TWI785071B - Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element - Google Patents

Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element Download PDF

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TWI785071B
TWI785071B TW107124130A TW107124130A TWI785071B TW I785071 B TWI785071 B TW I785071B TW 107124130 A TW107124130 A TW 107124130A TW 107124130 A TW107124130 A TW 107124130A TW I785071 B TWI785071 B TW I785071B
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meth
acrylate
liquid crystal
weight
crystal display
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TW107124130A
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TW201908453A (en
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松井慶枝
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日商積水化學工業股份有限公司
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • 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

Abstract

本發明之目的在於提供一種塗佈性、硬化性及低液晶污染性優異之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property. Moreover, the object of this invention is to provide the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

本發明係一種液晶顯示元件用密封劑，含有硬化性樹脂及聚合起始劑，上述硬化性樹脂含有部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)、部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)及非酚醛清漆型環氧(甲基)丙烯酸酯(C)，上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之含量於上述硬化性樹脂100重量份中為3重量份以上，9重量份以下，上述部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)之含量於上述硬化性樹脂100重量份中為25重量份以下，且上述部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)相對於上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之比率為1以上，上述非酚醛清漆型環氧(甲基)丙烯酸酯(C)之含量於上述硬化性樹脂100重量份中為10重量份以上且45重量份以下，上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之重量平均分子量為700以上，2000以下。 The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a polymerization initiator. Modified non-novolac type epoxy resin (B) and non-novolac type epoxy (meth) acrylate (C), the content of the above-mentioned part (meth) acrylic modified novolac type epoxy resin (A) is In 100 parts by weight of the above-mentioned curable resin, it is more than 3 parts by weight and not more than 9 parts by weight. The content of the above-mentioned partially (meth)acrylic modified non-novolac epoxy resin (B) is 25 parts by weight or less, and the ratio of the above-mentioned partially (meth)acrylic-modified non-novolac epoxy resin (B) to the above-mentioned partially (meth)acrylic-modified novolak-type epoxy resin (A) is 1 or more , the content of the above-mentioned non-novolac type epoxy (meth)acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the above-mentioned curable resin, and the above-mentioned part of the (meth)acrylic acid modified novolac The weight average molecular weight of type epoxy resin (A) is more than 700 and less than 2000.

Description

液晶顯示元件用密封劑、上下導通材料及液晶顯示元件 Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element

本發明係關於一種塗佈性、硬化性及低液晶污染性優異之液晶顯示元件用密封劑。又，本發明係關於一種使用該液晶顯示元件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 sealant for liquid crystal display elements which is excellent in applicability, curability and low liquid crystal contamination. Moreover, this invention relates to the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間(tact time)縮短、使用液晶量之最佳化等觀點而言，一直使用如專利文獻1、專利文獻2揭示之使用光熱併用硬化型密封劑的被稱為滴下法之液晶滴下方式。 In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the perspectives of shortening the production time (tact time) and optimizing the amount of liquid crystals used, the methods disclosed in Patent Document 1 and Patent Document 2 have been used. The liquid crystal dropping method is called the dropping method, which combines light and heat with a hardening sealant.

於滴下法中，首先，於2片附電極之基板中之一者，藉由滴塗(dispense)而形成長方形之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴下至基板之密封框內，於真空下重疊另一基板，對密封部照射紫外線等光而進行預硬化。然後，加熱而進行正式硬化，從而製作液晶顯示元件。目前，該滴下法為液晶顯示元件製造方法之主流。 In the dropping method, first, a rectangular seal pattern is formed by dispensing on one of the two substrates with electrodes. Next, liquid crystal droplets are dropped into the sealing frame of the substrate while the sealant is not hardened, another substrate is superimposed under vacuum, and the sealed portion is irradiated with light such as ultraviolet rays to pre-cure. Then, it heats and hardens mainly, and manufactures a liquid crystal display element. At present, the dropping method is the mainstream of the method for manufacturing liquid crystal display elements.

另外，於行動電話、可攜式遊戲機等各種附液晶面板之移動機器普及之現代，裝置小型化為最迫切之課題。作為小型化之方法，可列舉液晶顯示部之窄邊框化，例如進行將密封部之位置配置於黑矩陣下方之步驟(以下，亦稱為窄邊框設計)。 In addition, in the modern age when various mobile devices with liquid crystal panels such as mobile phones and portable game consoles are popularized, miniaturization of devices is the most urgent issue. As a method of miniaturization, narrowing the frame of the liquid crystal display part can be mentioned, for example, performing a step of arranging the position of the sealing part under the black matrix (hereinafter, also referred to as narrow frame design).

伴隨此種窄邊框設計，存在如下問題：於液晶顯示元件中，像素區域與密 封劑間之距離變近，容易產生因液晶被密封劑污染所引起之顯示不均。 Along with this kind of narrow frame design, there is the following problem: In the liquid crystal display element, the distance between the pixel area and the sealant becomes shorter, and the display unevenness caused by the contamination of the liquid crystal by the sealant tends to occur.

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Document]

專利文獻1：日本專利特開2001-133794號公報 Patent Document 1: Japanese Patent Laid-Open 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塗佈性、硬化性及低液晶污染性優異之液晶顯示元件用密封劑。又，本發明之目的在於提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property. Moreover, the object of this invention is to provide the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

本發明係一種液晶顯示元件用密封劑，含有硬化性樹脂及聚合起始劑，上述硬化性樹脂含有部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)、部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)及非酚醛清漆型環氧(甲基)丙烯酸酯(C)，上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之含量於上述硬化性樹脂100重量份中為3重量份以上，9重量份以下，上述部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)之含量於上述硬化性樹脂100重量份中為25重量份以下，且上述部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)相對於上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之比率為1以上，上述非酚醛清漆型環氧(甲基)丙烯酸酯(C)之含量於上述硬化性樹脂100重量份中為10重量份以上且45重量份以下，上述部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之重量平均分子量為700以上，2000以下。 The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a polymerization initiator. Modified non-novolac type epoxy resin (B) and non-novolac type epoxy (meth) acrylate (C), the content of the above-mentioned part (meth) acrylic modified novolac type epoxy resin (A) is In 100 parts by weight of the above-mentioned curable resin, it is more than 3 parts by weight and not more than 9 parts by weight. The content of the above-mentioned partially (meth)acrylic modified non-novolac epoxy resin (B) is 25 parts by weight or less, and the ratio of the above-mentioned partially (meth)acrylic-modified non-novolac epoxy resin (B) to the above-mentioned partially (meth)acrylic-modified novolak-type epoxy resin (A) is 1 or more , the content of the above-mentioned non-novolac type epoxy (meth)acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the above-mentioned curable resin, and the above-mentioned part of the (meth)acrylic acid modified novolac The weight average molecular weight of type epoxy resin (A) is more than 700 and less than 2000.

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

本發明人為了提昇液晶顯示元件用密封劑之低液晶污染性，研究使用分子量相對較高之部分(甲基)丙烯酸改質環氧樹脂作為硬化性樹脂。然而，於使用此種硬化性樹脂之情形時，有所獲得之液晶顯示元件用密封劑變成塗佈性或硬化性較差者之情況。因此，本發明人研究以分別成為特定之含有比率之方式將部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂、部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂及非酚醛清漆型環氧(甲基)丙烯酸酯加以組合而使用。其結果為可獲得塗佈性、硬化性及低液晶污染性優異之液晶顯示元件用密封劑，從而完成了本發明。 In order to improve the low liquid crystal contamination of the sealant for liquid crystal display elements, the present inventors researched the use of a relatively high molecular weight partially (meth)acrylic modified epoxy resin as a curable resin. However, when such a curable resin is used, the obtained sealant for liquid crystal display elements may be poor in applicability or curability. Therefore, the inventors of the present invention have studied to mix a part of (meth)acrylic acid modified novolac type epoxy resin, a part of (meth)acrylic acid modified non-novolac type epoxy resin and a non-novolac Type epoxy (meth)acrylates are used in combination. As a result, the sealant for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property was obtained, and completed this invention.

本發明之液晶顯示元件用密封劑含有硬化性樹脂。 The sealing compound for liquid crystal display elements of this invention contains curable resin.

上述硬化性樹脂含有部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)(以下，亦稱為「(A)成分」)、部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)(以下，亦稱為「(B)成分」)及非酚醛清漆型環氧(甲基)丙烯酸酯(C)(以下，亦稱為「(C)成分」)。藉由以含有比率分別成為下述範圍之方式含有上述(A)成分、上述(B)成分及上述(C)成分，本發明之液晶顯示元件用密封劑成為塗佈性、硬化性及低液晶污染性優異者。 The above curable resin contains a part of (meth)acrylic modified novolac epoxy resin (A) (hereinafter also referred to as "(A) component"), a part of (meth)acrylic modified non-novolac epoxy Resin (B) (hereinafter also referred to as "component (B)") and non-novolac epoxy (meth)acrylate (C) (hereinafter also referred to as "component (C)"). By containing the above-mentioned (A) component, the above-mentioned (B) component, and the above-mentioned (C) component so that the content ratio becomes the following range respectively, the sealant for liquid crystal display elements of this invention becomes coating property, curability, and low liquid crystal Those with excellent pollution.

再者，於本說明書中，上述「部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂」意指酚醛清漆型環氧樹脂之一部分環氧基與(甲基)丙烯酸進行反應，導入有(甲基)丙烯醯基者。 Furthermore, in this specification, the above-mentioned "partial (meth)acrylic acid modified novolak type epoxy resin" means that a part of the epoxy group of the novolak type epoxy resin reacts with (meth)acrylic acid, and the ( Meth)acryl.

上述「部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂」意指不為酚醛清漆型之環氧樹脂(以下，亦稱為「非酚醛清漆型環氧樹脂」)之一部分環氧基與(甲基)丙烯酸進行反應，導入有(甲基)丙烯醯基者。 The above-mentioned "partial (meth)acrylic modified non-novolac epoxy resin" refers to a part of the epoxy resin that is not a novolak type epoxy resin (hereinafter, also referred to as "non-novolac epoxy resin") React with (meth)acrylic acid to introduce (meth)acryl group.

