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TWI858118B - Curable resin composition, sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element - Google Patents

Curable resin composition, sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element Download PDF

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TWI858118B
TWI858118B TW109128941A TW109128941A TWI858118B TW I858118 B TWI858118 B TW I858118B TW 109128941 A TW109128941 A TW 109128941A TW 109128941 A TW109128941 A TW 109128941A TW I858118 B TWI858118 B TW I858118B
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meth
liquid crystal
acrylate
crystal display
curable resin
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TW202115222A (en
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高橋駿介
小林洋
林秀幸
竹田幸平
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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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C08G59/4035—Hydrazines; Hydrazides
    • 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
    • C08G59/50—Amines
    • 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
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • C08G59/68—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 catalysts used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • 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
    • C08G2170/00—Compositions for adhesives
    • 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
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)

Abstract

本發明之目的在於提供一種保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物。又，本發明之目的在於提供一種使用該硬化性樹脂組成物而成之液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件。 本發明係一種硬化性樹脂組成物，其係含有硬化性樹脂及熱硬化劑者，且上述熱硬化劑包含醯肼化合物，上述醯肼化合物包含在至少1個醯肼基末端具有烷基之醯肼化合物。The purpose of the present invention is to provide a curable resin composition having excellent storage stability, adhesion, and low liquid crystal contamination when used as a sealant for liquid crystal display elements. In addition, the purpose of the present invention is to provide a sealant for liquid crystal display elements, a vertical conductive material, and a liquid crystal display element formed using the curable resin composition. The present invention is a curable resin composition, which contains a curable resin and a thermosetting agent, and the thermosetting agent contains a hydrazide compound, and the hydrazide compound contains a hydrazide compound having an alkyl group at at least one hydrazide end.

Description

硬化性樹脂組成物、液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件Curable resin composition, sealant for liquid crystal display element, upper and lower conductive material, and liquid crystal display element

本發明係關於一種保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物。又，本發明係關於一種使用該硬化性樹脂組成物而成之液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件。The present invention relates to a curable resin composition having excellent storage stability, adhesion, and low liquid crystal contamination when used as a sealant for a liquid crystal display element. The present invention also relates to a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element made of the curable resin composition.

近年來，作為液晶顯示單元等液晶顯示元件之製造方法，就產距時間（tact time）縮短、使用液晶量之最佳化等觀點而言，利用如專利文獻1、專利文獻2所揭示之使用密封劑之被稱為滴下法之液晶滴下方式。 滴下法中，首先，藉由分滴而於2片附電極之基板之一片基板中形成框狀之密封圖案。繼而，於密封劑未硬化之狀態下將液晶之微滴滴加至密封圖案之框內，並於真空下重疊另一基板，其後使密封劑硬化，而製作液晶顯示元件。當前該滴下法成為液晶顯示元件之製造方法之主流。In recent years, as a manufacturing method for liquid crystal display elements such as liquid crystal display units, from the perspective of shortening the tact time and optimizing the amount of liquid crystal used, a liquid crystal dripping method called a dripping method using a sealant as disclosed in Patent Documents 1 and 2 is used. In the dripping method, first, a frame-shaped sealing pattern is formed in one of two substrates with electrodes by dripping. Then, tiny drops of liquid crystal are added to the frame of the sealing pattern in a state where the sealant is not cured, and another substrate is overlapped under vacuum, and then the sealant is cured to produce a liquid crystal display element. Currently, the dripping method has become the mainstream manufacturing method for liquid crystal display elements.

另一方面，現在行動電話、攜帶型遊戲機等各種附液晶面板之行動機器正逐漸普及，在此情況下機器之小型化係最迫切要求之課題。作為機器小型化之方法，可列舉液晶顯示部之窄邊緣化，例如將密封部之位置配置於黑矩陣下（以下亦稱為窄邊緣設計）。On the other hand, various mobile devices with LCD panels, such as mobile phones and portable game consoles, are becoming increasingly popular. Under such circumstances, miniaturization of the devices is the most pressing issue. As a method of miniaturization of the devices, narrowing the edge of the LCD display part can be cited, for example, arranging the position of the sealing part under the black matrix (hereinafter also referred to as narrow edge design).

然而，由於窄邊緣設計中將密封劑配置於黑矩陣之正下方，故而若進行滴下法，則使密封劑光硬化時照射之光被遮蔽，光不易到達密封劑之內部，從而以往之密封劑硬化不充分。若如上所述密封劑之硬化不充分，則有未硬化之密封劑成分溶出至液晶中而容易產生液晶污染之問題。尤其是，近年來伴隨著液晶之高極性化，對密封劑要求更低之液晶污染性。However, since the sealant is placed directly below the black matrix in the narrow edge design, if the drip method is used, the light irradiated during the photocuring of the sealant is shielded, and the light is not easy to reach the inside of the sealant, so the sealant is not fully cured in the past. If the sealant is not fully cured as described above, there is a problem that the uncured sealant components are dissolved into the liquid crystal and the liquid crystal is easily contaminated. In particular, in recent years, with the high polarization of liquid crystals, the sealant is required to have lower liquid crystal contamination.

於難以使密封劑光硬化之情形時，考慮藉由加熱使其硬化，作為藉由加熱使密封劑硬化之方法，於密封劑中摻合熱硬化劑。然而，於為了提昇密封劑之硬化性或接著性而使用反應性較高之熱硬化劑之情形時，有時所獲得之密封劑之保存穩定性欠佳。 先前技術文獻 專利文獻When it is difficult to cure the sealant by light, curing by heating is considered. As a method of curing the sealant by heating, a thermosetting agent is mixed into the sealant. However, when a highly reactive thermosetting agent is used to improve the curability or adhesion of the sealant, the storage stability of the obtained sealant is sometimes poor. Prior Art 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 Publication No. 2001-133794 Patent document 2: International Publication No. 02/092718

[發明所欲解決之課題][The problem that the invention wants to solve]

本發明之目的在於提供一種保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物。又，本發明之目的在於提供一種使用該硬化性樹脂組成物而成之液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件。 [解決課題之技術手段]The purpose of the present invention is to provide a curable resin composition having excellent storage stability, adhesion, and low liquid crystal contamination when used as a sealant for liquid crystal display elements. In addition, the purpose of the present invention is to provide a sealant for liquid crystal display elements, a top-bottom conductive material, and a liquid crystal display element made using the curable resin composition. [Technical means to solve the problem]

本發明係一種硬化性樹脂組成物，其係含有硬化性樹脂及熱硬化劑者，且上述熱硬化劑包含醯肼化合物，上述醯肼化合物包含在至少1個醯肼基末端具有烷基之醯肼化合物。 以下對本發明進行詳細敘述。The present invention is a curable resin composition, which contains a curable resin and a thermosetting agent, wherein the thermosetting agent contains a hydrazide compound, and the hydrazide compound contains a hydrazide compound having an alkyl group at at least one hydrazide terminal. The present invention is described in detail below.

本發明人經努力研究，結果發現，藉由使用具有特定結構之熱硬化劑，可獲得保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物，從而完成本發明。 又，本發明之硬化性樹脂組成物於用作液晶顯示元件用密封劑之情形時低液晶污染性優異。The inventors of the present invention have made great efforts to study and found that by using a thermosetting agent with a specific structure, a curable resin composition with excellent preservation stability, adhesion, and low liquid crystal contamination when used as a sealant for liquid crystal display elements can be obtained, thereby completing the present invention. In addition, the curable resin composition of the present invention has excellent low liquid crystal contamination when used as a sealant for liquid crystal display elements.

本發明之硬化性樹脂組成物含有熱硬化劑。 上述熱硬化劑包含醯肼化合物。 上述醯肼化合物包含在至少1個醯肼基末端具有烷基之醯肼化合物。以下，亦將在至少1個醯肼基末端具有烷基之醯肼化合物稱為「本發明之醯肼化合物」。藉由含有本發明之醯肼化合物，本發明之硬化性樹脂組成物成為保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性均優異者。 再者，本說明書中，「在至少1個醯肼基末端具有烷基」意指醯肼基末端之氮原子與至少1個烷基鍵結。又，本發明之醯肼化合物係具有2個以上醯肼基之多官能醯肼化合物之情形意指本發明之醯肼化合物之一部分或全部醯肼基末端之氮原子與至少1個烷基鍵結。The curable resin composition of the present invention contains a thermosetting agent. The thermosetting agent contains a hydrazine compound. The hydrazine compound contains a hydrazine compound having an alkyl group at at least one hydrazine group terminal. Hereinafter, the hydrazine compound having an alkyl group at at least one hydrazine group terminal is also referred to as the "hydrazine compound of the present invention". By containing the hydrazine compound of the present invention, the curable resin composition of the present invention is excellent in storage stability, adhesion, and low liquid crystal contamination when used as a sealant for liquid crystal display elements. In addition, in this specification, "having an alkyl group at at least one hydrazine group terminal" means that the nitrogen atom at the hydrazine group terminal is bonded to at least one alkyl group. Furthermore, when the hydrazide compound of the present invention is a multifunctional hydrazide compound having two or more hydrazide groups, it means that the nitrogen atom at the terminal of a part or all of the hydrazide groups of the hydrazide compound of the present invention is bonded to at least one alkyl group.

