei Industrial Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A , U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U -122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600, AT-600, UA-306H, Al-600, UA-101T, UA -101I, UA-306T, UA-306I (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

關於上述其他(甲基)丙烯酸化合物，就抑制對液晶之不良 影響之方面而言，較佳為具有-OH基、-NH-基、-NH2基等氫鍵性官能基者。 The other (meth)acrylic compound is preferably a hydrogen bond functional group such as an -OH group, a -NH- group or a -NH 2 group in terms of suppressing adverse effects on the liquid crystal.

本發明之液晶滴下法用密封劑含有熱自由基聚合起始劑。 藉由含有上述熱自由基聚合起始劑，本發明之液晶滴下法用密封劑成為可藉由加熱而迅速地硬化者。 The sealing agent for liquid crystal dropping methods of the present invention contains a thermal radical polymerization initiator. The sealing agent for liquid crystal dropping methods of the present invention can be rapidly cured by heating by containing the above-mentioned thermal radical polymerization initiator.

作為上述熱自由基聚合起始劑，例如可列舉有機過氧化物、 偶氮化合物等。其中，較佳為由高分子偶氮化合物構成之高分子偶氮起始劑。 As the thermal radical polymerization initiator, for example, an organic peroxide, Azo compounds and the like. Among them, a polymer azo initiator comprising a polymer azo compound is preferred.

再者，於本說明書中，所謂高分子偶氮起始劑，意指具有偶氮基，生成可藉由熱而使(甲基)丙烯醯氧基硬化之自由基，數量平均分子量為300以上之化合物。 In the present specification, the term "polymer azo initiator" means an azo group, which generates a radical which can cure a (meth) propylene oxime by heat, and has a number average molecular weight of 300 or more. Compound.

上述高分子偶氮起始劑之數量平均分子量之較佳下限為 1000，較佳上限為30萬。若上述高分子偶氮起始劑之數量平均分子量未達1000，則有高分子偶氮起始劑對液晶產生不良影響之情況。若上述高分子偶氮起始劑之數量平均分子量超過30萬，則有向硬化性樹脂中之混合變得困難之情況。上述高分子偶氮起始劑之數量平均分子量之更佳下限為5000，更佳上限為10萬，進而較佳下限為1萬，進而較佳上限為9萬。 The preferred lower limit of the number average molecular weight of the above polymer azo initiator is 1000, the upper limit is 300,000. When the number average molecular weight of the above polymer azo initiator is less than 1,000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the above polymer azo initiator is more than 300,000, mixing into the curable resin may become difficult. A lower limit of the number average molecular weight of the above polymer azo initiator is 5,000, a higher limit is 100,000, and a lower limit is preferably 10,000, and a preferred upper limit is 90,000.

再者，於本說明書中，上述數量平均分子量係藉由凝膠滲透層析法(GPC)進行測定，以聚苯乙烯換算所求出之值。作為利用GPC測定以聚苯乙烯換算之數量平均分子量時之管柱，例如可列舉：Shodex LF-804(昭和電工公司製造)等。 In the present specification, the above-mentioned number average molecular weight is measured by gel permeation chromatography (GPC) and is determined in terms of polystyrene. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) or the like can be mentioned.

作為上述高分子偶氮起始劑，例如可列舉：具有經由偶氮基 而鍵結有複數個聚環氧烷或聚二甲基矽氧烷等單元之結構。 As the above polymer azo initiator, for example, it is possible to have an azo group. The structure is bonded to a plurality of units such as polyalkylene oxide or polydimethyl siloxane.

作為具有上述經由偶氮基而鍵結有複數個聚環氧烷等單元之結構之高分子偶氮起始劑，較佳為具有聚環氧乙烷結構者。作為此種高分子偶氮起始劑，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之聚縮合物、或4,4'-偶氮雙(4-氰基戊酸)與末端具有胺基之聚二甲基矽氧烷之 聚縮合物等。 The polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polyethylene oxide structure. Examples of such a polymer azo initiator include a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and a polyalkylene glycol, or 4,4'-even. Nitrogen bis(4-cyanovaleric acid) and polydimethyl methoxyoxane having an amine group at the terminal Polycondensate and the like.

作為上述有機過氧化物，例如可列舉：過氧化酮、過氧縮酮、過氧化氫、過氧化二烷基、過氧酯、過氧化二醯基、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, dinonyl peroxide, and peroxydicarbonate.

作為上述熱自由基聚合起始劑中之市售者，例如可列舉：PERBUTYL O、PERHEXYL O、PERBUTYL PV(均為日油公司製造)、V-30、V-501、V-601、VPE-0201、VPE-0401、VPE-0601(均為和光純藥工業公司製造)等。 As a commercial one of the above-mentioned thermal radical polymerization initiators, for example, PERBUTYL O, PERHEXYL O, PERBUTYL PV (all manufactured by Nippon Oil Co., Ltd.), V-30, V-501, V-601, VPE- 0201, VPE-0401, VPE-0601 (all manufactured by Wako Pure Chemical Industries, Ltd.).

上述熱自由基聚合起始劑之含量相對於上述硬化性樹脂100重量份，較佳下限為0.01重量份，較佳上限為10重量份。若上述熱自由基聚合起始劑之含量未達0.01重量份，則有無法使所獲得之液晶滴下法用密封劑充分硬化之情況。若上述熱自由基聚合起始劑之含量超過10重量份，則有儲藏穩定性降低之情況。 The content of the thermal radical polymerization initiator is preferably 0.01 parts by weight, and preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the above-mentioned thermal radical polymerization initiator is less than 0.01 part by weight, the obtained sealing compound for liquid crystal dropping method may not be sufficiently cured. When the content of the above thermal radical polymerization initiator exceeds 10 parts by weight, the storage stability may be lowered.

就抑制液晶污染之觀點而言，本發明之液晶滴下法用密封劑較佳為除上述熱自由基聚合起始劑以外，亦含有光自由基聚合起始劑。 The liquid crystal dropping method sealing agent of the present invention preferably contains a photoradical polymerization initiator in addition to the above-mentioned thermal radical polymerization initiator, from the viewpoint of suppressing liquid crystal contamination.

作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮系化合物、苯乙酮系化合物、醯基氧化膦系化合物、二茂鈦系化合物、肟酯系化合物、安息香醚系化合物、9-氧硫系化合物等。 Examples of the photoradical polymerization initiator include a benzophenone compound, an acetophenone compound, a fluorenyl phosphine oxide compound, a titanocene compound, an oxime ester compound, and a benzoin ether compound. 9-oxygen sulfur A compound or the like.

