TW202003623A - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

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

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TW202003623A
TW202003623A TW108116689A TW108116689A TW202003623A TW 202003623 A TW202003623 A TW 202003623A TW 108116689 A TW108116689 A TW 108116689A TW 108116689 A TW108116689 A TW 108116689A TW 202003623 A TW202003623 A TW 202003623A
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liquid crystal
crystal display
meth
compound
acrylate
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TWI813686B (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

Abstract

A purpose of the present invention is to provide a sealant for a liquid crystal display element, said sealant having superior preservation stability and curability, and being able to suppress the occurrence of display defects even when used in a thin liquid crystal display element. Another purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element that are obtained using said sealant for a liquid crystal display element. This sealant for a liquid crystal display element includes a curable resin and a thermal curing agent, wherein the thermal curing agent includes a compound (A) that has the following characteristics (a), (b), (c), and (d): (a) has a hydroxyl group-including hydrazide compound residue; (b) has an isocyanate compound residue; (c) has the structure indicated by formula (1); (d) does not have an isocyanate group. In formula (1), * indicates a bonding location.

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 materials, and liquid crystal display element

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 sealant for a liquid crystal display element that 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. In addition, the present invention relates to an upper and lower conduction material and a liquid crystal display element formed by 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 method of manufacturing a liquid crystal display element such as a liquid crystal display unit, from the viewpoints of shortening the production tact time and optimizing the amount of liquid crystal used, as disclosed in Patent Document 1 and Patent Document 2 A liquid crystal dropping method called a dropping process using a sealant. In the dropping process, first, a frame-shaped sealing pattern is formed on one of the two substrates with electrodes by drip coating. Then, the fine droplets of liquid crystal are dropped into the frame of the seal pattern in a state where the sealant is not hardened, and another substrate is overlapped in a vacuum, and then the sealant is hardened to manufacture a liquid crystal display element. At present, the dropping process has become the mainstream of the manufacturing method of 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, various mobile devices with LCD panels, such as mobile phones and portable game consoles, are becoming popular. The miniaturization of the devices is the most demanding issue. As a method of miniaturizing the device, a narrow edge of the liquid crystal display portion can be cited. For example, the position of the sealing portion is arranged under the black matrix (hereinafter, also referred to as a 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 arranged directly under the black matrix, if the dripping process is performed, the light irradiated when the sealant is hardened is blocked, and the light hardly reaches the inside of the sealant. In the known sealant, hardening becomes insufficient. If the hardening of the sealant becomes insufficient in this way, there is a problem that the uncured sealant component easily dissolves into the liquid crystal to cause liquid crystal contamination.

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 harden the sealant by light, it is thought to harden the sealant by heating, and as a method for hardening the sealant by heating, blending the heat hardener into the sealant is performed. However, in the case of using a heat hardener with a high reactivity to heat to improve the hardenability of the sealant, there is a case where the storage stability of the obtained sealant is poor. In addition, in recent years, the thinning of liquid crystal display elements is progressing, but when a conventional sealant is used for a thin liquid crystal display element, there is a problem that display defects occur. Prior technical literature Patent Literature

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 Laid-Open No. 2001-133794 Patent Literature 2: International Publication No. 02/092718

[發明所欲解決之課題][Problems 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 sealant 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. In addition, an object of the present invention is to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element. [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 sealant for a liquid crystal display element, which contains a curable resin and a thermosetting agent, and the thermosetting agent includes the following features (a), (b), (c), and (d) Compound (A), (A) Residues of hydrazide compounds containing hydroxyl groups; (B) Has residues of isocyanate compounds; (C) has a structure represented by the following formula (1); (D) Without isocyanate group; That is, the present invention is a sealant for a liquid crystal display element, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains an hydrazide compound residue having a hydroxyl group, an isocyanate compound residue, and the following The compound represented by the formula (1) and having no isocyanate group.