藉由使用本發明之醯肼化合物，所獲得之硬化性樹脂組成物可兼具保存穩定性及接著性，認為其原因如下。 即，認為藉由在至少1個醯肼基末端具有烷基，醯肼基末端之氮原子附近體積變大，保存穩定性提昇，並且氫鍵結性降低，熔點降低，藉此可提高反應性。By using the hydrazide compound of the present invention, the obtained curable resin composition can have both storage stability and adhesiveness, and the reason is considered to be as follows. That is, it is considered that by having an alkyl group at the end of at least one hydrazide group, the volume near the nitrogen atom at the end of the hydrazide group becomes larger, the storage stability is improved, and the hydrogen bonding property is reduced, the melting point is lowered, and the reactivity can be improved.

就反應性之觀點而言，本發明之醯肼化合物較佳為具有2個以上醯肼基之多官能醯肼化合物。 尤其是，作為本發明之醯肼化合物，就兼具保存穩定性及反應性之效果更優異且將所獲得之硬化性樹脂組成物用於液晶顯示元件用密封劑之情形時低液晶污染性更優異而言，較佳為下述式（1）所表示之化合物。From the viewpoint of reactivity, the hydrazide compound of the present invention is preferably a polyfunctional hydrazide compound having two or more hydrazide groups. In particular, as the hydrazide compound of the present invention, the compound represented by the following formula (1) is preferred in terms of having a better effect of combining storage stability and reactivity and having a better low liquid crystal contamination property when the obtained curable resin composition is used as a sealant for liquid crystal display elements.

式（1）中，R1 係碳數1以上且15以下之烷基，R2 係氫原子或碳數1以上且15以下之烷基，X係可含有氮原子及/或氧原子且碳數1以上且20以下之有機基。In formula (1), R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and X is an organic group having 1 to 20 carbon atoms and may contain a nitrogen atom and/or an oxygen atom.

上述式（1）中之R1 較佳為碳數1以上且15以下之烷基。 上述式（1）中之R2 為烷基之情形時，較佳為碳數1以上且15以下之烷基。In the above formula (1), R1 is preferably an alkyl group having 1 to 15 carbon atoms. In the case where R2 in the above formula (1) is an alkyl group, it is preferably an alkyl group having 1 to 15 carbon atoms.

作為製造本發明之醯肼化合物之方法，例如可列舉以下方法等。 即，首先使所有醯肼基之末端均為-NH2 基之醯肼化合物及酮化合物或甲醛溶解於甲醇等溶劑中。繼而，向所獲得之溶液中添加乙酸鈉、乙酸、及氰基硼氫化鈉，使其反應。反應結束後，藉由進行分液操作，可獲得本發明之醯肼化合物。As a method for producing the hydrazide compound of the present invention, for example, the following method can be cited. That is, first, a hydrazide compound in which all hydrazide groups have -NH2 groups at their ends and a ketone compound or formaldehyde are dissolved in a solvent such as methanol. Then, sodium acetate, acetic acid, and sodium cyanoborohydride are added to the obtained solution to react. After the reaction is completed, the hydrazide compound of the present invention can be obtained by performing a liquid separation operation.

作為上述所有醯肼基之末端均為-NH2 基之醯肼化合物，可較佳地使用有機酸醯肼。 作為上述有機酸醯肼，例如可列舉：1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲、癸二酸二醯肼、間苯二甲酸二醯肼、己二酸二醯肼、丙二酸二醯肼、2,2-二甲基戊二酸二醯肼、卡肼、丁二酸二醯肼、十二烷二酸二醯肼、酒石酸二醯肼、蘋果酸二醯肼、3-羥基戊二酸二醯肼、異三聚氰酸三(2-羧基乙基)酯之肼衍生物等。As the hydrazide compound in which all the hydrazide groups are terminated with -NH2 groups, organic acid hydrazides can be preferably used. Examples of the organic acid hydrazides include 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, 2,2-dimethylglutaric acid dihydrazide, carbohydrazide, succinic acid dihydrazide, dodecanedioic acid dihydrazide, tartaric acid dihydrazide, apple acid dihydrazide, 3-hydroxyglutaric acid dihydrazide, and hydrazine derivatives of tris(2-carboxyethyl)isocyanurate.

上述酮化合物或上述甲醛係根據於醯肼基末端進行取代之烷基之種類適當決定。例如，於醯肼基末端具有甲基之情形時，使用甲醛，於醯肼基末端具有異丙基之情形時，使用丙酮。The ketone compound or formaldehyde is appropriately determined according to the type of the alkyl group substituted at the terminal of the hydrazide group. For example, when the hydrazide group has a methyl group at the terminal, formaldehyde is used, and when the hydrazide group has an isopropyl group at the terminal, acetone is used.

相對於硬化性樹脂100重量份，本發明之醯肼化合物之含量之較佳之下限為0.5重量份，較佳之上限為20重量份。藉由本發明之醯肼化合物之含量為0.5重量份以上，所獲得之硬化性樹脂組成物之硬化性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性變得更優異。藉由本發明之醯肼化合物之含量為20重量份以下，所獲得之硬化性樹脂組成物之保存穩定性變得更優異。本發明之醯肼化合物之含量之更佳之下限為1重量份，更佳之上限為15重量份。The preferred lower limit of the content of the hydrazide compound of the present invention is 0.5 parts by weight, and the preferred upper limit is 20 parts by weight relative to 100 parts by weight of the curable resin. When the content of the hydrazide compound of the present invention is 0.5 parts by weight or more, the curability, adhesion, and low liquid crystal contamination of the obtained curable resin composition when used as a sealant for liquid crystal display elements become more excellent. When the content of the hydrazide compound of the present invention is 20 parts by weight or less, the storage stability of the obtained curable resin composition becomes more excellent. The preferred lower limit of the content of the hydrazide compound of the present invention is 1 part by weight, and the preferred upper limit is 15 parts by weight.

本發明之醯肼化合物中導入有烷基之醯肼基之比率（改質率）較佳為30莫耳%以上。藉由上述改質率為30%莫耳以上，可更加降低液晶污染性。上述改質率更佳為50莫耳%以上，進而較佳為70莫耳%以上。 再者，上述改質率可利用NMR（nuclear magnetic resonance，核磁共振儀），根據醯肼基末端之NH2 之峰值與導入烷基後之NH之峰值之比率而求得。The ratio of the hydrazide group introduced with the alkyl group (modification rate) in the hydrazide compound of the present invention is preferably 30 mol% or more. By making the modification rate 30 mol% or more, the liquid crystal contamination can be further reduced. The modification rate is more preferably 50 mol% or more, and further preferably 70 mol% or more. Furthermore, the modification rate can be obtained by using NMR (nuclear magnetic resonance) based on the ratio of the peak value of NH2 at the end of the hydrazide group to the peak value of NH after the alkyl group is introduced.

本發明之硬化性樹脂組成物亦可於不妨礙本發明之目的之範圍內，除含有本發明之醯肼化合物以外，還含有其他熱硬化劑。 作為上述其他熱硬化劑，例如可列舉上述有機酸醯肼、或咪唑衍生物、胺化合物、多酚系化合物、酸酐等。The curable resin composition of the present invention may also contain other thermosetting agents in addition to the hydrazide compound of the present invention within the scope that does not hinder the purpose of the present invention. As the above-mentioned other thermosetting agents, for example, the above-mentioned organic acid hydrazide, or imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc. can be listed.

本發明之硬化性樹脂組成物含有硬化性樹脂。 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、環氧丙烷加成雙酚A型環氧樹脂、間苯二酚型環氧樹脂、聯苯型環氧樹脂、硫醚型環氧樹脂、二苯醚型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、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、萘酚酚醛清漆型環氧樹脂、環氧丙胺型環氧樹脂、烷基多元醇型環氧樹脂、橡膠改質型環氧樹脂、環氧丙酯化合物等。The curable resin composition of the present invention contains a 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, 2,2'-diallylbisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, 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）、EPICLON850（DIC公司製）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）、EPICLON EXA-830CRP（DIC公司製）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）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）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）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）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）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（長瀨化成公司製）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）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）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）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）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）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）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）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）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）等。 作為上述萘酚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）等。 作為上述環氧丙胺型環氧樹脂中之市售者，例如可列舉：jER630（三菱化學公司製）、EPICLON430（DIC公司製）、TETRAD-X（三菱瓦斯化學公司製）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）、EPICLON726（DIC公司製）、Epolight 80MFA（共榮社化學公司製）、DENACOL EX-611（長瀨化成公司製）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）、Epolead PB（Daicel公司製）等。 作為上述環氧丙酯化合物中之市售者，例如可列舉DENACOL EX-147（長瀨化成公司製）等。 作為上述環氧化合物中之其他市售者，例如可列舉：YDC-1312、YSLV-80XY、YSLV-90CR（均為日鐵化學材料公司製）、XAC4151（旭化成公司製）、jER1031、jER1032（均為三菱化學公司製）、EXA-7120（DIC公司製）、TEPIC（日產化學公司製）等。Examples of commercially available bisphenol A epoxy resins include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON850 (manufactured by DIC Corporation). Examples of commercially available bisphenol F epoxy resins include jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation), and EPICLON EXA-830CRP (manufactured by DIC Corporation). Examples of commercially available bisphenol E epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals Co., Ltd.). Examples of commercially available bisphenol S epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation). As commercially available products of the above-mentioned 2,2'-diallylbisphenol A type epoxy resin, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) can be cited. As commercially available products of the above-mentioned hydrogenated bisphenol type epoxy resin, for example, EPICLON EXA-7015 (manufactured by DIC Corporation) can be cited. As commercially available products of the above-mentioned propylene oxide-added bisphenol A type epoxy resin, for example, EP-4000S (manufactured by ADEKA Corporation) can be cited. As commercially available products of the above-mentioned resorcinol type epoxy resin, for example, EX-201 (manufactured by Nagase Chemicals Co., Ltd.) can be cited. Examples of commercially available biphenyl epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available sulfide epoxy resins include YSLV-50TE (manufactured by Nippon Steel Chemical Materials Co., Ltd.). Examples of commercially available diphenyl ether epoxy resins include YSLV-80DE (manufactured by Nippon Steel Chemical Materials Co., Ltd.). Examples of commercially available dicyclopentadiene epoxy resins include EP-4088S (manufactured by ADEKA Corporation). Examples of commercially available naphthalene-based epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation). Examples of commercially available phenol-based novolac-type epoxy resins include EPICLON N-770 (manufactured by DIC Corporation). Examples of commercially available o-cresol novolac-type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC Corporation). Examples of commercially available dicyclopentadiene novolac-type epoxy resins include EPICLON HP-7200 (manufactured by DIC Corporation). Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthol novolac epoxy resins include ESN-165S (manufactured by Nippon Steel Chemical Materials Co., Ltd.). Examples of commercially available glycidylamine epoxy resins include jER630 (manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Examples of commercially available alkyl polyol epoxy resins include ZX-1542 (manufactured by Nippon Steel Chemicals Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and DENACOL EX-611 (manufactured by Nagase Chemicals Co., Ltd.). Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (manufactured by Nippon Steel Chemicals Co., Ltd.), and Epolead PB (manufactured by Daicel Corporation). Examples of commercially available glycidyl compounds include DENACOL EX-147 (manufactured by Nagase Chemicals Co., Ltd.). Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel Chemical Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031 and jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), and TEPIC (manufactured by Nissan Chemical Co., Ltd.).