作為上述光自由基聚合起始劑中所市售者，例如可列舉：IRGACURE 184、IRGACURE 369、IRGACURE 379、IRGACURE 651、IRGACURE 819、IRGACURE 907、IRGACURE 2959、IRGACURE OXE01、Lucirin TPO(均為BASF公司製造)、NCI-930(ADEKA公司製造)、SPEEDCURE EMK(日本SiberHegner公司製造)、安息香甲醚、安息香***、 安息香丙醚(均為東京化成工業公司製造)等。 The commercially available ones of the photoradical polymerization initiators include, for example, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucirin TPO (all of which are BASF Corporation). Manufactured, NCI-930 (made by ADEKA), SPEEDCURE EMK (made by Siber Hegner, Japan), benzoin methyl ether, benzoin ethyl ether, Benzoin (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

於含有上述光自由基聚合起始劑之情形時，上述熱自由基聚 合起始劑與上述光自由基聚合起始劑之含有比率以重量比計較佳為上述熱自由基聚合起始劑：上述光自由基聚合起始劑=1：0.1~1：10。藉由使上述熱自由基聚合起始劑與上述光自由基聚合起始劑之含有比率為該範圍，可使本發明之液晶滴下法用密封劑成為抑制硬化性、液晶污染之效果、及接著性更優異者。 In the case of containing the above photoradical polymerization initiator, the above thermal radical polymerization The content ratio of the initiator to the photoradical polymerization initiator is preferably the above-mentioned thermal radical polymerization initiator: the above photoradical polymerization initiator = 0.1 to 1:10. When the content ratio of the thermal radical polymerization initiator to the photoradical polymerization initiator is within this range, the sealing compound for liquid crystal dropping method of the present invention can be used to suppress the effect of curing property and liquid crystal contamination, and then More excellent.

本發明之液晶滴下法用密封劑亦可含有熱硬化劑。 The sealing agent for liquid crystal dropping methods of the present invention may further contain a heat hardening agent.

作為上述熱硬化劑，例如可列舉：有機酸醯肼、咪唑衍生物、胺化合物、多酚系化合物、酸酐等。其中，可適宜地使用固形之有機酸醯肼。 Examples of the above-mentioned thermosetting agent include an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol compound, and an acid anhydride. Among them, a solid organic acid hydrazine can be suitably used.

作為上述固形之有機酸醯肼，例如可列舉：1,3-雙(肼基 羰乙基)-5-異丙基乙內醯脲、癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼等，作為市售者，例如可列舉：SDH、MDH(均為日本Finechem公司製造)、ADH(大塚化學公司製造)、Amicure VDH、Amicure VDH-J、Amicure UDH(均為Ajinomoto Fine-Techno公司製造)等。 Examples of the solid organic acid hydrazine include 1,3-bis(fluorenyl) Carboxyethyl)-5-isopropylhydantoin, bismuth sebacate, diammonium isophthalate, diammonium adipate, diammonium malonate, etc., as a commercial product, For example, SDH, MDH (all manufactured by Japan Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, and Amicure UDH (all manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like can be mentioned.

上述熱硬化劑之含量相對於上述硬化性樹脂100重量份，較 佳下限為1重量份，較佳上限為50重量份。若上述熱硬化劑之含量未達1重量份，則有無法使本發明之液晶滴下法用密封劑充分硬化之情況。若上述熱硬化劑之含量超過50重量份，則有本發明之液晶滴下法用密封劑之黏度升高，塗敷性變差之情況。上述熱硬化劑之含量之更佳上限為30重量份。 The content of the above-mentioned thermosetting agent is compared with 100 parts by weight of the above-mentioned curable resin. A preferred lower limit is 1 part by weight, and a preferred upper limit is 50 parts by weight. When the content of the above-mentioned thermosetting agent is less than 1 part by weight, the sealing agent for liquid crystal dropping methods of the present invention may not be sufficiently cured. When the content of the above-mentioned heat-hardening agent is more than 50 parts by weight, the viscosity of the sealing compound for liquid crystal dropping methods of the present invention is increased, and the coatability is deteriorated. A more preferable upper limit of the content of the above thermal curing agent is 30 parts by weight.

本發明之液晶滴下法用密封劑為了藉由應力分散效果所引 起之接著性改善、線膨脹率改善等，亦可進而含有填充劑。 The sealing agent for liquid crystal dropping method of the present invention is cited by the stress dispersion effect The adhesion is improved, the coefficient of linear expansion is improved, and the like, and the filler may be further contained.

作為上述填充劑，例如可列舉：滑石、石棉、二氧化矽、矽藻土、膨潤石、膨潤土、碳酸鈣、碳酸鎂、氧化鋁、蒙脫石、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、氫氧化鎂、氫氧化鋁、玻璃珠、氮化矽、硫酸鋇、石膏、矽酸鈣、絹雲母、活性白土、氮化鋁等無機填充劑，或聚酯微粒子、聚胺酯微粒子、乙烯基聚合物微粒子、丙烯酸聚合物微粒子等有機填充劑。 Examples of the filler include talc, asbestos, cerium oxide, diatomaceous earth, bentonite, bentonite, calcium carbonate, magnesium carbonate, aluminum oxide, montmorillonite, zinc oxide, iron oxide, magnesium oxide, and tin oxide. , titanium oxide, magnesium hydroxide, aluminum hydroxide, glass beads, tantalum nitride, barium sulfate, gypsum, calcium citrate, sericite, activated clay, aluminum nitride and other inorganic fillers, or polyester microparticles, polyurethane microparticles, An organic filler such as a vinyl polymer microparticle or an acrylic polymer microparticle.

本發明之液晶滴下法用密封劑100重量份中之上述填充劑 之含量之較佳下限為5重量份，較佳上限為70重量份。若上述填充劑之含量未達5重量份，則有無法充分地發揮接著性之改善等效果之情況。若上述填充劑之含量超過70重量份，則有所獲得之液晶滴下法用密封劑之黏度過度升高，塗敷性變差之情況。上述填充劑之含量之更佳下限為10重量份，更佳上限為60重量份。 The above filler in 100 parts by weight of the sealant for liquid crystal dropping method of the present invention A preferred lower limit of the content is 5 parts by weight, and a preferred upper limit is 70 parts by weight. When the content of the filler is less than 5 parts by weight, the effect of improving the adhesion may not be sufficiently exhibited. When the content of the filler exceeds 70 parts by weight, the viscosity of the obtained sealing compound for liquid crystal dropping methods is excessively increased, and the coatability is deteriorated. A more preferred lower limit of the content of the above filler is 10 parts by weight, and a still more preferred upper limit is 60 parts by weight.