上述「非酚醛清漆型環氧(甲基)丙烯酸酯」意指非酚醛清漆型環氧樹脂之全部環氧基與(甲基)丙烯酸進行反應，導入有(甲基)丙烯醯基者。 The above-mentioned "non-novolak epoxy (meth)acrylate" means that all the epoxy groups of the non-novolac epoxy resin react with (meth)acrylic acid to introduce (meth)acryl groups.

上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，「(甲基)丙烯酸酯」意指 丙烯酸酯或甲基丙烯酸酯，「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。 The above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryl" means acryl or methacrylate. Acrylyl.

上述(A)成分由於為酚醛清漆型，故而就低液晶污染性之觀點而言，即便使分子量相對較高，黏度上升亦緩慢，不易使塗佈性惡化。 Since the above-mentioned (A) component is a novolac type, from the viewpoint of low liquid crystal contamination, even if the molecular weight is made relatively high, the increase in viscosity is slow, and it is difficult to deteriorate the coatability.

上述(A)成分之重量平均分子量之下限為700，上限為2000。藉由使上述(A)成分之重量平均分子量為700以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性優異者。藉由使上述(A)成分之重量平均分子量為2000以下，所獲得之液晶顯示元件用密封劑成為塗佈性優異者。上述(A)成分之重量平均分子量之較佳下限為750，較佳上限為1500，更佳下限為800，更佳上限為1200。 The lower limit of the weight average molecular weight of the said (A) component is 700, and the upper limit is 2000. By making the weight average molecular weight of the said (A) component 700 or more, the sealing compound for liquid crystal display elements obtained becomes what is excellent in low liquid-crystal contamination property. By making the weight average molecular weight of the said (A) component into 2000 or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferable lower limit of the weight average molecular weight of the said (A) component is 750, the preferable upper limit is 1500, the more preferable lower limit is 800, and the more preferable upper limit is 1200.

再者，於本說明書中，上述重量平均分子量係利用凝膠滲透層析法(GPC)，使用四氫呋喃作為溶劑進行測定，藉由聚苯乙烯換算所求出之值。作為利用GPC測定基於聚苯乙烯換算之重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 addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column at the time of measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.

作為上述(A)成分，例如可列舉：部分(甲基)丙烯酸改質苯酚酚醛清漆型環氧樹脂、部分(甲基)丙烯酸改質鄰甲酚酚醛清漆型環氧樹脂、部分(甲基)丙烯酸改質二環戊二烯酚醛清漆型環氧樹脂、部分(甲基)丙烯酸改質聯苯酚醛清漆型環氧樹脂、部分(甲基)丙烯酸改質萘酚酚醛清漆型環氧樹脂等。其中，較佳為部分(甲基)丙烯酸改質苯酚酚醛清漆型環氧樹脂。 Examples of the above-mentioned (A) component include partially (meth)acrylic modified phenol novolac epoxy resins, partially (meth)acrylic modified o-cresol novolak epoxy resins, partially (meth)acrylic acid modified Acrylic modified dicyclopentadiene novolak type epoxy resin, partly (meth)acrylic acid modified biphenyl novolak type epoxy resin, partly (meth)acrylic acid modified naphthol novolak type epoxy resin, etc. Among them, a partially (meth)acrylic modified phenol novolak type epoxy resin is preferable.

上述(A)成分可藉由按照常規方法於鹼性觸媒之存在下使酚醛清漆型環氧樹脂之一部分環氧基與(甲基)丙烯酸進行反應，於上述(A)成分、酚醛清漆型環氧樹脂及酚醛清漆型環氧(甲基)丙烯酸酯之混合物中獲得。 The above-mentioned (A) component can be reacted with (meth)acrylic acid in part of the epoxy group of the novolac-type epoxy resin in the presence of an alkaline catalyst according to a conventional method, and the above-mentioned (A) component, novolac-type Obtained from a mixture of epoxy resin and novolac epoxy (meth)acrylate.

再者，於本說明書中，上述「酚醛清漆型環氧(甲基)丙烯酸酯」意指酚醛清漆型環氧樹脂之全部環氧基與(甲基)丙烯酸進行反應，導入有(甲基)丙烯醯基者。 In addition, in this specification, the above-mentioned "novolak-type epoxy (meth)acrylate" means that all the epoxy groups of the novolac-type epoxy resin react with (meth)acrylic acid to introduce (meth) Acryl-based ones.

作為成為上述(A)成分之原料之酚醛清漆型環氧樹脂，例如可列舉：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等。 Examples of the novolak-type epoxy resin used as the raw material of the above-mentioned component (A) include: phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, dicyclopentadiene novolac-type epoxy resin , biphenyl novolac epoxy resin, naphthol novolac epoxy resin, etc.

上述(A)成分之含量於上述硬化性樹脂100重量份中，下限為3重量份，上限為9重量份。藉由使上述(A)成分之含量為3重量份以上，所獲得之液晶顯示元件用密封劑成為低液晶污染性優異者。藉由使上述(A)成分之含量為9重量份以下，所獲得之液晶顯示元件用密封劑成為塗佈性優異者。上述(A)成分之含量之較佳下限為4重量份，較佳上限為8重量份，更佳上限為7重量份。 The content of the said (A) component is 3 weight part with a minimum and 9 weight part with an upper limit in 100 weight part of said curable resins. By making content of the said (A) component 3 weight part or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in low liquid-crystal contamination property. By making content of the said (A) component 9 weight part or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferred lower limit of the content of the above-mentioned (A) component is 4 parts by weight, the preferred upper limit is 8 parts by weight, and the more preferred upper limit is 7 parts by weight.

作為上述(B)成分，例如可列舉：部分(甲基)丙烯酸改質雙酚A型環氧樹脂、部分(甲基)丙烯酸改質雙酚F型環氧樹脂、部分(甲基)丙烯酸改質雙酚E型環氧樹脂、部分(甲基)丙烯酸改質雙酚S型環氧樹脂、部分(甲基)丙烯酸改質2,2'-二烯丙基雙酚A型環氧樹脂、部分(甲基)丙烯酸改質氫化雙酚型環氧樹脂、部分(甲基)丙烯酸改質環氧丙烷加成雙酚A型環氧樹脂、部分(甲基)丙烯酸改質間苯二酚型環氧樹脂、部分(甲基)丙烯酸改質聯苯型環氧樹脂、部分(甲基)丙烯酸改質硫醚(sulfide)型環氧樹脂、部分(甲基)丙烯酸改質二苯醚型環氧樹脂、部分(甲基)丙烯酸改質二環戊二烯型環氧樹脂、部分(甲基)丙烯酸改質萘型環氧樹脂、部分(甲基)丙烯酸改質環氧丙胺型環氧樹脂、部分(甲基)丙烯酸改質烷基多元醇型環氧樹脂、部分(甲基)丙烯酸改質橡膠改質型環氧樹脂等。其中，較佳為部分(甲基)丙烯酸改質雙酚A型環氧樹脂。 As the above-mentioned (B) component, for example, partially (meth)acrylic modified bisphenol A epoxy resin, partially (meth)acrylic modified bisphenol F epoxy resin, partially (meth)acrylic modified High-quality bisphenol E epoxy resin, partially (meth)acrylic modified bisphenol S epoxy resin, partially (meth)acrylic modified 2,2'-diallyl bisphenol A epoxy resin, Partially (meth)acrylic modified hydrogenated bisphenol type epoxy resin, partially (meth)acrylic modified propylene oxide added bisphenol A type epoxy resin, partially (meth)acrylic modified resorcinol type Epoxy resin, partially (meth)acrylic modified biphenyl type epoxy resin, partially (meth)acrylic modified sulfide type epoxy resin, partially (meth)acrylic modified diphenyl ether type epoxy resin Oxygen resin, partly (meth)acrylic acid modified dicyclopentadiene type epoxy resin, partly (meth)acrylic acid modified naphthalene type epoxy resin, partly (meth)acrylic acid modified epoxypropylamine type epoxy resin , Partial (meth)acrylic modified alkyl polyol type epoxy resin, partial (meth)acrylic modified rubber modified epoxy resin, etc. Among them, partial (meth)acrylic acid modified bisphenol A epoxy resin is preferred.

上述(B)成分可藉由按照常規方法於鹼性觸媒之存在下使非酚醛清漆型環氧樹脂之一部分環氧基與(甲基)丙烯酸進行反應，於上述(B)成分、非酚醛清漆型環氧樹脂及非酚醛清漆型環氧(甲基)丙烯酸酯之混合物中獲得。 The above-mentioned (B) component can be reacted in the above-mentioned (B) component, non-phenolic epoxy resin by making a part of the epoxy group of the non-novolac type epoxy resin react with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method. Obtained from a mixture of varnish-type epoxy resin and non-novolak-type epoxy (meth)acrylate.

作為成為上述(B)成分之原料之非酚醛清漆型環氧樹脂，例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚E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、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等。 Examples of the non-novolac epoxy resin used as the raw material for the above-mentioned component (B) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, and bisphenol S epoxy resin. Epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin , biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, epoxypropylamine type epoxy resin, alkyl poly Alcohol epoxy resin, rubber modified epoxy resin, etc.

上述(B)成分之含量於上述硬化性樹脂100重量份中，上限為25重量份。藉由使上述硬化性樹脂100重量份中之上述(B)成分之含量為25重量份以下，所獲得之液晶顯示元件用密封劑成為低液晶污染性優異者。上述硬化性樹脂100重量份中之上述(B)成分之含量之較佳上限為22重量份，更佳上限為20重量份。 Content of the said (B) component is 25 weight part of upper limits in 100 weight part of said curable resins. By making content of the said (B) component in 100 weight part of said curable resins 25 weight part or less, the sealing compound for liquid crystal display elements obtained becomes what is excellent in low liquid crystal contamination property. The preferable upper limit of content of the said (B) component in 100 weight part of said curable resins is 22 weight part, and a more preferable upper limit is 20 weight part.

又，上述(B)成分相對於上述(A)成分之比率為1以上。藉由將上述(B)成分相對於上述(A)成分之比率設為1以上，所獲得之液晶顯示元件用密封劑成為塗佈性優異者。上述(B)成分相對於上述(A)成分之比率之較佳下限為1.2，更佳下限為1.5。 Moreover, the ratio of the said (B) component with respect to the said (A) component is 1 or more. By making the ratio of the said (B) component with respect to the said (A) component 1 or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferable lower limit of the ratio of the said (B) component with respect to the said (A) component is 1.2, and a more preferable lower limit is 1.5.