作為上述環氧化合物，亦可較佳地使用部分(甲基)丙烯酸改質環氧樹脂。 再者，本說明書中，上述部分(甲基)丙烯酸改質環氧樹脂意指可藉由使具有2個以上環氧基之環氧化合物的一部分環氧基與(甲基)丙烯酸反應而獲得之於1分子中分別具有1個以上環氧基及(甲基)丙烯醯基之化合物。 再者，本說明書中，上述「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸，上述「(甲基)丙烯醯基」意指丙烯醯基或甲基丙烯醯基。As the above-mentioned epoxy compound, a partially (meth)acrylic acid-modified epoxy resin can also be preferably used. Furthermore, in this specification, the above-mentioned partially (meth)acrylic acid-modified epoxy resin means a compound having one or more epoxy groups and (meth)acrylic acid groups in one molecule, which can be obtained by reacting a part of the epoxy groups of an epoxy compound having two or more epoxy groups with (meth)acrylic acid. Furthermore, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic acid group" means acrylyl group or methacrylic acid 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）等。Examples of commercially available partially (meth)acrylic acid-modified epoxy resins include UVACURE 1561 and KRM 8287 (both 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（urethane(meth)acrylate）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(甲基)丙烯醯基者。 再者，本說明書中，上述「(甲基)丙烯酸化合物」意指具有(甲基)丙烯醯基之化合物。又，上述「(甲基)丙烯酸酯」意指丙烯酸酯或甲基丙烯酸酯，上述「環氧(甲基)丙烯酸酯」表示使環氧化合物中之環氧基全部與(甲基)丙烯酸反應而得之化合物。Furthermore, the curable resin may also contain a (meth)acrylic compound. Examples of the (meth)acrylic compound include (meth)acrylic ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among them, epoxy (meth)acrylates are preferred. Furthermore, from the viewpoint of reactivity, the (meth)acrylic compound is preferably one having two or more (meth)acrylic groups in one molecule. Furthermore, in this specification, the "(meth)acrylic compound" refers to a compound having a (meth)acrylic group. Furthermore, the "(meth)acrylate" refers to an acrylate or a methacrylate, and the "epoxy (meth)acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

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)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-丁氧基乙酯、(甲基)丙烯酸2-苯氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、(甲基)丙烯酸醯亞胺酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、2-(甲基)丙烯醯氧基乙基丁二酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、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)丙烯酸環氧丙酯等。Examples of the monofunctional (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, 2-ethylhex ... Lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, isoborneol (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate 2-Butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrahydrofurfuryl (meth)acrylate Fluoropropyl ester, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 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型二(甲基)丙烯酸酯、環氧丙烷加成雙酚A型二(甲基)丙烯酸酯、環氧乙烷加成雙酚F型二(甲基)丙烯酸酯、二(甲基)丙烯酸二羥甲基二環戊二烯酯、環氧乙烷改質異三聚氰酸二(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己內酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。In addition, examples of the bifunctional (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and poly(meth)acrylate. Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide added bisphenol A type di(meth)acrylate, propylene oxide added bisphenol A type di(meth)acrylate, ethylene oxide added bisphenol F type di(meth)acrylate, dihydroxymethyl dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylate 2-hydroxy-3-(meth)acryloyloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)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-functional (meth)acrylate compounds include trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added trihydroxymethylpropane tri(meth)acrylate, propylene oxide-added trihydroxymethylpropane tri(meth)acrylate, caprolactone-modified trihydroxymethylpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide-added glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, di-trihydroxymethylpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.

作為上述環氧(甲基)丙烯酸酯，例如可列舉藉由依照慣例於鹼性觸媒之存在下使環氧化合物與(甲基)丙烯酸反應而得者等。Examples of the epoxy (meth)acrylate include those obtained by conventionally reacting an epoxy compound with (meth)acrylic acid in the presence of an alkaline catalyst.

作為用於合成上述環氧(甲基)丙烯酸酯之原料即環氧化合物，可使用與上文作為本發明之硬化性樹脂組成物所含有之硬化性樹脂敘述之環氧化合物相同者。As the raw material for synthesizing the epoxy (meth)acrylate, that is, the epoxy compound, the same as the epoxy compound described above as the curable resin contained in the curable resin composition 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、長瀨化成公司製造之環氧(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：EPOXYESTER M-600A、EPOXYESTER 40EM、EPOXYESTER 70PA、EPOXYESTER 200PA、EPOXYESTER 80MFA、EPOXYESTER 3002M、EPOXYESTER 3002A、EPOXYESTER 1600A、EPOXYESTER 3000M、EPOXYESTER 3000A、EPOXYESTER 200EA、EPOXYESTER 400EA等。 作為上述長瀨化成公司製造之環氧(甲基)丙烯酸酯，例如可列舉：Denacol Acrylate DA-141、Denacol Acrylate DA-314、Denacol Acrylate DA-911等。Examples of commercially available epoxy (meth)acrylates include epoxy (meth)acrylate manufactured by DAICEL-ALLNEX, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical, and epoxy (meth)acrylate manufactured by Nagase Chemicals. Examples of epoxy (meth) acrylates manufactured by the above-mentioned DAICEL-ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX63182. Examples of epoxy (meth) acrylates manufactured by the above-mentioned Shin-Nakamura Chemical Industry include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020. Examples of epoxy (meth) acrylates manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include EPOXYESTER M-600A, EPOXYESTER 40EM, EPOXYESTER 70PA, EPOXYESTER 200PA, EPOXYESTER 80MFA, EPOXYESTER 3002M, EPOXYESTER 3002A, EPOXYESTER 1600A, EPOXYESTER 3000M, EPOXYESTER 3000A, EPOXYESTER 200EA, EPOXYESTER 400EA, etc. Examples of epoxy (meth) acrylates manufactured by the aforementioned Nagase Chemical Co., Ltd. include Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911, etc.

上述(甲基)丙烯酸胺酯例如可藉由使具有羥基之(甲基)丙烯酸衍生物與異氰酸酯化合物於觸媒量之錫系化合物存在下反應而獲得。The (meth) acrylate 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.

作為上述(甲基)丙烯酸胺酯之原料即異氰酸酯化合物，例如可列舉：異佛爾酮二異氰酸酯、2,4-二異氰酸甲苯酯、2,6-二異氰酸甲苯酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、二苯基甲烷-4,4'-二異氰酸酯（MDI）、氫化MDI、聚合MDI、1,5-萘二異氰酸酯、降莰烷二異氰酸酯、聯甲苯胺二異氰酸酯、苯二甲基二異氰酸酯（XDI）、氫化XDI、離胺酸二異氰酸酯、三苯甲烷三異氰酸酯、三(異氰酸酯苯基)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 as a raw material of the (meth)acrylic amine ester include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl)phosphorothioate, tetramethylxylylene diisocyanate, and 1,6,11-undecane triisocyanate.

又，作為上述(甲基)丙烯酸胺酯之原料即異氰酸酯化合物，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伸長之異氰酸酯化合物。 作為上述多元醇，例如可列舉：乙二醇、丙二醇、甘油、山梨糖醇、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 raw material of the above-mentioned (meth)acrylic amine ester, i.e., the isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excess of the isocyanate compound can also be used. As the above-mentioned polyol, for example, ethylene glycol, propylene glycol, glycerin, sorbitol, trihydroxymethylpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. can be listed.

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-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸4-羥丁酯等。 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 a diol, mono(meth)acrylate or di(meth)acrylate of a triol, 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, etc. Examples of the diols include: ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc. Examples of the triols include: trihydroxymethylethane, trihydroxymethylpropane, glycerol, etc. Examples of the epoxy (meth)acrylate include bisphenol A type epoxy acrylate and the like.

