TWI813686B - 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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TWI813686B
TWI813686B TW108116689A TW108116689A TWI813686B TW I813686 B TWI813686 B TW I813686B TW 108116689 A TW108116689 A TW 108116689A TW 108116689 A TW108116689 A TW 108116689A TW I813686 B TWI813686 B TW I813686B
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liquid crystal
crystal display
meth
compound
acrylate
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TW202003623A (en
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林秀幸
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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
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • 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

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  • Chemical & Material Sciences (AREA)
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  • Optics & Photonics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

本發明之目的在於提供一種保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生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。 本發明係一種液晶顯示元件用密封劑，其含有硬化性樹脂及熱硬化劑，且上述熱硬化劑包含具有下述特徵（a）、（b）、（c）、及（d）之化合物（A）， （a）具有含羥基之醯肼化合物殘基； （b）具有異氰酸酯化合物殘基； （c）具有由下述式（1）所表示之結構； （d）不具有異氰酸基； 式（1）中，*為鍵結位置。 An object of the present invention is to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements. The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent includes a compound having the following characteristics (a), (b), (c), and (d) ( A), (a) has a hydroxyl-containing hydrazine compound residue; (b) has an isocyanate compound residue; (c) has a structure represented by the following formula (1); (d) does not have an isocyanate group ; In formula (1), * is the bonding position.

Description

液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件Sealants for liquid crystal display elements, upper and lower conductive materials, and liquid crystal display elements

本發明係關於一種保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生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 sealing compound for liquid crystal display elements that is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in thin liquid crystal display elements. Furthermore, the present invention relates to an upper and lower conductive material and a liquid crystal display element using the sealant 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，就生產節拍時間（tact time）縮短，使用液晶量之最佳化等觀點而言，利用如專利文獻1、專利文獻2中所揭示之使用密封劑之被稱為滴下工藝之液晶滴下方式。 於滴下工藝中，首先，藉由滴塗而於2片附電極之基板之一片形成框狀之密封圖案。然後，於密封劑未硬化之狀態下將液晶之微小液滴滴下至密封圖案之框內，於真空使另一基板重疊，之後使密封劑硬化而製作液晶顯示元件。目前，該滴下工藝成為液晶顯示元件之製造方法之主流。In recent years, as a manufacturing method of liquid crystal display elements such as a liquid crystal display unit, from the viewpoint of shortening the production tact time and optimizing the amount of liquid crystal used, methods such as those disclosed in Patent Document 1 and Patent Document 2 have been used. The liquid crystal dripping method using sealant is called the dripping process. In the dropping process, first, a frame-shaped sealing pattern is formed on one of the two substrates with electrodes by dropping coating. Then, while the sealant is not hardened, tiny droplets of liquid crystal are dropped into the frame of the sealing pattern, another substrate is overlapped in a vacuum, and then the sealant is hardened to produce a liquid crystal display element. Currently, the dropping process has become the mainstream method of manufacturing liquid crystal display elements.

然而，於行動電話、攜帶型遊戲機等各種附液晶面板之行動機器正在普及之現代，機器之小型化為要求最大之課題。作為機器之小型化之方法，可列舉液晶顯示部之窄邊緣化，例如，進行將密封部之位置配置於黑矩陣下（以下，亦稱為窄邊緣設計）。However, in today's era when various mobile devices with LCD panels, such as mobile phones and portable game consoles, are becoming more popular, miniaturization of the devices is the most demanding issue. An example of a method for miniaturizing the device is to narrow the edges of the liquid crystal display portion, for example, arranging the sealing portion under the black matrix (hereinafter also referred to as narrow edge design).

然而，於窄邊緣設計中，由於將密封劑配置於黑矩陣之正下方，故而若進行滴下工藝，則使密封劑光硬化時所照射之光被遮擋，光難以到達密封劑之內部，於習知之密封劑中，硬化變得不充分。若如此密封劑之硬化變得不充分，則存在未硬化之密封劑成分容易向液晶中溶出而產生液晶污染之問題。However, in the narrow edge design, since the sealant is placed directly under the black matrix, if the dropping process is performed, the light irradiated when the sealant is photocured will be blocked, making it difficult for the light to reach the inside of the sealant. In Zhizhi sealant, hardening becomes insufficient. If the curing of the sealant becomes insufficient in this way, there is a problem that uncured sealant components are easily eluted into the liquid crystal, causing contamination of the liquid crystal.

於如此難以使密封劑光硬化之情形時，想到藉由加熱而使其硬化，作為用於藉由加熱而使密封劑硬化之方法，進行將熱硬化劑摻合於密封劑。然而，於使用對熱之反應性較高之熱硬化劑以提高密封劑之硬化性的情形時，存在所獲得之密封劑之保存穩定性較差之情況。 又，近年來，液晶顯示元件之薄型化正在發展，但於將習知之密封劑用於薄型液晶顯示元件之情形時，存在產生顯示不良之問題。 先前技術文獻 專利文獻In such a case where it is difficult to light-cure the sealant, it is thought that the sealant is cured by heating. As a method for curing the sealant by heating, a thermosetting agent is blended into the sealant. However, when a thermosetting agent with high reactivity to heat is used to improve the hardening properties of a sealant, the storage stability of the obtained sealant may be poor. In addition, in recent years, liquid crystal display elements have become thinner. However, when a conventional sealant is used for a thin liquid crystal display element, there is a problem of display defects. Prior technical literature patent documents

專利文獻1：日本特開2001-133794號公報 專利文獻2：國際公開第02/092718號Patent Document 1: Japanese Patent Application Publication No. 2001-133794 Patent Document 2: International Publication No. 02/092718

[發明所欲解決之課題][Problem to be solved by the invention]

本發明之目的在於提供一種保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生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。 [解決課題之技術手段]An object of the present invention is to provide a sealing compound for a liquid crystal display element that is excellent in storage stability and curability and that can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, an object of the present invention is to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements. [Technical means to solve the problem]

本發明係一種液晶顯示元件用密封劑，其係含有硬化性樹脂及熱硬化劑者，且上述熱硬化劑包含具有下述特徵（a）、（b）、（c）、及（d）之化合物（A）， （a）具有含羥基之醯肼化合物殘基； （b）具有異氰酸酯化合物殘基； （c）具有由下述式（1）所表示之結構； （d）不具有異氰酸基； 即，本發明係一種液晶顯示元件用密封劑，其係含有硬化性樹脂及熱硬化劑者，且上述熱硬化劑包含具有含羥基之醯肼化合物殘基、異氰酸酯化合物殘基、及由下述式（1）所表示之結構，且不具有異氰酸基之化合物。The present invention is a sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent includes one having the following characteristics (a), (b), (c), and (d). Compound (A), (a) Having a hydroxyl-containing hydrazine compound residue; (b) Having an isocyanate compound residue; (c) Having a structure represented by the following formula (1); (d) Does not have isocyanate groups; That is, the present invention is a sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, and the thermosetting agent includes a hydroxyl-containing hydrazine compound residue, an isocyanate compound residue, and the following A compound having a structure represented by formula (1) and not having an isocyanate group.

式（1）中，*為鍵結位置。 以下，對本發明詳細地進行敍述。In formula (1), * is the bonding position. Hereinafter, the present invention will be described in detail.

應對液晶顯示元件之薄型化，使用包含具有氟基、氯基、氰基等極性基之液晶分子者作為液晶之情況居多。本發明者考慮到，於將習知之密封劑用於薄型液晶顯示元件之情形時產生顯示不良之原因在於：因此種包含具有極性基之液晶分子之液晶與密封劑之相容性（尤其是與密封劑中所包含之熱硬化劑之相容性）較高而導致容易產生液晶污染。因此，本發明者進行了專心研究，結果發現藉由使用具有特定之結構之熱硬化劑而獲得保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生之液晶顯示元件用密封劑，從而完成本發明。 再者，本發明之液晶顯示元件用密封劑相對於不包含具有極性基之液晶分子之習知之液晶而言相容性更低，因此，即便於使用此種習知之液晶之液晶顯示元件中，亦能夠抑制顯示不良之產生。In order to reduce the thickness of liquid crystal display elements, liquid crystal molecules containing polar groups such as fluorine groups, chlorine groups, and cyano groups are often used as liquid crystals. The inventors of the present invention considered that the cause of poor display when conventional sealants are used in thin liquid crystal display elements is due to the compatibility between the liquid crystal containing liquid crystal molecules having polar groups and the sealant (especially with the sealant). The compatibility of the thermal hardener contained in the sealant is relatively high, resulting in easy liquid crystal contamination. Therefore, the present inventors conducted intensive research and found that by using a thermosetting agent having a specific structure, excellent storage stability and curing properties can be obtained, and display defects can be suppressed even when used in a thin liquid crystal display element. The resulting sealant for liquid crystal display elements completes the present invention. Furthermore, the sealant for liquid crystal display elements of the present invention has lower compatibility than conventional liquid crystals that do not contain liquid crystal molecules with polar groups. Therefore, even in liquid crystal display elements using such conventional liquid crystals, It can also suppress the occurrence of display defects.