本發明之液晶滴下法用密封劑亦可含有矽烷偶合劑。 The sealant for liquid crystal dropping method of the present invention may further contain a decane coupling agent.

作為上述矽烷偶合劑，例如可適宜地使用：3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等可單獨使用，亦可併用兩種以上。 As the above decane coupling agent, for example, 3-aminopropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-isocyanate can be suitably used. Propyltrimethoxydecane, and the like. These may be used singly or in combination of two or more.

本發明之液晶滴下法用密封劑100重量份中之上述矽烷偶 合劑之含量之較佳下限為0.1重量份，較佳上限為20重量份。若上述矽烷偶合劑之含量未達0.1重量份，則有無法充分發揮藉由調配矽烷偶合劑所產生之效果之情況。若上述矽烷偶合劑之含量超過20重量份，則有所獲得之液晶滴下法用密封劑引起液晶污染之情況。上述矽烷偶合劑之含量之更佳下限為0.5重量份，更佳上限為10重量份。 The above-mentioned decane couple in 100 parts by weight of the sealant for liquid crystal dropping method of the present invention A preferred lower limit of the content of the mixture is 0.1 part by weight, and a preferred upper limit is 20 parts by weight. When the content of the above decane coupling agent is less than 0.1 part by weight, the effect by the preparation of the decane coupling agent may not be sufficiently exhibited. When the content of the above decane coupling agent exceeds 20 parts by weight, the obtained liquid crystal dropping method sealant may cause liquid crystal contamination. A more preferred lower limit of the content of the above decane coupling agent is 0.5 part by weight, and a more preferred upper limit is 10 parts by weight.

本發明之液晶滴下法用密封劑亦可含有遮光劑。藉由含有上 述遮光劑，本發明之液晶滴下法用密封劑可適宜地用作遮光密封劑。 The sealing agent for liquid crystal dropping methods of this invention may also contain an opacifier. By containing The sunscreen agent for a liquid crystal dropping method of the present invention can be suitably used as a light-shielding sealant.

作為上述遮光劑，例如可列舉：氧化鐵、鈦黑、苯胺黑、花青黑、富勒烯、碳黑、樹脂被覆型碳黑等。其中，較佳為鈦黑。 Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferred.

上述鈦黑係與對波長300~800nm之光之平均透過率相比，對紫外線區域附近、尤其是波長370~450nm之光之透過率升高之物質。即，上述鈦黑係藉由充分遮蔽可見光區域之波長之光而對本發明之液晶滴下法用密封劑賦予遮光性，另一方面，係具有使紫外線區域附近之波長之光透過之性質之遮光劑。因此，作為上述光自由基聚合起始劑或上述光陽離子聚合起始劑，藉由使用可藉由上述鈦黑之透過率升高之波長(370~450nm)之光而開始反應者，可進一步增大本發明之液晶滴下法用密封劑之光硬化性。又，另一方面，作為於本發明之液晶滴下法用密封劑中所含之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，亦適宜為鈦黑。 The titanium black is a substance having an increased transmittance to light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450 nm, as compared with the average transmittance of light having a wavelength of 300 to 800 nm. In other words, the titanium black is provided with a light-shielding property to the liquid crystal dropping method sealing agent of the present invention by sufficiently shielding the light of the wavelength of the visible light region, and is an optical agent having a property of transmitting light of a wavelength near the ultraviolet region. . Therefore, as the photoradical polymerization initiator or the photocationic polymerization initiator, the reaction can be started by using light having a wavelength (370 to 450 nm) which is increased in transmittance of the titanium black. The photocurability of the sealing compound for liquid crystal dropping methods of the present invention is increased. On the other hand, the light-shielding agent contained in the sealing compound for liquid crystal dropping methods of the present invention is preferably a material having high insulating properties, and is preferably a titanium black as a light-shielding agent having high insulating properties.

關於上述鈦黑，其每1μm之光學濃度(OD值)較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越好，上述鈦黑之OD值並無特別較佳上限，通常為5以下。 The optical density (OD value) per 1 μm of the titanium black is preferably 3 or more, and more preferably 4 or more. The higher the light blocking property of the titanium black, the better, and the OD value of the titanium black is not particularly preferably an upper limit, and is usually 5 or less.

上述鈦黑即便為未經表面處理者，亦發揮出充分之效果，可使用表面經偶合劑等有機成分處理者，或由氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等表面經處理之鈦黑。其中，由有機成分所處理者就可進一步提高絕緣性之方面而言較佳。 The titanium black described above exhibits sufficient effects even if it is not surface-treated, and can be treated with an organic component such as a surface coupler or cerium oxide, titanium oxide, cerium oxide, aluminum oxide, zirconium oxide, magnesium oxide, or the like. A surface treated titanium black such as an inorganic component. Among them, those which are treated by the organic component are more preferable in terms of further improving the insulating property.

又，使用含有上述鈦黑之本發明之液晶滴下法用密封劑作為遮光劑所製造之液晶顯示元件具有充分之遮光性，故而可實現無光之漏出且具有較 高之對比度，具有優異之圖像顯示品質之液晶顯示元件。 Further, the liquid crystal display element produced by using the sealing agent for liquid crystal dropping method of the present invention containing the above titanium black as a light-shielding agent has sufficient light-shielding property, so that light leakage can be achieved and compared High contrast ratio, liquid crystal display element with excellent image display quality.

作為上述鈦黑中所市售者，例如可列舉：12S、13M、13M -C、13R-N(均為Mitsubishi Materials公司製造)、Tilack D(赤穗化成公司製造)等。 As a commercially available one of the above titanium blacks, for example, 12S, 13M, and 13M can be cited. -C, 13R-N (all manufactured by Mitsubishi Materials Co., Ltd.), Tilack D (manufactured by Ako Chemical Co., Ltd.), and the like.

上述鈦黑之比表面積之較佳下限為13m2/g，較佳上限為 30m2/g，更佳下限為15m2/g，更佳上限為25m2/g。 A preferred lower limit of the specific surface area of the above titanium black is 13 m 2 /g, a preferred upper limit is 30 m 2 /g, a more preferred lower limit is 15 m 2 /g, and a more preferred upper limit is 25 m 2 /g.