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 (meth)acrylic amine esters include: (meth)acrylic amine esters manufactured by Toagosei Co., Ltd., (meth)acrylic amine esters manufactured by DAICEL-ALLNEX Co., Ltd., (meth)acrylic amine esters manufactured by Negami Kogyo Co., Ltd., (meth)acrylic amine esters manufactured by Shin-Nakamura Chemical Co., Ltd., and (meth)acrylic amine esters manufactured by Kyoeisha Chemical Co., Ltd. Examples of the (meth)acrylic amine esters manufactured by Toagosei Co., Ltd. include: M-1100, M-1200, M-1210, M-1600, etc. Examples of (meth)acrylic amines manufactured by the above-mentioned DAICEL-ALLNEX company include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, etc. Examples of (meth)acrylic amines manufactured by the aforementioned Negami Industries 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 (meth)acrylic amine esters manufactured by the aforementioned 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 (meth)acrylic amine esters manufactured by the aforementioned Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T.

作為上述硬化性樹脂，除含有上述環氧化合物以外還含有上述(甲基)丙烯酸化合物之情形時，或者含有上述部分(甲基)丙烯酸改質環氧化合物之情形時，較佳為將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)丙烯醯基之比率設為30莫耳%以上且95莫耳%以下。藉由上述(甲基)丙烯醯基之比率處於該範圍內，抑制產生液晶污染，並且所獲得之硬化性樹脂組成物之接著性變得更優異。When the curable resin contains the (meth)acrylic compound in addition to the epoxy compound, or contains the partially (meth)acrylic modified epoxy compound, the ratio of the (meth)acrylic group in the total of the epoxy group and the (meth)acrylic group in the curable resin is preferably set to 30 mol% or more and 95 mol% or less. When the ratio of the (meth)acrylic group is within this range, liquid crystal contamination is suppressed and the adhesiveness of the obtained curable resin composition becomes more excellent.

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 基等氫鍵結性之單元者。From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has a hydrogen-bonding unit such as an -OH group, a -NH- group, or a -NH 2 group.

就速硬化性等觀點而言，本發明之硬化性樹脂組成物進而較佳為含有熱自由基聚合起始劑。From the viewpoint of rapid curing, etc., the curable resin composition of the present invention further preferably contains a thermal radical polymerization initiator.

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2種以上使用。 再者，本說明書中，上述「高分子偶氮化合物」意指具有偶氮基並生成可藉由加熱使(甲基)丙烯醯基硬化之自由基之數量平均分子量為300以上之化合物。As the above-mentioned thermal free radical polymerization initiator, for example, those composed of azo compounds or organic peroxides can be listed. Among them, from the viewpoint of suppressing liquid crystal contamination, the initiator composed of azo compounds (hereinafter, also referred to as "azo initiator") is preferred, and the initiator composed of high molecular azo compounds (hereinafter, also referred to as "high molecular azo initiator") is more preferred. The above-mentioned thermal free radical polymerization initiator can be used alone or in combination of two or more. Furthermore, in this specification, the above-mentioned "high molecular azo compound" means a compound having an azo group and generating a radical that can cure a (meth)acrylic group by heating, and the number average molecular weight is 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處於該範圍內，可防止對液晶產生之不良影響，並且容易與硬化性樹脂混合。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，本說明書中，上述數量平均分子量係利用凝膠滲透層析法（GPC）使用四氫呋喃作為溶劑進行測定並藉由聚苯乙烯換算而求得之值。作為利用GPC測定基於聚苯乙烯換算之數量平均分子量時之管柱，例如可列舉Shodex LF-804（昭和電工公司製）等。The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 1000, and the preferred upper limit is 300,000. By the number average molecular weight of the above-mentioned high molecular weight azo compound being within this range, adverse effects on liquid crystal can be prevented, and it is easy to mix with the curable resin. The preferred lower limit of the number average molecular weight of the above-mentioned high molecular weight azo compound is 5000, and the preferred upper limit is 100,000, and the further preferred lower limit is 10,000, and the further preferred upper limit is 90,000. Furthermore, in this specification, the above-mentioned number average molecular weight is a value obtained by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC) and converted to polystyrene. Examples of columns used when measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).

作為上述高分子偶氮化合物，例如可列舉具有複數個聚環氧烷或聚二甲基矽氧烷等單元經由偶氮基鍵結之結構者。 作為具有複數個聚環氧烷等單元經由偶氮基鍵結之結構的上述高分子偶氮化合物，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及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（均為富士膠片和光純藥公司製）等。 又，作為非高分子之偶氮起始劑，例如可列舉：V-65、V-501（均為富士膠片和光純藥公司製）等。As the above-mentioned high molecular weight azo compound, for example, there can be cited a structure having a plurality of units such as polyoxyalkylene or polydimethylsiloxane bonded via an azo group. As the above-mentioned high molecular weight azo compound having a structure having a plurality of units such as polyoxyalkylene bonded via an azo group, it is preferably a structure having polyethylene oxide. As the above-mentioned high molecular weight azo compound, specifically, for example, there can be cited: a condensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol and a condensate of 4,4'-azobis(4-cyanovaleric acid) and polydimethylsiloxane having a terminal amino group. 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 Koshun Chemical Co., Ltd.). In addition, examples of non-polymer azo initiators include V-65 and V-501 (all manufactured by Fuji Film and Koshun Chemical Co., Ltd.).

作為上述有機過氧化物，例如可列舉：酮過氧化物、過氧縮酮、氫過氧化物、二烷基過氧化物、過氧酯、二乙醯過氧化物、過氧化二碳酸酯等。Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacetyl peroxide, and peroxydicarbonate.

相對於上述硬化性樹脂100重量份，上述熱自由基聚合起始劑之含量之較佳之下限為0.2重量份，較佳之上限為10重量份。藉由上述熱自由基聚合起始劑之含量處於該範圍內，所獲得之硬化性樹脂組成物之液晶污染得到抑制，並且保存穩定性及熱硬化性變得更優異。上述熱自由基聚合起始劑之含量之更佳之下限為0.5重量份，更佳之上限為5重量份。The preferred lower limit of the content of the thermal free radical polymerization initiator is 0.2 parts by weight and the preferred upper limit is 10 parts by weight relative to 100 parts by weight of the curable resin. When the content of the thermal free radical polymerization initiator is within this range, the liquid crystal contamination of the obtained curable resin composition is suppressed, and the storage stability and thermal curability become better. The preferred lower limit of the content of the thermal free radical polymerization initiator is 0.5 parts by weight and the preferred upper limit is 5 parts by weight.

本發明之硬化性樹脂組成物亦可含有光自由基聚合起始劑。 作為上述光自由基聚合起始劑，例如可列舉：二苯甲酮化合物、苯乙酮化合物、醯基氧化膦化合物、二茂鈦化合物、肟酯化合物、安息香醚化合物、9-氧硫𠮿化合物等。 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-嗎啉苯基)-1-丁酮、2-(二甲胺基)-2-((4-甲苯基)甲基)-1-(4-(4-嗎啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲基噻吩基)-2-嗎啉丙烷-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2種以上使用。The curable resin composition of the present invention may also contain a photo-radical polymerization initiator. Examples of the photo-radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxysulfonium compounds, Compounds, etc. As the above-mentioned photoradical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinophenyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis(2,4, 6-trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-(4-methylthienyl)-2-morpholinopropane-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzoyloxime), 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. The above-mentioned photoradical polymerization initiators may be used alone or in combination of two or more.

相對於上述硬化性樹脂100重量份，上述光自由基聚合起始劑之含量之較佳之下限為0.5重量份，較佳之上限為10重量份。藉由上述光自由基聚合起始劑之含量處於該範圍內，所獲得之硬化性樹脂組成物之液晶污染得到抑制，並且保存穩定性及光硬化性變得更優異。上述光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7重量份。The preferred lower limit of the content of the photo-radical polymerization initiator is 0.5 parts by weight, and the preferred upper limit is 10 parts by weight relative to 100 parts by weight of the curable resin. When the content of the photo-radical polymerization initiator is within this range, the liquid crystal contamination of the obtained curable resin composition is suppressed, and the storage stability and photocurability become better. The preferred lower limit of the content of the photo-radical polymerization initiator is 1 part by weight, and the preferred upper limit is 7 parts by weight.

為了提昇黏度、利用應力分散效應之接著性之改善、改善線膨脹率、提昇硬化物之耐濕性等，本發明之硬化性樹脂組成物亦可含有填充劑。The curable resin composition of the present invention may also contain a filler in order to increase viscosity, improve adhesion by utilizing stress dispersion effect, improve linear expansion rate, and improve 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：二氧化矽、滑石、玻璃珠、石棉、石膏、矽藻土、膨潤石、膨潤土、蒙脫石、絹雲母、活性白土、氧化鋁、氧化鋅、氧化鐵、氧化鎂、氧化錫、氧化鈦、碳酸鈣、碳酸鎂、氫氧化鎂、氫氧化鋁、氮化鋁、氮化矽、硫酸鋇、矽酸鈣等。 作為上述有機填充劑，例如可列舉聚酯微粒子、聚胺酯（polyurethane）微粒子、乙烯系聚合物微粒子、丙烯酸系聚合物微粒子等。 上述填充劑可單獨使用，亦可組合2種以上使用。As the above-mentioned filler, an inorganic filler or an organic filler can be used. As the above-mentioned inorganic filler, for example, there can be listed: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, aluminum oxide, 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. As the above-mentioned organic filler, for example, there can be listed polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, etc. The above-mentioned fillers can be used alone or in combination of two or more.

本發明之硬化性樹脂組成物100重量份中之上述填充劑之含量之較佳之下限為10重量份，較佳之上限為70重量份。藉由上述填充劑之含量處於該範圍內，接著性之改善等效果變得更優異而不會使塗佈性等變差。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 filler in 100 parts by weight of the curable resin composition of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. When the content of the filler is within this range, the effect of improving adhesion becomes more excellent without deteriorating the coating property. The preferred lower limit of the content of the filler is 20 parts by weight, and the preferred upper limit is 60 parts by weight.