本發明之液晶顯示元件用密封劑含有熱硬化劑。 上述熱硬化劑包含具有上述特徵（a）、（b）、（c）、及（d）之化合物（A）（以下，亦稱為「本發明之熱硬化劑」）。藉由含有本發明之熱硬化劑，本發明之液晶顯示元件用密封劑之保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生。 再者，於本說明書中，上述「殘基」係指原料成分中之供鍵結之官能基以外之部分的結構。具體而言，本發明之熱硬化劑之上述特徵（a）中之上述「含羥基之醯肼化合物殘基」係指來源於含羥基之醯肼化合物，且該含羥基之醯肼化合物中之醯肼基以外之部分之結構，即，不與異氰酸基發生反應而殘留之部分之結構。又，本發明之熱硬化劑之上述特徵（b）中之上述「異氰酸酯化合物殘基」係指來源於異氰酸酯化合物，且該異氰酸酯化合物中之異氰酸基以外之部分之結構，即不與醯肼基發生反應而殘留之部分之結構。再者，本發明之熱硬化劑由於為具有上述特徵（d），即不具有異氰酸基者，故而異氰酸酯化合物之所有異氰酸基用於由上述式（1）所表示之結構之形成。The sealing compound for liquid crystal display elements of the present invention contains a thermosetting agent. The thermosetting agent includes compound (A) having the above characteristics (a), (b), (c), and (d) (hereinafter, also referred to as "the thermosetting agent of the present invention"). By containing the thermosetting agent of the present invention, the sealing compound for liquid crystal display elements of the present invention has excellent storage stability and curability, and can suppress the occurrence of display defects even when used in thin liquid crystal display elements. In addition, in this specification, the above-mentioned "residue" refers to the structure of the part other than the functional group for bonding in the raw material component. Specifically, the above-mentioned "hydroxyl-containing hydrazine compound residue" in the above-mentioned feature (a) of the thermal hardener of the present invention refers to a residue derived from a hydroxyl-containing hydrazine compound, and in the hydroxyl-containing hydrazine compound The structure of the part other than the hydrazine group, that is, the structure of the part that does not react with the isocyanate group and remains. In addition, the above-mentioned "isocyanate compound residue" in the above-mentioned feature (b) of the thermal hardener of the present invention refers to a structure derived from an isocyanate compound and the part other than the isocyanate group in the isocyanate compound, that is, it does not have any structure with the isocyanate group. The structure of the remaining part after the reaction of the hydrazine group. Furthermore, since the thermal hardener of the present invention has the above characteristic (d), that is, it does not have an isocyanate group, all the isocyanate groups of the isocyanate compound are used to form the structure represented by the above formula (1). .

較佳為，成為上述特徵（a）中之含羥基之醯肼化合物殘基之來源的含羥基之醯肼化合物係於1分子中具有羥基及2個以上之醯肼基之化合物，且成為上述特徵（b）中之異氰酸酯化合物殘基之來源之異氰酸酯化合物係於1分子中具有2個以上之異氰酸基的化合物。Preferably, the hydroxyl-containing hydrazine compound that is the source of the hydroxyl-containing hydrazine compound residue in the above characteristic (a) is a compound having a hydroxyl group and two or more hydrazine groups in one molecule, and becomes the above-mentioned The isocyanate compound from which the isocyanate compound residue in characteristic (b) is derived is a compound having two or more isocyanate groups in one molecule.

上述特徵（c）中之由上述式（1）所表示之結構源自於上述含羥基之醯肼化合物之醯肼基與上述異氰酸酯化合物之異氰酸基。本發明之熱硬化劑藉由具有由上述式（1）所表示之結構，而所獲得之液晶顯示元件用密封劑為兼具液晶污染性與硬化性之效果優異者。The structure represented by the above formula (1) in the above feature (c) is derived from the hydrazine group of the above hydroxyl-containing hydrazine compound and the isocyanate group of the above isocyanate compound. By having the structure represented by the above-mentioned formula (1), the thermal curing agent of the present invention can obtain a sealing compound for a liquid crystal display element that is excellent in both liquid crystal contamination properties and curing properties.

作為上述含羥基之醯肼化合物，具體而言，例如可列舉：蘋果二醯肼、酒石二醯肼、2-羥基丙烷-1,2,3-三卡肼等。其中，較佳為蘋果二醯肼、酒石二醯肼。Specific examples of the hydroxyl-containing hydrazine compound include apple dihydrazine, tartar dihydrazine, 2-hydroxypropane-1,2,3-tricarbazine, and the like. Among them, apple dihydrazine and tartar dihydrazine are preferred.

作為上述異氰酸酯化合物，具體而言，例如可列舉：六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二苯基甲烷二異氰酸酯、甲苯二異氰酸酯等。其中，較佳為六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯。Specific examples of the isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and the like. Among them, hexamethylene diisocyanate and isophorone diisocyanate are preferred.

本發明之熱硬化劑之分子量之較佳的下限為300。藉由本發明之熱硬化劑之分子量為300以上，而對硬化性樹脂具有充分之溶解性，所獲得之液晶顯示元件用密封劑因低液晶污染性而優異。本發明之熱硬化劑之分子量之更佳的下限為350。 又，就所獲得之液晶顯示元件用密封劑之作業性等觀點而言，本發明之熱硬化劑之分子量之較佳的上限為2000。 再者，本發明之熱硬化劑之分子量係針對特定出分子結構的化合物自結構式求出之分子量，但對於聚合度之分布較廣之化合物及改質部位不特定之化合物，存在使用重量平均分子量來表示之情況。又，於本說明書中，上述「重量平均分子量」係藉由凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定，並利用聚苯乙烯換算而求出之值。藉由GPC測定利用聚苯乙烯換算所得之重量平均分子量時所使用之管柱，例如可列舉Shodex LF-804（昭和電工公司製造）等。The preferred lower limit of the molecular weight of the thermal hardener of the present invention is 300. Since the thermosetting agent of the present invention has a molecular weight of 300 or more and has sufficient solubility in curable resin, the obtained sealing compound for liquid crystal display elements is excellent in low liquid crystal contamination. A more preferable lower limit of the molecular weight of the thermal hardener of the present invention is 350. Moreover, from the viewpoint of the workability of the obtained sealing compound for liquid crystal display elements, the preferable upper limit of the molecular weight of the thermosetting agent of the present invention is 2,000. Furthermore, the molecular weight of the thermal hardening agent of the present invention is the molecular weight calculated from the structural formula for a compound with a specific molecular structure. However, for compounds with a wide distribution of polymerization degrees and compounds with unspecified modification sites, there is a need to use a weight average Expressed by molecular weight. In addition, in this specification, the above-mentioned "weight average molecular weight" is a value calculated by measuring it by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it to polystyrene. Examples of the column used when measuring the polystyrene-converted weight average molecular weight by GPC include Shodex LF-804 (manufactured by Showa Denko Co., Ltd.).

本發明之熱硬化劑具體而言，例如可列舉由下述式（2）所表示之化合物等。Specific examples of the thermosetting agent of the present invention include compounds represented by the following formula (2).

式（2）中，R1 分別獨立為含羥基之醯肼化合物殘基，R2 為異氰酸酯化合物殘基。In the formula (2), R 1 is independently a hydrazine compound residue containing a hydroxyl group, and R 2 is an isocyanate compound residue.

作為本發明之熱硬化劑的製造方法，例如可列舉以下之方法等。 即，首先於具備溫度計及攪拌機之三口燒瓶中使上述含羥基之醯肼化合物溶解於甲苯，於60℃進行攪拌。向所獲得之溶液中滴加上述異氰酸酯化合物之甲苯溶液，之後於60℃進行攪拌使其反應6小時。於過濾所獲得之反應液而將固形物分離之後，對所獲得之固形物進行水洗並乾燥，藉此可獲得本發明之熱硬化劑。Examples of methods for producing the thermosetting agent of the present invention include the following methods. That is, first, the above-mentioned hydroxyl-containing hydrazine compound was dissolved in toluene in a three-necked flask equipped with a thermometer and a stirrer, and the mixture was stirred at 60°C. The toluene solution of the above-mentioned isocyanate compound was added dropwise to the obtained solution, and then the mixture was stirred and reacted at 60° C. for 6 hours. After filtering the obtained reaction liquid to separate the solid matter, the obtained solid matter is washed with water and dried, thereby obtaining the thermosetting agent of the present invention.

