TW202104517A - Curable resin composition, sealing agent for liquid crystal display element, vertical conductive material, and liquid crystal display element - Google Patents

Abstract

The purpose of the present invention is to provide a curable resin composition excelling both in adhesion to an alignment film and in moisture permeation preventive properties. The purpose of the present invention is also to provide a sealing agent for a liquid crystal display element, obtained by using the curable resin composition, and a vertical conductive material and a liquid crystal display element. The present invention contains a curable resin and a polymerization initiator and/or a thermosetting agent, the curable resin being a curable resin composition including a compound represented by formula (1). In formula (1), m is an integer from 2 to 4, R1 represents an m-valent polyol-derived structure, R2 represents a structure derived from a dicarboxylic acid or an anhydride thereof which may be substituted, R3 represents a group represented by formula (2-1) or (2-2), X represents a cyclic lactone open-ring structure, n is 0 to 5 (average value), and Ep represents a structure derived from a bifunctional or higher epoxy compound. In formulas (2-1) and (2-2), * represents a bond position, and in formula (2-2), R4 represents a hydrogen atom or a methyl group.

Description

Curable resin composition, sealant for liquid crystal display element, vertical conduction material and liquid crystal display element

The present invention relates to a curable resin composition having excellent adhesion to an alignment film and moisture permeability resistance. Moreover, this invention relates to the sealing compound for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element using this curable resin composition.

In recent years, as a method for manufacturing liquid crystal display elements such as liquid crystal display units, from the viewpoint of shortening the production pitch and optimizing the amount of liquid crystal used, a curable resin composition as disclosed in Patent Document 1 and Patent Document 2 is used. The method of using the material as a sealant is called the dripping method. In the dropping method, first, a sealant is applied to one of the two substrates with electrodes to form a frame-shaped seal pattern. Then, in the state that the sealant is not hardened, droplets of liquid crystal are dropped into the sealing frame of the substrate, overlap another substrate under vacuum, and the sealant is cured by light irradiation or heating, thereby fabricating a liquid crystal display element . At present, this dropping method has become the mainstream of the manufacturing method of liquid crystal display elements. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2001-133794 A [Patent Document 2] International Publication No. 02/092718

[The problem to be solved by the invention]

In addition, in the modernization of the popularization of various mobile devices with LCD panels such as mobile phones and portable game consoles, the miniaturization of the devices is the most requested issue. As a method of miniaturization, the narrow edge of the liquid crystal display part can be cited. For example, a design in which the position of the sealing part is arranged under the black matrix (hereinafter, also referred to as narrow edge design). With this narrow-edge design, there are more cases where the sealant is applied on an alignment film such as polyimide.

In addition, with the popularization of tablet terminals or portable terminals, liquid crystal display elements are increasingly required to have moisture resistance and reliability when driving in a high-temperature and high-humidity environment, and sealants are further required to prevent the penetration of water from the outside. . In order to improve the moisture resistance reliability of the liquid crystal display element, and to prevent the penetration of water from the interface between the sealant and the substrate, it is necessary to improve the adhesion of the sealant to the substrate, etc., and to improve the moisture permeability of the sealant. As a method to improve the moisture permeability of the sealant, a method of blending fillers such as talc is considered. However, in the case of a strict moisture resistance reliability test, the liquid crystal display element may cause display unevenness. In particular, when the coating position of the sealant is located on an alignment film such as polyimide, it is difficult to balance the adhesion to the alignment film and the moisture permeability resistance.

The object of the present invention is to provide a curable resin composition having excellent adhesion to an alignment film and moisture permeability resistance. In addition, an object of the present invention is to provide a sealing compound for liquid crystal display elements, a vertical conduction material, and a liquid crystal display element using the curable resin composition. [Technical means to solve the problem]

The present invention is a curable resin composition containing a curable resin, a polymerization initiator and/or a thermosetting agent, and the curable resin includes a compound represented by the following formula (1).

In formula (1), m is an integer of 2 or more and 4 or less, R ¹ represents a structure derived from a m-valent polyol, R ² represents a structure derived from a substituted dicarboxylic acid or its anhydride, and R ³ represents the following The group represented by the formula (2-1) or (2-2), X represents the ring-opening structure of the cyclic lactone, n is 0 or more and 5 or less (average value), and Ep represents an epoxy compound derived from two or more functions的结构。 The structure.

In formulas (2-1) and (2-2), * represents a bonding position, and in formula (2-2), R ⁴ represents a hydrogen atom or a methyl group. Hereinafter, the present invention will be described in detail.

The inventors found that by using a compound having a specific structure as a curable resin, a curable resin composition having excellent adhesion to the alignment film and moisture permeability resistance can be obtained, thereby completing the present invention.

The curable resin composition of the present invention contains a curable resin. The said curable resin contains the compound represented by the said formula (1). By containing the compound represented by the above formula (1) as the curable resin, the curable resin composition of the present invention has excellent adhesion to the alignment film and moisture permeability resistance.

In the above formula (1), m is an integer of 2 or more and 4 or less. The above m is preferably 2.

In the above formula (1), R ¹ represents a structure derived from an m-valent polyol. The preferred upper limit of the molecular weight of the polyol used as the source of R ^{1 is 500.} When the molecular weight of the above-mentioned polyol is 500 or less, the curable resin composition obtained is more excellent in moisture permeability. A more preferable upper limit of the molecular weight of the above polyol is 400. Furthermore, in this specification, the above-mentioned "molecular weight" refers to the molecular weight obtained from the structural formula for compounds with a specific molecular structure, but for compounds with a wide distribution of degree of polymerization and compounds with unspecified modification sites, there are When using the number average molecular weight. In addition, in this specification, the above-mentioned number average molecular weight is a value calculated by polystyrene conversion using gel permeation chromatography (GPC) and using tetrahydrofuran as a solvent. As a column when the number average molecular weight converted by polystyrene is measured by GPC, for example, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) can be cited.

Specific examples of the polyol used as ^{the source of the above R 1} include: aliphatic diols with 2 to 60 carbons that may have a branched structure, and aliphatics of 2 to 60 carbons that may have a branched structure. Triols, aliphatic tetraols with 2 to 60 carbons that may have a branched structure, diols containing aromatic rings, etc. Among them, from the viewpoint of adhesiveness, aliphatic diols having 2 to 60 carbon atoms which may have a branched structure are preferred. Examples of aliphatic diols having 2 to 60 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. , Undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecanediol, hexadecanediol, heptadecanediol, octadecanediol, nonane Diol, or 2-butene-1,4-diol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane Diol, 1,3-cyclopentanediol, 1,2-cyclopentanediol, 1,3-adamantanediol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-Tetraoxspiro[5.5]undecane, 4,4'-bicyclohexanol, 4-(2-hydroxyethyl)hexanol, hydrogenated bisphenol A, etc. As the above-mentioned aromatic ring-containing diols, for example, bisphenol A, bisphenol F, bisphenol B, bisphenol E, bisphenol S, naphthalenediol, resorcinol, catechol, 4,4 '-Bis(hydroxymethyl)biphenyl, 9,9-bis(4-hydroxyphenyl)pyridium, 1,4-bis(3-hydroxyphenoxy)benzene, 4,4'-dihydroxybiphenyl, 9,9-Bis[4-(2-Hydroxyethoxy)phenyl]茀, glycerol-2-benzyl ether, 2,2'-oxobis(benzyl alcohol), 4,4'-cyclohexylidene bisphenol Wait.