Figure 02_image003
Figure 02_image003

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 devices, liquid crystal molecules containing polar groups such as fluorine groups, chlorine groups, and cyano groups are often used as liquid crystals. The inventors considered that the reason for the display failure when the conventional sealant is used in a thin liquid crystal display device is that the compatibility of the liquid crystal containing polar liquid crystal molecules with the sealant (especially with The compatibility of the thermosetting agent contained in the sealant is relatively high, leading to liquid crystal contamination. Therefore, the inventors conducted intensive studies and found that by using a thermosetting agent having a specific structure, excellent storage stability and curability are obtained, and display defects can be suppressed even when used in a thin liquid crystal display element The resulting sealant for liquid crystal display devices completes the present invention. Furthermore, the sealant for liquid crystal display elements of the present invention is less compatible with conventional liquid crystals that do not contain liquid crystal molecules having 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 this invention contains a thermosetting agent. The thermosetting agent includes the compound (A) having the above-mentioned characteristics (a), (b), (c), and (d) (hereinafter, also referred to as "thermosetting agent of the present invention"). By containing the thermosetting agent of the present invention, the sealing agent for a liquid crystal display element of the present invention is excellent in storage stability and curability, and can suppress the occurrence of display defects even when it is used in a thin liquid crystal display element. 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, in the above feature (a) of the thermosetting agent of the present invention, the "hydroxyl-containing hydrazide compound residue" refers to a hydroxyhydrazine-containing hydrazide compound, and The structure of the part other than the hydrazide group, that is, the structure of the part that does not react with the isocyanate group and remains. In addition, the "isocyanate compound residue" in the above feature (b) of the thermosetting agent of the present invention refers to a structure derived from an isocyanate compound, and a portion other than the isocyanate group in the isocyanate compound, that is, it does not interact with the compound The structure of the remaining part of the reaction of the hydrazine group. Furthermore, since the thermosetting agent of the present invention has the above characteristics (d), that is, it has no 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 hydrazide compound that becomes the source of the hydroxyl-containing hydrazide compound residue in the above feature (a) is a compound having a hydroxyl group and two or more hydrazide groups in one molecule, and becomes the above The isocyanate compound derived from the isocyanate compound residue in feature (b) 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 hydrazide group of the hydroxyhydrazine-containing hydrazine compound and the isocyanate group of the above-mentioned isocyanate compound. The thermosetting agent of the present invention has a structure represented by the above formula (1), and the obtained sealant for liquid crystal display elements is excellent in both the liquid crystal contamination property and the curability.

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 above-mentioned hydroxyl-containing hydrazide compound include apple dihydrazide, tartar dihydrazide, 2-hydroxypropane-1,2,3-tricarbazide, and the like. Among them, apple dihydrazide and tartar dihydrazide 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, and toluene diisocyanate. 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 preferable lower limit of the molecular weight of the thermosetting agent of the present invention is 300. Since the molecular weight of the thermosetting agent of the present invention is 300 or more, and has sufficient solubility in the curable resin, the obtained sealing compound for liquid crystal display elements is excellent due to low liquid crystal contamination. The lower limit of the molecular weight of the thermal hardener of the present invention is more preferably 350. In addition, from the viewpoint of the workability of the obtained sealing compound for liquid crystal display elements, the preferred upper limit of the molecular weight of the thermosetting agent of the present invention is 2000. In addition, the molecular weight of the thermosetting agent of the present invention is the molecular weight determined from the structural formula for a compound with a specific molecular structure, but for compounds with a wide distribution of polymerization degree and compounds with unspecified modification sites, there is a weight average Molecular weight. In the present specification, the "weight average molecular weight" is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is calculated in terms of polystyrene. Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC are Shodex LF-804 (manufactured by Showa Denko).

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).

Figure 02_image005
Figure 02_image005

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 formula (2), R 1 is independently a hydroxyl group-containing hydrazide compound residue, 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 the method for producing the thermosetting agent of the present invention include the following methods. That is, first, the hydroxyl-containing hydrazine compound was dissolved in toluene in a three-necked flask equipped with a thermometer and a stirrer, and stirred at 60°C. To the obtained solution, a toluene solution of the above isocyanate compound was added dropwise, followed by stirring at 60°C to react for 6 hours. After filtering the obtained reaction liquid to separate the solid matter, the obtained solid matter is washed with water and dried, whereby the thermal hardener of the present invention can be obtained.