又，上述鈦黑之體積電阻之較佳下限為0.5Ω‧cm，較佳上限為3Ω‧cm，更佳下限為1Ω‧cm，更佳上限為2.5Ω‧cm。 Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω ‧ cm, the upper limit is preferably 3 Ω ‧ cm, the lower limit is preferably 1 Ω ‧ cm, and the upper limit is more preferably 2.5 Ω ‧ cm

上述遮光劑之一次粒徑只要為液晶顯示元件之基板間之距 離以下，則無特別限定，較佳下限為1nm，較佳上限為5μm。若上述遮光劑之一次粒徑未達1nm，則有所獲得之液晶滴下法用密封劑之黏度或流動減黏性大幅度增大，作業性變差之情況。若上述遮光劑之一次粒徑超過5μm，則有所獲得之液晶滴下法用密封劑於基板上之塗佈性變差之情況。上述遮光劑之一次粒徑之更佳下限為5nm，更佳上限為200nm，進而較佳下限為10nm，進而較佳上限為100nm。 The primary particle diameter of the above-mentioned sunscreen agent is only the distance between the substrates of the liquid crystal display element The following is not particularly limited, and a preferred lower limit is 1 nm, and a preferred upper limit is 5 μm. When the primary particle diameter of the above-mentioned light-shielding agent is less than 1 nm, the viscosity or flow viscosity-reducing property of the obtained sealing compound for liquid crystal dropping methods is greatly increased, and workability is deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained sealing compound for liquid crystal dropping methods on the substrate may be deteriorated. A more preferred lower limit of the primary particle diameter of the above-mentioned opacifier is 5 nm, a more preferred upper limit is 200 nm, and a further preferred lower limit is 10 nm, and a further preferred upper limit is 100 nm.

本發明之液晶滴下法用密封劑100重量份中之上述遮光劑 之含量之較佳下限為5重量份，較佳上限為80重量份。若上述遮光劑之含量未達5重量份，則有無法獲得充分之遮光性之情況。若上述遮光劑之含量超過80重量份，則有所獲得之液晶滴下法用密封劑對基板之密接性或硬化後之強度降低，或繪圖性降低之情況。上述遮光劑之含量之更佳下限為10重量份，更佳上限為70重量份，進而較佳下限為30重量份，進而較佳上限為60重量份。 The above-mentioned sunscreen agent in 100 parts by weight of the sealant for liquid crystal dropping method of the present invention A preferred lower limit of the content is 5 parts by weight, and a preferred upper limit is 80 parts by weight. If the content of the above-mentioned sunscreen agent is less than 5 parts by weight, sufficient light-shielding properties may not be obtained. When the content of the above-mentioned light-shielding agent exceeds 80 parts by weight, the adhesion between the obtained liquid crystal dropping method sealant on the substrate and the strength after curing may be lowered, or the drawability may be lowered. A more preferred lower limit of the content of the above-mentioned opacifier is 10 parts by weight, more preferably 70 parts by weight, still more preferably 30 parts by weight, and still more preferably 60 parts by weight.

本發明之液晶滴下法用密封劑進而視需要亦可含有：用以調 整黏度之反應性稀釋劑、調整觸變性之觸變劑、用以調整面板間隙之聚合物顆粒等間隔件、消泡劑、整平劑、聚合抑制劑等其他公知之添加劑。 The sealing agent for liquid crystal dropping method of the present invention may further contain: if necessary Reactive diluent for integral viscosity, thixotropic agent for adjusting thixotropic property, spacer for polymer particles for adjusting panel gap, other known additives such as antifoaming agent, leveling agent, polymerization inhibitor, and the like.

作為製造本發明之液晶滴下法用密封劑之方法，例如可列 舉：將硬化性樹脂、熱自由基聚合起始劑、及視需要添加之矽烷偶合劑等，使用勻相分散機、均質攪拌機、萬能攪拌器、行星式混合機、捏合機、三輥等混合機進行混合之方法等。 As a method of producing the sealing agent for liquid crystal dropping method of the present invention, for example, it can be listed A hardening resin, a thermal radical polymerization initiator, and a decane coupling agent to be added as needed, and a homogeneous phase disperser, a homomixer, a universal agitator, a planetary mixer, a kneader, a three-roller, or the like is used. The method of mixing the machine, and the like.

關於本發明之液晶滴下法用密封劑，使用E型黏度計於25 ℃、1rpm之條件下所測得之黏度之較佳下限為100Pa‧s，較佳上限為800Pa‧s。藉由使上述黏度為該範圍，所獲得之液晶滴下法用密封劑成為塗佈性優異者。上述黏度之更佳下限為150Pa‧s，更佳上限為500Pa‧s。 Regarding the sealing agent for liquid crystal dropping method of the present invention, an E-type viscometer is used at 25 A preferred lower limit of the viscosity measured at ° C and 1 rpm is 100 Pa ‧ and a preferred upper limit is 800 Pa ‧ . When the viscosity is within this range, the obtained sealing compound for liquid crystal dropping methods is excellent in coatability. A lower limit of the above viscosity is 150 Pa‧s, and a lower limit is 500 Pa‧s.

藉由對本發明之液晶滴下法用密封劑調配導電性微粒子，可 製造上下導通材料。若使用此種上下導通材料，則可使電極間確實地導電連接。 By disposing the conductive fine particles with the sealing agent for liquid crystal dropping method of the present invention, Manufacture the upper and lower conductive materials. If such a top and bottom conductive material is used, the electrodes can be reliably electrically connected.

含有本發明之液晶滴下法用密封劑與導電性微粒子之上下導通材料亦係本發明之一。 The above-mentioned one of the present invention is also contained in the above-mentioned liquid crystal dropping method sealing agent and conductive fine particles.

作為上述導電性微粒子，例如可使用於金屬球、樹脂微粒子 之表面形成有導電金屬層者等。其中，於樹脂微粒子之表面形成有導電金屬層者因樹脂微粒子之優異彈性，而可於不損傷透明基板等之情況下進行導電連接，故而較佳。 The conductive fine particles can be used, for example, for metal balls or resin fine particles. The surface is formed with a conductive metal layer or the like. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferably electrically connected to each other without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

使用本發明之液晶滴下法用密封劑或本發明之上下導通材 料而成之液晶顯示元件亦係本發明之一。 The sealing agent for liquid crystal dropping method of the present invention or the upper and lower conductive materials of the present invention The liquid crystal display element is also one of the inventions.