本發明之熱硬化劑之含量相對於硬化性樹脂100重量份，較佳之下限為0.1重量份，較佳之上限為20重量份。藉由本發明之熱硬化劑之含量為0.1重量份以上，所獲得之液晶顯示元件用密封劑之硬化性更優異。藉由本發明之熱硬化劑之含量為20重量份以下，所獲得之液晶顯示元件用密封劑之保存穩定性更優異。本發明之熱硬化劑之含量之更佳的下限為1重量份，更佳之上限為18重量份，進而較佳之下限為2重量份，進而較佳之上限為15重量份，進而更佳之下限為3重量份，進而更佳之上限為12重量份，尤佳之下限為4重量份，尤佳之上限為10重量份，最佳之上限為8重量份。The content of the thermal hardener of the present invention is preferably lower limit is 0.1 parts by weight and upper limit is preferably 20 parts by weight relative to 100 parts by weight of the curable resin. When the content of the thermosetting agent of the present invention is 0.1 parts by weight or more, the sealing compound for liquid crystal display elements obtained has more excellent curing properties. When the content of the thermosetting agent of the present invention is 20 parts by weight or less, the sealing compound for liquid crystal display elements obtained has better storage stability. A more preferable lower limit of the content of the thermal hardener of the present invention is 1 part by weight, a more preferable upper limit is 18 parts by weight, a further preferable lower limit is 2 parts by weight, a further preferable upper limit is 15 parts by weight, and a further preferable lower limit is 3 Parts by weight, the more preferred upper limit is 12 parts by weight, the more preferred lower limit is 4 parts by weight, the more preferred upper limit is 10 parts by weight, and the most preferred upper limit is 8 parts by weight.

本發明之液晶顯示元件用密封劑含有硬化性樹脂。 上述硬化性樹脂較佳為包含環氧化合物。 作為上述環氧化合物，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、環氧丙烯加成雙酚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、酚系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、萘酚系酚醛清漆型環氧樹脂、縮水甘油胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、縮水甘油酯化合物等。The sealing compound for liquid crystal display elements of the present invention contains curable resin. The curable resin preferably contains an epoxy compound. Examples of the epoxy compound include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, and 2,2-diallyl. Bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, epoxy propylene addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenolic novolak type epoxy resin, o-cresol novolak type epoxy resin, dicyclopentadien Phenolic novolak type epoxy resin, biphenyl novolac type epoxy resin, naphthol type novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin Resins, glycidyl ester compounds, etc.

作為上述雙酚A型環氧樹脂中之市售者，例如可列舉：jER828EL、jER1004（均為三菱化學公司製造）、EPICLON850（DIC公司製造）等。 作為上述雙酚F型環氧樹脂中之市售者，例如可列舉：jER806、jER4004（均為三菱化學公司製造）、EPICLON EXA-830CRP（DIC公司製造）等。 作為上述雙酚E型環氧樹脂中之市售者，例如可列舉Epomic R710（三井化學公司製造）等。 作為上述雙酚S型環氧樹脂中之市售者，例如可列舉EPICLON EXA-1514（DIC公司製造）等。 作為上述2,2'-二烯丙基雙酚A型環氧樹脂中之市售者，例如可列舉RE-810NM（日本化藥公司製造）等。 作為上述氫化雙酚型環氧樹脂中之市售者，例如可列舉EPICLON EXA-7015（DIC公司製造）等。 作為上述環氧丙烷加成雙酚A型環氧樹脂中之市售者，例如可列舉EP-4000S（ADEKA公司製造）等。 作為上述間苯二酚型環氧樹脂中之市售者，例如可列舉EX-201（Nagase ChemteX公司製造）等。 作為上述聯苯型環氧樹脂中之市售者，例如可列舉jER YX-4000H（三菱化學公司製造）等。 作為上述硫醚型環氧樹脂中之市售者，例如可列舉YSLV-50TE（日鐵化學&材料公司製造）等。 作為上述二苯醚型環氧樹脂中之市售者，例如可列舉YSLV-80DE（日鐵化學&材料公司製造）等。 作為上述二環戊二烯型環氧樹脂中之市售者，例如可列舉EP-4088S（ADEKA公司製造）等。 作為上述萘型環氧樹脂中之市售者，例如可列舉：EPICLON HP-4032、EPICLON EXA-4700（均為DIC公司製造）等。 作為上述酚系酚醛清漆型環氧樹脂中之市售者，例如可列舉EPICLON N-770（DIC公司製造）等。 作為上述鄰甲酚酚醛清漆型環氧樹脂中之市售者，例如可列舉EPICLON N-670-EXP-S（DIC公司製造）等。 作為上述二環戊二烯酚醛清漆型環氧樹脂中之市售者，例如可列舉EPICLON HP-7200（DIC公司製造）等。 作為上述聯苯酚醛清漆型環氧樹脂中之市售者，例如可列舉NC-3000P（日本化藥公司製造）等。 作為上述萘酚系酚醛清漆型環氧樹脂中之市售者，例如可列舉ESN-165S（日鐵化學&材料公司製造）等。 作為上述縮水甘油胺型環氧樹脂中之市售者，例如可列舉：jER630（三菱化學公司製造）、EPICLON430（DIC公司製造）、TETRAD-X（三菱氣體化學公司製造）等。 作為上述烷基多元醇型環氧樹脂中之市售者，例如可列舉：ZX-1542（日鐵化學&材料公司製造）、EPICLON726（DIC公司製造）、EPOLIGHT80MFA（共榮社化學公司製造）、DENACOL EX-611（Nagase ChemteX公司製造）等。 作為上述橡膠改質型環氧樹脂中之市售者，例如可列舉：YR-450、YR-207（均為日鐵化學&材料公司製造）、Epolead PB（Daicel公司製造）等。 作為上述縮水甘油酯化合物中之市售者，例如可列舉DENACOL EX-147（Nagase ChemteX公司製造）等。 作為上述環氧化合物中的其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR（均為日鐵化學&材料公司製造）、XAC4151（旭化成公司製造）、jER1031、jER1032（均為三菱化學公司製造）、EXA-7120（DIC公司製造）、TEPIC（日產化學公司製造）等。Examples of commercially available bisphenol A-type epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like. Examples of commercially available bisphenol F-type epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), and the like. Examples of commercially available bisphenol E-type epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals Co., Ltd.). Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation). Examples of commercially available 2,2'-diallylbisphenol A-type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available hydrogenated bisphenol-type epoxy resins include EPICLON EXA-7015 (manufactured by DIC Corporation). Examples of commercially available propylene oxide-added bisphenol A-type epoxy resins include EP-4000S (manufactured by ADEKA). Examples of commercially available resorcinol-type epoxy resins include EX-201 (manufactured by Nagase ChemteX Co., Ltd.). Examples of commercially available biphenyl-type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available sulfide-type epoxy resins include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available dicyclopentadiene-type epoxy resins include EP-4088S (manufactured by ADEKA). Examples of commercially available naphthalene-type epoxy resins include EPICLON HP-4032, EPICLON EXA-4700 (both manufactured by DIC Corporation), and the like. Examples of commercially available phenolic novolac-type epoxy resins include EPICLON N-770 (manufactured by DIC Corporation). Examples of commercially available o-cresol novolak type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC Corporation). Examples of commercially available dicyclopentadiene novolak-type epoxy resins include EPICLON HP-7200 (manufactured by DIC Corporation). Examples of commercially available biphenyl novolak-type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthol-based novolak-type epoxy resins include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). Examples of commercially available glycidyl amine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. Examples of commercially available alkyl polyol type epoxy resins include: ZX-1542 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), EPICLON726 (manufactured by DIC Co., Ltd.), EPOLIGHT80MFA (manufactured by Kyeisha Chemical Co., Ltd.), DENACOL EX-611 (manufactured by Nagase ChemteX Corporation), etc. Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel Chemical & Materials Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), and the like. Examples of commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase ChemteX Corporation). Examples of other commercially available epoxy compounds mentioned above include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), etc.

作為上述環氧化合物，亦適宜使用部分(甲基)丙烯酸改質環氧樹脂。 再者，於本說明書中，上述部分(甲基)丙烯酸改質環氧樹脂係指可藉由使具有2個以上之環氧基之環氧化合物之一部分環氧基與(甲基)丙烯酸發生反應而獲得之於1分子中具有環氧基及(甲基)丙烯醯基各1個以上的化合物。 再者，於本說明書中，上述「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸，上述「(甲基)丙烯醯基」係指丙烯醯基或甲基丙烯醯基。As the above-mentioned epoxy compound, it is also suitable to use a partially (meth)acrylic acid-modified epoxy resin. Furthermore, in this specification, the above-mentioned partially (meth)acrylic acid-modified epoxy resin refers to a part of the epoxy compound having two or more epoxy groups that can be modified by reacting with (meth)acrylic acid. A compound having at least one epoxy group and one (meth)acrylyl group each in one molecule is obtained by the reaction. In addition, in this specification, the above-mentioned "(meth)acrylic acid" refers to acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylyl group" refers to an acrylyl group or a methacryloyl group.

作為上述部分(甲基)丙烯酸改質環氧樹脂中之市售者，例如可列舉：UVACURE1561、KRM8287（均為Daicel·Allnex公司製造）等。Examples of commercially available partially (meth)acrylic modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by Daicel Allnex Corporation).