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 thermosetting agent of the present invention is preferably 100 parts by weight of the curable resin, and the lower limit is preferably 0.1 parts by weight, and the upper limit is preferably 20 parts by weight. When the content of the thermosetting agent of the present invention is 0.1 part by weight or more, the obtained sealing compound for liquid crystal display elements has more excellent curability. When the content of the thermosetting agent of the present invention is 20 parts by weight or less, the obtained sealant for liquid crystal display elements is more excellent in storage stability. The more preferable lower limit of the content of the thermosetting agent of the present invention is 1 part by weight, the more preferred upper limit is 18 parts by weight, the further preferred lower limit is 2 parts by weight, the further preferred upper limit is 15 parts by weight, and the more preferred lower limit is 3 More preferably, the upper limit is 12 parts by weight, the lower limit is 4 parts by weight, the upper limit is 10 parts by weight, and the 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 this invention contains curable resin. The curable resin preferably contains an epoxy compound. Examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and 2,2,-diallyl. Bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, epoxy propylene addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide ring Oxygen resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, dicyclopentadiene Novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol 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 epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), and EPICLON850 (manufactured by DIC Corporation). Examples of commercially available bisphenol F-type epoxy resins include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), and the like. Examples of the commercially available bisphenol E-type epoxy resin include Epomic R710 (manufactured by Mitsui Chemicals). Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC). As a commercial item among the said 2,2'- diallyl bisphenol A type epoxy resin, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example. Examples of the commercially available hydrogenated bisphenol-type epoxy resin include EPICLON EXA-7015 (manufactured by DIC). Examples of the commercially available propylene oxide-added bisphenol A epoxy resin include EP-4000S (manufactured by ADEKA). Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX). Examples of the commercially available among the biphenyl epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like. Examples of commercially available thioether-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 the commercially available dicyclopentadiene-type epoxy resins include EP-4088S (made by ADEKA). Examples of the commercially available naphthalene-type epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (all manufactured by DIC Corporation). Examples of the commercially available phenolic novolac-type epoxy resins include EPICLON N-770 (manufactured by DIC Corporation) and the like. As a commercial item among the said o-cresol novolak-type epoxy resins, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example. Examples of the commercially available dicyclopentadiene novolac-type epoxy resins include EPICLON HP-7200 (manufactured by DIC Corporation) and the like. Examples of the commercially available ones of the biphenol novolak-type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like. As a marketer among the above naphthol novolak-type epoxy resins, for example, ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and the like can be cited. Examples of commercially available glycidylamine-type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation). Examples of the commercially available among the above alkyl polyol-type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Materials Co., Ltd.), EPICLON726 (manufactured by DIC), EPOLIGHT80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL EX-611 (made by Nagase ChemteX), etc. Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), Epolead PB (manufactured by Daicel Corporation), and the like. Examples of the commercially available glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase ChemteX) and the like. As other commercially available products among the above-mentioned epoxy compounds, for example, 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 made by Mitsubishi Chemical Corporation), EXA-7120 (made by DIC Corporation), TEPIC (made 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, a partially (meth)acrylic modified epoxy resin is also suitably used. Furthermore, in the present specification, the above-mentioned partially (meth)acrylic modified epoxy resin means that it is possible to cause one part of the epoxy group and (meth)acrylic acid of an epoxy compound having two or more epoxy groups The compound obtained by the reaction has one or more epoxy groups and (meth)acryloyl groups in one molecule. In addition, in this specification, the said "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the said "(meth)acryloyl group" means an acryloyl group or 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 the commercially available among the above-mentioned partially (meth)acrylic modified epoxy resins include UVACURE1561 and KRM8287 (all manufactured by Daicel·Allnex).