作為製造本發明之液晶顯示元件之方法，例如可列舉具有如下步驟之方法等：於具有ITO薄膜等之兩片基板之一者上，將本發明之液晶滴下法用密封劑藉由網版印刷、分注器塗佈等進行塗佈，而形成長方形狀之密封圖案之步驟；將液晶之微滴滴加塗佈至密封圖案之整個框內，於真空下重疊另一基板之步驟；進行加熱而使本發明之液晶滴下法用密封劑硬化之步驟等。又，亦可於進行加熱而使本發明之液晶滴下法用密封劑硬化之步驟之前，進行照射紫外線等光而使本發明之液晶滴下法用密封劑暫時硬化之步驟。 As a method of producing the liquid crystal display element of the present invention, for example, a method having the following steps: a screen printing method using the sealing compound for liquid crystal dropping method of the present invention on one of two substrates having an ITO film or the like a step of coating with a dispenser or the like to form a rectangular seal pattern; a step of applying a droplet of liquid crystal to the entire frame of the seal pattern, and superposing another substrate under vacuum; heating Further, the step of hardening the sealing compound for liquid crystal dropping method of the present invention or the like is used. Moreover, before the step of curing the sealing compound for liquid crystal dropping method of the present invention by heating, the step of temporarily curing the sealing compound for liquid crystal dropping method of the present invention by irradiating light such as ultraviolet rays may be performed.

根據本發明，可提供一種硬化速度較快、可抑制液晶污染、塗佈性及接著性優異之液晶滴下法用密封劑。又，根據本發明，可提高一種使用該液晶滴下法用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which has a high curing rate, can suppress liquid crystal contamination, and is excellent in coatability and adhesion. Moreover, according to the present invention, it is possible to improve the upper and lower conductive materials and the liquid crystal display element using the sealing compound for liquid crystal dropping methods.

以下，列舉實施例更詳細地說明本發明，但本發明並不僅限定於該等實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(3官能環氧丙烯酸酯A之製造) (Manufacture of 3-functional epoxy acrylate A)

一面送入空氣，一面將作為3官能之環氧化合物之三羥甲基丙烷三環氧丙醚(共榮社化學公司製造，「Epolight 100MF」)1000重量份、作為聚合 抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、及丙烯酸700重量份於90℃下回流攪拌5小時而使其等進行反應。為了吸附反應物中之離子性雜質，將所獲得之反應物100重量份利用填充有石英與高嶺土之天然結合物(HOFFMANN MINERAL公司製造，「Sillitin V85」)10重量份之管柱進行過濾，而獲得上述式(1)中之R1為乙基，R2均為氫，l、m、及n均為1之3官能環氧丙烯酸酯A。 1000 parts by weight of trimethylolpropane triglycidyl ether ("Epolight 100MF" manufactured by Kyoeisha Chemical Co., Ltd.) as a trifunctional epoxy compound, and a methoxy group as a polymerization inhibitor 2 parts by weight of phenol, 2 parts by weight of triethylamine as a reaction catalyst, and 700 parts by weight of acrylic acid were stirred at 90 ° C for 5 hours under reflux to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained reactant was filtered using a column packed with 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by HOFFMANN MINERAL Co., Ltd.). A trifunctional epoxy acrylate A in which R 1 in the above formula (1) is an ethyl group, R 2 is hydrogen, and l, m, and n are all 1 is obtained.

(4官能環氧丙烯酸酯A之製造) (Manufacture of 4-functional epoxy acrylate A)

一面送入空氣，一面將作為4官能之環氧化合物之新戊四醇聚氧乙烯醚(日本乳化劑公司製造，「PNT-40」)1000重量份、作為聚合抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、及丙烯酸500重量份於90℃下回流攪拌5小時而使其等進行反應。為了吸附反應物中之離子性雜質，將所獲得之反應物100重量份利用填充有石英與高嶺土之天然結合物(HOFFMANN MINERAL公司製造，「Sillitin V85」)10重量份之管柱進行過濾，而獲得上述式(1)中之R1為上述式(2)所表示之基(R3為氫，k為1)，R2均為氫，l、m、及n均為1之4官能環氧丙烯酸酯A。 1000 parts by weight of a pentaerythritol polyoxyethylene ether ("PNT-40" manufactured by Nippon Emulsifier Co., Ltd.) which is a tetrafunctional epoxy compound, and a p-methoxyphenol as a polymerization inhibitor 2 parts by weight, 2 parts by weight of triethylamine as a reaction catalyst, and 500 parts by weight of acrylic acid were stirred under reflux at 90 ° C for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reactant, 100 parts by weight of the obtained reactant was filtered using a column packed with 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by HOFFMANN MINERAL Co., Ltd.). R 4 in the above formula (1) is a group represented by the above formula (2) (R 3 is hydrogen, k is 1), R 2 is hydrogen, and l, m, and n are all 4 functional rings. Oxy acrylate A.

(部分甲基丙烯酸改質雙酚A型環氧樹脂之合成) (Synthesis of some methacrylic acid modified bisphenol A epoxy resin)

一面送入空氣，一面將雙酚A型環氧樹脂(三菱化學公司製造，「jER828EL」)1000重量份、作為聚合抑制劑之對甲氧基苯酚2重量份、作為反應觸媒之三乙胺2重量份、及甲基丙烯酸酸253重量份於90℃下回流攪拌5小時而使其等進行反應。為了吸附反應物中之離子性雜質，將所獲得之樹脂100重量份利用填充有石英與高嶺土之天然結合物(HOFFMANN MINERAL公司製造，「Sillitin V85」)10重量份之管柱進行過濾，而獲得50% 部分甲基丙烯酸改質雙酚A型環氧樹脂。 1000 parts by weight of bisphenol A type epoxy resin ("jer828EL" manufactured by Mitsubishi Chemical Corporation), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and triethylamine as a reaction catalyst, while introducing air 2 parts by weight and 253 parts by weight of methacrylic acid were stirred under reflux at 90 ° C for 5 hours to cause a reaction. In order to adsorb the ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered using a column packed with 10 parts by weight of a natural combination of quartz and kaolin ("Sillitin V85" manufactured by HOFFMANN MINERAL Co., Ltd.). 50% Part of methacrylic acid modified bisphenol A epoxy resin.