再者，「上述(B)成分相對於上述(A)成分之比率」意指上述(B)成分之含量/上述(A)成分之含量。 In addition, "the ratio of the said (B) component with respect to the said (A) component" means content of the said (B) component / content of the said (A) component.

作為上述(C)成分，例如可列舉：雙酚A型環氧(甲基)丙烯酸酯、雙酚F型環氧(甲基)丙烯酸酯、雙酚E型環氧(甲基)丙烯酸酯、雙酚S型環氧(甲基)丙烯酸酯、2,2'-二烯丙基雙酚A型環氧(甲基)丙烯酸酯、氫化雙酚型環氧(甲基)丙烯酸酯、環氧丙烷加成雙酚A型環氧(甲基)丙烯酸酯、間苯二酚型環氧(甲基)丙烯酸酯、聯苯型環氧(甲基)丙烯酸酯、硫醚型環氧(甲基)丙烯酸酯、二苯醚型環氧(甲基)丙烯酸酯、二環戊二烯型環氧(甲基)丙烯酸酯、萘型環氧(甲基)丙烯酸酯、環氧丙胺型環氧(甲基)丙烯酸酯、烷基多元醇型環氧(甲基)丙烯酸酯、橡膠改質型環氧(甲基)丙烯酸酯等。其中，較佳為雙酚A型環氧(甲基)丙烯酸酯。 As said (C)component, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, Bisphenol S type epoxy (meth)acrylate, 2,2'-diallyl bisphenol A type epoxy (meth)acrylate, hydrogenated bisphenol type epoxy (meth)acrylate, epoxy Propane addition bisphenol A type epoxy (meth)acrylate, resorcinol type epoxy (meth)acrylate, biphenyl type epoxy (meth)acrylate, thioether type epoxy (meth)acrylate ) acrylate, diphenyl ether type epoxy (meth) acrylate, dicyclopentadiene type epoxy (meth) acrylate, naphthalene type epoxy (meth) acrylate, epoxypropylamine type epoxy ( Meth)acrylate, alkyl polyol type epoxy (meth)acrylate, rubber modified epoxy (meth)acrylate, etc. Among these, bisphenol A type epoxy (meth)acrylate is preferable.

上述(C)成分可藉由按照常規方法於鹼性觸媒之存在下使非酚醛清漆型環氧樹脂之全部環氧基與(甲基)丙烯酸進行反應而獲得。 The above-mentioned (C) component can be obtained by reacting all the epoxy groups of the non-novolac type epoxy resin with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.

作為成為上述(C)成分之原料之非酚醛清漆型環氧樹脂，可列舉與成為上 述(B)成分之原料之非酚醛清漆型環氧樹脂相同者。 Examples of the non-novolak epoxy resin used as the raw material of the above-mentioned component (C) include the same ones as the non-novolac epoxy resin used as the raw material of the above-mentioned component (B).

上述(C)成分之含量於上述硬化性樹脂100重量份中，下限為10重量份，上限為45重量份。藉由使上述硬化性樹脂100重量份中之上述(C)成分之含量為10重量份以上，所獲得之液晶顯示元件用密封劑成為光硬化性優異者。藉由使上述(C)成分之含量為45重量份以下，所獲得之液晶顯示元件用密封劑成為接著性優異者。上述硬化性樹脂100重量份中之上述(C)成分之含量之較佳下限為14重量份，更佳下限為18重量份。 The content of the above-mentioned (C) component is 10 weight part with a minimum in 100 weight part of said curable resins, and an upper limit is 45 weight part. By making content of the said (C)component in 100 weight part of said curable resins 10 weight part or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in photocurability. By making content of the said (C)component 45 weight part or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in adhesiveness. The preferable lower limit of content of the said (C)component in 100 weight part of said curable resins is 14 weight part, and a more preferable lower limit is 18 weight part.

本發明之液晶顯示元件用密封劑亦可於不阻礙本發明之目的之範圍內，進而含有其他聚合性化合物作為上述硬化性樹脂。 The sealing compound for liquid crystal display elements of this invention may further contain another polymeric compound as said curable resin in the range which does not inhibit the object of this invention.

作為上述其他聚合性化合物，例如可列舉：上述酚醛清漆型環氧樹脂、上述非酚醛清漆型環氧樹脂、上述酚醛清漆型環氧(甲基)丙烯酸酯或其他(甲基)丙烯酸化合物等。 As said other polymeric compound, the said novolak type epoxy resin, the said non-novolac type epoxy resin, the said novolak type epoxy (meth)acrylate, other (meth)acryl compounds etc. are mentioned, for example.

作為上述其他(甲基)丙烯酸化合物，例如可列舉：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(甲基)丙烯酸酯化合物；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)丙烯酸胺基甲酸酯等。 Examples of other (meth)acrylic compounds include: (meth)acrylate compounds obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid; Urethane (meth)acrylate obtained by reacting acrylic acid derivatives with isocyanate compounds, etc.

就反應性之觀點而言，上述其他(甲基)丙烯酸化合物較佳為1分子中具有2個以上之(甲基)丙烯醯基者。 From the viewpoint of reactivity, it is preferable that the above-mentioned other (meth)acrylic compound has two or more (meth)acryl groups in one molecule.

作為上述(甲基)丙烯酸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)丙烯酸二環戊烯酯、(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、丁二酸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。 Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, Isodecyl (meth)acrylate, Lauryl (meth)acrylate, Isomyristyl (meth)acrylate, Stearyl (meth)acrylate, (Meth) 2-Hydroxyethyl acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, Cyclohexyl (meth)acrylate, ( Isocamphoryl methacrylate, Dicyclopentenyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, Phenoxy Diethylene Glycol (Meth) Acrylate, Phenoxy Polyethylene Glycol (Meth) Acrylate, Tetrahydrofurfuryl (Meth) Acrylate, Ethyl Carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H (meth)acrylate - Octafluoropentyl ester, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(methyl)succinate ) acryloxyethyl ester, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxyethyl phthalate, 2-hydroxypropyl phthalate, phosphoric acid 2-(meth)acryloxyethyl ester, glycidyl (meth)acrylate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之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、聚丙二醇二(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。 In addition, examples of bifunctional ones among the above-mentioned (meth)acrylate compounds include: 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di (meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl diacrylate Alcohol di(meth)acrylate, Ethylene oxide added bisphenol A di(meth)acrylate, Propylene oxide added bisphenol A di(meth)acrylate, Ethylene oxide added bisphenol F di(meth)acrylate, dimethyloldicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

又，作為上述(甲基)丙烯酸酯化合物中之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)丙烯醯氧基乙基]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。 In addition, examples of trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(methyl ) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric Acid tri(meth)acrylate, Glycerin tri(meth)acrylate, Propylene oxide added glycerol tri(meth)acrylate, Neopentylthritol tri(meth)acrylate, Phosphate tri[(meth)acrylate ) acryloxyethyl] ester, bis(trimethylolpropane) tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteopentylthritol penta(meth)acrylate , diperythritol hexa(meth)acrylate, etc.

作為上述(甲基)丙烯酸胺基甲酸酯，例如可藉由在觸媒量之錫系化合物之存在下，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而獲得。 The urethane (meth)acrylate can be obtained, for example, by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

作為上述異氰酸酯化合物，例如可列舉：異佛酮二異氰酸酯、2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、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、聚合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、伸茬基二異氰酸酯(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、四甲基伸茬基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。 Examples of the isocyanate compound include isophorone diisocyanate, 2,4-methylene diisocyanate, 2,6-methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene Diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylidine diisocyanate, stubble diisocyanate Isocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethyl stubble diisocyanate, 1,6,11- Undecane triisocyanate, etc.

又，作為上述異氰酸酯化合物，亦可使用藉由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。 In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyhydric alcohol with an excess of isocyanate compound can also be used.

作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨醇、三羥甲基丙烷、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己內酯二醇等。 Examples of the above-mentioned polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

作為上述具有羥基之(甲基)丙烯酸衍生物，例如可列舉：單(甲基)丙烯酸羥基烷基酯、二元醇之單(甲基)丙烯酸酯、三元醇之單(甲基)丙烯酸酯或二(甲基)丙烯酸酯等。 Examples of (meth)acrylic acid derivatives having a hydroxyl group include hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of diol, and mono(meth)acrylic acid of triol. ester or di(meth)acrylate, etc.

作為上述單(甲基)丙烯酸羥基烷基酯，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2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, etc.

作為上述二元醇，例如可列舉：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。 As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol etc. are mentioned, for example.

作為上述三元醇，例如可列舉：三羥甲基乙烷、三羥甲基丙烷、甘油等。 As said trivalent alcohol, trimethylolethane, trimethylolpropane, glycerin etc. are mentioned, for example.

就抑制液晶污染之觀點而言，上述其他(甲基)丙烯酸化合物較佳為具有-OH基、-NH-基、-NH2基等氫鍵結性之單元者。 From the viewpoint of suppressing liquid crystal contamination, the above-mentioned other (meth)acrylic compounds are preferably those having hydrogen-bonding units such as -OH group, -NH- group, and -NH 2 group.

本發明之液晶顯示元件用密封劑含有聚合起始劑。 The sealing compound for liquid crystal display elements of this invention contains a polymerization initiator.

作為上述聚合起始劑，例如可列舉自由基聚合起始劑或陽離子聚合起始劑等。 As said polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example.

作為上述自由基聚合起始劑，可使用藉由照光而產生自由基之光自由基聚合起始劑；或藉由加熱而產生自由基之熱自由基聚合起始劑。 As said radical polymerization initiator, the photo radical polymerization initiator which generate|occur|produces a radical by irradiation of light, or the thermal radical polymerization initiator which generates a radical by heating can be used.

作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、肟酯化合物、安息香醚化合物、9-氧硫

Figure 107124130-A0202-12-0010-3
化合物等。 Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxysulfur compounds, and
Figure 107124130-A0202-12-0010-3
compound etc.