又，上述硬化性樹脂亦可包含(甲基)丙烯酸化合物。 作為上述(甲基)丙烯酸化合物，例如可列舉：(甲基)丙烯酸酯化合物、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺酯等。其中，較佳為環氧(甲基)丙烯酸酯。又，就反應性之觀點而言，上述(甲基)丙烯酸化合物較佳為於1分子中具有2個以上之(甲基)丙烯醯基者。 再者，於本說明書中，上述「(甲基)丙烯酸化合物」係指具有(甲基)丙烯醯基之化合物。又，上述「(甲基)丙烯酸酯」係指丙烯酸酯或甲基丙烯酸酯，上述「環氧(甲基)丙烯酸酯」表示使環氧化合物中之所有環氧基與(甲基)丙烯酸發生反應而得之化合物。Moreover, the said curable resin may contain a (meth)acrylic acid compound. Examples of the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylic acid esters, (meth)acrylic acid amine esters, and the like. Among them, epoxy (meth)acrylate is preferred. Furthermore, from the viewpoint of reactivity, the (meth)acrylic acid compound preferably has two or more (meth)acrylyl groups in one molecule. In addition, in this specification, the said "(meth)acrylic acid compound" means the compound which has a (meth)acrylyl group. In addition, the above-mentioned "(meth)acrylate" refers to acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" refers to the reaction of all epoxy groups in the epoxy compound with (meth)acrylic acid. Compounds obtained by reaction.

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)丙烯酸第三丁酯、(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)丙烯酸異癸基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻基酯、(甲基)丙烯酸硬脂基酯、(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)丙烯酸異莰基酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸苄基酯、(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、2,2,2-(甲基)丙烯酸三氟乙酯、(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、(甲基)丙烯酸亞胺基酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、2-(甲基)丙烯醯氧基乙基六氫酞酸、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基2-羥基丙酯、磷酸2-(甲基)丙烯醯氧基乙酯、(甲基)丙烯酸縮水甘油酯等。Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid propyl ester, (meth)acrylic acid n-butyl ester Ester, isobutyl (meth)acrylate, tert-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, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate Ester, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (meth)acrylate 2-ethoxyethyl acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxyethyl acrylate Polyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Ethyl carbitol (meth)acrylate, 2,2,2-(meth)trifluoroethyl acrylate, (meth)acrylate 2,2,3,3-tetrafluoropropyl, (meth)acrylate 1H,1H,5H-Octafluoropentyl acrylate, (meth)acrylic acid imino ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, 2- (Meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl 2-hydroxypropyl phthalate Ester, 2-(meth)acryloyloxyethyl phosphate, 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、2-羥基-3-(甲基)丙烯醯氧基丙基(甲基)丙烯酸酯、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, examples of the bifunctional ones among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 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 diacrylate (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide added to bisphenol A di(meth)acrylate, propylene oxide added to bisphenol A di(meth)acrylate, ethylene oxide added to bisphenol F di(meth)acrylate, dihydroxymethyldicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, 2-hydroxy- 3-(meth)acryloxypropyl(meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate base) 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。Furthermore, examples of the above-mentioned (meth)acrylate compounds having trifunctional or higher functions include: trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, ) Acrylate, propylene oxide added to trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide added to isocyanuride Acid tri(meth)acrylate, glyceryl tri(meth)acrylate, propylene oxide addition glyceryl tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, phosphate tri(meth)acrylate Acryloxyethyl ester, di-trimethylolpropane tetra(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dineopenterythritol penta(meth)acrylate, dineopenterythritol Tetraol hexa(meth)acrylate, etc.

作為上述環氧(甲基)丙烯酸酯，例如可列舉：藉由按照慣例使環氧化合物與(甲基)丙烯酸於鹼性觸媒之存在下發生反應而獲得者等。Examples of the epoxy (meth)acrylate include those obtained by conventionally reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst.

作為成為用以合成上述環氧(甲基)丙烯酸酯之原料之環氧化合物，可使用與作為本發明之液晶顯示元件用密封劑所含有之硬化性樹脂之上述環氧化合物相同者。As the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compound as the curable resin contained in the sealing compound for liquid crystal display elements of the present invention can be used.

作為上述環氧(甲基)丙烯酸酯中之市售者，例如可列舉：Daicel·Allnex公司製造之環氧(甲基)丙烯酸酯、新中村化學工業公司製造之環氧(甲基)丙烯酸酯、共榮社化學公司製造之環氧(甲基)丙烯酸酯、Nagase ChemteX公司製造之環氧(甲基)丙烯酸酯等。 作為上述Daicel·Allnex公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3708、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182等。 作為上述新中村化學工業公司製造之環氧(甲基)丙烯酸酯，例如可列舉：EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020等。 作為上述共榮社化學公司製造之環氧(甲基)丙烯酸酯，例如可列舉：環氧酯M-600A、環氧酯40EM、環氧酯70PA、環氧酯200PA、環氧酯80MFA、環氧酯3002M、環氧酯3002A、環氧酯1600A、環氧酯3000M、環氧酯3000A、環氧酯200EA、環氧酯400EA等。 作為上述Nagase ChemteX公司製造之環氧(甲基)丙烯酸酯，例如可列舉：DENACOL丙烯酸酯DA-141、DENACOL丙烯酸酯DA-314、DENACOL丙烯酸酯DA-911等。Examples of commercially available epoxy (meth)acrylates include: epoxy (meth)acrylate manufactured by Daicel Allnex Co., Ltd., and epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , epoxy (meth)acrylate manufactured by Kyeisha Chemical Company, epoxy (meth)acrylate manufactured by Nagase ChemteX Company, etc. Examples of the epoxy (meth)acrylates manufactured by Daicel Allnex include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, and EBECRYL380. 0. EBECRYL6040, EBECRYL RDX63182, etc. Examples of the epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include: EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, and the like. Examples of the epoxy (meth)acrylates manufactured by Kyoeisha Chemical Co., Ltd. include: epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester Oxyester 3002M, epoxy ester 3002A, epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, etc. Examples of the epoxy (meth)acrylate manufactured by Nagase ChemteX include DENACOL acrylate DA-141, DENACOL acrylate DA-314, DENACOL acrylate DA-911, and the like.

上述(甲基)丙烯酸胺酯例如可藉由對異氰酸酯化合物使具有羥基之(甲基)丙烯酸衍生物於觸媒量之錫系化合物存在下發生反應而獲得。The (meth)acrylic acid amine ester 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：異佛爾酮二異氰酸酯、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、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯（norbornanediisocyanate）、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、三(異氰酸基苯基)硫代磷酸酯、四甲基苯二甲基二異氰酸酯、1,6,11-十一烷三異氰酸酯等。Examples of the isocyanate compound used as a raw material for the (meth)acrylic amine ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornanediisocyanate, combined Toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl)thiophosphate, tetramethylxylene Methyl diisocyanate, 1,6,11-undecane triisocyanate, etc.

又，作為成為上述(甲基)丙烯酸胺酯之原料之異氰酸酯化合物，亦可使用藉由多元醇與過量之異氰酸酯化合物之反應而獲得之鏈增長後之異氰酸酯化合物。 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。Furthermore, as the isocyanate compound used as a raw material for the above-mentioned (meth)acrylic amine ester, a chain-extended isocyanate compound obtained by reaction of a polyol and an excess isocyanate compound can also be used. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerol, 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、環氧(甲基)丙烯酸酯等。 作為上述單(甲基)丙烯酸羥烷基酯，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。 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。 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。 作為上述環氧(甲基)丙烯酸酯，例如可列舉雙酚A型環氧丙烯酸酯等。Examples of the (meth)acrylic acid derivatives having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the above-mentioned hydroxyalkyl mono(meth)acrylate include: (2-hydroxyethylmeth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of the glycol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, and the like. Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerin, and the like. Examples of the epoxy (meth)acrylate include bisphenol A-type epoxy acrylate.