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 compound. Examples of the (meth)acrylic compound include (meth)acrylate compounds, epoxy (meth)acrylates, and amine (meth)acrylates. Among them, epoxy (meth)acrylate is preferred. In addition, from the viewpoint of reactivity, the (meth)acrylic compound preferably has two or more (meth)acryl acetyl groups in one molecule. In addition, in this specification, the "(meth)acrylic compound" means a compound having a (meth)acryloyl group. In addition, the above "(meth)acrylate" means acrylate or methacrylate, and the above "epoxy (meth)acrylate" means that all epoxy groups in the epoxy compound and (meth)acrylic acid are generated The resulting compound.

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 in the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. 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, (methyl) 2-ethoxyethyl acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxy Based polyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Ethyl carbitol (meth)acrylate, trifluoroethyl 2,2,2-(meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, (meth) 1H, 1H, 5H-octafluoropentyl acrylate, imido (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2- (Meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, phthalic acid 2-(meth)acryloyloxyethyl 2-hydroxypropyl Ester, 2-(meth)acryloxyethyl 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。In addition, examples of the two functions in the (meth)acrylate compound 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 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 glycol Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, 2-hydroxy- 3-(meth)acryl oxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Group) 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。In addition, examples of the trifunctional or higher among the (meth)acrylate compounds include trimethylolpropane tri(meth)acrylate and ethylene oxide addition trimethylolpropane tri(methyl ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate Acid tri (meth) acrylate, glycerol tri (meth) acrylate, propylene oxide addition glycerol tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, phosphate tri (meth) Acryloyloxyethyl, di-trimethylolpropane tetra(meth)acrylate, neopentyl tetraol (meth)acrylate, dipentaerythritol penta(meth)acrylate, dineopentyl 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)acrylates include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of an alkaline catalyst in accordance with conventional practice.

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 resin as the curable resin contained in the sealant for liquid crystal display devices 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 the commercially available epoxy (meth)acrylates include epoxy (meth)acrylates manufactured by Daicel Allnex Corporation and epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. , Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Company, epoxy (meth)acrylate manufactured by Nagase ChemteX, etc. Examples of the epoxy (meth) acrylates manufactured by Daicel Allnex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL60800EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYL3800, EBECRYLL3800, EBECRYLL3800, EBECRYLL3800, EBECRYL3800, EBECRYLL3800, EBECRYL3800 Examples of the epoxy (meth)acrylates manufactured by Shin Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020. Examples of the epoxy (meth)acrylates manufactured by the Kyoeisha Chemical Company include: epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, ring 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 amine (meth)acrylate can be obtained, for example, by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalyst-based tin 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 that becomes the raw material of the amine (meth)acrylate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, Trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornanediisocyanate, biphenyl Toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylbenzene di 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。In addition, as the isocyanate compound that becomes the raw material of the amine (meth)acrylate, a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess of isocyanate compound can also be used. Examples of the above-mentioned polyols include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

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 hydroxyl groups include hydroxyalkyl mono(meth)acrylates, mono(meth)acrylates of glycols, and mono(meth)acrylic acid of triols. Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate and the like. Examples of the above-mentioned glycols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol. Examples of the triols include trimethylolethane, trimethylolpropane, and glycerin. Examples of the epoxy (meth)acrylate include bisphenol A 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 the commercially available among the above-mentioned (meth)acrylate amine esters include: (meth)acrylic acid amine ester manufactured by Toya Synthetic Corporation, Daicel Allnex (meth)acrylic acid amine ester, manufactured by Negami Industry Co., Ltd. Amine (meth)acrylate, amine (meth)acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd., amine (meth)acrylate manufactured by Kyoeisha Chemical Company, etc. Examples of the amine (meth)acrylate manufactured by the above-mentioned East Asia Synthesizer include M-1100, M-1200, M-1210, and M-1600. Examples of the amine (meth)acrylates manufactured by Daicel Allnex include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL8401, EBECRYL8401, EBECRYL6880, EBECRYL6700, EBECRYL67003 EBECRYL9260 and so on. Examples of the amine (meth)acrylates produced by the above-mentioned Kinsung Industries 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 amine (meth)acrylates 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 amine (meth)acrylate manufactured by the Kyoeisha Chemical Company 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。In the case where the above (meth)acrylic compound is included as the curable resin in addition to the above epoxy compound, or in the case where the above (meth)acrylic modified epoxy compound is included, it is preferable to make the above The ratio of the (meth)acryloyl group in the total of the epoxy group in the curable resin and the (meth)acryloyl group becomes 30 mol% or more and 95 mol% or less. When the ratio of the (meth)acryl acetyl group is within this range, the generation of liquid crystal contamination can be suppressed, and the obtained sealant for liquid crystal display elements is more excellent in 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 is preferably a unit having hydrogen bonding properties such as —OH group, —NH— group, and —NH 2 group.

