JP6609396B1 - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a sealing agent for a liquid crystal display element that is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element containing a curable resin and a thermosetting agent, and the thermosetting agent has the following characteristics (a), (b), (c), and (d): It is the sealing compound for liquid crystal display elements containing the compound (A) which has this. (A) having a hydroxyl group-containing hydrazide compound residue (b) having an isocyanate compound residue (c) having a structure represented by the following formula (1) (d) in formula (1) having no isocyanate group, * Is a bonding position. [Chemical 1]

Description

The present invention relates to a sealant for a liquid crystal display element that is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, dripping using a sealing agent as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. A liquid crystal dropping method called a construction method is used.
In the dropping method, first, a frame-like seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, liquid crystal microdroplets are dropped into the frame of the seal pattern in a state where the sealant is uncured, and after the other substrate is superposed under vacuum, the sealant is cured to produce a liquid crystal display element. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.

By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for downsizing the device, a narrow frame of the liquid crystal display unit can be cited. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).

However, in the narrow frame design, since the sealing agent is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing agent is blocked, and it is difficult for the light to reach the inside of the sealing agent. However, the conventional sealant is insufficiently cured. As described above, when the sealant is insufficiently cured, there is a problem in that the uncured sealant component is eluted in the liquid crystal and easily causes liquid crystal contamination.

When it is difficult to photocur the sealant in this way, it is conceivable that the sealant is cured by heating. As a method for curing the sealant by heating, a thermosetting agent is added to the sealant. It has been broken. However, when a thermosetting agent that is highly reactive to heat is used to improve the curability of the sealing agent, the resulting sealing agent may be inferior in storage stability.
In recent years, liquid crystal display elements have been made thinner. However, when a conventional sealant is used for a thin liquid crystal display element, there is a problem that display defects may occur.

JP 2001-133794 A International Publication No. 02/092718

An object of the present invention is to provide a sealing agent for a liquid crystal display element that is excellent in storage stability and curability and can suppress the occurrence of display defects even when used in a thin liquid crystal display element. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.

The present invention is a sealant for a liquid crystal display element containing a curable resin and a thermosetting agent, and the thermosetting agent has the following characteristics (a), (b), (c), and (d): It is the sealing compound for liquid crystal display elements containing the compound (A) which has this.
(A) having a hydroxyl group-containing hydrazide compound residue (b) having an isocyanate compound residue (c) having a structure represented by the following formula (1) (d) having no isocyanate group. A sealing agent for a liquid crystal display element comprising a curable resin and a thermosetting agent, wherein the thermosetting agent is represented by a hydroxyl group-containing hydrazide compound residue, an isocyanate compound residue, and the following formula (1): It is a sealing compound for liquid crystal display elements containing the compound which has a structure and does not have an isocyanate group.

In formula (1), * is a bonding position.
The present invention is described in detail below.

In response to the thinning of liquid crystal display elements, liquid crystals containing liquid crystal molecules having polar groups such as fluoro groups, chloro groups, and cyano groups are increasingly used. The present inventor has found that the cause of display failure when a conventional sealing agent is used in a thin liquid crystal display element is the compatibility between the liquid crystal containing such polar group-containing liquid crystal molecules and the sealing agent (especially the sealing agent). It was thought that liquid crystal contamination was likely to occur due to the high compatibility with the thermosetting agent contained in the liquid crystal. Therefore, as a result of intensive studies, the present inventors have used a thermosetting agent having a specific structure, which has excellent storage stability and curability and suppresses the occurrence of display defects even when used in thin liquid crystal display elements. The present inventors have found that a sealing agent for liquid crystal display elements that can be obtained is obtained, and have completed the present invention.
In addition, since the sealing agent for liquid crystal display elements of the present invention is further less compatible with conventional liquid crystals that do not contain liquid crystal molecules having polar groups, liquid crystal displays using such conventional liquid crystals. The occurrence of display defects can also be suppressed in the element.

The sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
The said thermosetting agent contains the compound (A) (henceforth "the thermosetting agent concerning this invention") which has the said characteristics (a), (b), (c), and (d). By containing the thermosetting agent according to the present invention, the sealing agent for liquid crystal display elements of the present invention has excellent storage stability and curability, and even when used in a thin liquid crystal display element, display failure occurs. It can be suppressed.
In the present specification, the “residue” means the structure of a portion other than the functional group used for bonding in the raw material component. Specifically, the “hydroxyl group-containing hydrazide compound residue” in the feature (a) of the thermosetting agent according to the present invention is a structure derived from a hydroxyl group-containing hydrazide compound and other than the hydrazide group in the hydroxyl group-containing hydrazide compound. This means the structure of the remaining part, that is, the structure of the part remaining without reacting with the isocyanate group. In addition, the “isocyanate compound residue” in the feature (b) of the thermosetting agent according to the present invention is a structure derived from an isocyanate compound and a structure of a portion other than the isocyanate group in the isocyanate compound, that is, a hydrazide group. It means the structure of the remaining part without reacting with. In addition, since the thermosetting agent concerning this invention has the said characteristic (d), ie, it does not have an isocyanate group, all the isocyanate groups of an isocyanate compound are the structures represented by the said Formula (1). Served for formation.

The hydroxyl group-containing hydrazide compound that is the origin of the hydroxyl group-containing hydrazide compound residue in the feature (a) is a compound having a hydroxyl group and two or more hydrazide groups in one molecule, and the isocyanate in the feature (b). The isocyanate compound from which the compound residue is derived is preferably a compound having two or more isocyanate groups in one molecule.

The structure represented by the formula (1) in the feature (c) is derived from the hydrazide group of the hydroxyl group-containing hydrazide compound and the isocyanate group of the isocyanate compound. When the thermosetting agent according to the present invention has the structure represented by the above formula (1), the obtained sealing agent for liquid crystal display elements is excellent in the effect of achieving both liquid crystal contamination and curability.

Specific examples of the hydroxyl group-containing hydrazide compound include malic acid dihydrazide, tartaric acid dihydrazide, 2-hydroxypropane-1,2,3-tricarbohydrazide and the like. Of these, malic acid dihydrazide and tartaric acid dihydrazide are preferable.

Specific examples of the isocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate. Of these, hexamethylene diisocyanate and isophorone diisocyanate are preferable.

A preferable lower limit of the molecular weight of the thermosetting agent according to the present invention is 300. When the molecular weight of the thermosetting agent according to the present invention is 300 or more, the thermosetting agent has sufficient solubility with respect to the curable resin, and the resulting liquid crystal display element sealing agent is more excellent in low liquid crystal contamination. . A more preferable lower limit of the molecular weight of the thermosetting agent according to the present invention is 350.
Further, from the viewpoint of workability of the obtained sealing agent for liquid crystal display elements, the preferable upper limit of the molecular weight of the thermosetting agent according to the present invention is 2000.
The molecular weight of the thermosetting agent according to the present invention is the molecular weight obtained from the structural formula for the compound whose molecular structure is specified, but for the compound with a wide distribution of polymerization degree and the compound whose modification site is unspecified. , Sometimes expressed using weight average molecular weight. In the present specification, the above “weight average molecular weight” is a value obtained by gel conversion chromatography (GPC) using tetrahydrofuran as a solvent and calculated in terms of polystyrene. As a column used when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko KK) etc. are mentioned, for example.

Specific examples of the thermosetting agent according to the present invention include compounds represented by the following formula (2).

In formula (2), R ¹ is independently a hydroxyl group-containing hydrazide compound residue, and R ² is an isocyanate compound residue.

Examples of the method for producing the thermosetting agent according to the present invention include the following methods.
That is, first, the hydroxyl group-containing hydrazide compound is dissolved in toluene in a three-necked flask equipped with a thermometer and a stirrer and stirred at 60 ° C. After the toluene solution of the above isocyanate compound is dropped into the obtained solution, the mixture is stirred at 60 ° C. for 6 hours to be reacted. The obtained reaction solution is filtered to separate a solid, and then the obtained solid is washed with water and dried to obtain the thermosetting agent according to the present invention.