作為上述(甲基)丙烯酸胺酯中之市售者，例如可列舉：東亞合成公司製造之(甲基)丙烯酸胺酯、Daicel·Allnex公司製造之(甲基)丙烯酸胺酯、根上工業公司製造之(甲基)丙烯酸胺酯、新中村化學工業公司製造之(甲基)丙烯酸胺酯、共榮社化學公司製造之(甲基)丙烯酸胺酯等。 作為上述東亞合成公司製造之(甲基)丙烯酸胺酯，例如可列舉：M-1100、M-1200、M-1210、M-1600等。作為上述Daicel·Allnex公司製造之(甲基)丙烯酸胺酯，例如可列舉：EBECRYL210、EBECRYL220、EBECRYL230、EBECRYL270、EBECRYL1290、EBECRYL2220、EBECRYL4827、EBECRYL4842、EBECRYL4858、EBECRYL5129、EBECRYL6700、EBECRYL8402、EBECRYL8803、EBECRYL8804、EBECRYL8807、EBECRYL9260等。 作為上述根上工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：Artresin UN-330、Artresin SH-500B、Artresin UN-1200TPK、Artresin UN-1255、Artresin UN-3320HB、Artresin UN-7100、Artresin UN-9000A、Artresin UN-9000H等。 作為上述新中村化學工業公司製造之(甲基)丙烯酸胺酯，例如可列舉：U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6HA、U-6LPA、U-10H、U-15HA、U-108、U-108A、U-122A、U-122P、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4000、UA-4100、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A等。 作為上述共榮社化學公司製造之(甲基)丙烯酸胺酯，例如可列舉：AH-600、AI-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T等。Examples of commercially available (meth)acrylic acid urethanes include Toagosei Co., Ltd.'s (meth)acrylic acid urethane, Daicel Allnex's (meth)acrylic acid urethane, and Negami Kogyo Co., Ltd.'s (meth)acrylic urethane, (meth)acrylic urethane manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth)acrylic amine ester manufactured by Kyeisha Chemical Co., Ltd., etc. Examples of the (meth)acrylic acid amine ester manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, M-1600, and the like. Examples of the above-mentioned (meth)acrylic amine esters manufactured by Daicel Allnex include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBEC RYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Examples of the above-mentioned (meth)acrylic acid urethane manufactured by Negami Kogyo Co., Ltd. include: Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN-7100, Artresin UN-9000A, Artresin UN-9000H, etc. Examples of the above-mentioned (meth)acrylic acid amine ester manufactured by Shin Nakamura Chemical Industry Co., Ltd. include: U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U -10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000 , UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc. Examples of the above-mentioned (meth)acrylic amine esters manufactured by Kyoeisha Chemical Co., Ltd. include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T etc.

於除了上述環氧化合物以外，還含有上述(甲基)丙烯酸化合物作為上述硬化性樹脂之情形時，或者於含有上述部分(甲基)丙烯酸改質環氧化合物之情形時，較佳為使上述硬化性樹脂中之環氧基與(甲基)丙烯醯基之合計中之(甲基)丙烯醯基的比率成為30莫耳%以上且95莫耳%以下。藉由上述(甲基)丙烯醯基之比率為該範圍，能夠抑制液晶污染之產生，並且所獲得之液晶顯示元件用密封劑之接著性更優異。When the above-mentioned (meth)acrylic compound is contained as the above-mentioned curable resin in addition to the above-mentioned epoxy compound, or when the above-mentioned partial (meth)acrylic acid-modified epoxy compound is contained, it is preferable that the above-mentioned The ratio of the (meth)acrylyl group in the total of the epoxy group and the (meth)acrylyl group in the curable resin is 30 mol% or more and 95 mol% or less. When the ratio of the above-mentioned (meth)acrylyl groups is within this range, the occurrence of liquid crystal contamination can be suppressed, and the sealing compound for a liquid crystal display element obtained has more excellent adhesiveness.

就進一步抑制液晶污染之觀點而言，上述硬化性樹脂較佳為具有-OH基、-NH-基、-NH2 基等氫鍵性之單元者。From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has hydrogen-bonding units such as -OH groups, -NH- groups, and -NH 2 groups.

本發明之液晶顯示元件用密封劑較佳為含有自由基聚合起始劑。 作為上述自由基聚合起始劑，可列舉藉由光照射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。The sealing compound for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation, or a thermal radical polymerization initiator that generates radicals by heating.

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、苯偶姻醚（Benzoin ether）化合物、9-氧硫 化合物等。 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-2-二甲胺基-1-(4-口末啉苯基)-1-丁酮、2-(二甲胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-口末啉基)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-甲基苯硫基)-2-口末啉基丙烷-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等。 上述光自由基聚合起始劑可單獨使用，亦可組合使用2種以上。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 etc. Specific examples of the photoradical polymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-terminophenyl) -1-Butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-endolinyl)phenyl)-1-butanone Ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl -1-(4-methylphenylthio)-2-ethylpropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl 1-propanyl-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyl oxime), 2,4,6-tri Methyl diphenylphosphine oxide, etc. The above-mentioned photo radical polymerization initiator may be used alone, or two or more types may be used in combination.

作為上述熱自由基聚合起始劑，例如可列舉由偶氮化合物或有機過氧化物等所構成者。其中，就抑制液晶污染之觀點而言，較佳為由偶氮化合物所構成之起始劑（以下，亦稱為「偶氮起始劑」），更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」）。 上述熱自由基聚合起始劑可單獨使用，亦可組合使用2種以上。 再者，於本說明書中，上述「高分子偶氮化合物」係指具有偶氮基且產生能夠藉由熱使(甲基)丙烯醯基硬化之自由基之數量平均分子量為300以上的化合物。Examples of the thermal radical polymerization initiator include azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter, also referred to as an "azo initiator") is preferred, and a polymeric azo compound is more preferred. initiator (hereinafter also referred to as "polymer azo initiator"). The above-mentioned thermal radical polymerization initiator may be used alone, or two or more types may be used in combination. In addition, in this specification, the above-mentioned "polymer azo compound" refers to a compound having an azo group and a number average molecular weight of 300 or more that generates radicals capable of curing (meth)acrylyl groups by heat.

上述高分子偶氮化合物之數量平均分子量之較佳之下限為1000，較佳之上限為30萬。藉由上述高分子偶氮化合物之數量平均分子量為該範圍，能夠防止對液晶之不良影響，並且易於混合至硬化性樹脂中。上述高分子偶氮化合物之數量平均分子量之更佳之下限為5000，更佳之上限為10萬，進而較佳之下限為1萬，進而較佳之上限為9萬。 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）使用四氫呋喃作為溶劑進行測定，並利用聚苯乙烯換算而求出之值。作為藉由GPC測定利用聚苯乙烯換算所得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。The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1,000, and the preferable upper limit is 300,000. By having the number average molecular weight of the above-mentioned polymer azo compound within this range, it is possible to prevent adverse effects on liquid crystal and to be easily mixed into the curable resin. A more preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a further preferable upper limit is 90,000. In addition, in this specification, the said number average molecular weight is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is the value calculated using polystyrene conversion. Examples of a column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko Co., Ltd.).

作為上述高分子偶氮化合物，例如可列舉具有多個聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結而成之結構者。 作為具有多個聚環氧烷等單元經由上述偶氮基鍵結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。 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。 作為上述高分子偶氮起始劑中之市售者，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。又，作為並非高分子之偶氮起始劑，例如可列舉：V-65、V-501（均為富士軟片和光純藥公司製造）等。Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide or polydimethylsiloxane are bonded via an azo group. As a polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the above-mentioned azo group, those having a polyethylene oxide structure are preferred. Specific examples of the polymeric azo compound include: a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or a 4,4'-azo compound. Condensation polymers of nitrogen bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups, etc. Examples of commercially available polymeric azo initiators include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.), etc. . Examples of azo initiators that are not polymers include V-65 and V-501 (both manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.).

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

上述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，較佳之下限為0.1重量份，較佳之上限為30重量份。藉由上述自由基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抑制液晶污染，並且保存穩定性或硬化性更優異。上述自由基聚合起始劑之含量之更佳之下限為1重量份，更佳之上限為10重量份，進而較佳之上限為5重量份。The content of the radical polymerization initiator is preferably 0.1 parts by weight and 30 parts by weight relative to 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is within this range, the sealing compound for a liquid crystal display element obtained suppresses liquid crystal contamination and is more excellent in storage stability or curability. A more preferable lower limit of the content of the above-mentioned radical polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a further preferable upper limit is 5 parts by weight.

本發明之液晶顯示元件用密封劑為了黏度之提高、應力分散效果之接著性之改善、線膨脹率之改善、硬化物之耐濕性之提高等，亦可含有填充劑。The sealant for liquid crystal display elements of the present invention may also contain a filler in order to improve the viscosity, the stress dispersion effect, the adhesion, the linear expansion coefficient, and the moisture resistance of the cured product.

作為上述填充劑，可使用無機填充劑或有機填充劑。 作為上述無機填充劑，例如可列舉：氧化矽、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、皂土（bentonite）、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。 作為上述有機填充劑，例如可列舉：聚酯微粒子、聚胺酯微粒子、乙烯聚合物微粒子、丙烯酸聚合物微粒子等。 上述填充劑可單獨使用，亦可組合使用2種以上。As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, and zinc oxide. , 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. Examples of the organic filler include polyester microparticles, polyurethane microparticles, ethylene polymer microparticles, and acrylic polymer microparticles. The above-mentioned fillers may be used alone or in combination of two or more types.

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之較佳的下限為10重量份，較佳之上限為70重量份。藉由上述填充劑之含量為該範圍，而不會使塗佈性等變差，接著性之改善等效果更優異。上述填充劑之含量之更佳之下限為20重量份，更佳之上限為60重量份。The preferred lower limit of the content of the above-mentioned filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. By keeping the content of the above-mentioned filler within this range, the coating properties will not be deteriorated, and the effects such as improving the adhesion will be more excellent. 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.

本發明之液晶顯示元件用密封劑亦可含有矽烷偶合劑。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。The sealing compound for liquid crystal display elements of the present invention may also contain a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to the substrate and the like.