In the above formula (1), R ² represents a structure derived from a substituted dicarboxylic acid or its anhydride. When the above-mentioned R ² is a structure derived from a substituted dicarboxylic acid or an acid anhydride thereof, the obtained curable resin composition has excellent moisture permeability.

As the substituent when the above-mentioned substituted dicarboxylic acid or its anhydride is substituted, for example, a carbon chain containing an aromatic ring and a carbon chain containing 1 to 60 carbons and a ring containing an unsaturated bond or a branched structure may have an unsaturated bond or a branched structure. The structure of the hydrocarbon skeleton and so on.

As the above-mentioned substituted dicarboxylic acid or its anhydride, specifically, for example, phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, 1,2 -Naphthalenedicarboxylic acid anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 4-tertiary butyl phthalic anhydride, phenyl maleic anhydride, phenyl succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-methylcyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1 ,2-Dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 4-methyl-4-ring Hexene-1,2-dicarboxylic anhydride, tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, allyl butane Diacid anhydride, isooctadecenyl succinic anhydride, butyl succinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2-dodecen-1-yl succinic anhydride, 2,2-dimethyl Succinic anhydride, 2-hexen-1-yl succinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic anhydride, 2-octenyl succinic anhydride, 4,9-decane Ene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 2-(2-carboxyl Ethyl)-3-methylmaleic anhydride, 7-oxobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride, and these dicarboxylic acids.

From the viewpoint of further improving the adhesiveness of the obtained curable resin composition to the alignment film, the above-mentioned R ^{2 is} preferably a structure represented by the following formula (3).

In the formula (3), * represents the bonding position, and R ⁵ and R ⁶ each independently represent a hydrogen atom, or an organic group having a carbon number of 1 or more and 60 or less, or a structure in which R ⁵ and R ^{6 are} bonded.

The structure represented by the above formula (3) may be a structure in which R ⁵ and R ^{6 are} not bonded, or a structure in which R ⁵ and R ^{6 are} bonded. From the viewpoint of improving moisture permeability, it is preferred It is a ^{structure in which R 5} and R ^{6 are} bonded, and is more preferably a structure represented by the following formula (4-1) or (4-2).

In the formula (4-1), * represents the bonding position, in the formula (4-1), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in the formula (4-2), R ⁸ Represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms.

Examples of the structure represented by the above formula (4-1) include structures derived from 1,2-cyclohexanedicarboxylic acid anhydride, 3-methylcyclohexane-1,2-dicarboxylic acid anhydride, and the like. Examples of the structure represented by the above formula (4-2) include: 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride , 3,4,5,6-tetrahydrophthalic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, etc. As the structure represented by the above formula (3), in addition to the structure represented by the above formula (4-1) or (4-2), the structure in which the above R ⁵ and R ^{6 are} bonded, for example: Camphene-2,3-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, 2-(2-carboxyethyl)-3-methylmaleic anhydride , The structure of 7-oxybicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, etc.

^{Examples of the structure in which R 5} and R ^{6 are} not bonded in the structure represented by the above formula (3) include: tetrapropenyl succinic anhydride, decyl succinic anhydride, tetradecyl succinic anhydride, tetradecyl succinic anhydride, Alkenyl succinic anhydride, hexadecyl succinic anhydride, isoctadecenyl succinic anhydride, butyl succinic anhydride, allyl succinic anhydride, 4-hexene-1,2-dicarboxylic anhydride, 2- Dodecen-1-ylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 4-methyl-4-pentene-1,2-dicarboxylic acid The structure of acid anhydride, 2-octenyl succinic anhydride, 4,9-decadiene-1,2-dicarboxylic acid anhydride, etc.

In the above formula (1), R ³ represents a group represented by the above formula (2-1) or (2-2). In the case of using the curable resin composition of the present invention in a sealing compound for liquid crystal display elements, it is preferable that at least one R ³ is the above-mentioned formula (2-2). The base expressed.

In the above formula (1), X represents the ring-opening structure of the cyclic lactone. Examples of the above-mentioned cyclic lactone include: γ-undecanoic acid lactone, ε-caprolactone, γ-decanolide, σ-laurolactone, γ-nonanolactone, and γ-heptanolide , Γ-valerolactone, σ-valerolactone, β-butyrolactone, γ-butyrolactone, β-propiolactone, σ-caprolactone, 7-butyl-2-oxocycloheptanone (7 -butyl-2-oxepanone) and so on. Among them, it is preferable that the carbon number of the linear part of the main skeleton is 5 or more and 7 or less when the ring is opened. Furthermore, even in the case where n in the above formula (1) is 0, that is, when the ring-opening structure of the cyclic lactone represented by X does not exist, the curable resin composition obtained has an aligned film The excellent adhesion and moisture permeability of hardened materials. In the case where n is 1 or more and 5 or less, the obtained curable resin composition is more excellent in adhesion to the alignment film.

In the above formula (1), Ep represents a structure derived from a bifunctional or higher epoxy compound. Examples of epoxy compounds that become the source of the above Ep include: bisphenol A epoxy compounds, bisphenol F epoxy compounds, bisphenol E epoxy compounds, bisphenol S epoxy compounds, hydrogenated bisphenols A type epoxy compound, hydrogenated bisphenol F type epoxy compound, hydrogenated bisphenol E type epoxy compound, hydrogenated bisphenol S type epoxy compound, resorcinol type epoxy compound, dicyclopentadiene type epoxy Compounds, naphthalene-type epoxy compounds, sulphur-type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, etc. Among them, the above-mentioned Ep is preferably a structure derived from a bisphenol A epoxy compound, a bisphenol F epoxy compound, or a bisphenol E epoxy compound.

The preferred upper limit of the molecular weight of the epoxy compound used as the source of Ep is 1,000. When the molecular weight of the epoxy compound is 1000 or less, the curable resin composition obtained has a low viscosity and excellent workability. The upper limit of the molecular weight of the epoxy compound is more preferably 500.

As a method of manufacturing the compound represented by the said formula (1), the following methods etc. are mentioned, for example. That is, first, a step of heating and stirring the above-mentioned polyol and the above-mentioned substituted dicarboxylic acid or its anhydride in the presence of a polymerization inhibitor is performed to obtain the reactant 1. Then, a step of adding the above-mentioned bifunctional or higher epoxy compound to the obtained reactant 1 and heating and stirring is performed to obtain a reactant 2. Thereafter, the compound represented by the above formula (1) can be obtained by a method having the following steps, that is, by adding (meth)acrylic acid to the obtained reactant 2 and heating and stirring, a part or all of the ring The oxy group reacts with (meth)acrylic acid. The above-mentioned polyol may also be reacted with the above-mentioned cyclic lactone before reacting with the above-mentioned substituted dicarboxylic acid or its anhydride. In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid.