With respect to the content of the thermosetting agent according to the present invention, a preferable lower limit is 0.1 part by weight and a preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent according to the present invention is 0.1 parts by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in curability. When the content of the thermosetting agent according to the present invention is 20 parts by weight or less, the obtained sealing agent for liquid crystal display elements is more excellent in storage stability. The more preferred lower limit of the content of the thermosetting agent according to the present invention is 1 part by weight, the more preferred upper limit is 18 parts by weight, the still more preferred lower limit is 2 parts by weight, the still more preferred upper limit is 15 parts by weight, and the still more preferred lower limit is 3 parts by weight. Parts, even more preferred upper limit is 12 parts by weight, particularly preferred lower limit is 4 parts by weight, particularly preferred upper limit is 10 parts by weight, and the most preferred upper limit is 8 parts by weight.

The sealing agent for liquid crystal display elements of this invention contains curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , Propylene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, orthocresol Novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphthalenephenol novolac And a glycidyl amine type epoxy resin, an alkyl polyol type epoxy resin, a rubber-modified epoxy resin, and a glycidyl ester compound.

As what is marketed among the said bisphenol A type epoxy resins, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), EPICLON850 (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make), EPICLON EXA-830CRP (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol E-type epoxy resins, Epomic R710 (made by Mitsui Chemicals) etc. is mentioned, for example.
As what is marketed among the said bisphenol S type epoxy resins, EPICLON EXA-1514 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said hydrogenated bisphenol-type epoxy resins, EPICLON EXA-7015 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said propylene oxide addition bisphenol A type epoxy resins, EP-4000S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by Nagase ChemteX Corporation) etc. are mentioned, for example.
As what is marketed among the said biphenyl type epoxy resins, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Nippon Steel Chemical & Material Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon Steel Chemical & Material Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said naphthalene type epoxy resins, EPICLON HP-4032, EPICLON EXA-4700 (all are the products made from DIC) etc. are mentioned, for example.
As what is marketed among the said phenol novolak-type epoxy resins, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said ortho cresol novolak-type epoxy resins, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, EPICLON HP-7200 (made by DIC) etc. are mentioned, for example.
As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said naphthalene phenol novolak-type epoxy resins, ESN-165S (made by Nippon Steel Chemical & Material Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said glycidyl amine type epoxy resins, jER630 (made by Mitsubishi Chemical Corporation), EPICLON430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Co., Inc.) etc. are mentioned, for example.
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.), Epolide PB (manufactured by Daicel Corp.), and the like.
As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase ChemteX Corporation) etc. is mentioned, for example.
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei), jER1031, and jER1032. (All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.

As the epoxy compound, a partial (meth) acryl-modified epoxy resin is also preferably used.
In the present specification, the partial (meth) acryl-modified epoxy resin can be obtained by reacting an epoxy group of a part of an epoxy compound having two or more epoxy groups with (meth) acrylic acid. It means a compound having at least one epoxy group and one (meth) acryloyl group in the molecule.
In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acryloyl” means acryloyl or methacryloyl.

Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 and KRM8287 (both manufactured by Daicel Ornex).

Moreover, the said curable resin may contain the (meth) acryl compound.
Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
In the present specification, the “(meth) acrylic compound” means a compound having a (meth) acryloyl group. The “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” is a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid. Represents that.

Among the above (meth) acrylic acid ester compounds, as monofunctional ones, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Til (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (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, tetrahydroflur Furyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 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) acrylic Examples include leuoxyethyl phosphate and glycidyl (meth) acrylate.

Moreover, as a bifunctional thing among the said (meth) acrylic acid ester compounds, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol 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, poly Lopylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol Dicyclopentadienyl di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol Di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol (Meth) acrylate.

Further, among the above (meth) acrylic acid ester compounds, those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.

As an epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, the thing similar to the epoxy compound mentioned above as a curable resin which the sealing compound for liquid crystal display elements of this invention contains can be used.

Examples of commercially available epoxy (meth) acrylates include, for example, an epoxy (meth) acrylate manufactured by Daicel Ornex, an epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., and an epoxy ( Examples include (meth) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylates manufactured by Daicel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702,
Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, and the like.
Examples of the epoxy (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, epoxy ester 1600A, Epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, and the like can be given.
Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

As an isocyanate compound used as the raw material of the urethane (meth) acrylate, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene 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) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.