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 agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator. Examples of the radical polymerization initiator include a photoradical 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

Figure 108116689-A0304-12-01
Figure 108116689-A0304-12-02
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 photo-radical polymerization initiator include benzophenone compounds, acetophenone compounds, acetylphosphine oxide compounds, titanocene compounds, oxime ester compounds, and benzoin ether compounds. 9-oxygen sulfur
Figure 108116689-A0304-12-01
Figure 108116689-A0304-12-02
Compounds etc. Specific examples of the above-mentioned photo-radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1-(4-pteroline phenyl) -1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-ortholinyl)phenyl)-1-butan Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-methyl -1-(4-methylphenylthio)-2-portalolinylpropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl 1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzyl oxime), 2,4,6-tri Methyl benzoyl diphenyl phosphine oxide and so on. The above-mentioned photo radical polymerization initiator may be used alone, or two or more kinds 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 above-mentioned 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 is preferred (hereinafter, also referred to as "azo initiator"), and more preferably composed of a polymer azo compound Initiator (hereinafter, also referred to as "polymer azo initiator"). The above-mentioned thermal radical polymerization initiator may be used alone or in combination of two or more. In addition, in this specification, the above-mentioned "polymer azo compound" refers to a compound having an azo group and generating a radical capable of hardening a (meth)acryloyl group by heat with 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 polymer azo compound is 1,000, and the preferable upper limit is 300,000. With the number average molecular weight of the above-mentioned polymer azo compound being in this range, it is possible to prevent adverse effects on the liquid crystal, and it is easy to mix into the 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. In addition, in this specification, the said number average molecular weight is measured by the gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and it is the value calculated by polystyrene conversion. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).

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. The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide is bonded via the azo group is preferably a polyethylene oxide structure. Specific examples of the polymer azo compound include, for example, a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'-a Polycondensates of bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine groups. Examples of the commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fuji Film and Koko Pure Chemicals), etc. . In addition, examples of azo initiators that are not polymers include V-65 and V-501 (all manufactured by Fuji Film and Koko Pure Chemical Industries).

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 peroxides include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

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 relative to 100 parts by weight of the curable resin is preferably a lower limit of 0.1 part by weight, and a preferred upper limit of 30 parts by weight. When the content of the radical polymerization initiator is within this range, the obtained sealant for a liquid crystal display element suppresses liquid crystal contamination, and is more excellent in storage stability or curability. The more preferable lower limit of the content of the radical polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the more 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 sealing compound for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesion of the stress dispersion effect, improving the linear expansion rate, and improving 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, alumina, 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 fine particles, polyurethane fine particles, ethylene polymer fine particles, acrylic polymer fine particles, and the like. 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 preferable lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is within this range, the coating properties and the like are not deteriorated, and the effect of improving the adhesiveness and the like is more excellent. The more preferable lower limit of the content of the filler is 20 parts by weight, and the 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 agent for liquid crystal display elements of this invention may contain a silane coupling agent. The above-mentioned silane coupling agent mainly has a role as an adhesion aid for good adhesion of the sealant and the substrate.