本發明之硬化性樹脂組成物亦可含有矽烷偶合劑。上述矽烷偶合劑主要具有作為接著助劑之作用，該接著劑用以將硬化性樹脂組成物與基板等良好地接著。The curable resin composition of the present invention may also contain a silane coupling agent. The silane coupling agent mainly serves as a bonding aid, and the bonding agent is used to bond the curable resin composition to a substrate or the like in a good manner.

作為上述矽烷偶合劑，例如可較佳地使用3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-異氰酸酯基丙基三甲氧基矽烷等。該等之提昇與基板等之接著性之效果優異，且可藉由與硬化性樹脂化學鍵結而抑制硬化性樹脂流出至液晶中。 上述矽烷偶合劑可單獨使用，亦可組合2種以上使用。As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-butylpropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. can be preferably used. These have excellent effects on improving adhesion with substrates, etc., and can inhibit the curable resin from flowing out into the liquid crystal by chemically bonding with the curable resin. The above-mentioned silane coupling agents can be used alone or in combination of two or more.

本發明之硬化性樹脂組成物100重量份中之上述矽烷偶合劑之含量之較佳之下限為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處於該範圍內，抑制產生液晶污染，並且提昇接著性之效果變得更優異。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 silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 parts by weight, and the preferred upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of suppressing liquid crystal contamination and improving adhesion becomes more excellent. The preferred lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the preferred upper limit is 5 parts by weight.

本發明之硬化性樹脂組成物亦可含有遮光劑。藉由含有上述遮光劑，本發明之硬化性樹脂組成物可較佳地用作遮光密封劑。The curable resin composition of the present invention may also contain a sunscreen. By containing the sunscreen, the curable resin composition of the present invention can be preferably used as a sunscreen sealant.

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

上述鈦黑係對紫外線區域附近、尤其是波長370 nm以上且450 nm以下之光之透過率高於對波長300 nm以上且800 nm以下之光之平均透過率之物質。即，上述鈦黑係具有如下性質之遮光劑：藉由充分地遮蔽可見光區域之波長之光而對本發明之硬化性樹脂組成物賦予遮光性，另一方面，使紫外線區域附近之波長之光透過。因此，使用可藉由上述鈦黑之透過率較高之波長之光使反應起始者作為上述光自由基聚合起始劑，可進一步提高本發明之硬化性樹脂組成物之光硬化性。又，另一方面，作為本發明之硬化性樹脂組成物所含有之遮光劑，較佳為絕緣性較高之物質，鈦黑作為絕緣性較高之遮光劑亦較佳。 上述鈦黑之每1 μm之光學密度（OD值）較佳為3以上，更佳為4以上。上述鈦黑之遮光性越高越佳，上述鈦黑之OD值並不特別存在較佳之上限，通常為5以下。The titanium black is a substance having a transmittance near the ultraviolet region, especially light with a wavelength of 370 nm or more and 450 nm or less, higher than the average transmittance of light with a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black is a light-shielding agent having the following properties: by sufficiently shielding light with a wavelength in the visible light region, the curable resin composition of the present invention is given a light-shielding property, while on the other hand, light with a wavelength near the ultraviolet region is transmitted. Therefore, by using a substance that can initiate a reaction with light of a wavelength with a higher transmittance of the titanium black as the photo-radical polymerization initiator, the photocurability of the curable resin composition of the present invention can be further improved. On the other hand, the sunscreen contained in the curable resin composition of the present invention is preferably a substance with high insulation, and titanium black is also preferably a sunscreen with high insulation. The optical density (OD value) of the titanium black per 1 μm is preferably 3 or more, and more preferably 4 or more. The higher the light shielding property of the titanium black, the better. The OD value of the titanium black does not have a particularly good upper limit, and is usually below 5.

上述鈦黑即便未經表面處理亦發揮充分之效果，但亦可使用經表面處理之鈦黑，例如表面由偶合劑等有機成分進行處理者、或表面由氧化矽、氧化鈦、氧化鍺、氧化鋁、氧化鋯、氧化鎂等無機成分被覆者等。其中，於可進一步提昇絕緣性之方面，較佳為由有機成分進行處理之鈦黑。 又，使用摻合了上述鈦黑作為遮光劑之本發明之硬化性樹脂組成物而製造的液晶顯示元件具有充分之遮光性，故而可實現不漏光且具有較高之對比度而具有優異之影像顯示品質之液晶顯示元件。The titanium black mentioned above can exert sufficient effects even without surface treatment, but titanium black that has been surface treated can also be used, for example, titanium black whose surface is treated with an organic component such as a coupling agent, or titanium black whose surface is coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Among them, titanium black treated with an organic component is preferred in terms of further improving the insulation. In addition, the liquid crystal display element manufactured using the curable resin composition of the present invention mixed with the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding properties, so that a liquid crystal display element with no light leakage, high contrast and excellent image display quality can be realized.

作為上述鈦黑中之市售者，例如可列舉三菱綜合材料公司製造之鈦黑、赤穗化成公司製造之鈦黑等。 作為上述三菱綜合材料公司製造之鈦黑，例如可列舉：12S、13M、13M-C、13R-N、14M-C等。 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 titanium blacks on the market include titanium blacks manufactured by Mitsubishi Materials Corporation and titanium blacks manufactured by Ako Chemicals Co., Ltd. Examples of the titanium blacks manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C. Examples of the titanium blacks manufactured by Ako Chemicals Co., Ltd. include Tilack D.

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 more preferred lower limit is 15 m 2 /g, and the more preferred upper limit is 25 m 2 /g. In addition, the preferred lower limit of the volume resistivity of the titanium black is 0.5 Ω·cm, the more 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無特別限定，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處於該範圍內，可不使所獲得之硬化性樹脂組成物之塗佈性等變差而使遮光性變得更優異。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），使上述遮光劑分散於溶劑（水、有機溶劑等）中而進行測定。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. The preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. By having the primary particle size of the above-mentioned light-shielding agent within this range, the light-shielding property of the obtained curable resin composition can be improved without deteriorating the coating property. The preferred lower limit of the primary particle size of the above-mentioned light-shielding agent is 5 nm, the preferred upper limit is 200 nm, the further preferred lower limit is 10 nm, and the further preferred upper limit is 100 nm. The primary particle size of the sunscreen can be measured by dispersing the sunscreen in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

本發明之硬化性樹脂組成物100重量份中之上述遮光劑之含量之較佳之下限為5重量份，較佳之上限為80重量份。藉由上述遮光劑之含量處於該範圍內，可發揮更優異之遮光性而不大幅降低所獲得之硬化性樹脂組成物之接著性、硬化後之強度、及描繪性。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 sunscreen in 100 parts by weight of the curable resin composition of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. When the content of the sunscreen is within this range, a better light-shielding property can be exerted without significantly reducing the adhesion, strength after curing, and drawing property of the obtained curable resin composition. The preferred lower limit of the content of the sunscreen is 10 parts by weight, and the preferred upper limit is 70 parts by weight, and the further preferred lower limit is 30 parts by weight, and the further preferred upper limit is 60 parts by weight.

本發明之硬化性樹脂組成物亦可視需要進一步含有應力緩和劑、反應性稀釋劑、觸變劑、間隔件、硬化促進劑、消泡劑、調平劑、聚合抑制劑等添加劑。The curable resin composition of the present invention may further contain additives such as stress relievers, reactive diluents, thixotropic agents, spacers, curing accelerators, defoamers, leveling agents, polymerization inhibitors, etc. as needed.

作為製造本發明之硬化性樹脂組成物之方法，例如可列舉使用混合機將硬化性樹脂、熱硬化劑、及視需要添加之熱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（homo disper）、均質攪拌機（homo mixer）、萬能攪拌機、行星式攪拌機、捏合機、三輥研磨機等。As a method for producing the curable resin composition of the present invention, for example, there can be cited a method of mixing the curable resin, the thermosetting agent, and the thermal free radical polymerization initiator added as needed using a mixer. As the above-mentioned mixer, for example, there can be cited: a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll grinder, etc.

本發明之硬化性樹脂組成物較佳地用作液晶顯示元件用密封劑。使用本發明之硬化性樹脂組成物而製成之液晶顯示元件用密封劑亦係本發明之一。The curable resin composition of the present invention is preferably used as a sealant for a liquid crystal display element. A sealant for a liquid crystal display element made using the curable resin composition of the present invention is also one of the present invention.

藉由將導電性微粒子摻合於本發明之硬化性樹脂組成物中，可製造上下導通材料。此種含有本發明之硬化性樹脂組成物及導電性微粒子之上下導通材料亦係本發明之一。By mixing conductive microparticles into the curable resin composition of the present invention, a vertical conductive material can be produced. Such a vertical conductive material containing the curable resin composition of the present invention and conductive microparticles 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導電金屬層而成者等。其中，於樹脂微粒子之表面形成導電金屬層而成者因樹脂微粒子之優異之彈性，而可在不損傷透明基板等之情況下進行導電連接，故而較佳。As the conductive particles, for example, metal spheres, resin particles with a conductive metal layer formed on the surface, etc. can be used. Of these, the conductive metal layer formed on the surface of the resin particles is preferred because the resin particles have excellent elasticity and can be electrically connected without damaging the transparent substrate.