As said polymerization inhibitor, hydroquinone, p-methoxyphenol, etc. are mentioned, for example.

The lower limit of the content of the compound represented by the formula (1) in 100 parts by weight of the curable resin is preferably 5 parts by weight, and the upper limit is preferably 95 parts by weight. When the content of the compound represented by the above formula (1) is within this range, the obtained curable resin composition is more excellent in the effects of both adhesiveness to the alignment film and moisture permeability prevention. The lower limit of the content of the compound represented by the above formula (1) is more preferably 10 parts by weight, and the upper limit is more preferably 90 parts by weight.

The curable resin composition of the present invention may further contain curable resins other than the compound represented by the above formula (1) as the curable resin within a range that does not impair the purpose of the present invention. As said other curable resin, other epoxy compounds other than the compound represented by the said formula (1), other (meth)acrylic compounds, etc. are mentioned, for example. In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, and the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acryloyl group.

As the above-mentioned other epoxy compounds, for example, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2,2'-diallyl bisphenol A type epoxy compounds, Compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, thioether type epoxy compound, diphenyl ether type Epoxy compounds, dicyclopentadiene epoxy compounds, naphthalene epoxy compounds, phenol novolac epoxy compounds, o-cresol novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds, Biphenol novolac type epoxy compounds, naphthol novolac type epoxy compounds, glycidamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber modified type epoxy compounds, glycidyl ester compounds, etc.

Examples of commercially available bisphenol A epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like. Examples of commercially available bisphenol F-type epoxy compounds include jER806, jER4004 (all manufactured by Mitsubishi Chemical Co., Ltd.), and the like. Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC Corporation) and the like. As a commercially available one among the above-mentioned 2,2'-diallyl bisphenol A epoxy compounds, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. As a commercially available one among the said hydrogenated bisphenol-type epoxy compound, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the said propylene oxide addition bisphenol A epoxy compound, EP-4000S (made by ADEKA company) etc. are mentioned, for example. As a commercially available one among the above-mentioned resorcinol-type epoxy compounds, EX-201 (manufactured by Nagase chemteX) etc. are mentioned, for example. As a commercially available one among the above-mentioned biphenyl type epoxy compounds, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be cited. Examples of commercially available sulfide epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). As a commercially available one among the above-mentioned diphenyl ether type epoxy compounds, for example, YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned dicyclopentadiene-type epoxy compounds, EP-4088S (manufactured by ADEKA Corporation) etc. are mentioned, for example. As commercially available among the above-mentioned naphthalene-type epoxy compounds, for example, EPICLON HP4032, EPICLON EXA-4700 (all manufactured by DIC Corporation), etc. can be cited. As a commercially available one among the said phenol novolak type epoxy compounds, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the said o-cresol novolak type epoxy compounds, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the said dicyclopentadiene novolak type epoxy compounds, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example. As a commercially available one among the above-mentioned biphenol novolac type epoxy compounds, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like can be cited. As a commercially available one among the above-mentioned naphthol novolak type epoxy compounds, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like can be cited. Examples of commercially available glycidamine-type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Corporation), and the like. As commercially available among the above-mentioned alkyl polyol type epoxy compounds, for example, ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) ), DENACOL EX-611 (manufactured by Nagase chemteX), etc. As a commercially available one among the above-mentioned rubber-modified epoxy compounds, YR-450, YR-207 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolead PB (manufactured by Daicel), etc. are mentioned, for example. As a commercially available one among the above-mentioned glycidyl ester compounds, for example, DENACOL EX-147 (manufactured by Nagase chemteX) and the like can be cited. As other commercially available ones among the above epoxy compounds, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 ( All are manufactured by Mitsubishi Chemical Company), EXA-7120 (manufactured by DIC Company), TEPIC (manufactured by Nissan Chemical Company), etc.

In addition, the above-mentioned curable resin may contain a part of (meth)acrylic modified epoxy resin as the above-mentioned other epoxy compound. In addition, in this specification, the above-mentioned partially (meth)acrylic modified epoxy resin means that, for example, a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule can be used. It reacts with (meth)acrylic acid to obtain a compound having one or more epoxy groups and (meth)acrylic groups in one molecule.

As said other (meth)acrylic compound, (meth)acrylate compound, epoxy (meth)acrylate, (meth)acrylate (urethane (meth)acrylate), etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. Moreover, regarding the said (meth)acrylic compound, from a viewpoint of reactivity, it is preferable that it has two or more (meth)acrylic acid groups in 1 molecule. Furthermore, in this specification, the above-mentioned "(meth)acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth)acrylate" means making all of the epoxy compounds The compound obtained by reacting epoxy group with (meth)acrylic acid.

Examples of the monofunctional among the above-mentioned (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate Ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth) Base) acrylate, phenoxy diethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methyl tetrahydrofuran (meth)acrylate, ethyl carbitol (methyl) )Acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-(meth)acrylate Fluoropentyl ester, imine (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acrylic acid succinate Ethyl ester, hexahydrophthalic acid 2-(meth)acryloyloxyethyl, phthalic acid 2-(meth)acryloyloxyethyl 2-hydroxypropyl, phosphoric acid 2-(methyl) Oxyethyl acrylate, glycidyl (meth)acrylate and the like.

In addition, examples of the bifunctional one among the above-mentioned (meth)acrylate compounds include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol two (Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl diacrylate Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-hydroxy-3-(meth)acryloxy propyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth) Acrylate, polycaprolactonediol di(meth)acrylate, polybutadienediol di(meth)acrylate, etc.

In addition, examples of the above-mentioned (meth)acrylate compounds having three or more functions include trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) )Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric acid Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, ginseng phosphate (meth) Acrylic oxyethyl, ditrimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentyl pentaerythritol penta (meth) acrylate, dineopentaerythritol Alcohol hexa (meth) acrylate and the like.

Examples of the above-mentioned epoxy (meth)acrylate include those obtained by reacting an epoxy compound and (meth)acrylic acid in the presence of a basic catalyst in accordance with a conventional method.

As the epoxy compound used as a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compound as the other epoxy compound described above can be used.

Examples of commercially available epoxy (meth)acrylates among the above-mentioned epoxy (meth)acrylates include: epoxy (meth)acrylate manufactured by DAICEL ALLNEX, epoxy (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd., Epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase chemteX, etc. As the epoxy (meth)acrylate manufactured by DAICEL ALLNEX, for example, EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3708, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182, KRM8076, etc. Examples of the epoxy (meth)acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, and the like. Examples of epoxy (meth)acrylates manufactured by the above-mentioned Kyoeisha Chemical Company include: Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 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, and DENACOL ACRYLATE DA-911.