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, 3-isocyanatopropyl Based on trimethoxysilane and so on. These effects of improving the adhesion with the substrate and the like are excellent, and it is possible to suppress the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin. The aforementioned silane coupling agent 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 preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. With the content of the silane coupling agent in this range, the generation of liquid crystal contamination is suppressed, and the effect of improving the adhesion is more excellent. The lower limit of the content of the silane coupling agent is more preferably 0.3 part by weight, and the upper limit is more preferably 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 this invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used suitably 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, and resin-coated carbon black. 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。The above-mentioned titanium black is compared with the average transmittance of light with a wavelength of 300 nm or more and 800 nm or less, and it has a high transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 nm or more and 450 nm or less. . That is, the above-mentioned titanium black imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently blocking light in the wavelength region of the visible light, and on the other hand has the property of transmitting light at wavelengths in the vicinity of the ultraviolet region. Therefore, by using a lighter that can use the above-mentioned titanium black to transmit light at a wavelength with a higher transmittance as the above-mentioned photo-radical polymerization initiator, the photo-curability of the sealant for liquid crystal display elements of the present invention can be further increased . On the other hand, as the light-shielding agent contained in the sealant for liquid crystal display elements of the present invention, a material with high insulation is preferable, and the light-shielding agent with high insulation is preferably titanium black. The titanium black preferably has an optical density (OD value) of 3 or more per 1 μm, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The upper limit of the OD value of the titanium black does not particularly exist, 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。Even if the above-mentioned titanium black is not surface-treated, it can exert sufficient effects, but it is also possible to use a surface treated with an organic component such as a coupling agent, or silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide Titanium black after surface treatment such as those coated with inorganic components. Among them, in terms of being able to further improve the insulating property, those treated with organic components are preferred. In addition, the liquid crystal display element manufactured by using the sealing agent for liquid crystal display elements of the present invention doped with the above titanium black as a light-shielding agent has sufficient light-shielding properties, so it can realize light-free leakage, has high contrast, 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 the commercially available titanium black mentioned above include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Chemical Corporation. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium black manufactured by Ako Chemical 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 preferable lower limit of the specific surface area of the above titanium black is 13 m 2 /g, the preferable upper limit is 30 m 2 /g, the more preferable lower limit is 15 m 2 /g, and the more preferable upper limit is 25 m 2 /g. In addition, the preferable lower limit of the volume resistance of the titanium black is 0.5 Ω·cm, the preferable upper limit is 3 Ω·cm, the more preferable lower limit is 1 Ω·cm, and the more preferable 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 diameter of the light-shielding agent is not particularly limited as long as the distance between the substrates of the liquid crystal display element is not exceeded, but the lower limit is preferably 1 nm, and the upper limit is preferably 5000 nm. When the primary particle diameter of the above-mentioned light-shielding agent is in this range, the coatability of the obtained sealing compound for liquid crystal display elements is not deteriorated, and the light-shielding property can be made more excellent. The preferred lower limit of the primary particle size of the above-mentioned opacifier is 5 nm, the more preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. In addition, the primary particle diameter of the said sunscreen agent can be measured using NICOMP 380ZLS (made by PARTICLE SIZING SYSTEMS) to disperse the said sunscreen agent in a solvent (water, organic solvent, etc.).

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 preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the above-mentioned light-shielding agent is in this range, the adhesion, the strength after curing, and the drawability of the obtained sealant for liquid crystal display elements are not greatly reduced, and more excellent light-shielding properties can be exerted. The lower limit of the content of the above-mentioned opacifier is more preferably 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the 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、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 sealing agent for liquid crystal display elements of this invention may further contain additives, such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor, etc. 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。As a method of manufacturing the sealing agent for liquid crystal display elements of the present invention, for example, a method of mixing a curable resin, a thermosetting agent, and a radical polymerization initiator, etc., if necessary, using a mixer, etc. can be mentioned. Examples of the above-mentioned mixer include a homogenous disperser, a homogeneous mixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill.