作為上述光自由基聚合起始劑，具體而言，例如可列舉：1-羥基環己基苯基酮、2-苄基-2-二甲基胺基-1-(4-N-

Figure 107124130-A0202-12-0010-4
啉基苯基)丁酮、1,2-(二甲基胺基)-2-((4-甲基苯基)甲基)-1-(4-(4--
Figure 107124130-A0202-12-0010-5
啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-N-
Figure 107124130-A0202-12-0010-6
啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮-2-(O-苯甲醯基肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香***、安息香異丙醚等。 As the above-mentioned photoradical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-N-
Figure 107124130-A0202-12-0010-4
Linylphenyl) butanone, 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4--
Figure 107124130-A0202-12-0010-5
Linyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl ) phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-N-
Figure 107124130-A0202-12-0010-6
Linylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(benzene Thio)phenyl)-1,2-octanedione-2-(O-benzoyl oxime), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ether, Benzoin ether, benzoin isopropyl ether, etc.

上述光自由基聚合起始劑可單獨使用，亦可組合2種以上而使用。 The said photoradical polymerization initiator may be used individually, and may use it in combination of 2 or more types.

作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物、有機過氧化物等所構成者。其中，較佳為由高分子偶氮化合物所構成之起始劑(以下，亦稱為「高分子偶氮起始劑」)。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, an initiator composed of a high-molecular azo compound (hereinafter, also referred to as a "high-molecular azo initiator") is preferable.

上述熱自由基聚合起始劑可單獨使用，亦可組合2種以上而使用。 The said thermal radical polymerization initiator may be used individually, and may use it in combination of 2 or more types.

再者，於本說明書中，高分子偶氮化合物意指具有偶氮基且藉由熱而生成可使(甲基)丙烯醯基硬化之自由基的數量平均分子量為300以上之化合物。 In addition, in this specification, a high molecular weight azo compound means the compound which has an azo group and generates the radical which hardens (meth)acryl group by heat, and has a number average molecular weight of 300 or more.

上述高分子偶氮化合物之數量平均分子量之較佳下限為1000，較佳上限為30萬。藉由使上述高分子偶氮化合物之數量平均分子量為該範圍，可抑制液晶污染，並且與硬化性樹脂容易地混合。上述高分子偶氮化合物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 preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1000, and the preferable upper limit is 300,000. By making the number average molecular weight of the said high molecular weight azo compound into this range, liquid crystal contamination can be suppressed, and it can mix easily with curable resin. The more preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 5000, the more preferable upper limit is 100,000, the more preferable lower limit is 10,000, and the more preferable upper limit is 90,000.

再者，於本說明書中，上述數量平均分子量係利用凝膠滲透層析法(GPC)，使用四氫呋喃作為溶劑進行測定，藉由聚苯乙烯換算所求出之值。作為利用GPC測定基於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 addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column at the time of measuring the number average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko Co., Ltd.) etc. are mentioned, for example.

作為上述高分子偶氮化合物，例如可列舉具有聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結多個而成之結構者。 As said high molecular azo compound, the thing which has the structure which unit, such as polyalkylene oxide and polydimethylsiloxane, couple|bonds via an azo group, is mentioned, for example.

作為上述具有聚環氧烷等單元經由偶氮基鍵結多個而成之結構之高分子偶氮化合物，較佳為具有聚環氧乙烷結構者。 As the polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, one having a polyethylene oxide structure is preferable.

作為上述高分子偶氮化合物，具體而言，例如可列舉：4,4'-偶氮雙(4-氰基戊酸)與聚伸烷基二醇之縮聚物、或4,4'-偶氮雙(4-氰基戊酸)與具有末端胺基之聚二甲基矽氧烷之縮聚物等。 Specific examples of the polymeric azo compound include: a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation product of nitrogen bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amino group, etc.

作為上述高分子偶氮化合物中之市售者，例如可列舉：VPE-0201、VPE -0401、VPE-0601、VPS-0501、VPS-1001(均為富士軟片和光純藥公司製造)等。 As what is marketed among the said polymeric azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are made by Fujifilm Wako Pure Chemical Industries, Ltd.) etc. are mentioned, for example.

又，作為以不為高分子之偶氮化合物之形式市售者，例如可列舉：V-65、V-501(均為富士軟片和光純藥公司製造)等。 Moreover, what is marketed as an azo compound which is not a polymer includes, for example, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like.

作為上述有機過氧化物，例如可列舉：過氧化酮、過氧化縮酮、過氧化氫、二烷基過氧化物(dialkyl peroxide)、過氧化酯、二醯基過氧化物(diacyl peroxide)、過氧化二碳酸酯等。 Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, Peroxydicarbonate, etc.

作為上述陽離子聚合起始劑，可較佳地使用光陽離子聚合起始劑。 As the above cationic polymerization initiator, a photocationic polymerization initiator can be preferably used.

上述光陽離子聚合起始劑若為藉由照光而產生質子酸或路易斯酸者則並無特別限定，可為離子性光酸產生型者，亦可為非離子性光酸產生型。 The above-mentioned photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by irradiation of light, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

作為上述光陽離子聚合起始劑，例如可列舉：芳香族重氮鹽、芳香族鏀鹽(halonium salt)、芳香族鋶鹽等鎓鹽類；鐵-芳烴錯合物、二茂鈦錯合物、芳基矽烷醇-鋁錯合物等有機金屬錯合物類等。 Examples of the above-mentioned photocationic polymerization initiator include: onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic halonium salts; iron-arene complexes and titanocene complexes; , aryl silanol-aluminum complexes and other organometallic complexes, etc.

作為上述光陽離子聚合起始劑中之市售者，例如可列舉：Adeka Optomer SP-150、Adeka Optomer SP-170(均為ADEKA公司製造)等。 As what is marketed among the said photocationic polymerization initiators, Adeka Optomer SP-150, Adeka Optomer SP-170 (all are the ADEKA company make), etc. are mentioned, for example.

上述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。藉由使上述聚合起始劑之含量為該範圍，所獲得之液晶顯示元件用密封劑成為抑制液晶污染，並且保存穩定性或硬化性更優異者。上述聚合起始劑之含量之更佳下限為0.1重量份，更佳上限為5重量份。 With respect to 100 parts by weight of the above-mentioned curable resin, the lower limit of the content of the polymerization initiator is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight. By making content of the said polymerization initiator into this range, the obtained sealing compound for liquid crystal display elements suppresses contamination of a liquid crystal, and is more excellent in storage stability or curability. A more preferable lower limit of the content of the above-mentioned polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.

本發明之液晶顯示元件用密封劑較佳為含有熱硬化劑。 It is preferable that the sealing compound for liquid crystal display elements of this invention contains a thermosetting 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，可較佳地使用固體有機酸醯肼。 As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, a polyphenol type compound, an acid anhydride, etc. are mentioned, for example. Among them, solid organic acid hydrazide can be preferably used.

上述熱硬化劑可單獨使用，亦可組合2種以上而使用。 The above thermosetting agents may be used alone or in combination of two or more.

作為上述固體有機酸醯肼，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、己二酸醯肼、丙二酸醯肼等。 Examples of the solid organic acid hydrazide include: 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, dihydrazide sebacate, dihydrazide isophthalate, Adipic acid hydrazine, malonate hydrazine, etc.

作為上述固體有機酸醯肼中之市售者，例如可列舉：大塚化學公司製造之有機酸醯肼、Japan Finechem公司製造之有機酸醯肼、Ajinomoto Fine-Techno公司製造之有機酸醯肼等。 Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Japan Finechem, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno.

作為上述大塚化學公司製造之有機酸醯肼，例如可列舉：SDH、ADH等。 Examples of the organic acid hydrazide produced by the aforementioned Otsuka Chemical Co., Ltd. include SDH, ADH, and the like.

作為上述Japan Finechem公司製造之有機酸醯肼，例如可列舉MDH等。 Examples of the organic acid hydrazide produced by Japan Finechem include MDH and the like.

作為上述Ajinomoto Fine-Techno公司製造之有機酸醯肼，例如可列舉：Amicure VDH、Amicure VDH-J、Amicure UDH等。 Examples of the organic acid hydrazide manufactured by the above-mentioned Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, and the like.

上述熱硬化劑之含量相對於硬化性樹脂整體100重量份，較佳下限為1重量份，較佳上限為50重量份。藉由使上述熱硬化劑之含量為該範圍，所獲得之液晶顯示元件用密封劑成為於維持優異之塗佈性或保存穩定性之狀態下，硬化性更優異者。上述熱硬化劑之含量之更佳上限為30重量份。 With respect to 100 parts by weight of the curable resin as a whole, the content of the above-mentioned thermosetting agent has a preferable lower limit of 1 part by weight, and a preferable upper limit of 50 parts by weight. By making content of the said thermosetting agent into this range, the obtained sealing compound for liquid crystal display elements becomes what is more excellent in curability in the state which maintained the excellent applicability or storage stability. The more preferable upper limit of the content of the said thermosetting agent is 30 weight part.

本發明之液晶顯示元件用密封劑較佳為以黏度之提昇、由應力分散效果所帶來之接著性之進一步提昇、線膨脹率之改善、硬化物之耐濕性之提昇等為目的而含有填充劑。 The sealant for liquid crystal display elements of the present invention is preferably for the purpose of increasing the viscosity, further improving the adhesiveness brought about by the stress dispersion effect, improving the linear expansion rate, and improving the moisture resistance of the cured product. filler.

作為上述填充劑，可使用無機填充劑或有機填充劑。 As said filler, an inorganic filler or an organic filler can be used.

作為上述無機填充劑，例如可列舉：二氧化矽、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺基甲酸酯微粒子、 乙烯基聚合物微粒子、丙烯酸聚合物微粒子等。 As said organic filler, a polyester microparticle, a polyurethane microparticle, a vinyl polymer microparticle, an acrylic polymer microparticle etc. are mentioned, for example.

上述填充劑可單獨使用，亦可組合2種以上而使用。 These fillers may be used alone or in combination of two or more.

本發明之液晶顯示元件用密封劑100重量份中之上述填充劑之含量的較佳下限為10重量份，較佳上限為70重量份。藉由使上述填充劑之含量為該範圍，可抑制塗佈性等之惡化，並且進一步發揮接著性之提昇等效果。上述填充劑之含量之更佳下限為20重量份，更佳上限為60重量份。 The preferable lower limit of content of the said filler in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part. By making content of the said filler into this range, deterioration of applicability etc. can be suppressed, and effects, such as improvement of adhesiveness, can be exhibited further. A more preferable lower limit of the content of the above filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

就提昇硬化物之柔軟性或接著性等，或者抑制液晶***至密封劑或密封劑溶出至液晶中等觀點而言，本發明之液晶顯示元件用密封劑較佳為含有柔軟粒子。 The sealant for liquid crystal display elements of the present invention preferably contains soft particles from the viewpoint of improving the flexibility and adhesiveness of the cured product, or suppressing the insertion of liquid crystal into the sealant or the dissolution of the sealant into the liquid crystal.