(實施例1) (Example 1)

藉由將作為硬化性樹脂之3官能環氧丙烯酸酯A2重量份、作為2官能環氧丙烯酸酯之雙酚A型環氧丙烯酸酯(Daicel Allnex公司製造，「EBECRYL3700」73重量份、及部分甲基丙烯酸改質雙酚A型環氧樹脂25重量份、作為光自由基聚合起始劑之2,2-二甲氧基-2-苯基苯乙酮(BASF公司製造，「IRGACURE 651」)2重量份、作為熱自由基聚合起始劑之偶氮化合物(和光純藥工業公司製造，「V-30」)3重量份、作為熱硬化劑之丙二酸二醯肼(日本Finechem公司製造，「MDH」)4重量份、作為填充劑之二氧化矽(Admatechs公司製造，「Admafine SO-C2」)30重量份、作為矽烷偶合劑之3-環氧丙氧基丙基三甲氧基矽烷(Chisso公司製造，「S510」)2重量份使用行星式攪拌機(Thinky公司製造，「去泡攪拌太郎」)進行混合後，進而使用三輥進行混合，而製備實施例1之液晶滴下法用密封劑。 A bisphenol A type epoxy acrylate (manufactured by Daicel Allnex Co., Ltd., "EBECRYL 3700", 73 parts by weight, and a part of A, which is a bifunctional epoxy acrylate A 2 parts by weight of a curable resin. 25 parts by weight of a acryl-modified bisphenol A type epoxy resin, 2,2-dimethoxy-2-phenylacetophenone (manufactured by BASF Corporation, "IRGACURE 651") as a photoradical polymerization initiator 2 parts by weight of an azo compound ("V-30" manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 3 parts by weight of diammonium malonate (manufactured by Japan Finechem Co., Ltd.) as a heat curing agent , "MDH"), 4 parts by weight, as a filler, 30 parts by weight of cerium oxide ("Admafine SO-C2", manufactured by Admatech Co., Ltd.), 3-glycidoxypropyltrimethoxydecane as a decane coupling agent 2 parts by weight (manufactured by Chisso Co., Ltd., "S510"), which were mixed by using a planetary mixer (manufactured by Thinky Co., Ltd., "defoaming and stirring"), and then mixed by using three rolls, and the sealing liquid crystal dropping method of Example 1 was prepared. Agent.

(實施例2~12、比較例1、2) (Examples 2 to 12, Comparative Examples 1, 2)

使用表1、2中所記載之調配比之各材料，除此以外，以與實施例1相同之方式製備實施例2~12、比較例1、2之液晶滴下法用密封劑。 The sealing agents for liquid crystal dropping methods of Examples 2 to 12 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the materials of the mixing ratios shown in Tables 1 and 2 were used.

<評價> <evaluation>

針對實施例及比較例中所獲得之各液晶滴下法用密封劑進行以下之評價。將結果示於表1、2。 The following evaluations were performed for each of the liquid crystal dropping method sealants obtained in the examples and the comparative examples. The results are shown in Tables 1 and 2.

(1)黏度 (1) Viscosity

針對實施例及比較例中所獲得之各液晶滴下法用密封劑，使用E型黏度計(Brookfield公司製造，「DV-III」)測定25℃、1rpm之條件下之黏度。 For each liquid crystal dropping method sealant obtained in the examples and the comparative examples, the viscosity at 25 ° C and 1 rpm was measured using an E-type viscometer ("DV-III" manufactured by Brookfield Co., Ltd.).

(2)硬化性 (2) Sturability

將實施例及比較例中所獲得之各液晶滴下法用密封劑填充至滴塗用之注射器(Musashi Engineering公司製造，「PSY-10E」)，進行脫泡處理。繼而，使用分注器(Musashi Engineering公司製造，「SHOTMASTER300」)，於兩片附ITO薄膜之透明電極基板中之一者以描繪長方形之框之方式塗佈密封劑。繼而，將TN液晶(Chisso公司製造，「JC-5001LA」)之微滴滴加塗佈至液晶滴下裝置，將另一透明基板藉由真空貼合裝置於5Pa之減壓下進行貼合，而獲得單元。藉由對所獲得之單元藉由金屬鹵化物燈照射3000mJ/cm2之紫外線後，於120℃加熱60分鐘使密封劑熱硬化而製作液晶顯示元件，測得所獲得之液晶顯示元件之液晶洩漏率。 Each of the liquid crystal dropping methods obtained in the examples and the comparative examples was filled in a syringe for dripping ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), and subjected to a defoaming treatment. Then, using a dispenser ("SHOTMASTER 300" manufactured by Musashi Engineering Co., Ltd.), one of the two transparent electrode substrates with an ITO film was coated with a sealant so as to draw a rectangular frame. Then, a droplet of TN liquid crystal (manufactured by Chisso Co., Ltd., "JC-5001LA") was dropped and applied to a liquid crystal dropping device, and another transparent substrate was attached by a vacuum bonding device under a reduced pressure of 5 Pa. Get the unit. After the obtained unit was irradiated with ultraviolet rays of 3000 mJ/cm 2 by a metal halide lamp, and then heated at 120 ° C for 60 minutes to thermally cure the sealant to prepare a liquid crystal display element, the liquid crystal leakage of the obtained liquid crystal display element was measured. rate.

將液晶洩漏率為0%之情形設為「◎」，將液晶洩漏率超過0%且為5%以下之情形設為「○」，將超過5%且為10%以下之情形設為「△」，將超過10%之情形設為「×」而評價密封劑之硬化性。 When the liquid crystal leakage rate is 0%, the case where the liquid crystal leakage rate is more than 0% and 5% or less is set to "○", and when the liquid crystal leakage rate is more than 5% and is 10% or less, it is set to "△". In the case where the amount is more than 10%, the hardenability of the sealant is evaluated.

再者，針對實施例11及實施例12中所獲得之液晶滴下法用密封劑，不進行藉由金屬鹵化物燈之紫外線之照射而僅於120℃下進行60分鐘加熱。 Further, the sealing agents for liquid crystal dropping methods obtained in Example 11 and Example 12 were heated at 120 ° C for only 60 minutes without irradiation with ultraviolet rays of a metal halide lamp.