Moreover, as an isocyanate compound used as the raw material of the said urethane (meth) acrylate, the chain-extended isocyanate compound obtained by reaction with a polyol and an excess isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of divalent alcohol, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol. And epoxy (meth) acrylate.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, and the like.
Examples of the trivalent alcohol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate.

Examples of commercially available urethane (meth) acrylates include, for example, urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, and M-1600.
The urethane (meth) acrylate manufactured by the Daicel Orunekusu Inc., for example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 etc. Can be mentioned.
Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, Art Resin UN- 7100, Art Resin UN-9000A, Art Resin UN-9000H, and the like.
Examples of the urethane (meth) acrylate manufactured by Shin-Nakamura Chemical 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, and the like.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, and UA-306T. It is done.

When the curable resin contains the (meth) acrylic compound in addition to the epoxy compound, or when it contains the partial (meth) acryl-modified epoxy compound, the epoxy group in the curable resin and (meth) The ratio of (meth) acryloyl groups in the total with acryloyl groups is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is within this range, the resulting liquid crystal display element sealant is more excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.

From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has a hydrogen bonding unit such as an —OH group, —NH— group, and —NH ₂ group.

The sealing agent for liquid crystal display elements of the present invention preferably contains a radical polymerization initiator.
Examples of the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation and a thermal radical polymerization initiator that generates radicals by heating.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino). ) -2-((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis ( 2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) 2-hydroxy-2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione 2 (O-benzoyl oxime), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and the like.
The said radical photopolymerization initiator may be used independently and 2 or more types may be used in combination.

As said thermal radical polymerization initiator, what is comprised with an azo compound, an organic peroxide, etc. is mentioned, for example. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as “azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as “polymer azo”). (Also referred to as “initiator”) is more preferred.
The said thermal radical polymerization initiator may be used independently, and 2 or more types may be used in combination.
In the present specification, the “polymer azo compound” means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more. To do.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it can be easily mixed into the curable resin while preventing adverse effects on the liquid crystal. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion, measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group.
Examples of commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). Can be mentioned.
Examples of the azo initiator that is not a polymer include V-65 and V-501 (both manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

The content of the radical polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. The minimum with more preferable content of the said radical polymerization initiator is 1 weight part, A more preferable upper limit is 10 weight part, Furthermore, a preferable upper limit is 5 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and improving the moisture resistance of the cured product.

As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The said filler may be used independently and 2 or more types may be used in combination.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is within this range, the effect of improving adhesiveness and the like is improved without deteriorating applicability and the like. The minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a silane coupling agent. The silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesion to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
The said silane coupling agent may be used independently and 2 or more types may be used in combination.

The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness is suppressed while suppressing the occurrence of liquid crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.

The sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal display elements of this invention can be used suitably 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. Of these, titanium black is preferable.

Titanium black is a substance having higher transmittance for light in the vicinity of the ultraviolet region, particularly for light with a wavelength of 370 nm to 450 nm, compared to the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region. A shading agent. Therefore, the photo-curing property of the sealing agent for liquid crystal display elements of the present invention is further increased by using a photo-radical polymerization initiator that can initiate a reaction with light having a wavelength that increases the transmittance of the titanium black. Can be made. On the other hand, the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
The titanium black preferably has an optical density (OD value) per μm of 3 or more, more preferably 4 or more. The higher the light-shielding property of the titanium black, the better. The OD value of the titanium black is not particularly limited, but is usually 5 or less.

The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium black include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd.
Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13R-N, and 14M-C.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilac D.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.
Further, 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.

Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
The primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, a superior light-shielding property is exhibited without greatly reducing the adhesiveness, strength after curing, and drawing property of the obtained sealing agent for liquid crystal display elements. be able to. The more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention is further added with a stress relaxation agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc., if necessary. An agent may be contained.

As a method for producing the sealing agent for liquid crystal display elements of the present invention, for example, using a mixer, a curable resin, a thermosetting agent, and a radical polymerization initiator added as necessary are mixed. Methods and the like.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.