作為上述柔軟粒子，例如可列舉：聚矽氧系粒子、乙烯基系粒子、胺基甲酸酯系粒子、氟系粒子、腈系粒子等。其中，較佳為聚矽氧系粒子、乙烯基系粒子。 Examples of the soft particles include silicone-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among them, silicone-based particles and vinyl-based particles are preferable.

上述柔軟粒子可單獨使用，亦可組合2種以上而使用。 The above soft particles may be used alone or in combination of two or more.

作為上述聚矽氧系粒子，就對樹脂之分散性之觀點而言，較佳為聚矽氧橡膠粒子。 As the above-mentioned silicone-based particles, silicone rubber particles are preferable from the viewpoint of dispersibility to resin.

作為上述乙烯基系粒子，可較佳地使用(甲基)丙烯酸粒子。 (meth)acrylic particles can be preferably used as the above-mentioned vinyl particles.

上述(甲基)丙烯酸粒子可藉由利用公知之方法使成為原料之單體進行聚合而獲得。具體而言，例如可列舉如下方法等：於自由基聚合起始劑之存在下使單體進行懸浮聚合；於自由基聚合起始劑之存在下使非交聯之種子粒子吸收單體，藉此使種子粒子膨潤而進行種子聚合。 The said (meth)acrylic particle can be obtained by polymerizing the monomer used as a raw material by a well-known method. Specifically, for example, the following methods can be mentioned: Suspension polymerization of the monomer in the presence of a radical polymerization initiator; Absorption of the monomer by non-crosslinked seed particles in the presence of a radical polymerization initiator, by This swells the seed particles to carry out seed polymerization.

作為成為用以形成上述(甲基)丙烯酸粒子之原料之單體，例如可列舉：(甲基)丙烯酸烷基酯類、含氧原子(甲基)丙烯酸酯類、含腈單體、含氟(甲基)丙烯酸酯類等單官能單體。 Examples of monomers used as raw materials for forming the (meth)acrylic particles include alkyl (meth)acrylates, oxygen atom-containing (meth)acrylates, nitrile-containing monomers, fluorine-containing Monofunctional monomers such as (meth)acrylates.

作為上述(甲基)丙烯酸烷基酯類，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)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯等。 Examples of the alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate, Base) hexyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate Esters, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.

作為上述含氧原子(甲基)丙烯酸酯類，例如可列舉：(甲基)丙烯酸2-羥基乙酯、甘油(甲基)丙烯酸酯、聚氧乙烯(甲基)丙烯酸酯、(甲基)丙烯酸環氧丙酯等。 Examples of the above-mentioned oxygen atom-containing (meth)acrylates include: 2-hydroxyethyl (meth)acrylate, glycerin (meth)acrylate, polyoxyethylene (meth)acrylate, (meth) Glycidyl acrylate, etc.

作為上述含腈單體，例如可列舉(甲基)丙烯腈等。 As said nitrile-containing monomer, (meth)acrylonitrile etc. are mentioned, for example.

作為上述含氟(甲基)丙烯酸酯類，例如可列舉：(甲基)丙烯酸三氟甲酯、(甲基)丙烯酸五氟乙酯等。 As said fluorine-containing (meth)acrylate, trifluoromethyl (meth)acrylate, pentafluoroethyl (meth)acrylate, etc. are mentioned, for example.

其中，就均聚物之Tg低，可使施加1g負載時之變形量較大之方面而言，較佳為(甲基)丙烯酸烷基酯類。 Among them, alkyl (meth)acrylates are preferred because the Tg of the homopolymer is low and the amount of deformation when a load of 1 g is applied can be increased.

又，為了使之具有交聯結構，亦可使用多官能單體作為成為用以形成上述(甲基)丙烯酸粒子之原料之單體。 Moreover, in order to make it have a crosslinked structure, you may use a polyfunctional monomer as a monomer used as a raw material for forming the said (meth)acryl particle.

作為上述多官能單體，例如可列舉：四羥甲基甲烷四(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)四亞甲基二醇二(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、異三聚氰酸骨架三(甲基)丙烯酸酯等。其中，就交聯點間分子量較大，可使施加1g負載時之變形量較大之方面而言，較佳為(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、(聚)四亞甲基二醇二(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。 Examples of the polyfunctional monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, diperythritol hexa(meth)acrylate, diperythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di (Meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, isocyanuric acid skeleton tri(meth)acrylate, etc. Among them, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di( Meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Acrylate.

上述交聯性單體之使用量係於成為用以形成上述(甲基)丙烯酸粒子之原料之單體整體中，較佳下限為1重量%，較佳上限為90重量%。藉由使 上述交聯性單體之使用量為1重量%以上，耐溶劑性提昇，於與其他密封劑成分混練時不會引起膨潤等問題，容易均勻地分散。藉由使上述交聯性單體之使用量為90重量%以下，可降低恢復率。上述交聯性單體之使用量之更佳下限為3重量%，更佳上限為80重量%。 The usage-amount of the said crosslinkable monomer is based on the whole monomer used as a raw material for forming the said (meth)acrylic particle, Preferably the lower limit is 1 weight%, and a more preferable upper limit is 90 weight%. By making the amount of the above-mentioned cross-linking monomer to be more than 1% by weight, the solvent resistance is improved, and it is easy to uniformly disperse without causing problems such as swelling when kneading with other sealant components. The recovery rate can be reduced by making the usage-amount of the said crosslinkable monomer into 90 weight% or less. The more preferable lower limit of the usage-amount of the said crosslinkable monomer is 3 weight%, and the more preferable upper limit is 80 weight%.

進而，除該等丙烯酸系單體以外，亦可使用苯乙烯系單體、乙烯醚類、羧酸乙烯酯類、不飽和烴、含鹵素單體、氰尿酸三烯丙酯、異氰尿酸三烯丙酯、偏苯三酸三烯丙酯、二乙烯基苯、鄰苯二甲酸二烯丙酯、二烯丙基丙烯醯胺、二烯丙醚、γ-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷等單體。 Furthermore, in addition to these acrylic monomers, styrene monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, isocyanuric acid tris Allyl ester, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)acryloxy Propyltrimethoxysilane, vinyltrimethoxysilane and other monomers.

作為上述苯乙烯系單體，例如可列舉：苯乙烯、α-甲基苯乙烯、三甲氧基矽基苯乙烯等。 As said styrene-type monomer, styrene, (alpha)-methylstyrene, trimethoxysilylstyrene, etc. are mentioned, for example.

作為上述乙烯醚類，例如可列舉：甲基乙烯醚、乙基乙烯醚、丙基乙烯醚等。 As said vinyl ethers, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

作為上述羧酸乙烯酯類，例如可列舉：乙酸乙烯酯、丁酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯等。 As said vinyl carboxylate, vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, etc. are mentioned, for example.

作為上述不飽和烴，例如可列舉：乙烯、丙烯、異戊二烯、丁二烯等。 As said unsaturated hydrocarbon, ethylene, propylene, isoprene, butadiene etc. are mentioned, for example.

作為上述含鹵素單體，例如可列舉：氯乙烯、氟乙烯、氯苯乙烯等。 As said halogen-containing monomer, vinyl chloride, vinyl fluoride, chlorostyrene, etc. are mentioned, for example.

作為上述(甲基)丙烯酸粒子，亦可較佳地使用核殼(甲基)丙烯酸酯共聚物微粒子。 As the above-mentioned (meth)acrylic particles, core-shell (meth)acrylate copolymer fine particles can also be preferably used.

作為上述核殼(甲基)丙烯酸酯共聚物微粒子中之市售者，例如可列舉F351(Aica Kogyo公司製造)等。 As what is marketed among the said core-shell (meth)acrylate copolymer microparticles|fine-particles, F351 (made by Aica Kogyo company) etc. are mentioned, for example.

又，作為上述乙烯基系粒子，例如亦可使用聚二乙烯基苯粒子、聚氯平(polychloroprene)粒子、丁二烯橡膠粒子等。 In addition, as the above-mentioned vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, etc. can also be used.

上述柔軟粒子之平均粒徑之較佳下限為0.01μm，較佳上限為10 μm。藉由使上述柔軟粒子之平均粒徑為該範圍，提昇所獲得之液晶顯示元件用密封劑之硬化物之柔軟性或接著性的效果更優異。上述柔軟粒子之平均粒徑之更佳下限為0.1μm，更佳上限為8μm。 The preferred lower limit of the average particle size of the soft particles is 0.01 μm, and the preferred upper limit is 10 μm. By making the average particle diameter of the said flexible particle into this range, the effect of improving the flexibility or adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the average particle diameter of the soft particles is 0.1 μm, and a more preferable upper limit is 8 μm.

再者，於本說明書中，上述柔軟粒子之平均粒徑意指藉由使用雷射繞射式粒度分佈測定裝置進行測定所獲得之值。作為上述雷射繞射式粒度分佈測定裝置，可使用Mastersizer 2000(Malvern公司製造)等。 In addition, in this specification, the average particle diameter of the said soft particle means the value obtained by measuring using the laser diffraction particle size distribution measuring apparatus. As the above-mentioned laser diffraction particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Co., Ltd.) or the like can be used.

上述柔軟粒子之硬度之較佳下限為10，較佳上限為50。藉由使上述柔軟粒子之硬度為該範圍，提昇所獲得之液晶顯示元件用密封劑之硬化物之柔軟性或接著性的效果更優異。上述柔軟粒子之硬度之更佳下限為20，更佳上限為40。 The preferred lower limit of the hardness of the soft particles is 10, and the preferred upper limit is 50. By making the hardness of the said flexible particle into this range, the effect of improving the flexibility or adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the hardness of the soft particles is 20, and a more preferable upper limit is 40.

再者，於本說明書中，上述柔軟粒子之硬度意指藉由依據JIS K 6253之方法測得之A型硬度計硬度。 In addition, in this specification, the hardness of the said soft particle|grain means the A-type durometer hardness measured by the method based on JISK 6253.