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係本發明之一。A liquid crystal display element made by using the sealant for liquid crystal display element of the present invention or the top-bottom conductive material of the present invention is also one of the present invention.

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，較佳為液晶顯示部之周圍之框部分之寬度為2 mm以下。 又，較佳為製造本發明之液晶顯示元件時之本發明之硬化性樹脂組成物之塗佈寬度為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, it is preferred that the width of the frame portion around the liquid crystal display portion is 2 mm or less. In addition, it is preferred that the coating width of the curable resin composition of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.

本發明之硬化性樹脂組成物可較佳地用於藉由液晶滴下法製造液晶顯示元件。 作為藉由液晶滴下法製造本發明之液晶顯示元件之方法，例如可列舉以下方法等。 首先，進行如下步驟：於基板上，對本發明之液晶顯示元件用密封劑進行網版印刷、分滴器（dispenser）塗佈等，藉此形成框狀之密封圖案。繼而，進行如下步驟：於本發明之液晶顯示元件用密封劑未硬化之狀態下將液晶之微滴滴下塗佈於密封圖案之框內整個面上，然後立即重疊另一基板。其後，藉由進行將密封劑加熱使其硬化之步驟之方法，可獲得液晶顯示元件。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而使密封劑暫時硬化之步驟。 [發明之效果]The curable resin composition of the present invention can be preferably used to manufacture a liquid crystal display element by a liquid crystal dropping method. As a method for manufacturing the liquid crystal display element of the present invention by a liquid crystal dropping method, for example, the following method can be listed. First, the following steps are performed: on a substrate, the sealant for the liquid crystal display element of the present invention is screen-printed, applied by a dispenser, etc., thereby forming a frame-shaped sealing pattern. Then, the following steps are performed: when the sealant for the liquid crystal display element of the present invention is not cured, droplets of liquid crystal are applied to the entire surface of the frame of the sealing pattern, and then another substrate is immediately overlapped. Thereafter, a liquid crystal display element can be obtained by performing a step of heating the sealant to cure it. Furthermore, before the step of heating the sealant to harden it, a step of temporarily hardening the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed. [Effect of the invention]

根據本發明，可提供一種保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物。又，根據本發明，可提供一種使用該硬化性樹脂組成物而成之液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件。According to the present invention, a curable resin composition having excellent storage stability, adhesion, and low liquid crystal contamination when used as a sealant for a liquid crystal display element can be provided. In addition, according to the present invention, a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element made of the curable resin composition can be provided.

以下，列舉實施例對本發明更詳細地進行說明，但本發明不僅限定於該等實施例。The present invention is described in more detail below with reference to the following embodiments, but the present invention is not limited to these embodiments.

（化合物A之合成） 於具備溫度計及攪拌機之三口燒瓶中，使丙二酸二醯肼132 g（1莫耳）及丙酮145 g（2.5莫耳）溶解於甲醇500 mL中。向所獲得之溶液中添加乙酸鈉164 g（2莫耳）、乙酸240 g（2莫耳）、及氰基硼氫化鈉46.1 g（0.7莫耳），一面進行氮氣置換，一面於25℃攪拌2小時，使其反應。反應結束後，進行分液操作，藉此獲得化合物A作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物A係下述式（2）所表示之化合物。(Synthesis of Compound A) In a three-necked flask equipped with a thermometer and a stirrer, 132 g (1 mol) of malonic acid dihydrazide and 145 g (2.5 mol) of acetone were dissolved in 500 mL of methanol. To the obtained solution, 164 g (2 mol) of sodium acetate, 240 g (2 mol) of acetic acid, and 46.1 g (0.7 mol) of sodium cyanoborohydride were added, and the mixture was stirred at 25°C for 2 hours while replacing the atmosphere with nitrogen to allow the mixture to react. After the reaction was completed, a liquid separation operation was performed to obtain Compound A as the hydrazide compound of the present invention. Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that the obtained Compound A was a compound represented by the following formula (2).

（化合物B之合成） 將氰基硼氫化鈉之添加量變更為23.1 g（0.35莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方式獲得化合物B作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物B中醯肼基50莫耳%被烷基化，且確認到所獲得之化合物B包含下述式（3）所表示之化合物。(Synthesis of Compound B) Compound B was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that the amount of sodium cyanoborohydride added was changed to 23.1 g (0.35 mol). Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that 50 mol% of the hydrazide group in the obtained compound B was alkylated, and that the obtained compound B contained the compound represented by the following formula (3).

（化合物C之合成） 將丙酮145 g變更為甲醛75 g（2.5莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方式獲得化合物C作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物C係下述式（4）所表示之化合物。(Synthesis of Compound C) Compound C was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that 145 g of acetone was replaced with 75 g (2.5 mol) of formaldehyde. Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that the obtained compound C was a compound represented by the following formula (4).

（化合物D之合成） 將丙二酸二醯肼132 g變更為癸二酸二醯肼230 g（1莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方法獲得化合物D作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物D係下述式（5）所表示之化合物。(Synthesis of Compound D) Compound D was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that 132 g of malonic acid dihydrazide was replaced with 230 g (1 mol) of sebacic acid dihydrazide. Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that the obtained compound D was a compound represented by the following formula (5).

（化合物E之合成） 將丙二酸二醯肼132 g變更為1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲314 g（1莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方式獲得化合物E作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物E係下述式（6）所表示之化合物。(Synthesis of Compound E) Compound E was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that 132 g of malonic acid dihydrazide was replaced with 314 g (1 mol) of 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin. Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that the obtained compound E was a compound represented by the following formula (6).

（2,2-二甲基戊二酸二醯肼之合成） 於具備溫度計及攪拌機之三口燒瓶中，使2,2-二甲基戊二酸28.0 g（0.175莫耳）溶解於甲醇150 mL中，並向其中添加濃硫酸1.8 g，進行24小時回流後，對甲醇進行減壓濃縮，使結晶析出。利用乙醇使所獲得之結晶再結晶化，獲得2,2-二甲基戊二酸酯中間物。 繼而，於具備回流冷卻器、溫度計及攪拌機之三口燒瓶中，使水合肼75.1 g（1.5莫耳）溶解於甲醇50 mL及水10 mL中，並滴加2,2-二甲基戊二酸酯中間物18.8 g（0.1莫耳）。滴加結束後，於回流下進行反應3小時。反應結束後，藉由冰浴進行冷卻，藉此將所析出之固形物分離。使所分離之固形物溶解於甲醇中，並進行冷卻使之再次析出，藉由進行該操作，獲得2,2-二甲基戊二酸二醯肼。 再者，藉由1 H-NMR、MS、及FT-IR，確認所獲得之2,2-二甲基戊二酸二醯肼之結構。(Synthesis of 2,2-dimethylglutaric acid dihydrazide) In a three-necked flask equipped with a thermometer and a stirrer, 28.0 g (0.175 mol) of 2,2-dimethylglutaric acid was dissolved in 150 mL of methanol, and 1.8 g of concentrated sulfuric acid was added thereto. After reflux for 24 hours, the methanol was concentrated under reduced pressure to precipitate crystals. The obtained crystals were recrystallized with ethanol to obtain a 2,2-dimethylglutaric acid intermediate. Subsequently, in a three-necked flask equipped with a reflux cooler, a thermometer and a stirrer, 75.1 g (1.5 mol) of hydrazine hydrate was dissolved in 50 mL of methanol and 10 mL of water, and 18.8 g (0.1 mol) of the 2,2-dimethylglutaric acid intermediate was added dropwise. After the addition was completed, the reaction was carried out under reflux for 3 hours. After the reaction was completed, the reaction was cooled in an ice bath to separate the precipitated solid. The separated solid was dissolved in methanol and cooled to precipitate again. By carrying out this operation, 2,2-dimethylglutaric acid dihydrazide was obtained. Furthermore, the structure of the obtained 2,2-dimethylglutaric acid dihydrazide was confirmed by 1 H-NMR, MS, and FT-IR.

（化合物F之合成） 將丙二酸二醯肼132 g變更為2,2-二甲基戊二酸二醯肼188 g（1莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方式獲得化合物F作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物F係下述式（7）所表示之化合物。(Synthesis of Compound F) Compound F was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that 132 g of malonic acid dihydrazide was replaced with 188 g (1 mol) of 2,2-dimethylglutaric acid dihydrazide. Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that the obtained compound F was a compound represented by the following formula (7).

（化合物G之合成） 將氰基硼氫化鈉之添加量變更為13.9 g（0.21莫耳），除此以外，以與上述「（化合物A之合成）」同樣之方式獲得化合物G作為本發明之醯肼化合物。 再者，藉由1 H-NMR、MS、及FT-IR，確認到所獲得之化合物G中醯肼基30莫耳%被烷基化，且確認到所獲得之化合物G包含上述式（3）所表示之化合物。(Synthesis of Compound G) Compound G was obtained as the hydrazide compound of the present invention in the same manner as in the above "(Synthesis of Compound A)" except that the amount of sodium cyanoborohydride added was changed to 13.9 g (0.21 mol). Furthermore, by 1 H-NMR, MS, and FT-IR, it was confirmed that 30 mol% of the hydrazide group in the obtained compound G was alkylated, and that the obtained compound G contained the compound represented by the above formula (3).

（實施例1～9、比較例1～5） 依照表1所記載之摻合比，使用行星式攪拌機（Thinky公司製造之「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1～5之各硬化性樹脂組成物。(Examples 1 to 9, Comparative Examples 1 to 5) After mixing the materials according to the blending ratios listed in Table 1 using a planetary mixer ("Defoaming Mixer Taro" manufactured by Thinky Co.), the materials were further mixed using a three-roll mill to prepare the curable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 5.