A vertical conduction material can be produced by blending conductive fine particles with the sealing agent for liquid crystal display elements of the present invention. Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.

As said electroconductive fine particles, what formed the conductive metal layer on the surface of a metal ball, resin microparticles | fine-particles etc. can be used, for example. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
The sealing agent for liquid crystal display elements of the present invention has low compatibility with liquid crystal molecules having a polar group, and therefore when the liquid crystal display element of the present invention is a liquid crystal containing liquid crystal molecules having a polar group, The effect of suppressing display defects is more significant than conventional sealing agents. That is, the liquid crystal display element of the present invention preferably uses a liquid crystal containing liquid crystal molecules having a polar group.
Examples of the polar group of the liquid crystal molecule include a fluoro group, a chloro group, and a cyano group.

As the liquid crystal display element of the present invention, a liquid crystal display element having a narrow frame design is preferable. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.
Moreover, it is preferable that the application | coating width | variety of the sealing compound for liquid crystal display elements of this invention at the time of manufacturing the liquid crystal display element of this invention is 1 mm or less.

The sealing agent 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.
Examples of the method for producing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of forming a frame-shaped seal pattern on the substrate by screen printing, dispenser application, or the like of the sealing agent for liquid crystal display elements of the present invention is performed. Next, in a state where the sealant for the liquid crystal display element of the present invention is uncured, a droplet of liquid crystal is dropped on the entire surface of the frame of the seal pattern, and another substrate is immediately superimposed. Thereafter, a liquid crystal display element can be obtained by a method of heating and curing the sealing agent. Moreover, you may perform the process of irradiating light, such as an ultraviolet-ray, to a seal pattern part, and preliminarily hardening a sealing agent before the process of heating and hardening a sealing agent.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability and sclerosis | hardenability, and can provide the sealing compound for liquid crystal display elements which can suppress generation | occurrence | production of a display defect, when it uses for a thin liquid crystal display element. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

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

(Synthesis of Compound A)
In a three-necked flask equipped with a thermometer and a stirrer, 16.2 parts by weight of malic dihydrazide was dissolved in 100 parts by weight of toluene and stirred at 60 ° C. A solution prepared by dissolving 3.4 parts by weight of hexamethylene diisocyanate in 50 parts by weight of toluene was added dropwise to the obtained solution at a dropping rate of 5 mL / min, and then stirred at 60 ° C. for 6 hours for reaction. After filtering the obtained reaction liquid and isolate | separating a solid substance, the obtained solid substance was washed with water, and the compound A was obtained as a thermosetting agent concerning this invention by drying.
In addition, it was confirmed by MS and FT-IR that the obtained compound A was a compound represented by formula (2) (R ¹ is a malic acid dihydrazide residue, R ² is a hexamethylene diisocyanate residue). .

(Synthesis of Compound B)
Compound B was obtained as a thermosetting agent according to the present invention in the same manner as in “(Synthesis of Compound A)” except that 16.2 parts by weight of malic acid dihydrazide was changed to 17.8 parts by weight of tartaric acid dihydrazide. .
In addition, it was confirmed by MS and FT-IR that the obtained compound B was a compound represented by the formula (2) (R ¹ was a tartaric acid dihydrazide residue and R ² was a hexamethylene diisocyanate residue).

(Synthesis of Compound C)
Except for changing 3.4 parts by weight of hexamethylene diisocyanate to 4.4 parts by weight of isophorone diisocyanate, Compound C was obtained as a thermosetting agent according to the present invention in the same manner as in the above “(Synthesis of Compound A)”. .
In addition, it was confirmed by MS and FT-IR that the obtained compound C was a compound represented by the formula (2) (R ¹ is a malic acid dihydrazide residue and R ² is an isophorone diisocyanate residue).

(Synthesis of Compound D)
Similar to “(Synthesis of Compound A)” except that 16.2 parts by weight of malic acid dihydrazide was changed to 13.2 parts by weight of malonic acid dihydrazide, a hydrazide compound residue having no hydroxyl group and an isocyanate compound Compound D which is a compound having a residue was obtained.
In addition, according to MS and FT-IR, in the obtained compound D, the portion corresponding to R ¹ in the formula (2) is a malonic acid dihydrazide residue, and the portion corresponding to R ² is a hexamethylene diisocyanate residue. It was confirmed to be a compound.