作為上述矽烷偶合劑，例如適當使用3-胺基丙基三甲氧基矽烷、3-巰丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-異氰酸基丙基三甲氧基矽烷等。該等提高與基板等之接著性之效果優異，能夠藉由與硬化性樹脂化學鍵結而抑制硬化性樹脂向液晶中流出。 上述矽烷偶合劑可單獨使用，亦可組合使用2種以上。As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyl are appropriately used. Trimethoxysilane, etc. These have an excellent effect of improving the adhesion with the substrate and the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. The above-mentioned silane coupling agents may be used alone, or two or more types may be used in combination.

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之較佳的下限為0.1重量份，較佳之上限為10重量份。藉由上述矽烷偶合劑之含量為該範圍，而抑制液晶污染之產生，並且提高接著性之效果更優異。上述矽烷偶合劑之含量之更佳之下限為0.3重量份，更佳之上限為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 preferred upper limit is 10 parts by weight. By setting the content of the silane coupling agent within this range, the generation of liquid crystal contamination is suppressed and the effect of improving adhesion is more excellent. 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適當用作遮光密封劑。The sealing compound for liquid crystal display elements of the present invention may also contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing compound for liquid crystal display elements of the present invention can be suitably used as a light-shielding sealing agent.

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, resin-coated carbon black, and the like. Among them, titanium black is preferred.

上述鈦黑係與對波長300 nm以上且800 nm以下之光之平均穿透率相比較，對紫外線區域附近，尤其是對波長370 nm以上且450 nm以下之光之穿透率較高之物質。即，上述鈦黑一方面藉由充分遮斷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，另一方面具有使紫外線區域附近之波長之光穿透之性質。因此，藉由使用可利用上述鈦黑之穿透率較高之波長之光開始反應者作為上述光自由基聚合起始劑，能夠進一步增大本發明之液晶顯示元件用密封劑之光硬化性。又，另一方面，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，絕緣性較高之遮光劑中，較佳亦為鈦黑。 上述鈦黑較佳為每1 μm之光學濃度（OD值）為3以上，更佳為4以上。上述鈦黑之遮光性越高則越佳，上述鈦黑之OD值之較佳之上限並不特別存在，但通常成為5以下。Compared with the average transmittance of light with wavelengths above 300 nm and below 800 nm, the above-mentioned titanium black is a substance with high transmittance near the ultraviolet region, especially for light with wavelengths above 370 nm and below 450 nm. . That is, the above-mentioned titanium black not only imparts light-shielding properties to the sealing compound for liquid crystal display elements of the present invention by fully blocking light of wavelengths in the visible light range, but also has the property of transmitting light of wavelengths near the ultraviolet range. Therefore, by using as the above-mentioned photo radical polymerization initiator one that can initiate a reaction using light of a wavelength with a high transmittance of the titanium black, the photocurability of the sealing compound for liquid crystal display elements of the present invention can be further increased. . On the other hand, the light-shielding agent contained in the sealing compound for liquid crystal display elements of the present invention is preferably a substance with high insulation properties, and among the light-shielding agents with high insulation properties, titanium black is also preferred. The above-mentioned titanium black preferably has an optical density (OD value) per 1 μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black is, the better it is. There is no particular upper limit for the OD value of the titanium black, but it is usually 5 or less.

上述鈦黑即便為不進行表面處理者，亦發揮充分之效果，但亦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經表面處理後之鈦黑。其中，就能夠進一步提高絕緣性之方面而言，較佳為經有機成分處理者。 又，使用摻合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製造之液晶顯示元件由於具有充分的遮光性，故而能夠實現無光之漏出，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。The above-mentioned titanium black can still exert a sufficient effect even if it does not undergo surface treatment. However, it can also be used with the surface treated with organic components such as coupling agents, or made of silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide. Titanium black coated with inorganic components and surface treated. Among them, those treated with organic components are preferred in terms of further improving insulation properties. In addition, the liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of the present invention mixed with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so it can achieve no light leakage, has a high 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：三菱材料公司製造之鈦黑、赤穗化成公司製造之鈦黑等。 作為上述三菱材料公司製造之鈦黑，例可列舉：12S、13M、13M-C、13R-N、14M-C等。 作為上述赤穗化成公司製造之鈦黑，例如可列舉Tilack D等。Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Chemicals Co., Ltd., and the like. Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M, 13M-C, 13R-N, 14M-C, and the like. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilack D and the like.

上述鈦黑之比表面積之較佳之下限為13 m2 /g，較佳之上限為30 m2 /g，更佳之下限為15 m2 /g，更佳之上限為25 m2 /g。 又，上述鈦黑之體積電阻之較佳之下限為0.5 Ω·cm，較佳之上限為3 Ω·cm，更佳之下限為1 Ω·cm，更佳之上限為2.5 Ω·cm。The preferred lower limit of the specific surface area of the titanium black is 13 m 2 /g, the preferred upper limit is 30 m 2 /g, the preferred lower limit is 15 m 2 /g, and the preferred upper limit is 25 m 2 /g. In addition, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 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，則並無特別限定，但較佳之下限為1 nm，較佳之上限為5000 nm。藉由上述遮光劑之一次粒徑為該範圍，而不會使所獲得之液晶顯示元件用密封劑之塗佈性等變差，能夠使遮光性更優異。上述遮光劑之一次粒徑之更佳之下限為5 nm，更佳之上限為200 nm，進而較佳之下限為10 nm，進而較佳之上限為100 nm。 再者，上述遮光劑之一次粒徑可使用NICOMP 380ZLS（PARTICLE SIZING SYSTEMS公司製造）使上述遮光劑分散於溶劑（水、有機溶劑等）進行測定。The primary particle size of the above-mentioned light-shielding agent is not particularly limited as long as it is less than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. By having the primary particle diameter of the light-shielding agent within this range, the light-shielding property can be further improved without deteriorating the coating properties of the sealing compound for liquid crystal display elements obtained. A more preferable lower limit of the primary particle size of the above-mentioned sunscreen agent is 5 nm, a more preferable upper limit is 200 nm, a further preferable lower limit is 10 nm, and a further preferable upper limit is 100 nm. In addition, the primary particle size of the above-mentioned light-shielding agent can be measured by dispersing the above-mentioned light-shielding agent in a solvent (water, organic solvent, etc.) using 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之較佳的下限為5重量份，較佳之上限為80重量份。藉由上述遮光劑之含量為該範圍，而不會使所獲得之液晶顯示元件用密封劑之接著性、硬化後之強度、及繪圖性下降較大，能夠發揮更優異之遮光性。上述遮光劑之含量之更佳之下限為10重量份，更佳之上限為70重量份，進而較佳之下限為30重量份，進而較佳之上限為60重量份。The preferred lower limit of the content of the above-mentioned light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. By setting the content of the light-shielding agent within this range, the obtained sealing compound for liquid crystal display elements can exhibit more excellent light-shielding properties without greatly reducing the adhesiveness, strength after curing, and drawing properties. 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 further preferable lower limit is 30 parts by weight, and a further 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、觸變劑、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 a liquid crystal display element of the present invention may further contain additives such as a stress reliever, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, and a polymerization inhibitor as needed.

作為本發明之液晶顯示元件用密封劑之製造方法，例如可列舉使用混合機將硬化性樹脂、熱硬化劑、及視需要而添加之自由基聚合起始劑等混合之方法等。 作為上述混合機，例如可列舉：勻相分散機、均質攪拌機、萬能攪拌機、行星式攪拌機、捏合機、三輥研磨機等。Examples of a method for producing the sealing compound for liquid crystal display elements of the present invention include a method of mixing a curable resin, a thermosetting agent, and optionally a radical polymerization initiator using a mixer. Examples of the mixer include a homogeneous disperser, a homogeneous mixer, a universal mixer, a planetary mixer, a kneader, a three-roller mill, and the like.

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，能夠製造上下導通材料。又，此種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 blending conductive fine particles into the sealing compound for liquid crystal display elements of the present invention, a vertical conductive material can be produced. In addition, such an upper and lower conductive material containing the sealant for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

作為上述導電性微粒子，例如可使用金屬球、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能夠進行導電連接，故而較佳。As the conductive fine particles, for example, metal balls or resin fine particles having a conductive metal layer formed on their surfaces can be used. Among them, those in which a conductive metal layer is formed on the surface of the resin particles are preferable because the excellent elasticity of the resin particles enables conductive connection without damaging the transparent substrate or the like.