＜評價＞ 對實施例及比較例中所獲得之各硬化性樹脂組成物進行以下評價。將結果示於表1中。<Evaluation> Each of the curable resin compositions obtained in the Examples and Comparative Examples was evaluated as follows. The results are shown in Table 1.

（保存穩定性） 對實施例及比較例中所獲得之各硬化性樹脂組成物，測定剛製造後之初始黏度及製造後於25℃保管1週後之黏度。將（保管後之黏度）/（初始黏度）設為增黏率，將增黏率未達1.1者設為「◎」，將增黏率為1.1以上且未達1.5者設為「○」，將增黏率為1.5以上且未達2.0者設為「△」，將增黏率為2.0以上者設為「×」，而評價保存穩定性。 再者，硬化性樹脂組成物之黏度係使用E型黏度計（BROOK FIELD公司製造之「DV-III」）於25℃以旋轉速度1.0 rpm之條件下進行測定。(Storage stability) For each hardening resin composition obtained in the embodiment and the comparative example, the initial viscosity immediately after production and the viscosity after storage at 25°C for 1 week after production were measured. The viscosity increase ratio was set as (viscosity after storage)/(initial viscosity), and the viscosity increase ratio less than 1.1 was set as "◎", the viscosity increase ratio of 1.1 or more and less than 1.5 was set as "○", the viscosity increase ratio of 1.5 or more and less than 2.0 was set as "△", and the viscosity increase ratio of 2.0 or more was set as "×", and the storage stability was evaluated. In addition, the viscosity of the hardening resin composition was measured using an E-type viscometer ("DV-III" manufactured by Brookfield) at 25°C and a rotation speed of 1.0 rpm.

（接著性） 將實施例及比較例中獲得之各硬化性樹脂組成物填充於分滴用之注射器（武藏高科技公司製造之「PSY-10E」）中，進行消泡處理。利用分滴器（武藏高科技公司製造之「SHOTMASTER300」）將消泡處理後之硬化性樹脂組成物自玻璃基板（150 mm×150 mm）之端部向內側30 mm之四方分滴，並於真空下重疊另一玻璃基板（110 mm×110 mm）進行貼合。使用高壓水銀燈照射100 mW/cm2 之紫外線30秒，使硬化性樹脂組成物暫時硬化，繼而，於120℃加熱1小時使硬化性樹脂組成物熱硬化，而獲得接著試驗片。使用半徑5 mm之金屬棒以5 mm/min之速度將所獲得之接著試驗片之基板之端部壓入時，會引起面板剝離，測定此時之強度（kgf），算出接著力（kg/cm）。 將接著力為3.5 kg/cm以上之情形設為「◎」，將接著力為3.0 kg/cm以上且未達3.5 kg/cm之情形設為「○」，將接著力為2.0 kg/cm以上且未達3.0 kg/cm之情形設為「△」，將接著力未達2.0 kg/cm之情形設為「×」，而評價接著性。(Adhesion) Each of the curable resin compositions obtained in the Examples and Comparative Examples was filled into a syringe for droplet dispensing ("PSY-10E" manufactured by Musashi High-Tech Co., Ltd.) and defoamed. The defoamed curable resin composition was dropped from the end of a glass substrate (150 mm × 150 mm) to the four sides 30 mm inward using a dropper ("SHOTMASTER300" manufactured by Musashi High-Tech Co., Ltd.), and another glass substrate (110 mm × 110 mm) was overlapped under vacuum for bonding. The curable resin composition was temporarily cured by irradiating with 100 mW/ cm2 ultraviolet light from a high-pressure mercury lamp for 30 seconds, and then the curable resin composition was thermally cured by heating at 120°C for 1 hour to obtain a bonding test piece. When the end of the substrate of the obtained bonding test piece was pressed in with a metal rod with a radius of 5 mm at a speed of 5 mm/min, the panel peeled off. The strength (kgf) at this time was measured and the bonding force (kg/cm) was calculated. Adhesion was evaluated by setting "◎" for a adhesion force of 3.5 kg/cm or more, "○" for a adhesion force of 3.0 kg/cm or more but less than 3.5 kg/cm, "△" for a adhesion force of 2.0 kg/cm or more but less than 3.0 kg/cm, and "×" for a adhesion force less than 2.0 kg/cm.

（低液晶污染性（NI點）） 向樣品瓶中添加實施例及比較例中所獲得之各硬化性樹脂組成物0.1 g及液晶（東京化成工業公司製造之「4-戊基-4-聯苯腈」）1 g。將該樣品瓶投入至120℃之烘箱中1小時，其後將其靜置，待其恢復至25℃後取出液晶部分，藉由0.2 μm過濾器進行過濾，而製成評價用液晶樣品。將所獲得之評價用液晶樣品10 mg封入至鋁樣品盤中，使用示差掃描型熱量計（TA instrument公司製造之「DSC-Q100」），以升溫速度5℃/分鐘之條件下進行NI點之測定。再者，將硬化性樹脂組成物及未接觸之上述液晶10 mg封入至鋁樣品盤中，以升溫速度5℃/分鐘之條件進行NI點之測定，將所得之結果作為空白樣品。 將評價用液晶樣品中測得之NI點與空白樣品之NI點之差為-2℃以上之情形設為「◎」，將該差為-3℃以上且未達-2℃之情形設為「○」，將該差為-5℃以上且未達-3℃之情形設為「△」，將該差未達-5℃之情形設為「×」，而評價低液晶污染性。(Low liquid crystal contamination (NI point)) Add 0.1 g of each curable resin composition obtained in the example and comparative example and 1 g of liquid crystal ("4-pentyl-4-biphenylnitrile" manufactured by Tokyo Chemical Industry Co., Ltd.) to the sample bottle. Put the sample bottle into a 120°C oven for 1 hour, then let it stand until it returns to 25°C, take out the liquid crystal part, and filter it through a 0.2 μm filter to prepare a liquid crystal sample for evaluation. 10 mg of the obtained liquid crystal sample for evaluation was sealed in an aluminum sample plate, and the NI point was measured using a differential scanning calorimeter ("DSC-Q100" manufactured by TA instrument) at a heating rate of 5°C/min. Furthermore, the curable resin composition and 10 mg of the above-mentioned liquid crystal without contact were sealed in an aluminum sample plate, and the NI point was measured at a temperature increase rate of 5°C/min. The result was used as a blank sample. When the difference between the NI point measured in the evaluation liquid crystal sample and the NI point of the blank sample was -2°C or more, it was set as "◎", when the difference was -3°C or more and less than -2°C, it was set as "○", when the difference was -5°C or more and less than -3°C, it was set as "△", and when the difference was less than -5°C, it was set as "×", and low liquid crystal contamination was evaluated.

（液晶顯示元件之顯示性能） 使平均粒徑5 μm之間隔微粒子（積水化學工業公司製造之「Micropearl SI-H050」）1重量份分散於實施例及比較例中所獲得之各硬化性樹脂組成物100重量份中，並填充於注射器中，利用離心消泡機（AWATRON AW-1）進行消泡。使用分滴器，於噴嘴直徑0.4 mm、噴嘴間距42 μm、注射器之噴出壓力100～400 kPa、塗佈速度60 mm/sec之條件下，將消泡處理後之硬化性樹脂組成物呈框狀地塗佈於2片附配向膜及ITO之基板之一個基板上。此時，以硬化性樹脂組成物之線寬成為約1.5 mm之方式調整噴出壓力。繼而，將液晶（東京化成工業公司製造之「4-戊基-4-聯苯腈」）之微滴滴下塗佈於塗佈有硬化性樹脂組成物之基板之硬化性樹脂組成物之框內整個面上，並於真空下貼合另一基板。貼合後立即使用金屬鹵素燈對硬化性樹脂組成物部分照射100 mW/cm2 之紫外線30秒，使硬化性樹脂組成物暫時硬化。繼而，於120℃加熱1小時，進行正式硬化，製成液晶顯示元件。 對於實施例及比較例中所獲得之各硬化性樹脂組成物，製作3個液晶顯示元件，對於所得之各液晶顯示元件，藉由目測確認剛製作液晶顯示元件後之硬化性樹脂組成物附近之液晶配向混亂。配向混亂係根據顯示部之顏色不均進行判斷，將液晶顯示元件之周邊部完全未觀察到顯示不均之情形設為「◎」，將液晶顯示元件之周邊部觀察到略淡之顯示不均之情形設為「○」，將液晶顯示元件之周邊部有明顯較濃之顯示不均之情形設為「△」，將明顯較濃之顯示不均不僅存在於周邊部分而且亦擴展至中央部分之情形設為「×」，而評價液晶顯示元件之顯示性能。 再者，評價為「◎」、「○」之液晶顯示元件係於實用上完全不存在問題之水準。(Display performance of liquid crystal display element) 1 part by weight of spacer microparticles with an average particle size of 5 μm ("Micropearl SI-H050" manufactured by Sekisui Chemical Industry Co., Ltd.) was dispersed in 100 parts by weight of each hardening resin composition obtained in the embodiment and the comparative example, and filled into a syringe, and defoamed using a centrifugal defoamer (AWATRON AW-1). Using a dropper, a nozzle with a diameter of 0.4 mm was used. , nozzle spacing of 42 μm, syringe ejection pressure of 100 to 400 kPa, and coating speed of 60 mm/sec, the defoamed curable resin composition is applied in a frame shape on one of the two substrates with alignment films and ITO. At this time, the ejection pressure is adjusted so that the line width of the curable resin composition becomes about 1.5 mm. Then, droplets of liquid crystal ("4-pentyl-4-biphenylnitrile" manufactured by Tokyo Chemical Industry Co., Ltd.) are applied to the entire surface of the curable resin composition frame of the substrate coated with the curable resin composition, and the other substrate is bonded under vacuum. Immediately after lamination, the curable resin composition was partially irradiated with ultraviolet light at 100 mW/cm2 for 30 seconds using a metal halogen lamp to temporarily cure the curable resin composition. Subsequently, the curing was performed at 120°C for 1 hour to formally cure the composition to produce a liquid crystal display element. Three liquid crystal display elements were produced for each of the curable resin compositions obtained in the embodiment and the comparative example. For each of the obtained liquid crystal display elements, the disorder of the liquid crystal alignment near the curable resin composition immediately after the liquid crystal display element was produced was confirmed by visual inspection. The alignment disorder is judged based on the color unevenness of the display part. The situation where no display unevenness is observed at the periphery of the liquid crystal display element is set as "◎", the situation where slightly light display unevenness is observed at the periphery of the liquid crystal display element is set as "○", the situation where there is obvious and strong display unevenness at the periphery of the liquid crystal display element is set as "△", and the situation where obvious and strong display unevenness exists not only at the periphery but also extends to the central part is set as "×", and the display performance of the liquid crystal display element is evaluated. In addition, the liquid crystal display element evaluated as "◎" and "○" is at a level where there is no problem at all in practical use.