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 mixing conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be manufactured. Moreover, such a top-to-bottom conducting material containing the sealing compound for liquid crystal display elements of this invention and conductive fine particles is also one of this 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, a metal ball, a conductive metal layer formed on the surface of the resin fine particles, or the like can be used. Among them, those having a conductive metal layer formed on the surface of the resin microparticles are preferred because the excellent elasticity of the resin microparticles 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。Moreover, the liquid crystal display element using the sealing compound for liquid crystal display elements of this invention or the upper-lower conduction material of this invention is also one of this 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 Compared with known sealants, the effect of suppressing display defects is more remarkable. That is, the liquid crystal display element of the present invention is preferably formed using liquid crystal containing liquid crystal molecules having polar groups. Examples of the polar groups of the liquid crystal molecules include fluorine groups, chlorine groups, and cyano groups.

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。As the liquid crystal display element of the present invention, a liquid crystal display element with a narrow edge design is preferred. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2 mm or less. In addition, when the liquid crystal display element of the present invention is manufactured, 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 sealing agent for liquid crystal display elements of this invention can be suitably used for manufacture of a liquid crystal display element by the liquid crystal dropping process. As a method of manufacturing the liquid crystal display element of the present invention by a liquid crystal dropping process, for example, the following methods can be cited. First, a step of forming a frame-like seal pattern by screen printing, dispenser coating, or the like, in which the sealant for a liquid crystal display element of the present invention is equal to a substrate. Then, the following steps are carried out: with the liquid crystal display element sealant for the present invention uncured, fine droplets of liquid crystal are dropped and applied to the entire surface of the frame of the seal pattern, and other substrates are immediately overlapped. Thereafter, a liquid crystal display element can be obtained by performing a method of heating and hardening the sealant. In addition, a step of temporarily curing the sealant may be performed by irradiating ultraviolet light or the like to the seal pattern portion before the step of heating the sealant to harden it. [Effect of 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 sealant 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. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

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 with examples, but the present invention is not limited 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 dihydrazide was dissolved in 100 parts by weight of toluene, and stirred at 60°C. To the obtained solution, a solution obtained by dissolving 3.4 parts by weight of hexamethylene diisocyanate in 50 parts by weight of toluene was dropped at a dropping rate of 5 mL/min, and then stirred at 60°C to react 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 thermal hardener 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 dihydrazide 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) Except that 16.2 parts by weight of apple dihydrazide was changed to 17.8 parts by weight of tartar dihydrazide, except that compound B was obtained in the same manner as the above "(Synthesis of Compound A)" Invented thermal hardener. 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 dihydrazide residue, 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) Except that 3.4 parts by weight of hexamethylene diisocyanate was changed to 4.4 parts by weight of isophorone diisocyanate, a compound was obtained in the same manner as the above "(Synthesis of Compound A)" 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 dihydrazide 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) 16.2 parts by weight of apple dihydrazide was changed to 13.2 parts by weight of malonic acid dihydrazide, except that it was the same as the above "(Synthesis of Compound A)" The compound D having a hydroxyl-free hydrazide compound residue and an isocyanate compound residue is obtained. Furthermore, by MS and FT-IR, it was confirmed that the obtained compound D was equivalent to R 1 in formula (2) as a malonate dihydrazide residue, and the equivalent R 2 was hexamethylene 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) The materials were mixed using a planetary mixer (Thinky Corporation, "defoaming and stirring Taro") according to the blending ratios described in Tables 1 and 2, and further mixed using a three-roll mill to prepare Examples 1 to 9. Sealants for liquid crystal display elements 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 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.

（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 sealant for each liquid crystal display element obtained in the Examples and Comparative Examples was measured for the initial viscosity immediately after production and the viscosity after storage for 48 hours in a gas environment of 25°C and 50% RH after production. (Set the viscosity after storage)/(Initial viscosity) to the viscosity increase rate, set the viscosity increase rate to less than 1.2 to "○", set the value from 1.2 or more to less than 1.3 to "A", and set the value to 1.3 or more Set to "×" to evaluate storage stability. In addition, the viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, "DV-III") at 25°C at 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。(Curability) The sealants for liquid crystal display elements obtained in Examples and Comparative Examples were sprayed onto one of two transparent substrates, and the other transparent substrate was superimposed, and then irradiated with a metal halogen lamp for 100 mW/cm 2 30 seconds of ultraviolet light. Then, it heated at 120 degreeC for 1 hour, and the sealing compound for liquid crystal display elements was thermally hardened. The transparent substrate was peeled off, and the hardened material remaining on the transparent substrate was measured using an infrared spectrometer (manufactured by Agilent Technologies, "UMA600"). The obtained measurement results and the pre-measured measurement before curing were measured according to the following formula As a result, the hardening rate is calculated. Hardening rate (%) = 100 × (1-(peak area of epoxy group after hardening) / (peak area of epoxy group before hardening)) Set a hardening rate of 90% or more to "○", set 70% or more and less than 90% are set as "A", and less than 70% are set as "×" to evaluate the hardenability.