(3)接著性 (3) Adhesiveness

於實施例及比較例中所獲得之各液晶滴下法用密封劑中，調配二氧化矽間隔件(積水化學工業公司製造，「SI-H055」)1重量%，對兩片附ITO膜之鹼玻璃試片(30×40mm)中之一者進行微滴加，於其上以十字狀貼合另一玻璃試片，對該貼合而成者藉由金屬鹵化物燈照射3000mJ/cm2之紫外線後，於120℃加熱60分鐘，藉此獲得接著試片。進行於接著試片之上下配置鐵棒而推壓之試驗(5mm/sec)。將所獲得之測定值(kgf)除以密 封塗佈直徑(cm)所得之值為3.0kgf/cm2以上之情形設為「◎」，將2.5kgf/cm2以上且未達3.0kgf/cm2之情形設為「○」，將2.0kgf/cm2以上且未達2.5kgf/cm2之情形設為「△」，將0kgf/cm2以上且未達2.0kgf/cm2未達之情形設為「×」而評價接著性。 In each of the sealing compounds for liquid crystal dropping methods obtained in the examples and the comparative examples, a cerium oxide spacer ("SI-H055" manufactured by Sekisui Chemical Co., Ltd.) was added in an amount of 1% by weight, and two bases of the ITO film were attached. One of the glass test pieces (30×40 mm) was subjected to microdropping, and another glass test piece was attached thereto in a cross shape, and the laminated body was irradiated with a metal halide lamp at 3000 mJ/cm 2 . After the ultraviolet ray, it was heated at 120 ° C for 60 minutes, whereby a test piece was obtained. A test (5 mm/sec) in which an iron bar was placed under the test piece and pressed was carried out. The case of two or more of the obtained measurement value (kgf) obtained by dividing the diameter of a sealing coating (cm) is 3.0kgf / cm is set to "◎" to 2.5kgf / cm 2 or more and less than 3.0kgf / cm In the case of 2, it is set to "○", and when 2.0 kgf/cm 2 or more and less than 2.5 kgf/cm 2 is set to "△", the case where 0 kgf/cm 2 or more and less than 2.0 kgf/cm 2 are not reached is used. Set "X" to evaluate the adhesion.

再者，針對實施例11及實施例12中所獲得之液晶滴下法用密封劑，不進行藉由金屬鹵化物燈之紫外線之照射，而僅於120℃加熱60分鐘。 Further, the sealing agent for liquid crystal dropping method obtained in Example 11 and Example 12 was heated at 120 ° C for 60 minutes without being irradiated with ultraviolet rays by a metal halide lamp.

(4)防透濕性 (4) moisture permeability

將實施例及比較例中所獲得之各液晶滴下法用密封劑利用塗佈機平滑之脫模膜狀地塗敷為厚度200~300μm。繼而，利用金屬鹵化物燈照射3000mJ/cm2之紫外線後，於120℃加熱60分鐘，藉此獲得透濕度測定用硬化膜。利用基於JIS Z0208之防濕包裝材料之透濕度試驗方法(杯式法)之方法而製作透濕度試驗用杯，安裝所獲得之透濕度測定用硬化膜，投入至溫度80℃濕度90%RH之高溫高濕烘箱中並測定透濕度。將所獲得之透濕度之值為70g/m2‧24hr以下之情形設為「◎」，將超過60g/m2‧24hr且為90g/m2‧24hr以下之情形設為「○」，將超過90g/m2‧24hr且未達110g/m2‧24hr之情形設為「△」，將110g/m2‧24hr以上之情形設為「×」而評價防透濕性。 Each of the sealing compounds for liquid crystal dropping methods obtained in the examples and the comparative examples was applied in a release film shape smooth by a coater to have a thickness of 200 to 300 μm. Then, after irradiating ultraviolet rays of 3000 mJ/cm 2 with a metal halide lamp, the film was heated at 120 ° C for 60 minutes to obtain a cured film for moisture permeability measurement. A moisture permeability test cup was prepared by a method of moisture permeability test method (cup method) of a moisture-proof packaging material according to JIS Z0208, and the obtained cured film for moisture permeability measurement was attached to a temperature of 80 ° C and a humidity of 90% RH. The moisture permeability was measured in a high temperature and high humidity oven. When the value of the obtained moisture permeability is 70 g/m 2 ‧24 hr or less, it is set to "◎", and when it is more than 60 g/m 2 ‧24 hr and 90 g/m 2 ‧24 hr or less, it is set to "○". When it is more than 90 g/m 2 ‧24 hr and not more than 110 g/m 2 ‧24 hr, it is set to "△", and when it is 110 g/m 2 ‧24 hr or more, it is set to "x", and the moisture permeability is evaluated.

再者，針對實施例11及實施例12中所獲得之液晶滴下法用密封劑，不進行藉由金屬鹵化物燈之紫外線之照射，而僅於120℃加熱60分鐘。 Further, the sealing agent for liquid crystal dropping method obtained in Example 11 and Example 12 was heated at 120 ° C for 60 minutes without being irradiated with ultraviolet rays by a metal halide lamp.

(5)液晶顯示元件之顯示性能(於高溫高濕下保管後所驅動之液晶顯示元件之顏色不均評價) (5) Display performance of liquid crystal display element (evaluation of color unevenness of liquid crystal display element driven after storage under high temperature and high humidity)

將實施例及比較例中所獲得之各液晶滴下法用密封劑填充至滴塗用之 注射器(Musashi Engineering公司製造，「PSY-10E」)，進行脫泡處理。繼而，使用分注器(Musashi Engineering公司製造，「SHOTMASTER300」)，於兩片附ITO薄膜之透明電極基板中之一者以描繪長方形之框之方式塗佈密封劑。繼而，將TN液晶(Chisso公司製造，「JC-5001LA」)之微滴利用液晶滴下裝置進行滴加塗佈，將另一透明基板利用真空貼合裝置於5Pa之減壓下進行貼合，而獲得單元。藉由對所獲得之單元利用金屬鹵化物燈照射3000mJ/cm2之紫外線後，於120℃加熱60分而使密封劑熱硬化，針對各密封劑各製作5片液晶顯示元件。 Each of the liquid crystal dropping methods obtained in the examples and the comparative examples was filled in a syringe for dripping ("PSY-10E" manufactured by Musashi Engineering Co., Ltd.), and subjected to a defoaming treatment. Then, using a dispenser ("SHOTMASTER 300" manufactured by Musashi Engineering Co., Ltd.), one of the two transparent electrode substrates with an ITO film was coated with a sealant so as to draw a rectangular frame. Then, the droplets of TN liquid crystal ("JC-5001LA" manufactured by Chisso Co., Ltd.) were dropped and applied by a liquid crystal dropping device, and the other transparent substrate was bonded by a vacuum bonding apparatus under a reduced pressure of 5 Pa. Get the unit. After the obtained unit was irradiated with ultraviolet rays of 3000 mJ/cm 2 by a metal halide lamp, the sealant was thermally cured by heating at 120 ° C for 60 minutes, and five liquid crystal display elements were produced for each of the sealants.