The (meth)acrylic 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.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenyl Methyl methane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, toluidine diisocyanate, xylidine diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, ginseng (isocyanatophenyl) phosphorothioate, tetramethyl diisocyanate, 1,6,11-undecane triisocyanate, etc. .

In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by the reaction of a polyol and an excess isocyanate compound can also be used. Examples of the above-mentioned polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of the (meth)acrylic acid derivative having a hydroxyl group include: hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol Ester or di(meth)acrylate, epoxy (meth)acrylate, etc. As the above-mentioned hydroxyalkyl mono(meth)acrylate, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (Meth) 4-hydroxybutyl acrylate and the like. Examples of the diols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, and the like. As said triol, trimethylolethane, trimethylolpropane, glycerol, etc. are mentioned, for example. As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

Examples of commercially available amine (meth)acrylates include: (meth)acrylate manufactured by Toagosei Co., Ltd., (meth)acrylate manufactured by DAICEL ALLNEX, and manufactured by Negami Kogyo Co., Ltd. (Meth) acrylate, (meth) acrylate manufactured by Shinnakamura Chemical Industry Co., Ltd., (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., etc. As the (meth)acrylate amine ester manufactured by the Toagosei Co., Ltd., for example, M-1100, M-1200, M-1210, M-1600, etc. can be cited. Examples of (meth)acrylic acid amine esters manufactured by the DAICEL ALLNEX company include: EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858, EBECRYL 5129, EEBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260, etc. Examples of (meth)acrylate amine esters manufactured by the aforementioned Negami Kogyo Co., Ltd. include ArtResin UN-330, ArtResin SH-500B, ArtResin UN-1200TPK, ArtResin UN-1255, ArtResin UN-3320HB, ArtResin UN-7100, ArtResin UN-9000A, ArtResin UN-9000H, etc. Examples of the (meth) amine acrylate 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 (meth)acrylate amine esters manufactured by the above-mentioned Kyoeisha Chemical Company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA -306T and so on.

Regarding the aforementioned other (meth)acrylic compounds, from the viewpoint of suppressing liquid crystal contamination, those having hydrogen bonding units such _{as -OH groups, -NH- groups, and -NH 2 groups are preferred.}

The curable resin composition of the present invention contains a polymerization initiator and/or a thermosetting agent. As said polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example. In addition, the above-mentioned "polymerization initiator and/or thermosetting agent" means either or both of the polymerization initiator and the thermosetting agent.

Examples of the radical polymerization initiator include photoradical polymerization initiators that generate radicals by light irradiation, thermal radical polymerization initiators that generate radicals by heating, and the like.

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-(N-𠰌啉基)苯基)丁酮、1,2-(二甲胺基)-2-((4-甲基苯基)甲基)-1-(4-(4-(N-𠰌啉基))苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯乙-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-(N-𠰌啉基)丙-1-酮、1-(4-(2-羥基乙氧基)苯基)-2-羥基-2-甲基-1-丙-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮2-(O-苯甲醯基肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香乙醚、安息香異丙醚等。Examples of the aforementioned photoradical polymerization initiator include: benzophenone compounds, acetophenone compounds, phosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and 9-oxosulfur compounds.

Compound etc. Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-(N-𠰌lineyl) )Phenyl)butanone, 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-(N-𠰌olinyl))benzene Yl)-1-butanone, 2,2-dimethoxy-1,2-benzophene-1-one, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, 2-Methyl-1-(4-methylthiophenyl)-2-(N-𠰌olinyl)propan-1-one, 1-(4-(2-hydroxyethoxy)phenyl)-2 -Hydroxy-2-methyl-1-propan-1-one, 1-(4-(phenylthio)phenyl)-1,2-octanedione 2-(O-benzyloxime), 2 ,4,6-Trimethylbenzyl diphenyl phosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc.

Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, a starter composed of a polymer azo compound (hereinafter, also referred to as a "polymer azo starter") is preferred. Furthermore, in this specification, the term "polymer azo compound" refers to a compound having an azo group and generating a number-average molecular weight of 300 or more radicals that can harden the (meth)acryloyl group by heat generation.

The preferred lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and the preferred upper limit is 300,000. When the number average molecular weight of the polymer azo compound is in this range, liquid crystal contamination can be suppressed, and it can be easily mixed with the curable resin. The lower limit of the number average molecular weight of the above-mentioned polymer azo compound is more preferably 5,000, the upper limit is more preferably 100,000, the lower limit is more preferably 10,000, and the upper limit is more preferably 90,000.

Examples of the above-mentioned 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 are bonded via an azo group is preferably one having a polyethylene oxide structure. As the above-mentioned polymer azo compound, specifically, for example, a condensation polymer of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation polymer of azobis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amine group, etc. Examples of commercially available ones among the above-mentioned polymer azo compounds include: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) and the like. Moreover, as for the commercially available non-polymer azo compound, for example, V-65, V-501 (all manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) and the like can be cited.

As said organic peroxide, for example, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, etc. are mentioned.

As the cationic polymerization initiator, a photocationic polymerization initiator is preferably used. The photocationic polymerization initiator is not particularly limited as long as it generates a proton acid or a Lewis acid by light irradiation, and may be an ionic photo acid generating type or a nonionic photo acid generating type.

Examples of the aforementioned photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic haloonium salts, and aromatic sulfonium salts; iron-diene complexes, titanocene complexes, aromatic Organometallic complexes such as silanol-aluminum complexes, etc.

As a commercially available one among the above-mentioned photocationic polymerization initiators, for example, Adeka Optomer SP-150, Adeka Optomer SP-170 (all manufactured by ADEKA), etc. can be cited.

The content of the polymerization initiator relative to 100 parts by weight of the curable resin has a preferred lower limit of 0.01 parts by weight, and a preferred upper limit of 10 parts by weight. When the content of the polymerization initiator is within this range, when the curable resin composition obtained is used as a sealing agent for liquid crystal display elements, liquid crystal contamination can be suppressed, and storage stability or curability is more excellent. The lower limit of the content of the polymerization initiator is more preferably 0.1 parts by weight, and the upper limit is more preferably 5 parts by weight.

As said thermosetting agent, organic acid hydrazine, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, etc. are mentioned, for example. Among them, it is preferable to use a solid organic acid hydrazine.

Examples of the above-mentioned solid organic acid hydrazine include: 1,3-bis(hydrazinocarbonylethyl)-5-isopropyl allantoin, sebacic hydrazine, dihydrazine isophthalate, and hexamethylene dihydrazide. Dihydrazine, malondihydrazine, etc. Examples of the commercially available solid organic acid hydrazine include: organic acid hydrazine manufactured by Otsuka Chemical Company, organic acid hydrazine manufactured by JAPAN FINECHEM, organic acid hydrazine manufactured by Ajinomoto Fine-Techno, etc. . As an organic acid hydrazine manufactured by the said Otsuka Chemical Company, SDH, ADH, etc. are mentioned, for example. As an organic acid hydrazine manufactured by the said JAPAN FINECHEM company, MDH etc. are mentioned, for example. Examples of the organic acid hydrazine manufactured by the aforementioned Ajinomoto Fine-Techno company include Amicure VDH, Amicure VDH-J, and Amicure UDH.