（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 element) The sealant for each liquid crystal display element obtained in the Examples and Comparative Examples was applied to the two rubbed alignment films and transparent belt electrodes in a manner of drawing a square frame using a dispenser One of the substrates forms a sealing pattern. A sealant for liquid crystal display elements is sprayed on the inside of the formed seal pattern. Then, tiny droplets of liquid crystal containing liquid crystal molecules having a cyano group as a polar group (manufactured by Tokyo Chemical Industry Co., Ltd., "4-pentyl-4-diphenylcarbonitrile") were dropped onto the substrate with a transparent electrode The entire surface of the frame of the sealant overlaps another substrate in a vacuum. After the vacuum was released, a metal halogen lamp was used to irradiate 100 mW/cm 2 of ultraviolet light to the sealed portion of the outer frame for 30 seconds. At this time, the sealing agent for liquid crystal display elements after spot spraying is shielded so as not to be irradiated with ultraviolet rays. Thereafter, the liquid crystal was annealed at 120° C. for 1 hour, and the sealant for liquid crystal display elements was thermally cured to obtain a liquid crystal display element. For the obtained liquid crystal display element, after setting the voltage application state for 500 hours in an environment of 60°C and 90% RH, the liquid crystal alignment around the sealant for liquid crystal display element after spot spraying was visually confirmed under the energized state (display Uneven). Set the case where the display unevenness does not occur to "◎", the case where the display unevenness occurs but disappears immediately after the occurrence is set to "○", and the case where the distance between the remaining and the sealing edge is less than 1 mm is set For "Δ", the display unevenness where the distance between the residual and the sealing edge exceeds 1 mm is set to "×" to evaluate the display performance of the liquid crystal display element.

[表1]

Figure 108116689-A0304-0001
[Table 1]
Figure 108116689-A0304-0001

[表2]

Figure 108116689-A0304-0002
[產業上之可利用性][Table 2]
Figure 108116689-A0304-0002
 [Industry 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 sealant 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. In addition, according to the present invention, it is possible to provide an upper and lower conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.

無no

無no

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 03_image007
式（1）中，*為鍵結位置。A sealing agent for liquid crystal display elements, which contains a curable resin and a thermosetting agent, characterized in that the thermosetting agent includes the following features (a), (b), (c), and (d) The compound (A), (a) has a hydrazide compound residue containing a hydroxyl group; (b) has an isocyanate compound residue; (c) has a structure represented by the following formula (1); (d) does not have isocyanide Acid group
Figure 03_image007
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 compound for liquid crystal display elements as described in claim 1, wherein, The hydroxyhydrazine-containing hydrazide compound that becomes the source of the hydroxyhydrazine-containing hydrazide compound residue in the above feature (a) is a compound having a hydroxy group and two or more hydrazide groups in one molecule, and The isocyanate compound that becomes the source of the isocyanate compound residue in the above feature (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，上述硬化性樹脂100重量份中之上述化合物（A）之含量為0.1重量份以上且20重量份以下。The sealant for a liquid crystal display element according to claim 1 or 2, wherein the content of the compound (A) in 100 parts by weight of the curable resin is 0.1 parts by weight or more and 20 parts by weight or less. 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。An up-and-down conduction material containing the sealing compound 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 formed by using the sealant for liquid crystal display elements according to any one of claims 1, 2 or 3 or the top-to-bottom 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 is formed by using liquid crystal containing liquid crystal molecules having polar groups.
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