再者，針對實施例11及實施例12中所獲得之液晶滴下法用密封劑，不進行藉由金屬鹵化物燈之紫外線之照射，而僅於120℃加熱60分鐘。 Further, the sealing agent for liquid crystal dropping method obtained in Example 11 and Example 12 was heated at 120 ° C for 60 minutes without being irradiated with ultraviolet rays by a metal halide lamp.

將所獲得之液晶顯示元件於溫度80℃、濕度90%RH之環境下保管36小時後，使AC 3.5V之電壓驅動，以目視觀察半色調之密封劑周邊。將於密封劑部周邊完全無顏色不均之情形設為「◎」，將有微少顏色不均之情形設為「○」，將有少許顏色不均之情形設為「△」，將有許多顏色不均之情形設為「×」而評價液晶污染性。 The obtained liquid crystal display element was stored in an environment of a temperature of 80 ° C and a humidity of 90% RH for 36 hours, and then a voltage of 3.5 V was applied to drive the periphery of the halftone sealant visually. In the case where there is no color unevenness around the sealant portion, it is set to "◎", and when there is little color unevenness, it is set to "○", and when there is a little color unevenness, it is set to "△", and there are many In the case of uneven color, "X" was used to evaluate liquid crystal contamination.

再者，評價為「◎」、「○」之液晶顯示元件係實用上完全無問題之水準，「△」係有因液晶顯示元件之顯示設計而成為問題之可能性之水準，「×」係不耐於實用之水準。 In addition, the liquid crystal display elements evaluated as "◎" and "○" are practically problem-free, and "△" is a standard that is a problem due to the display design of the liquid crystal display element. Not tolerant of practical standards.

[產業上之可利用性] [Industrial availability]

根據本發明，可提供一種硬化速度較快、可抑制液晶污染、塗佈性及接著性優異之液晶滴下法用密封劑。又，根據本發明，可提供一種使用該液晶滴下法用密封劑而成之上下導通材料及液晶顯示元件。 According to the present invention, it is possible to provide a sealing compound for a liquid crystal dropping method which has a high curing rate, can suppress liquid crystal contamination, and is excellent in coatability and adhesion. Moreover, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealing compound for a liquid crystal dropping method.

Claims (8)

一種液晶滴下法用密封劑，含有硬化性樹脂與熱自由基聚合起始劑，其特徵在於：上述硬化性樹脂含有於1分子中具有3個以上(甲基)丙烯醯氧基之3官能以上之環氧(甲基)丙烯酸酯。 A sealing agent for a liquid crystal dropping method, comprising a curable resin and a thermal radical polymerization initiator, wherein the curable resin contains three or more functional groups having three or more (meth) acryloxy groups in one molecule. Epoxy (meth) acrylate. 如申請專利範圍第1項之液晶滴下法用密封劑，其中，3官能以上之環氧(甲基)丙烯酸酯係不具有芳香族環之脂肪族環氧(甲基)丙烯酸酯。 The sealant for a liquid crystal dropping method according to the first aspect of the invention, wherein the trifunctional or higher epoxy (meth) acrylate is an aliphatic epoxy (meth) acrylate having no aromatic ring. 如申請專利範圍第1或2項之液晶滴下法用密封劑，其中，3官能以上之環氧(甲基)丙烯酸酯具有如下結構：分別具有1個(甲基)丙烯醯氧基之3條以上之分子鏈從1個碳原子分支而成的結構。 The sealant for a liquid crystal dropping method according to the first or second aspect of the invention, wherein the epoxy functional (meth) acrylate having three or more functional groups has the following structure: 3 each having one (meth) acryloxy group The structure in which the above molecular chain is branched from one carbon atom. 如申請專利範圍第1、2或3項之液晶滴下法用密封劑，其中，3官能以上之環氧(甲基)丙烯酸酯所具有之反應性官能基僅為(甲基)丙烯醯氧基。 The sealant for liquid crystal dropping method according to the first, second or third aspect of the patent application, wherein the reactive functional group having three or more functional epoxy (meth) acrylates is only (meth) acryloxy group . 如申請專利範圍第1、2、3或4項之液晶滴下法用密封劑，其含有3官能環氧(甲基)丙烯酸酯及/或4官能環氧(甲基)丙烯酸酯作為3官能以上之環氧(甲基)丙烯酸酯。 A sealant for liquid crystal dropping method according to claim 1, 2, 3 or 4, which contains a trifunctional epoxy (meth) acrylate and/or a tetrafunctional epoxy (meth) acrylate as a trifunctional or higher functional group. Epoxy (meth) acrylate. 如申請專利範圍第1、2、3、4或5項之液晶滴下法用密封劑，其含有下述式(1)所表示之化合物作為3官能以上之環氧(甲基)丙烯酸酯， 式(1)中，R1為氫、碳數1~5之烷基、或下述式(2)所表示之基，各R2分別獨立地為氫或甲基，l、m、及n分別獨立地為1~5之整數； 式(2)中，R3為氫或甲基，k為1~5之整數。 The sealant for a liquid crystal dropping method according to the first, second, third, fourth or fifth aspect of the invention, which comprises a compound represented by the following formula (1) as a trifunctional or higher epoxy (meth) acrylate, In the formula (1), R 1 is hydrogen, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following formula (2), and each R 2 is independently hydrogen or methyl, and l, m, and n are each independently Independently being an integer from 1 to 5; In the formula (2), R 3 is hydrogen or a methyl group, and k is an integer of from 1 to 5. 一種上下導通材料，含有申請專利範圍第1、2、3、4、5或6項之液晶滴下法用密封劑與導電性微粒子。 A top-bottom conductive material comprising a sealing compound for liquid crystal dropping method and conductive fine particles of the first, second, third, fourth, fifth or sixth aspect of the patent application. 一種液晶顯示元件，其係使用申請專利範圍第1、2、3、4、5或6項之液晶滴下法用密封劑或申請專利範圍第7項之上下導通材料而製造。 A liquid crystal display element produced by using a liquid crystal dropping method sealing agent according to the first, second, third, fourth, fifth or sixth aspect of the patent application or a lower conductive material in the seventh aspect of the patent application.
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