The content of the thermosetting agent is preferably 1 part by weight in the lower limit and 50 parts by weight in the upper limit with respect to 100 parts by weight of the entire curable resin. When the content of the thermosetting agent is in this range, the obtained curable resin composition has more excellent curability while maintaining excellent coating properties or storage stability. The more preferable upper limit of the content of the thermal hardening agent is 30 parts by weight.

Regarding the curable resin composition of the present invention, in order to increase the viscosity, further improve the adhesion due to the stress dispersion effect, improve the linear expansion rate, and further improve the moisture permeability of the cured product, it is preferable to contain a filler.

As the above-mentioned filler, an inorganic filler or an organic filler can be used. Examples of the above-mentioned inorganic fillers include: silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, oxide Zinc, 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 said organic filler, polyester microparticles, polyurethane microparticles, ethylene polymer microparticles, acrylic polymer microparticles, etc. are mentioned, for example.

The lower limit of the content of the filler in 100 parts by weight of the curable resin composition of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, it is possible to suppress deterioration of coatability and the like, and further exhibit effects such as improvement in adhesiveness. The lower limit of the filler content is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

Regarding the curable resin composition of the present invention, in order to further improve adhesiveness, it is preferable to contain a silane coupling agent. The above-mentioned silane coupling agent mainly has a function as an adhesive auxiliary agent for bonding the curable resin composition to a substrate and the like well. As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. are preferably used.

The 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 preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight. When the content of the silane coupling agent is in this range, when the curable resin composition obtained is used as a sealing agent for liquid crystal display elements, the occurrence of liquid crystal contamination can be suppressed, and the effect of improving adhesiveness can be further exerted. The lower limit of the content of the silane coupling agent is more preferably 0.3 parts by weight, and the upper limit is more preferably 5 parts by weight.

The curable resin composition of the present invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the curable resin composition of the present invention can be preferably used as a light-shielding sealing agent.

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.

The above-mentioned titanium black is a substance that has a higher transmittance in the vicinity of the ultraviolet region, especially light with a wavelength of 370 nm or more and 450 nm or less, compared to the average transmittance of light with a wavelength of 300 nm or more and 800 nm or less. That is, the above-mentioned titanium black is a light-shielding agent having the following properties: on the one hand, it imparts light-shielding properties to the curable resin composition of the present invention by sufficiently shielding light of wavelengths in the visible light region, and on the other hand, makes light of wavelengths in the vicinity of the ultraviolet region light-shielding. penetrate. The light-shielding agent contained in the curable resin composition of the present invention is preferably a substance with high insulation, and as the light-shielding agent with high insulation, titanium black is also preferable.

The above-mentioned titanium black has a sufficient effect even if it is not surface-treated, and it can also be used: the surface has been treated with organic ingredients such as coupling agent; or the use of silicon oxide, titanium oxide, germanium oxide, aluminum oxide, and zirconium oxide , Magnesium oxide and other inorganic ingredients coated with surface-treated titanium black. Among them, in terms of further improving insulation properties, those that have been treated with organic components are preferred. In addition, the liquid crystal display element manufactured by using the curable resin composition of the present invention containing the above-mentioned titanium black as a light-shielding agent as a sealing agent for liquid crystal display elements has sufficient light-shielding properties, and therefore can achieve no light leakage, and has high Contrast, a liquid crystal display element with excellent image display quality.

Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Co., Ltd., titanium black manufactured by Ako Kasei Co., Ltd., and the like. As the titanium black manufactured by Mitsubishi Materials, for example, 12S, 13M, 13M-C, 13R-N, 14M-C, etc. can be cited. As the titanium black manufactured by Ako Kasei Co., Ltd., for example, Tilack D and the like can be cited.

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 resistance of the titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The preferred lower limit of the primary particle size of the sunscreen is 1 nm, and the preferred upper limit is 5 μm. When the primary particle size of the light-shielding agent is in this range, the obtained curable resin composition is more excellent in coatability without greatly increasing the viscosity or thixotropy. The lower limit of the primary particle size of the sunscreen is more preferably 5 nm, the upper limit is more preferably 200 nm, the lower limit is still more preferably 10 nm, and the upper limit is more preferably 100 nm. Furthermore, the primary particle size of the above-mentioned sunscreen can be measured using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

The lower limit of the content of the sunscreen in 100 parts by weight of the curable resin composition of the present invention is preferably 5 parts by weight, and the upper limit is preferably 80 parts by weight. When the content of the light-shielding agent is in this range, the adhesiveness, strength after curing, and drawing properties of the curable resin composition obtained can be maintained, and the effect of improving light-shielding properties can be further exhibited. The lower limit of the content of the sunscreen is more preferably 10 parts by weight, the upper limit is more preferably 70 parts by weight, the lower limit is still more preferably 30 parts by weight, and the upper limit is more preferably 60 parts by weight.

The curable resin composition of the present invention may further contain additives such as a stress reliever, a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoamer, a leveling agent, and a polymerization inhibitor, if necessary.

As a method of producing the curable resin composition of the present invention, for example, a method of mixing curable resin, polymerization initiator and/or thermosetting agent, and optionally silane coupling agent and other additives using a mixer can be cited Wait. As said mixer, for example, a homogenous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, etc. may be mentioned.

The curable resin composition of the present invention can be used as an adhesive, and is particularly preferably used as a sealing agent for liquid crystal display elements. The sealing compound for liquid crystal display elements which uses the curable resin composition of this invention is also one of this invention. In addition, by blending conductive fine particles into the sealing compound for liquid crystal display elements of the present invention, a vertical conduction material can be produced. The sealing compound for liquid crystal display elements of the present invention and a top and bottom conduction material containing conductive fine particles are also one of the present invention.

As the conductive fine particles, a metal ball, a conductive metal layer formed on the surface of a resin fine particle, or the like can be used. Among them, a conductive metal layer formed on the surface of the resin particles is preferable because of the excellent elasticity of the resin particles, which can realize conductive connection without damaging the transparent substrate or the like.

A liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention or a cured product of the upper and lower conduction material of the present invention is also one of the present invention.