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。 本發明之液晶顯示元件用密封劑對具有極性基之液晶分子之相容性較低，因此，於本發明之液晶顯示元件係使用包含具有極性基之液晶分子之液晶者之情形時，與習知之密封劑相比，抑制顯示不良之效果更為顯著。即，本發明之液晶顯示元件較佳為使用包含具有極性基之液晶分子之液晶而成。 作為上述液晶分子之極性基，例如可列舉：氟基、氯基、氰基等。In addition, a liquid crystal display element using the sealant for liquid crystal display elements of the present invention or the upper and lower conductive materials of the present invention is also one of the present invention. The sealant for liquid crystal display elements of the present invention has low compatibility with liquid crystal molecules having polar groups. Therefore, when the liquid crystal display element of the present invention uses liquid crystals containing liquid crystal molecules having polar groups, it is different from conventional liquid crystal molecules. Compared with other sealants, the effect of inhibiting display defects is more significant. That is, the liquid crystal display element of the present invention is preferably made of liquid crystal containing liquid crystal molecules having polar groups. Examples of the polar groups of the liquid crystal molecules include fluorine group, chlorine group, cyano group, and the like.

作為本發明之液晶顯示元件，較佳為窄邊緣設計之液晶顯示元件。具體而言，液晶顯示部之周圍之框部分之寬度較佳為2 mm以下。 又，製造本發明之液晶顯示元件時之本發明之液晶顯示元件用密封劑之塗佈寬度較佳為1 mm以下。The liquid crystal display element of the present invention is preferably a liquid crystal display element with a narrow edge design. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less. Moreover, when manufacturing the liquid crystal display element of the present invention, the coating width of the sealant for liquid crystal display elements of the present invention is preferably 1 mm or less.

本發明之液晶顯示元件用密封劑可適當用於利用液晶滴下工藝所進行之液晶顯示元件之製造。 作為利用液晶滴下工藝製造本發明之液晶顯示元件之方法，例如可列舉以下之方法等。 首先，進行藉由網版印刷、分注器塗佈等將本發明之液晶顯示元件用密封劑等於基板形成框狀之密封圖案之步驟。然後進行如下步驟：於本發明之液晶顯示元件用密封劑等為未硬化之狀態下將液晶之微小液滴滴下塗佈於密封圖案之框內整個面，立即使其他基板重疊。其後，可藉由進行將密封劑加熱使其硬化之步驟的方法而獲得液晶顯示元件。又，亦可於將密封劑加熱使其硬化之步驟之前進行對密封圖案部分照射紫外線等光使密封劑暫時硬化之步驟。 [發明之效果]The sealant for liquid crystal display elements of the present invention can be suitably used for manufacturing liquid crystal display elements using a liquid crystal dropping process. Examples of the method for manufacturing the liquid crystal display element of the present invention using the liquid crystal dropping process include the following methods. First, a step of forming a frame-shaped sealing pattern on the substrate using the sealant for liquid crystal display elements of the present invention is performed by screen printing, dispenser coating, or the like. Then, the following steps are performed: while the sealant for liquid crystal display elements of the present invention is not yet hardened, tiny droplets of liquid crystal are dropped and applied to the entire surface of the frame of the sealing pattern, and other substrates are immediately overlapped. Thereafter, a liquid crystal display element can be obtained by performing a step of heating and hardening the sealant. In addition, before the step of heating and hardening the sealant, a step of irradiating the sealing pattern portion with light such as ultraviolet light to temporarily harden the sealant may be performed. [Effects of the invention]

根據本發明，可提供一種保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生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, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements.

以下，列舉實施例更詳細地對本發明進行說明，但本發明並非僅限定於該等實施例。Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited only to these examples.

（化合物A之合成） 於具備溫度計及攪拌機之三口燒瓶中使16.2重量份之蘋果二醯肼溶解於100重量份之甲苯，於60℃進行攪拌。向所獲得之溶液中以5 mL/min之滴下速度滴下使3.4重量份之六亞甲基二異氰酸酯溶解於50重量份之甲苯而得的溶液，之後於60℃進行攪拌使其反應6小時。於過濾所獲得之反應液而將固形物分離之後，對所獲得之固形物進行水洗並乾燥，藉此獲得化合物A作為本發明之熱硬化劑。 再者，藉由MS及FT-IR，確認出所獲得之化合物A係由式（2）所表示之化合物（R1 為蘋果二醯肼殘基，R2 為六亞甲基二異氰酸酯殘基）。(Synthesis of Compound A) In a three-necked flask equipped with a thermometer and a stirrer, 16.2 parts by weight of apple dihydrazine was dissolved in 100 parts by weight of toluene, and the mixture was stirred at 60°C. A solution obtained by dissolving 3.4 parts by weight of hexamethylene diisocyanate in 50 parts by weight of toluene was dropped into the obtained solution at a dropping speed of 5 mL/min, and was then stirred and allowed to react at 60° C. for 6 hours. After filtering the obtained reaction liquid to separate the solid matter, the obtained solid matter is washed with water and dried, thereby obtaining compound A as the thermosetting agent of the present invention. Furthermore, it was confirmed by MS and FT-IR that the obtained compound A was a compound represented by formula (2) (R 1 is an apple dihydrazine residue, and R 2 is a hexamethylene diisocyanate residue) .

（化合物B之合成） 將16.2重量份之蘋果二醯肼變更為17.8重量份之酒石二醯肼，除此以外，以與上述「（化合物A之合成）」相同之方式獲得化合物B作為本發明之熱硬化劑。 再者，藉由MS及FT-IR，確認出所獲得之化合物B係由式（2）所表示之化合物（R1 為酒石二醯肼殘基，R2 為六亞甲基二異氰酸酯殘基）。(Synthesis of Compound B) Compound B was obtained in the same manner as the above "(Synthesis of Compound A)" except that 16.2 parts by weight of apple dihydrazine was changed to 17.8 parts by weight of tartar dihydrazide. Thermal hardener invented. Furthermore, by MS and FT-IR, it was confirmed that the obtained compound B was a compound represented by formula (2) (R 1 is a tartaric acid hydrazine residue, and R 2 is a hexamethylene diisocyanate residue) ).

（化合物C之合成） 將3.4重量份之六亞甲基二異氰酸酯變更為4.4重量份之異佛爾酮二異氰酸酯，除此以外，以與上述「（化合物A之合成）」相同之方式獲得化合物C作為本發明之熱硬化劑。 再者，藉由MS及FT-IR，確認出所獲得之化合物C係由式（2）所表示之化合物（R1 為蘋果二醯肼殘基，R2 為異佛爾酮二異氰酸酯殘基）。(Synthesis of Compound C) A compound was obtained in the same manner as the above "(Synthesis of Compound A)" except that 3.4 parts by weight of hexamethylene diisocyanate was changed to 4.4 parts by weight of isophorone diisocyanate. C serves as the thermal hardener of the present invention. Furthermore, by MS and FT-IR, it was confirmed that the obtained compound C was a compound represented by formula (2) (R 1 is an apple dihydrazine residue, and R 2 is an isophorone diisocyanate residue) .

（化合物D之合成） 將16.2重量份之蘋果二醯肼變更為13.2重量份之丙二酸二醯肼（malonic acid dihydrazide），除此以外，以與上述「（化合物A之合成）」相同之方式獲得具有無羥基之醯肼化合物殘基及異氰酸酯化合物殘基之化合物即化合物D。 再者，藉由MS及FT-IR，確認出所獲得之化合物D係相當於式（2）中之R1 之部分為丙二酸二醯肼殘基，相當於R2 之部分為六亞甲基二異氰酸酯殘基之化合物。(Synthesis of Compound D) Except for changing 16.2 parts by weight of apple dihydrazide to 13.2 parts by weight of malonic acid dihydrazide, the same procedure as in the above "(Synthesis of Compound A)" In this way, a compound having a hydroxyl-free hydrazine compound residue and an isocyanate compound residue, namely compound D, is obtained. Furthermore, through MS and FT-IR, it was confirmed that the part corresponding to R 1 in formula (2) of the obtained compound D was a malonate dihydrazide residue, and the part corresponding to R 2 was hexamethylene Compounds based on diisocyanate residues.

（實施例1～9、比較例1～4） 按照表1、2中所記載之摻合比使用行星式攪拌機（Thinky公司製造，「去泡攪拌太郎」）將各材料混合之後，進一步使用三輥研磨機進行混合，藉此製備實施例1～9、比較例1～4之各液晶顯示元件用密封劑。(Examples 1 to 9, Comparative Examples 1 to 4) After mixing each material according to the blending ratio described in Tables 1 and 2 using a planetary mixer ("Defoaming Mixer Taro" manufactured by Thinky Co., Ltd.), and further mixing using a three-roller mill, Examples 1 to 1 were prepared. 9. Sealing compound for each liquid crystal display element of Comparative Examples 1 to 4.