本發明之液晶顯示元件用密封劑100重量份中之上述柔軟粒子之含量的較佳下限為5重量份，較佳上限為50重量份。藉由使上述柔軟粒子之含量為該範圍，提昇所獲得之液晶顯示元件用密封劑之硬化物之柔軟性或接著性的效果更優異。上述柔軟粒子之含量之更佳下限為10重量份，更佳上限為30重量份。 The preferred lower limit of the content of the soft particles in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the upper limit is preferably 50 parts by weight. By making content of the said flexible particle into this range, the effect of improving the flexibility or adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the content of the soft particles is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.

本發明之液晶顯示元件用密封劑較佳為以進一步提昇接著性為目的而含有矽烷偶合劑。上述矽烷偶合劑主要具有作為用以將密封劑與基板等良好地接著之接著助劑之作用。 It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent for the purpose of further improving adhesiveness. The above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for bonding the sealant and the substrate etc. well.

作為上述矽烷偶合劑，例如可較佳地使用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等。 As said silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. can be preferably used.

上述矽烷偶合劑可單獨使用，亦可組合2種以上而使用。 The above-mentioned silane coupling agents may be used alone or in combination of two or more.

本發明之液晶顯示元件用密封劑100重量份中之上述矽烷偶合劑 之含量的較佳下限為0.1重量份，較佳上限為10重量份。藉由使上述矽烷偶合劑之含量為該範圍，可抑制液晶污染之產生，並且進一步發揮提昇接著性之效果。上述矽烷偶合劑之含量之更佳下限為0.3重量份，更佳上限為5重量份。 The preferred lower limit of the content of the above-mentioned silane coupling agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. By making content of the said silane coupling agent into this range, generation|occurrence|production of liquid crystal contamination can be suppressed, and the effect of improving adhesiveness can be exhibited further. A more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

本發明之液晶顯示元件用密封劑亦可含有遮光劑。藉由含有上述遮光劑，本發明之液晶顯示元件用密封劑可較佳地用作遮光密封劑。 The sealing compound for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing compound for liquid crystal display elements of this invention can be used preferably as a light-shielding sealing compound.

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。 As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black etc. are mentioned, for example. Among them, titanium black is preferred.

上述遮光劑可單獨使用，亦可組合2種以上而使用。 The said sunscreen agent may be used individually, and may use it in combination of 2 or more types.

上述鈦黑係與對波長300nm以上且800nm以下之光之平均透過率相比，對紫外線區域附近、尤其是波長370nm以上且450nm以下之光之透過率變高之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮蔽可見光區域之波長之光而對本發明之液晶顯示元件用密封劑賦予遮光性，另一方面，使紫外線區域附近之波長之光透過。作為本發明之液晶顯示元件用密封劑中所含有之遮光劑，較佳為絕緣性較高之物質，作為絕緣性較高之遮光劑，亦較佳為鈦黑。 The above-mentioned titanium black is a material having a higher transmittance for light in the vicinity of the ultraviolet region, especially for light with a wavelength of 370 nm to 450 nm, than the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of imparting light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible region, and, on the other hand, shielding light of wavelengths near the ultraviolet region. through. As the light-shielding agent contained in the sealing compound for liquid crystal display elements of this invention, it is preferable that it is a substance with high insulating property, and as a light-shielding agent with high insulating property, titanium black is also preferable.

上述鈦黑即便為未進行表面處理者亦發揮充分之效果，亦可使用表面經偶合劑等有機成分處理者、或經氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等經表面處理之鈦黑。其中，經有機成分處理者就可進一步提昇絕緣性之方面而言較佳。 Even if the above-mentioned titanium black is not surface-treated, it can also exert sufficient effects. It is also possible to use those whose surface has been treated with organic components such as coupling agents, or those treated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black with surface treatment such as component coating. Among them, those treated with an organic component are preferable in terms of further improving insulation properties.

又，使用含有上述鈦黑作為遮光劑之本發明之液晶顯示元件用密封劑所製造之液晶顯示元件由於具有充分之遮光性，故而可實現不存在光之漏出，具有較高之對比度，且具有優異之圖像顯示品質之液晶顯示元件。 Also, the liquid crystal display element manufactured by using the sealant for liquid crystal display element of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so it can realize that there is no leakage of light, has a higher contrast ratio, and has Liquid crystal display element with excellent image display quality.

作為上述鈦黑中之市售者，例如可列舉：三菱綜合材料公司製造之鈦黑、赤穗化成公司製造之鈦黑等。 As what is marketed among the said titanium blacks, the titanium black by Mitsubishi Materials Corporation, the titanium black by Ako Kasei Corporation, etc. are mentioned, for example.

作為上述三菱綜合材料公司製造之鈦黑，例如可列舉：12S、13M、13M-C、13R-N、14M-C等。 Examples of titanium black manufactured by Mitsubishi Materials Corp. include 12S, 13M, 13M-C, 13R-N, and 14M-C.

作為上述赤穗化成公司製造之鈦黑，例如可列舉Tilack D等。 As titanium black manufactured by the said Ako Kasei Co., Ltd., Tilack D etc. are mentioned, for example.

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。 The lower limit of the specific surface area of the titanium black is preferably 13m 2 /g, the upper limit is 30m 2 /g, the lower limit is 15m 2 /g, and the upper limit is 25m 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。 Also, the lower limit of the volume resistance of the titanium black is preferably 0.5Ω‧cm, the upper limit is 3Ω‧cm, the lower limit is 1Ω‧cm, and the upper limit is 2.5Ω‧cm.

上述遮光劑之一次粒徑若為液晶顯示元件之基板間之距離以下則並無特別限定，較佳下限為1nm，較佳上限為5μm。藉由使上述遮光劑之一次粒徑為該範圍，所獲得之液晶顯示元件用密封劑之黏度或搖變性不會大幅增大，塗佈性更優異。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 size of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the lower limit is preferably 1 nm, and the upper limit is preferably 5 μm. By making the primary particle diameter of the said light-shielding agent into this range, the viscosity and thixotropy of the sealing compound for liquid crystal display elements obtained will not increase significantly, and it will become more excellent in applicability. The more preferable lower limit of the primary particle diameter of the above-mentioned light-shielding agent is 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm.

再者，上述遮光劑之一次粒徑可使用粒度分佈計(例如PARTICLE SIZING SYSTEMS公司製造，「NICOMP 380ZLS」)，使上述遮光劑分散於溶劑(水、有機溶劑等)中進行測定。 In addition, the primary particle diameter of the said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

本發明之液晶顯示元件用密封劑100重量份中之上述遮光劑之含量的較佳下限為5重量份，較佳上限為80重量份。藉由使上述遮光劑之含量為該範圍，可於所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度及繪圖性不大幅降低之情況下，進一步發揮提昇遮光性之效果。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 preferable lower limit of the content of the said light-shielding agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 5 weight part, and a preferable upper limit is 80 weight part. By making content of the said light-shielding agent into this range, the effect of improving light-shielding property can be exhibited further, when the adhesiveness of the sealing compound for liquid crystal display elements obtained, the intensity|strength after hardening, and drawing property do not fall significantly. A more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

本發明之液晶顯示元件用密封劑亦可進而視需要含有應力緩和劑、反應性稀釋劑、搖變劑、間隔劑、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。 The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relieving agents, reactive diluents, thixotropic agents, spacers, hardening accelerators, defoamers, leveling agents, and polymerization inhibitors as necessary.

作為製造本發明之液晶顯示元件用密封劑之方法，例如可列舉如下方法等：使用勻相分散機、均質混合器、萬能混合器、行星式混合器、捏合機、三輥研磨機等混合機，將硬化性樹脂、聚合起始劑、及熱硬化劑或視需要添加之矽烷偶合劑等添加劑進行混合。 As a method of producing the sealing agent for liquid crystal display elements of the present invention, for example, the following methods are mentioned: using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. , Mix curable resin, polymerization initiator, thermosetting agent or additives such as silane coupling agent if necessary.

本發明之液晶顯示元件用密封劑使用E型黏度計於25℃、1rpm之條件下測得之黏度的較佳下限為100Pa‧s，較佳上限為800Pa‧s。藉由使上述黏度為該範圍，所獲得之液晶顯示元件用密封劑成為塗佈性優異者。上述黏度之更佳下限為200Pa‧s，更佳上限為700Pa‧s。 The preferred lower limit of the viscosity of the sealant for liquid crystal display elements of the present invention is 100 Pa‧s, and the preferred upper limit is 800 Pa‧s measured using an E-type viscometer at 25°C and 1 rpm. By making the said viscosity into this range, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. A more preferable lower limit of the above viscosity is 200Pa‧s, and a more preferable upper limit is 700Pa‧s.

藉由在本發明之液晶顯示元件用密封劑中摻合導電性微粒子，可製造上下導通材料。又，含有本發明之液晶顯示元件用密封劑及導電性微粒子之上下導通材料亦為本發明之一。 By mixing conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, vertical conduction materials can be produced. Moreover, the upper-bottom conduction material containing the sealing compound for liquid crystal display elements of this invention, and electroconductive fine particle is also one of this invention.

作為上述導電性微粒子，可使用金屬球、於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由於藉由樹脂微粒子之優異之彈性，可不損傷透明基板等而實現導電連接，故而較佳。 As said electroconductive microparticles|fine-particles, what formed the electroconductive metal layer on the surface of a metal ball, the resin microparticles, etc. can be used. Among them, the one having the conductive metal layer formed on the surface of the resin fine particles is preferable because conductive connection can be realized without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

又，使用本發明之液晶顯示元件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為本發明之一。 Moreover, the liquid crystal display element which used the sealing compound for liquid crystal display elements of this invention, or the upper-bottom conduction material of this invention is also one of this invention.

作為製造本發明之液晶顯示元件之方法，可較佳地使用液晶滴下法，具體而言，例如可列舉具有以下之各步驟之方法等。 As a method of manufacturing the liquid crystal display element of this invention, the liquid crystal dropping method can be used preferably, Specifically, the method etc. which have the following each process are mentioned, for example.