The sealing compound for liquid crystal display elements of this invention can be used suitably for manufacture of the liquid crystal display element by a liquid crystal dropping method. As a method of manufacturing the liquid crystal display element of this invention using the sealing compound for liquid crystal display elements of this invention, it is preferable to use a liquid crystal dropping method, and specifically, the method etc. which have the following steps are mentioned, for example. First, a step of applying the sealant for liquid crystal display elements of the present invention to one of two transparent substrates having electrodes such as ITO film by screen printing, dispenser coating, etc., to form a frame-shaped seal pattern . Then, a step of applying small droplets of liquid crystal to the entire surface of the frame of the sealing pattern and superimposing another transparent substrate under vacuum is performed. Thereafter, a step of irradiating light such as ultraviolet rays to the seal pattern portion to temporarily harden the sealant, and a step of heating the temporarily hardened sealant to fully harden it, a liquid crystal display element can be obtained by this method. [Effects of Invention]

According to the present invention, it is possible to provide a curable resin composition having excellent adhesion to an alignment film and moisture permeability resistance. Furthermore, according to the present invention, it is possible to provide a sealing compound for a liquid crystal display element, a vertical conduction material, and a liquid crystal display element using the curable resin composition.

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples.

(Production of curable resin A) 118 parts by weight of 1,6-hexanediol, 296 parts by weight of phthalic anhydride, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were added to the reaction flask. Stir at 90°C for 5 hours. To the obtained reactant, 760 parts by weight of bisphenol A diglycidyl ether was added, and 0.5 part by weight of triphenylphosphine was further added, and the mixture was stirred at 110°C for 5 hours. Thereafter, 144 parts by weight of acrylic acid was added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, whereby curable resin A was obtained. The structure of curable resin A was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin A series formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is The group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol A diglycidyl ether.

(Production of curable resin B) Change 118 parts by weight of 1,6-hexanediol to 258 parts by weight of 1,16-hexadecanediol, and in addition to the above "(Production of curable resin A) )” The curable resin B is obtained in the same way. The structure of curable resin B was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin B system formula (1) was 2, R ¹ was a structure derived from 1,16-hexadecanediol, R ² was a structure derived from phthalic anhydride, and R ³ is a group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol A diglycidyl ether.

(Production of curable resin C) 118 parts by weight of 1,6-hexanediol was changed to 234 parts by weight of bisphenol A, and 760 parts by weight of bisphenol A diglycidyl ether was changed to dicyclopentadiene bicyclic ring Except for 536 parts by weight of oxypropyl ether, curable resin C was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of curable resin C was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin C system formula (1) was 2, R ¹ was a structure derived from bisphenol A, R ² was a structure derived from phthalic anhydride, and R ³ was a formula (2- 2) The represented group (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of dicyclopentadiene diglycidyl ether.

(Production of curable resin D) Change 760 parts by weight of bisphenol A diglycidyl ether to 720 parts by weight of bisphenol F diglycidyl ether.的Manufacture)" The curable resin D is obtained in the same way. The structure of curable resin D was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the formula (1) of the curable resin D is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is The group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol F diglycidyl ether.

(Production of curable resin E) 296 parts by weight of phthalic anhydride was changed to 536 parts by weight of tetrapropenyl succinic anhydride, and 760 parts by weight of bisphenol A diglycidyl ether was changed to bisphenol F diepoxy Except for 720 parts by weight of propyl ether, curable resin E was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of curable resin E was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin E system formula (1) was 2, R ¹ was a structure derived from 1,6-hexanediol, R ² was a structure derived from tetrapropenyl succinic anhydride, and R ³ It is a group represented by formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol F diglycidyl ether.

(Production of curable resin F) 296 parts by weight of phthalic anhydride was changed to 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride, and 760 parts by weight of bisphenol A diglycidyl ether Except for changing the part to 720 parts by weight of bisphenol F diglycidyl ether, curable resin F was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of curable resin F was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin F system formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2 -The structure of dicarboxylic anhydride, R ³ is a group represented by formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol F diglycidyl ether.

(Production of curable resin G) Except that 144 parts by weight of acrylic acid was changed to 168 parts by weight of methacrylic acid, curable resin G was obtained in the same manner as in the above-mentioned "(Production of curable resin F)". The structure of curable resin G was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin G system formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2 -The structure of dicarboxylic anhydride, R ³ is a group represented by formula (2-2) (R ⁴ is a methyl group), n is 0, and Ep is a compound derived from the structure of bisphenol F diglycidyl ether.

(Production of curable resin H) 118 parts by weight of 1,6-hexanediol, 228 parts by weight of ε-caprolactone, and 0.1 parts by weight of hydroquinone as a polymerization inhibitor were added to the reaction flask. Stir at 90°C for 5 hours. Then, 296 parts by weight of phthalic anhydride was added, and further stirred for 5 hours. To the obtained reactant, 760 parts by weight of bisphenol A diglycidyl ether was added, and 0.5 part by weight of triphenylphosphine was further added, and the mixture was stirred at 110°C for 5 hours. Thereafter, 144 parts by weight of acrylic acid was added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, whereby curable resin H was obtained. The structure of the curable resin H was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin H-based formula (1) was 2, R ¹ was a structure derived from 1,6-hexanediol, R ² was a structure derived from phthalic anhydride, and R ³ was The group represented by formula (2-2) (R ⁴ is a hydrogen atom), X is the ring-opening structure of ε-caprolactone, n is 1.9 (average value), and Ep is derived from bisphenol A diglycidyl ether The structure of the compound.

(Production of curable resin I) Except that the blending amount of acrylic acid was changed to 72 parts by weight, curable resin I was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of the curable resin I was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that curable resin I contained 52% by weight of compound I-1 represented by formula (1), 23% by weight of compound 1-2 represented by formula (1), and 23% by weight of bisphenol A Diglycidyl ether. Compound I-1 is in formula (1) where m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and ^{one of R 3} is formula (2 -1) The group represented by the formula (2-2), the other is the group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol A diglycidyl ether . Compound I-2 is in formula (1) where m is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is formula (2-2) The represented group (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of bisphenol A diglycidyl ether.

(Production of curable resin J) Add 118 parts by weight of 1,6-hexanediol, 336 parts by weight of 4-methylcyclohexane-1,2-dicarboxylic anhydride, and p-benzene as a polymerization inhibitor to the reaction flask 0.1 parts by weight of diphenol was stirred at 90°C for 5 hours using a heating mantle. To the obtained reactant, 720 parts by weight of bisphenol F diglycidyl ether was added, and 0.5 parts by weight of triphenylphosphine was further added, and the mixture was stirred at 110° C. for 5 hours, thereby obtaining curable resin J. The structure of curable resin J was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin J system formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, and R ² is derived from 4-methylcyclohexane-1,2 -The structure of dicarboxylic anhydride, R ³ is a group represented by formula (2-1), n is 0, and Ep is a compound derived from the structure of bisphenol F diglycidyl ether.

(Production of curable resin K) Changed 760 parts by weight of bisphenol A diglycidyl ether to 9,9-bis(4-glycidoxy-3-phenyl)diglycidyl ether 924 Except for the parts by weight, curable resin K was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of curable resin K was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin K system formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is a formula (2-2) The group represented by (R ⁴ is a hydrogen atom), n is 0, and Ep is derived from 9,9-bis(4-glycidoxy-3-phenyl)diglycidyl ether The structure of the compound.