＜評價＞ 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。＜Evaluation＞ The following evaluations were performed on each sealing compound for liquid crystal display elements obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

（保存穩定性） 對實施例及比較例中所獲得之各液晶顯示元件用密封劑測定剛製造後之初始黏度、及製造後於25℃、50%RH之氣體環境保管48小時之後之黏度。（將保管後之黏度）/（初始黏度）設為增黏率，將增黏率未達1.2者設為「○」，將1.2以上且未達1.3者設為「A」，將1.3以上者設為「×」來評價保存穩定性。 再者，密封劑之黏度係使用E型黏度計（BROOK FIELD公司製造，「DV-III」），於25℃在旋轉速度1.0 rpm之條件進行測定。(storage stability) The initial viscosity of each liquid crystal display element sealant obtained in the Examples and Comparative Examples was measured immediately after production and the viscosity after storage in an air environment of 25° C. and 50% RH for 48 hours after production. (Viscosity after storage)/(initial viscosity) was set as the thickening rate. The thickening rate less than 1.2 was marked as "○". The thickening rate was set as "A" when it was 1.2 or more but less than 1.3. The thickening rate was set as "A" or more than 1.3. Set "×" to evaluate storage stability. Furthermore, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C and a rotation speed of 1.0 rpm.

（硬化性） 將實施例及比較例中所獲得之各液晶顯示元件用密封劑點噴於2片透明基板之一片，並使另一片透明基板重疊，之後使用金屬鹵素燈照射100 mW/cm2 之紫外線30秒。其後，於120℃加熱1小時，使液晶顯示元件用密封劑熱硬化。將透明基板剝離，使用紅外分光計（Agilent Technologies公司製造，「UMA600」）對殘留於透明基板上之硬化物進行測定，按照下述式自所獲得之測定結果及預先測定出之硬化前之測定結果計算硬化率。 硬化率（%）＝100×（1－（硬化後之環氧基之波峰面積）/（硬化前之環氧基之波峰面積）） 將硬化率為90%以上者設為「○」，將70%以上且未達90%者設為「A」，將未達70%者設為「×」來評價硬化性。(Cureability) The sealant for each liquid crystal display element obtained in the Examples and Comparative Examples was sprayed onto one of the two transparent substrates, and the other transparent substrate was overlapped, and then irradiated with a metal halogen lamp at 100 mW/cm 2 UV rays for 30 seconds. Thereafter, it was heated at 120° C. for 1 hour to thermally harden the liquid crystal display element sealing compound. The transparent substrate is peeled off, and the cured material remaining on the transparent substrate is measured using an infrared spectrometer (manufactured by Agilent Technologies, "UMA600"). From the measurement results obtained and the previously measured measurement before curing, the following formula is used: The hardening rate is calculated as a result. Hardening rate (%) = 100 × (1 - (peak area of epoxy group after hardening) / (peak area of epoxy group before hardening)) If the hardening rate is more than 90%, it is regarded as "○", and The hardenability was evaluated by setting the value of 70% or more and less than 90% as "A" and the value of less than 70% as "×".

（液晶顯示元件之顯示性能） 利用分注器將實施例及比較例中所獲得之各液晶顯示元件用密封劑以描繪正方形之框之方式塗佈於2片摩擦完畢之配向膜及透明帶電極之基板的一片而形成密封圖案。將液晶顯示元件用密封劑點噴於所形成之密封圖案之內側。 繼而，將包含具有氰基作為極性基之液晶分子之液晶（東京化成工業公司製造，「4-戊基-4-二苯基碳腈」）之微小液滴滴下塗佈於附透明電極之基板之密封劑的框內整個面，並於真空中使另一基板重疊。於解除真空之後，使用金屬鹵素燈對外框密封部分照射100 mW/cm2 之紫外線30秒。此時，對點噴後之液晶顯示元件用密封劑以不受到紫外線照射之方式進行遮罩。其後，於120℃進行液晶退火1小時，使液晶顯示元件用密封劑熱硬化而獲得液晶顯示元件。 針對所獲得之液晶顯示元件，於在60℃、90%RH之環境設為電壓施加狀態500小時之後，於通電狀態下目視確認點噴後之液晶顯示元件用密封劑周邊之液晶配向混亂（顯示不均）。 將不產生顯示不均之情形設為「◎」，將產生顯示不均但產生後即刻消失之情形設為「○」，將殘留與密封邊緣之距離為1 mm以下之顯示不均之情形設為「Δ」，將殘留與密封邊緣之距離超過1 mm之顯示不均之情形設為「×」來評價液晶顯示元件之顯示性能。(Display performance of liquid crystal display elements) Use a dispenser to apply the sealant for each liquid crystal display element obtained in the Examples and Comparative Examples to the two rubbed alignment films and transparent strip electrodes in a manner that draws a square frame. A sealing pattern is formed on one piece of the substrate. Dot spray the sealant for the liquid crystal display element inside the formed sealing pattern. Next, tiny droplets of liquid crystal containing liquid crystal molecules having a cyano group as a polar group ("4-pentyl-4-diphenylcarbonitrile" manufactured by Tokyo Chemical Industry Co., Ltd.) are dropwise applied to the substrate with a transparent electrode. The sealant is applied to the entire surface of the frame and overlapped with another substrate in a vacuum. After releasing the vacuum, use a metal halide lamp to irradiate the sealed part of the outer frame with ultraviolet light of 100 mW/ cm2 for 30 seconds. At this time, the liquid crystal display element after dot spraying is masked with a sealant so as not to be exposed to ultraviolet rays. Thereafter, liquid crystal annealing was performed at 120° C. for 1 hour, the sealing compound for liquid crystal display elements was thermally cured, and a liquid crystal display element was obtained. After the obtained liquid crystal display element was placed in a voltage application state in an environment of 60°C and 90% RH for 500 hours, the liquid crystal alignment disorder around the sealant for liquid crystal display element after spraying was visually confirmed in the power-on state (display uneven). Set the case where display unevenness does not occur as "◎". Set the case where display unevenness occurs but disappears immediately after it occurs as "○". Set the case where display unevenness remains 1 mm or less from the sealing edge. is "Δ", and the display unevenness that remains more than 1 mm from the sealing edge is regarded as "×" to evaluate the display performance of the liquid crystal display element.

[表1] [Table 1]

[表2] [產業上之可利用性][Table 2] [Industrial availability]

根據本發明，可提供一種保存穩定性及硬化性優異，且即便在用於薄型液晶顯示元件之情形時亦能夠抑制顯示不良之產生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, it is possible to provide a sealing compound for a liquid crystal display element which is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Furthermore, according to the present invention, it is possible to provide an upper and lower conductive material and a liquid crystal display element using the sealant for liquid crystal display elements.

無without

無without

Claims (6)

一種液晶顯示元件用密封劑，其係含有硬化性樹脂及熱硬化劑者，其特徵在於：上述熱硬化劑包含具有下述特徵(a)、(b)、(c)、及(d)之化合物(A)，(a)具有含羥基之醯肼化合物殘基；(b)具有異氰酸酯化合物殘基；(c)具有由下述式(1)所表示之結構；(d)不具有異氰酸基；
Figure 108116689-A0305-02-0029-1
 式(1)中，*為鍵結位置。 A sealing compound for liquid crystal display elements, which contains a curable resin and a thermosetting agent, characterized in that the thermosetting agent includes one having the following characteristics (a), (b), (c), and (d) Compound (A), (a) has a hydroxyl-containing hydrazine compound residue; (b) has an isocyanate compound residue; (c) has a structure represented by the following formula (1); (d) does not have isocyanate acid group;
Figure 108116689-A0305-02-0029-1
 In formula (1), * is the bonding position. 如請求項1所述之液晶顯示元件用密封劑，其中，成為上述特徵(a)中之含羥基之醯肼化合物殘基之來源的含羥基之醯肼化合物係於1分子中具有羥基及2個以上之醯肼基之化合物，且成為上述特徵(b)中之異氰酸酯化合物殘基之來源之異氰酸酯化合物係於1分子中具有2個以上之異氰酸基的化合物。 The sealing agent for a liquid crystal display element according to claim 1, wherein the hydroxyl-containing hydrazine compound that is the source of the hydroxyl-containing hydrazine compound residue in the above characteristic (a) has a hydroxyl group and 2 A compound having more than one hydrazine group, and the isocyanate compound that is the source of the isocyanate compound residue in the above characteristic (b) is a compound having two or more isocyanate groups in one molecule. 如請求項1或2所述之液晶顯示元件用密封劑，其中，相對於上述硬化性樹脂100重量份，上述化合物(A)之含量為0.1重量份以上且20重量份以下。 The sealant for liquid crystal display elements according to claim 1 or 2, wherein the content of the compound (A) is 0.1 to 20 parts by weight relative to 100 parts by weight of the curable resin. 一種上下導通材料，其含有請求項1、2或3中任一項所述之液晶顯示元件用密封劑及導電性微粒子。 A vertical conductive material containing the sealant for liquid crystal display elements according to any one of claims 1, 2, or 3, and conductive fine particles. 一種液晶顯示元件，其係使用請求項1、2或3中任一項所述之液晶顯示元件用密封劑或請求項4所述之上下導通材料而成。 A liquid crystal display element made of the sealant for liquid crystal display elements described in any one of Claim 1, 2 or 3 or the upper and lower conductive material described in Claim 4. 如請求項5所述之液晶顯示元件，其係使用包含具有極性基之液 晶分子之液晶而成。 The liquid crystal display element according to claim 5, which uses a liquid containing a polar group It is made of liquid crystal of crystal molecules.
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