首先，進行如下步驟：於附ITO薄膜等電極之玻璃基板或聚對酞酸乙二酯基板等2片基板中之一者，藉由網版印刷、點膠機塗佈等塗佈本發明之液晶顯示元件用密封劑並形成為框狀之密封圖案。繼而，進行如下步驟：於本發明之液晶顯示元件用密封劑未硬化之狀態下將液晶之微滴滴下塗佈於基板之密封圖案之框內，於真空下重疊另一基板。然後，藉由進行如下步驟之方法，可獲得液晶顯示元件：對本發明之液晶顯示元件用密封劑之密封圖案部分照射紫外線等光 而使密封劑預硬化；及對經預硬化之密封劑進行加熱而進行正式硬化。 First, the following steps are carried out: on one of the two substrates, such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate, apply the film of the present invention by screen printing, dispenser coating, etc. Sealant for liquid crystal display elements and form a frame-shaped seal pattern. Then, the following steps are carried out: in the uncured state of the sealant for liquid crystal display elements of the present invention, droplets of liquid crystal are drop-coated in the frame of the seal pattern of the substrate, and another substrate is superimposed under vacuum. Then, a liquid crystal display element can be obtained by performing the following steps: irradiating light such as ultraviolet rays to the sealing pattern portion of the sealant for liquid crystal display elements of the present invention to precure the sealant; and heating the precured sealant For formal hardening.

根據本發明，可提供一種塗佈性、硬化性及低液晶污染性優異之液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件用密封劑而成之上下導通材料及液晶顯示元件。 According to this invention, the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property can be provided. Moreover, according to this invention, the upper-bottom conduction material and the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

以下，揭示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, examples are disclosed and the present invention will be described in more detail, but the present invention is not limited to these examples.

(酚醛清漆型硬化性樹脂混合物(A1)之製作) (Production of Novolac Type Curable Resin Mixture (A1))

使苯酚酚醛清漆型環氧樹脂(DIC公司製造，「EPICLON N-740」)557重量份溶解於甲苯900mL中後，加入三苯基膦0.3g，製成均勻之溶液。於所獲得之溶液中於回流攪拌下滴下丙烯酸122重量份2小時後，進而進行6小時回流攪拌。繼而，藉由將甲苯減壓去除，獲得酚醛清漆型硬化性樹脂混合物(A1)。 After dissolving 557 parts by weight of a phenol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLON N-740") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After dripping 122 parts by weight of acrylic acid in the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a novolac type curable resin mixture (A1).

藉由1H-NMR、13C-NMR及FT-IR，確認到酚醛清漆型硬化性樹脂混合物(A1)係含有11.8重量%之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂、68.6重量%之苯酚酚醛清漆型環氧樹脂、19.6重量%之苯酚酚醛清漆型環氧丙烯酸酯之混合物。 By 1 H-NMR, 13 C-NMR and FT-IR, it was confirmed that the novolac type curable resin mixture (A1) contained 11.8% by weight of a part of acrylic modified phenol novolak type epoxy resin, 68.6% by weight of A mixture of phenol novolac epoxy resin and 19.6% by weight of phenol novolak epoxy acrylate.

又，所獲得之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂之重量平均分子量為1200。 In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 1,200.

(酚醛清漆型硬化性樹脂混合物(A2)之製作) (Production of Novolac Type Curable Resin Mixture (A2))

使苯酚酚醛清漆型環氧樹脂(DIC公司製造，「EPICLONN-730S」)395重量份溶解於甲苯900mL中後，加入三苯基膦0.3g，製成均勻之溶液。於所獲得之溶液中於2小時之回流攪拌下滴下丙烯酸94重量份後，進而進行6小時回流攪拌。繼而，藉由將甲苯減壓去除，獲得酚醛清漆型硬化性樹脂混合物(A2)。 After dissolving 395 parts by weight of a phenol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLONN-730S") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After dripping 94 parts by weight of acrylic acid in the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Then, a novolak type curable resin mixture (A2) was obtained by depressurizingly removing toluene.

藉由1H-NMR、13C-NMR及FT-IR，確認到酚醛清漆型硬化性樹脂混合物(A2)係含有11.8重量%之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂、68.6重量%之苯酚酚醛清漆型環氧樹脂、19.6重量%之苯酚酚醛清漆型環氧丙烯酸酯之混合物。 By 1 H-NMR, 13 C-NMR and FT-IR, it was confirmed that the novolac type curable resin mixture (A2) contained 11.8% by weight of a part of acrylic modified phenol novolak type epoxy resin, 68.6% by weight of A mixture of phenol novolac epoxy resin and 19.6% by weight of phenol novolak epoxy acrylate.

又，所獲得之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂之重量平均分子量為800。 In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 800.

(酚醛清漆型硬化性樹脂混合物(A3)之製作) (Production of Novolac Type Curable Resin Mixture (A3))

使苯酚酚醛清漆型環氧樹脂(DIC公司製造，「EPICLON N-770」)965重量份溶解於甲苯1800mL中後，加入三苯基膦0.3g，製成均勻之溶液。於所獲得之溶液中於2小時之回流攪拌下滴下丙烯酸216重量份後，進而進行6小時回流攪拌。繼而，藉由將甲苯減壓去除，獲得酚醛清漆型硬化性樹脂混合物(A3)。 After dissolving 965 parts by weight of a phenol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLON N-770") in 1800 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. In the obtained solution, 216 weight part of acrylic acid was dripped under reflux stirring for 2 hours, and then reflux stirring was performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a novolac type curable resin mixture (A3).

藉由1H-NMR、13C-NMR及FT-IR，確認到酚醛清漆型硬化性樹脂混合物(A3)係含有11.8重量%之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂、68.6重量%之苯酚酚醛清漆型環氧樹脂、19.6重量%之苯酚酚醛清漆型環氧丙烯酸酯之混合物。 By 1 H-NMR, 13 C-NMR and FT-IR, it was confirmed that the novolac type curable resin mixture (A3) contained 11.8% by weight of a part of acrylic modified phenol novolak type epoxy resin, 68.6% by weight of A mixture of phenol novolac epoxy resin and 19.6% by weight of phenol novolak epoxy acrylate.

又，所獲得之部分丙烯酸改質苯酚酚醛清漆型環氧樹脂之重量平均分子量為2500。 In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 2,500.

(非酚醛清漆型硬化性樹脂混合物(B1)之製作) (Preparation of Non-Novolac Type Curable Resin Mixture (B1))

使雙酚A型環氧樹脂(Mitsubishi Chemical公司製造，「jER 828EL」)326重量份溶解於甲苯900mL中後，加入三苯基膦0.3g，製成均勻之溶液。於所獲 得之溶液中於2小時之回流攪拌下滴下丙烯酸72重量份後，進而進行6小時回流攪拌。繼而，藉由將甲苯減壓去除，獲得非酚醛清漆型硬化性樹脂混合物(B1)。 After dissolving 326 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical, "jER 828EL") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After 72 parts by weight of acrylic acid was dropped into the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Next, by removing toluene under reduced pressure, a non-novolac type curable resin mixture (B1) was obtained.

藉由1H-NMR、13C-NMR及FT-IR，確認到非酚醛清漆型硬化性樹脂混合物(B1)係含有50重量%之部分丙烯酸改質雙酚A型環氧樹脂、25重量%之雙酚A型環氧樹脂、25重量%之雙酚A型環氧丙烯酸酯之混合物。 By 1 H-NMR, 13 C-NMR and FT-IR, it was confirmed that the non-novolac type curable resin mixture (B1) contained 50% by weight of a part of acrylic modified bisphenol A type epoxy resin, 25% by weight A mixture of bisphenol A type epoxy resin and 25% by weight of bisphenol A type epoxy acrylate.

(實施例1~10、比較例1~8) (Examples 1-10, Comparative Examples 1-8)

按照表1、2中所記載之摻合比，藉由行星式攪拌裝置(Thinky公司製造，「去泡攪拌太郎」)攪拌各材料後，藉由陶瓷三輥研磨機均勻地混合而獲得實施例1~10、比較例1~8之液晶顯示元件用密封劑。 According to the blending ratios recorded in Tables 1 and 2, after stirring each material with a planetary stirring device (manufactured by Thinky Corporation, "Foaming Stirring Taro"), the examples were obtained by uniformly mixing with a ceramic three-roll mill 1~10. Sealants for liquid crystal display elements of comparative examples 1~8.

<評價> <Evaluation>

對實施例及比較例中所獲得之各液晶顯示元件用密封劑進行以下之評價。將結果示於表1、2。 The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in the Example and the comparative example. The results are shown in Tables 1 and 2.

(黏度) (viscosity)

對實施例及比較例中所獲得之各液晶顯示元件用密封劑，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。 About each sealing compound for liquid crystal display elements obtained in the Example and the comparative example, the viscosity on the conditions of 25 degreeC and 1 rpm was measured using the E-type viscometer (made by Brookfield company, "DV-III").

(塗佈性) (coatability)

使用點膠機(武藏高科技公司製造，「SHOTMASTER 300」)，將實施例及比較例中所獲得之各液晶顯示元件用密封劑塗佈於玻璃基板上。將於將點膠噴嘴固定為400μm，將噴嘴間隙固定為30μm，將噴出壓固定為300kPa進行塗佈時，無模糊或塌邊而成功塗佈之情形設為「○」，將雖不存在塗佈裂紋但產生模糊或塌邊之情形設為「△」，將產生塗佈裂紋或者完全無法塗佈之情形設為「×」而評價塗佈性。 The sealing compound for each liquid crystal display element obtained in the Example and the comparative example was apply|coated on the glass substrate using the dispenser ("SHOTMASTER 300" manufactured by Musashi High-tech Co., Ltd.). When the dispensing nozzle is fixed at 400 μm, the nozzle gap is fixed at 30 μm, and the discharge pressure is fixed at 300 kPa to apply, the case of successful coating without blurring or sagging is set as "○", although there is no coating The case where the fabric was cracked but blurred or sagging occurred was rated as "△", and the case where coating cracked or coating was not possible at all was rated as "×" to evaluate the coatability.