[表1] 實施例 比較例 1 2 3 4 5 6 7 8 9 1 2 3 4 5 組成 (重量份) 硬化性樹脂 雙酚A型環氧丙烯酸酯 （DAICEL-ALLNEX公司製造之「EBECRYL3700」） 60 60 60 60 60 60 60 60 60 60 60 60 60 60 己內酯改質雙酚A型環氧丙烯酸酯 （DAICEL-ALLNEX公司製造之「EBECRYL3708」） 25 25 25 25 25 25 25 25 25 25 25 25 25 25 雙酚A型環氧樹脂 （DIC公司製造之「EPICLON EXA-850CRP」） 15 15 15 15 15 15 15 15 15 15 15 15 15 15 熱硬化劑 本發明之醯肼化合物 化合物A 7.5 2.5 15 - - - - - - - - - - - 化合物B - - - 7.5 - - - - - - - - - - 化合物C - - - - 7.5 - - - - - - - - - 化合物D - - - - - 7.5 - - - - - - - - 化合物E - - - - - - 7.5 - - - - - - - 化合物F - - - - - - - 7.5 - - - - - - 化合物G - - - - - - - - 7.5 - - - - - 其他 丙二酸二醯肼 （Japan Finechem公司製造之「MDH」） - - - - - - - - - 7.5 - - - - 己二酸二醯肼 （大塚化學公司製造之「ADH」） - - - - - - - - - - 7.5 - - - 癸二酸二醯肼 （大塚化學公司製造之「SDH」） - - - - - - - - - - - 7.5 - - 1,3-雙(肼基羰乙基)-5-異丙基乙內醯脲 （Ajinomoto Fine-Techno公司製造之「Amicure VDH」） - - - - - - - - - - - - 7.5 - 2,2-二甲基戊二酸二醯肼 - - - - - - - - - - - - - 7.5 光自由基聚合起始劑 2,2-二甲氧基-1,2-二苯乙烷-1-酮 （IGM Resins公司製造之「Omnirad 651」） 2 2 2 2 2 2 2 2 2 2 2 2 2 2 熱自由基聚合起始劑 高分子偶氮起始劑 （富士膠片和光純藥公司製造之「VPE-0201」） 2 2 2 2 2 2 2 2 2 2 2 2 2 2 填充劑 二氧化矽 （Admatechs公司製，「Admafine SO-C2」） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 矽烷偶合劑 3-甘油氧丙基三甲氧基矽烷 （信越化學工業公司製造之「KBM-403」） 1 1 1 1 1 1 1 1 1 1 1 1 1 1 評價 保存穩定性 ◎ ◎ ○ △ ◎ ◎ △ ◎ △ × △ ○ × ○ 接著性 ◎ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ ○ ○ ○ ○ 低液晶污染性（NI點） ◎ ○ ◎ ○ ◎ ◎ ◎ ◎ ○ △ × × ○ × 液晶顯示元件之顯示性能 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ × × × ◎ △ [產業上之可利用性][Table 1] Embodiment Comparison Example 1 2 3 4 5 6 7 8 9 1 2 3 4 5 Composition (parts by weight) Hardening resin Bisphenol A epoxy acrylate ("EBECRYL3700" manufactured by DAICEL-ALLNEX) 60 60 60 60 60 60 60 60 60 60 60 60 60 60 Caprolactone-modified bisphenol A epoxy acrylate ("EBECRYL3708" manufactured by DAICEL-ALLNEX) 25 25 25 25 25 25 25 25 25 25 25 25 25 25 Bisphenol A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation) 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Heat hardener The hydrazide compound of the present invention Compound A 7.5 2.5 15 - - - - - - - - - - - Compound B - - - 7.5 - - - - - - - - - - Compound C - - - - 7.5 - - - - - - - - - Compound D - - - - - 7.5 - - - - - - - - Compound E - - - - - - 7.5 - - - - - - - Compound F - - - - - - - 7.5 - - - - - - Compound G - - - - - - - - 7.5 - - - - - other Malonate dihydrazide ("MDH" manufactured by Japan Finechem) - - - - - - - - - 7.5 - - - - Adipic acid dihydrazide ("ADH" manufactured by Otsuka Chemical Co., Ltd.) - - - - - - - - - - 7.5 - - - Sebacate dihydrazide ("SDH" manufactured by Otsuka Chemical Co., Ltd.) - - - - - - - - - - - 7.5 - - 1,3-Bis(hydrazinocarbonylethyl)-5-isopropylhydantoin ("Amicure VDH" manufactured by Ajinomoto Fine-Techno) - - - - - - - - - - - - 7.5 - 2,2-Dimethylglutaric acid dihydrazide - - - - - - - - - - - - - 7.5 Photoradical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethane-1-one ("Omnirad 651" manufactured by IGM Resins) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Thermal free radical polymerization initiator High molecular weight azo initiator ("VPE-0201" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Filler Silicon dioxide (Admafine SO-C2, manufactured by Admatechs) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Silane coupling agent 3-Glyceryloxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Reviews Preserve stability ◎ ◎ ○ △ ◎ ◎ △ ◎ △ × △ ○ × ○ Adhesion ◎ ○ ◎ ○ ○ ○ ◎ ○ ○ ○ ○ ○ ○ ○ Low liquid crystal contamination (NI point) ◎ ○ ◎ ○ ◎ ◎ ◎ ◎ ○ △ × × ○ × Display performance of liquid crystal display devices ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ × × × ◎ △ [Industrial Availability]

根據本發明，可提供一種保存穩定性、接著性、及用於液晶顯示元件用密封劑之情形時之低液晶污染性優異之硬化性樹脂組成物。又，根據本發明，可提供一種使用該硬化性樹脂組成物而成之液晶顯示元件用密封劑、上下導通材料、及液晶顯示元件。According to the present invention, a curable resin composition having excellent storage stability, adhesion, and low liquid crystal contamination when used as a sealant for a liquid crystal display element can be provided. In addition, according to the present invention, a sealant for a liquid crystal display element, a vertical conductive material, and a liquid crystal display element made of the curable resin composition can be provided.

無without

無without

Claims (5)

一種液晶顯示元件用密封劑，其係使用含有硬化性樹脂及熱硬化劑之硬化性樹脂組成物而成者，其特徵在於：上述熱硬化劑包含醯肼化合物，且上述醯肼化合物包含在至少1個醯肼基末端具有烷基之醯肼化合物。 A sealant for a liquid crystal display element, which is formed using a curable resin composition containing a curable resin and a thermosetting agent, wherein the thermosetting agent contains a hydrazide compound, and the hydrazide compound contains a hydrazide compound having an alkyl group at the end of at least one hydrazide group. 如請求項1之液晶顯示元件用密封劑，其中，上述在至少1個醯肼基末端具有烷基之醯肼化合物係下述式(1)所表示之化合物，
Figure 109128941-A0305-02-0030-1
 式(1)中，R1係碳數1以上且15以下之烷基，R2係氫原子或碳數1以上且15以下之烷基，X係可含有氮原子及/或氧原子且碳數1以上且20以下之有機基。 The sealant for liquid crystal display element of claim 1, wherein the hydrazide compound having an alkyl group at the end of at least one hydrazide group is a compound represented by the following formula (1):
Figure 109128941-A0305-02-0030-1
 In formula (1), R1 is an alkyl group having 1 to 15 carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and X is an organic group having 1 to 20 carbon atoms and may contain a nitrogen atom and/or an oxygen atom. 如請求項1或2之液晶顯示元件用密封劑，其進而含有熱自由基聚合起始劑。 The sealant for liquid crystal display elements as claimed in claim 1 or 2 further contains a thermal free radical polymerization initiator. 一種上下導通材料，其含有請求項1、2或3之液晶顯示元件用密封劑及導電性微粒子。 A vertical conductive material, which contains a sealant for a liquid crystal display element according to claim 1, 2 or 3 and conductive microparticles. 一種液晶顯示元件，其係使用請求項1、2或3之液晶顯示元件用密封劑或請求項4之上下導通材料而成。 A liquid crystal display element, which is made using the sealant for liquid crystal display elements of claim 1, 2 or 3 or the upper and lower conductive material of claim 4.
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