(Production of curable resin L) Changed 760 parts by weight of bisphenol A diglycidyl ether to 1,6-bis(2,3-glycidyl-1-yloxy)naphthalene diglycidyl ether Except for 544 parts by weight, curable resin L was obtained in the same manner as in the above-mentioned "(Production of curable resin A)". The structure of the curable resin L was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin L-based formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is The group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is derived from 1,6-bis(2,3-glycid-1-yloxy)naphthalene diglycidide The compound of the structure of the base ether.

(Production of curable resin M) 760 parts by weight of bisphenol A diglycidyl ether was changed to 444 parts by weight of resorcinol diglycidyl ether. Production of A)" The curable resin M is obtained in the same way. The structure of the curable resin M was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin M system formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is The group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of resorcinol diglycidyl ether.

(Production of curable resin N) Change 760 parts by weight of bisphenol A diglycidyl ether to 706 parts by weight of hydrogenated bisphenol A diglycidyl ether. Production of A)" The curable resin N is obtained in the same way. The structure of curable resin N was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that m in the curable resin N-based formula (1) is 2, R ¹ is a structure derived from 1,6-hexanediol, R ² is a structure derived from phthalic anhydride, and R ³ is The group represented by the formula (2-2) (R ⁴ is a hydrogen atom), n is 0, and Ep is a compound derived from the structure of hydrogenated bisphenol A diglycidyl ether.

(Production of curable resin O) Add 298 parts by weight of 1,6-hexanediol diglycidyl ether and 456 parts by weight of bisphenol A to the reaction flask, use a heating mantle to raise the temperature to 150°C, and add 4% NaOH aqueous solution 1 part by weight and stirred at 150°C for 3 hours. After confirming that the liquid temperature had dropped to 60° C., 500 parts by weight of chloroform were added, and washing was performed 5 times with 500 parts by weight of 1% NaOH aqueous solution, and 3 times washing with 1000 parts by weight of water. Thereafter, 295 parts by weight of epichlorohydrin was added to the reactant obtained by drying with magnesium sulfate, filtering, and distilling off the solvent under reduced pressure, and the mixture was stirred at 80°C for 2 hours. Thereafter, 144 parts by weight of acrylic acid was added to the obtained reactant, and the mixture was stirred at 110° C. for 5 hours, whereby curable resin O was obtained. The structure of the curable resin O was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that the curable resin O is a compound represented by the following formula (5).

(Production of curable resin P) Add 298 parts by weight of 1,6-hexanediol diglycidyl ether and 456 parts by weight of bisphenol A to the reaction flask, use a heating mantle to raise the temperature to 150°C, and add 4% NaOH aqueous solution 1 part by weight and stirred at 150°C for 3 hours. After confirming that the liquid temperature had dropped to 60° C., 500 parts by weight of chloroform were added, and washing was performed 5 times with 500 parts by weight of 1% NaOH aqueous solution, and 3 times washing with 1000 parts by weight of water. Thereafter, 295 parts by weight of epichlorohydrin was added to the reactant obtained by drying with magnesium sulfate, filtering, and distilling off the solvent under reduced pressure, and stirred at 80° C. for 2 hours, thereby obtaining curable resin P. The structure of the curable resin P was analyzed by ¹ H-NMR and ^{13 C-NMR.} As a result, it was confirmed that the curable resin P is a compound represented by the following formula (6).

(Examples 1 to 16, Comparative Examples 1 to 4) According to the blending ratios described in Tables 1 and 2, the materials were stirred by a planetary stirring device, and then uniformly mixed by a ceramic three-roll mill to obtain the hardening of Examples 1 to 16 and Comparative Examples 1 to 4性resin composition. As the planetary stirring device, defoaming stirring Taro (manufactured by Thinky) was used.

＜Evaluation＞ The following evaluations were performed for each curable resin composition obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

(Adhesion to alignment film) The glass substrate with ITO film is coated with an imide resin by spin coating, pre-baked at 80°C, and then fired at 230°C to produce a substrate with alignment film . As the imine resin, SE7492 (manufactured by Nissan Chemical Co., Ltd.) was used. With the planetary stirring device, 1 part by weight of the silica spacer was uniformly dispersed with respect to 100 parts by weight of each curable resin composition obtained in the Examples and Comparative Examples. As the silica spacer, SI-H055 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. Then, the curable resin composition dispersed with the silicon dioxide spacer is added dropwise to the alignment film of the substrate with the alignment film. On the substrate with the alignment film to which the curable resin composition is dropped, another substrate with the alignment film is cross-bonded through the curable resin composition, and ^{after irradiating 3000 mJ/cm 2} of ultraviolet rays with a metal halide lamp, By heating at 120°C for 60 minutes, an adhesive test piece was obtained. Measure the strength when a metal cylinder with a radius of 5 mm is used to press in the end of the substrate of the produced test piece at a speed of 5 mm/min when the panel peels off. If the value obtained by dividing the measured value (kgf) by the seal diameter (cm) is 3.0 kgf/cm or more, set it as "◎", and if it is 2.5 kgf/cm or more and less than 3.0 kgf/cm, set it It is "○", the case of 2.0 kgf/cm or more and less than 2.5 kgf/cm is set to "△", and the case of less than 2.0 kgf/cm is set to "×" to evaluate the adhesion to the alignment film.

(Anti-moisture permeability) Using a coater, each curable resin composition obtained in the examples and comparative examples was applied to a smooth release film so that the thickness became 200 μm or more and 300 μm or less. Then, after irradiating 3000 mJ/cm ² of ultraviolet rays with a metal halide lamp, it was heated at 120° C. for 60 minutes to obtain a film for measuring moisture permeability. Use the method according to JIS Z 0208 for moisture permeability test method (cup method) to make a moisture permeability test cup, install the obtained film for moisture permeability measurement, and put it in a temperature of 80°C and a humidity of 90%RH The moisture permeability is measured in a constant temperature and humidity oven. Set the value of the obtained moisture permeability below 50 g/m ² ·24 hours as "◎", and set the case where 50 g/m ² ·24 hours or more and less than 60 g/m ² ·24 hours If it is "○", set the case of 60 g/m ² · 24 hours or more and less than 70 g/m ² · 24 hours to "△", and set the case of 70 g/m ² · 24 hours or more to "× "And evaluate the moisture permeability.