(硬化性) (hardening)

將實施例及比較例中所獲得之各液晶顯示元件用密封劑塗佈於玻璃基板上 約5μm後，重疊相同尺寸之玻璃基板。繼而，使用金屬鹵化物燈，照射3000mJ/cm2之波長365nm之紫外線。使用紅外分光裝置(BIORAD公司製造，「FTS3000」)，測定來自(甲基)丙烯醯基之波峰於照光前後之變化量(減少率)。 After applying the sealants for liquid crystal display elements obtained in Examples and Comparative Examples to about 5 μm on a glass substrate, glass substrates of the same size were stacked. Next, using a metal halide lamp, 3000 mJ/cm 2 of ultraviolet light with a wavelength of 365 nm was irradiated. Using an infrared spectrometer (manufactured by BIORAD, "FTS3000"), the amount of change (decrease rate) of the peak derived from the (meth)acryl group before and after irradiation was measured.

將照光後之來自(甲基)丙烯醯基之波峰之減少率為95%以上的情形設為「◎」，將85%以上且未達95%之情形設為「○」，將75%以上且未達85%之情形設為「△」，將未達75%之情形設為「×」而評價硬化性。 When the reduction rate of the peak derived from the (meth)acryl group after irradiation was 95% or more, it was rated as "◎", when it was 85% or more and less than 95%, it was rated as "○", and when it was 75% or more Moreover, the case of less than 85% was set as "△", and the case of less than 75% was set as "×" to evaluate the curability.

(低液晶污染性) (low liquid crystal contamination)

於實施例及比較例中所獲得之各液晶顯示元件用密封劑中摻合1重量%之二氧化矽間隔劑(積水化學工業公司製造，「SI-H055」)，進行脫泡處理而去除密封劑中之氣泡後，填充至點膠用注射器(武藏高科技公司製造，「PSY-10E」)中，再次進行脫泡處理。繼而，使用點膠機(武藏高科技公司製造，「SHOTMASTER 300」)，以於2片附ITO薄膜之玻璃基板中之一者畫框之方式塗佈密封劑。繼而，藉由液晶滴下裝置將TN液晶(Chisso公司製造，「JC-5001LA」)之微滴滴下塗佈於密封劑之框內，重疊另一附ITO薄膜之玻璃基板，藉由真空貼合裝置於5Pa之減壓下貼合2片基板。藉由金屬鹵化物燈對貼合後之單元照射3000mJ/cm2之紫外線後，於120℃加熱60分鐘，藉此使密封劑熱硬化，製作液晶顯示元件。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100小時後，進行AC 3.5V之電壓驅動，藉由目測觀察顯示不均(色不均)之有無。將完全未見顯示不均之情形設為「○」，將於液晶顯示元件之周邊部存在顯示不均之情形設為「△」，將顯示不均不僅存在於液晶顯示元件之周邊部且亦擴散至中央部之情形設為「×」而評價低液晶污染性。 1% by weight of a silica spacer (manufactured by Sekisui Chemical Industry Co., Ltd., "SI-H055") was blended with each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples, and the sealant was removed by defoaming treatment. After removing air bubbles in the agent, fill it into a dispensing syringe (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"), and perform defoaming treatment again. Then, using a dispenser ("SHOTMASTER 300" manufactured by Musashi High-tech Co., Ltd.), the sealant was applied to form a picture frame on one of the two glass substrates with ITO films. Then, droplet coating of TN liquid crystal (manufactured by Chisso, "JC-5001LA") in the frame of sealant by liquid crystal dropping device, overlap another glass substrate with ITO film, and use vacuum bonding device Two substrates were bonded under a reduced pressure of 5 Pa. The bonded unit was irradiated with 3000mJ/cm 2 of ultraviolet rays by a metal halide lamp, and then heated at 120°C for 60 minutes to thermally harden the sealant and produce a liquid crystal display element. After storing the obtained liquid crystal display element in an environment with a temperature of 80°C and a humidity of 90%RH for 100 hours, it was driven with a voltage of AC 3.5V, and the presence or absence of display unevenness (color unevenness) was visually observed. The case where display unevenness is not seen at all is set as "○", and the case where display unevenness is present in the peripheral part of the liquid crystal display element is set as "△". Display unevenness is not only present in the peripheral part of the liquid crystal display element but The case where it diffused to the central part was made into "x" and low liquid crystal contamination property was evaluated.

Figure 107124130-A0202-12-0025-1
Figure 107124130-A0202-12-0025-1

Figure 107124130-A0202-12-0026-2
Figure 107124130-A0202-12-0026-2

[產業上之可利用性] [Industrial availability]

根據本發明，可提供一種塗佈性、硬化性及低液晶污染性優異之 液晶顯示元件用密封劑。又，根據本發明，可提供一種使用該液晶顯示元件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, there can be provided a sealant for liquid crystal display elements excellent in applicability, curability and low liquid crystal contamination. Moreover, according to this invention, the upper-bottom conduction material and the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

Claims (3)

一種液晶顯示元件用密封劑，含有硬化性樹脂及聚合起始劑，其特徵在於：該硬化性樹脂含有部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)、部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)及非酚醛清漆型環氧(甲基)丙烯酸酯(C)，該部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之含量於該硬化性樹脂100重量份中，為3重量份以上，9重量份以下，該部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)之含量於該硬化性樹脂100重量份中，為25重量份以下，且該部分(甲基)丙烯酸改質非酚醛清漆型環氧樹脂(B)相對於該部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之比率為1以上，該非酚醛清漆型環氧(甲基)丙烯酸酯(C)之含量於該硬化性樹脂100重量份中，為10重量份以上且45重量份以下，該部分(甲基)丙烯酸改質酚醛清漆型環氧樹脂(A)之重量平均分子量為700以上，2000以下。 A sealant for liquid crystal display elements, containing curable resin and polymerization initiator, characterized in that: the curable resin contains part of (meth)acrylic acid modified novolak type epoxy resin (A), part of (meth) Acrylic modified non-novolac epoxy resin (B) and non-novolac epoxy (meth)acrylate (C), the content of this part of (meth)acrylic modified novolac epoxy resin (A) In 100 parts by weight of the hardening resin, it is more than 3 parts by weight and less than 9 parts by weight. The content of the part of (meth)acrylic modified non-novolac epoxy resin (B) is in 100 parts by weight of the hardening resin wherein, is 25 parts by weight or less, and the ratio of the part of the (meth)acrylic modified non-novolac epoxy resin (B) to the part of the (meth)acrylic modified novolac epoxy resin (A) 1 or more, the content of the non-novolak epoxy (meth)acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the curable resin, and the part of the (meth)acrylic modified The weight average molecular weight of the novolac type epoxy resin (A) is 700 or more and 2,000 or less. 一種上下導通材料，其含有請求項1所述之液晶顯示元件用密封劑及導電性微粒子。 A vertical conduction material, which contains the sealant for liquid crystal display elements described in Claim 1 and conductive fine particles. 一種液晶顯示元件，其係使用請求項1所述之液晶顯示元件用密封劑或請求項2所述之上下導通材料而成。 A liquid crystal display element, which is formed by using the sealant for liquid crystal display elements described in claim 1 or the upper and lower conductive materials described in claim 2.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232368A (en) * 2004-02-20 2005-09-02 Sekisui Chem Co Ltd Curable resin composition, sealing agent for liquid crystal dropping method, vertically conducting material and liquid crystal display device
TW200825113A (en) * 2006-09-07 2008-06-16 Mitsui Chemicals Inc Liquid crystal sealant, liquid crystal display panel and fabricating method thereof using the same
TW201132667A (en) * 2010-03-26 2011-10-01 Mitsui Chemicals Inc Liquid crystal sealing agent, method for fabricating liquid crystal display panel using the same and liquid crystal display panel
TW201329588A (en) * 2011-12-23 2013-07-16 Korea Kumho Petrochem Co Ltd Black sealing agent composition for liquid crystal display materials
TWI420205B (en) * 2007-02-20 2013-12-21 Mitsui Chemicals Inc Hardening resin composition for liquid crystal sealing and manufacturing method for liquid crystal display panel using the same
JP2017091772A (en) * 2015-11-09 2017-05-25 積水化学工業株式会社 Sealant for organic electroluminescent display element
TW201723129A (en) * 2015-12-22 2017-07-01 陶氏全球科技有限責任公司 Acrylic/epoxy hybrid materials for laminating adhesive applications

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3583326B2 (en) 1999-11-01 2004-11-04 協立化学産業株式会社 Sealant for dripping method of LCD panel
KR100906926B1 (en) * 2001-05-16 2009-07-10 세키스이가가쿠 고교가부시키가이샤 Curing Resin Composition and Sealants and End-Sealing Materials for Displays
JP4845667B2 (en) * 2006-10-12 2011-12-28 三井化学株式会社 Liquid crystal sealant, liquid crystal display panel manufacturing method using the same, and liquid crystal display panel
KR101194202B1 (en) * 2008-04-18 2012-10-25 세키스이가가쿠 고교가부시키가이샤 Sealing agent for use in liquid crystal dropping process, sealing agent for liquid crystal panel, vertical-conduction material, and liquid crystal display element
JP5503763B2 (en) * 2013-02-20 2014-05-28 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
DE202015106142U1 (en) * 2015-11-13 2017-02-15 Rehau Ag + Co. bonding
JP6197020B2 (en) * 2015-12-17 2017-09-13 三井化学株式会社 Photocurable resin composition, display element sealant, liquid crystal sealant, liquid crystal display panel, and method for producing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232368A (en) * 2004-02-20 2005-09-02 Sekisui Chem Co Ltd Curable resin composition, sealing agent for liquid crystal dropping method, vertically conducting material and liquid crystal display device
TW200825113A (en) * 2006-09-07 2008-06-16 Mitsui Chemicals Inc Liquid crystal sealant, liquid crystal display panel and fabricating method thereof using the same
TWI420205B (en) * 2007-02-20 2013-12-21 Mitsui Chemicals Inc Hardening resin composition for liquid crystal sealing and manufacturing method for liquid crystal display panel using the same
TW201132667A (en) * 2010-03-26 2011-10-01 Mitsui Chemicals Inc Liquid crystal sealing agent, method for fabricating liquid crystal display panel using the same and liquid crystal display panel
TW201329588A (en) * 2011-12-23 2013-07-16 Korea Kumho Petrochem Co Ltd Black sealing agent composition for liquid crystal display materials
JP2017091772A (en) * 2015-11-09 2017-05-25 積水化学工業株式会社 Sealant for organic electroluminescent display element
TW201723129A (en) * 2015-12-22 2017-07-01 陶氏全球科技有限責任公司 Acrylic/epoxy hybrid materials for laminating adhesive applications

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