(Display performance of liquid crystal display element) The glass substrate with ITO film is coated with an imide resin by spin coating, pre-baked at 80°C, and then fired at 230°C to produce a substrate with alignment film . As the imine resin, SE7492 (manufactured by Nissan Chemical Co., Ltd.) was used. With a planetary stirring device, 1 part by weight of the silica spacer is uniformly dispersed with respect to 100 parts by weight of each curable resin composition obtained in the examples and comparative examples, and the defoaming treatment is performed to remove the curable resin After the bubbles in the composition are removed, it is filled into the dispensing syringe, and the defoaming treatment is performed again. As the silica spacer, SI-H055 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used, and as the syringe for dispensing, PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used. Then, the curable resin composition is coated on the alignment film of the substrate with the alignment film using a dispenser to draw a frame. As the dispenser, SHOTMASTER 300 (manufactured by Musashi Engineering) was used. Then, the minute droplets of the TN liquid crystal are dripped and applied to the frame of the curable resin composition by the liquid crystal dripping device. On the substrate with the alignment film coated with TN liquid crystal, another substrate with the alignment film is superimposed via the curable resin composition, and the two substrates are bonded by a vacuum bonding device under a reduced pressure of 5 Pa. Get the unit. As the TN liquid crystal, JC-5001LA (manufactured by Chisso Corporation) was used. The obtained cell was irradiated with 3000 mJ/cm ² of ultraviolet rays by a metal halide lamp, and then heated at 120° C. for 60 minutes to harden the curable resin composition, thereby fabricating a liquid crystal display element. After storing the obtained liquid crystal display element in an environment with a temperature of 80° C. and a humidity of 90% RH for 144 hours, it was driven with a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed. Set the case where there is no display unevenness at the periphery of the liquid crystal display element as "◎", the case where the display unevenness is visible slightly lighter is set to "○", and the case where there is obviously darker display unevenness is set as "○""△", the display unevenness that is obviously deeper not only exists in the peripheral part, but also extends to the center part is set to "×" to evaluate the display performance of the liquid crystal display element. In addition, the liquid crystal display elements evaluated as "◎" and "○" are at a level of practically no problem at all.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Composition (parts by weight) Hardening resin Curing resin A 30 - - - - - - - - - - - - - - - Curing resin B - 30 - - - - - - - - - - - - - - Curing resin C - - 30 - - - - - - - - - - - - - Curing resin D - - - 30 - - - - - - - - - - - - Curing resin E - - - - 30 - - - - - - - - - - - Curing resin F - - - - - 30 - - - - - - - - 10 80 Curing resin G - - - - - - 30 - - - - - - - - - Curing resin H - - - - - - - 30 - - - - - - - - Curing resin I - - - - - - - - 30 - - - - - - - Curing resin J - - - - - - - - - 30 - - - - - - Curing resin K - - - - - - - - - - 30 - - - - - Curing resin L - - - - - - - - - - - 30 - - - - Curing resin M - - - - - - - - - - - - 30 - - - Curing resin N - - - - - - - - - - - - - 30 - - Bisphenol A epoxy acrylate ("EBECRYL 3700" manufactured by DAICEL ALLNEX) 60 60 60 60 60 60 60 60 70 70 60 60 60 60 80 10 Bisphenol A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation) 10 10 10 10 10 10 10 10 - - 10 10 10 10 10 10 Light radical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethyl-1-one ("IRGACURE 651" manufactured by BASF Corporation) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Thermal radical polymerization initiator Macromolecular azo compound ("VPE-0201" manufactured by FUJIFILM Wako Pure Chemical) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Thermal hardener Malondihydrazine ("MDH" manufactured by JAPAN FINECHEM) 2 2 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 20 20 Silane coupling agent 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Evaluation Adhesion to alignment film ○ ◎ ○ ○ ◎ ◎ ○ ◎ ◎ ◎ ○ ○ ◎ ◎ ○ ◎ Anti-moisture permeability ◎ ○ ◎ ◎ ○ ◎ ◎ ○ ◎ ○ ◎ ◎ ○ ○ ○ ◎ Display performance of liquid crystal display element ◎ ○ ○ ◎ ○ ◎ ◎ ○ ○ ○ ○ ○ ○ ○ ○ ◎

[Table 2] Comparative example 1 2 3 4 Composition (parts by weight) Hardening resin Curing resin O 30 - - - Curing resin P - 30 - - Caprolactone modified bisphenol A epoxy acrylate ("EBECRYL 3708" manufactured by DAICEL ALLNEX) - - 30 - Bisphenol A epoxy acrylate ("EBECRYL 3700" manufactured by DAICEL ALLNEX) 60 70 60 90 Bisphenol A epoxy resin ("EPICLON EXA-850CRP" manufactured by DIC Corporation) 10 - 10 10 Light radical polymerization initiator 2,2-Dimethoxy-1,2-diphenylethan-1-one ("IRGACURE 651" manufactured by BASF) 1 1 1 1 Thermal radical polymerization initiator Macromolecular azo compound ("VPE-0201" manufactured by FUJIFILM Wako Pure Chemical) 1 1 1 1 Thermal hardener Malondihydrazine ("MDH" manufactured by JAPAN FINECHEM) 2 3 2 2 Filler Silicon dioxide ("Admafine SO-C2" manufactured by Admatechs) 20 20 20 20 Silane coupling agent 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 1 1 1 1 Evaluation Adhesion to alignment film ○ ○ ◎ X Anti-moisture permeability X X X ○ Display performance of liquid crystal display element ○ △ △ ○ [Industrial availability]

According to the present invention, it is possible to provide a curable resin composition having excellent adhesion to an alignment film and moisture permeability resistance. Furthermore, according to the present invention, it is possible to provide a sealing compound for a liquid crystal display element, a vertical conduction material, and a liquid crystal display element using the curable resin composition.

no

no

Claims (6)

A curable resin composition comprising: a curable resin, and a polymerization initiator and/or a thermosetting agent, and the curable resin includes a compound represented by the following formula (1),

In formula (1), m is an integer of 2 or more and 4 or less, R ¹ represents a structure derived from a m-valent polyol, R ² represents a structure derived from a substituted dicarboxylic acid or its anhydride, and R ³ represents the following The group represented by the formula (2-1) or (2-2), X represents the ring-opening structure of the cyclic lactone, n is 0 or more and 5 or less (average value), and Ep represents an epoxy compound derived from two or more functions The structure;

In formulas (2-1) and (2-2), * represents a bonding position, and in formula (2-2), R ⁴ represents a hydrogen atom or a methyl group. The curable resin composition of claim 1, wherein, in the above formula (1), R ² is a structure represented by the following formula (3),

In the formula (3), * represents the bonding position, and R ⁵ and R ⁶ each independently represent a hydrogen atom, or an organic group having a carbon number of 1 or more and 60 or less, or a structure in which R ⁵ and R ^{6 are} bonded. The curable resin composition of claim 2, wherein, in the above formula (1), R ² is a structure represented by the following formula (4-1) or (4-2),

In the formula (4-1), * represents the bonding position, in the formula (4-1), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and in the formula (4-2), R ⁸ Represents a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms. A sealant for liquid crystal display elements, which is formed by using the curable resin composition of claim 1, 2 or 3. An up-and-down conduction material containing the sealant for liquid crystal display elements of claim 4 and conductive fine particles. A liquid crystal display element having a cured product of the sealant for a liquid crystal display element of claim 4, or a cured product of the upper and lower conduction material of claim 5.