(Examples 1-9, Comparative Examples 1-4)
According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls The sealing agent for each liquid crystal display element of Examples 1-9 and Comparative Examples 1-4 was prepared.

<Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(Storage stability)
For each liquid crystal display element sealant obtained in the Examples and Comparative Examples, the initial viscosity immediately after production and the viscosity after storage in an atmosphere of 25 ° C. and 50% RH for 48 hours were measured. (Viscosity after storage) / (Initial viscosity) is a thickening rate, “○” indicates that the thickening rate is less than 1.2, and “△” indicates that the viscosity is 1.2 or more and less than 1.3. The storage stability was evaluated as “x” when the value was 1.3 or more.
The viscosity of the sealant was measured using an E-type viscometer (manufactured by BROOK FIELD, “DV-III”) at 25 ° C. and a rotation speed of 1.0 rpm.

(Curable)
Each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples was spotted on one of the two transparent substrates, and the other transparent substrate was overlaid, and then 100 mW / cm ² using a metal halide lamp. Irradiated with ultraviolet rays for 30 seconds. Then, it heated at 120 degreeC for 1 hour, and heat-cured the sealing compound for liquid crystal display elements. The transparent substrate is peeled off, and the cured product remaining on the transparent substrate is measured using an infrared spectrometer (manufactured by Agilent Technologies, “UMA600”), and the obtained measurement result and the pre-curing measurement that has been measured in advance. From the results, the curing rate was calculated by the following formula.
Curing rate (%) = 100 × (1- (peak area of epoxy group after curing) / (peak area of epoxy group before curing))
The curability was evaluated as “◯” when the curing rate was 90% or more, “Δ” when 70% or more and less than 90%, and “X” when less than 70%.

(Display performance of liquid crystal display elements)
A seal pattern was formed on one of the two rubbed alignment films and the substrate with a transparent electrode by applying each liquid crystal display element sealant obtained in Examples and Comparative Examples with a dispenser so as to draw a square frame. . A sealant for a liquid crystal display element was spotted on the inner side of the formed seal pattern.
Subsequently, fine droplets of liquid crystal containing a liquid crystal molecule having a cyano group as a polar group (“4-pentyl-4-biphenylcarbonitrile” manufactured by Tokyo Chemical Industry Co., Ltd.) are applied to the entire surface of the sealing agent frame of the substrate with a transparent electrode. Then, the other substrate was superposed in a vacuum. After releasing the vacuum, the outer frame seal portion was irradiated with ultraviolet rays of 100 mW / cm ² for 30 seconds using a metal halide lamp. At this time, the masked sealant for the liquid crystal display element was masked so as not to be irradiated with ultraviolet rays. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour, and the liquid crystal display element sealant was thermally cured to obtain a liquid crystal display element.
The obtained liquid crystal display element was subjected to a voltage application state for 500 hours in an environment of 60 ° C. and 90% RH, and then the liquid crystal alignment disorder (display unevenness) around the dotted sealing agent for the liquid crystal display element was visually observed. Confirmed by.
“◎” indicates that display unevenness has not occurred, “○” indicates that display unevenness has occurred but disappeared immediately after the occurrence, and “△” indicates that display unevenness with a distance of 1 mm or less from the seal remains. The display performance of the liquid crystal display element was evaluated as “x” when display unevenness with a distance exceeding 1 mm from the seal was left.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in storage stability and sclerosis | hardenability, and can provide the sealing compound for liquid crystal display elements which can suppress generation | occurrence | production of a display defect, when it uses for a thin liquid crystal display element. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

Claims (5)

A sealing agent for a liquid crystal display element containing a curable resin and a thermosetting agent,
The said thermosetting agent contains the compound (A) which has the following characteristics (a), (b), (c), and (d), The sealing compound for liquid crystal display elements characterized by the above-mentioned.
(A) having a hydroxyl group-containing hydrazide compound residue (b) having an isocyanate compound residue (c) having a structure represented by the following formula (1) (d) having no isocyanate group

In formula (1), * is a bonding position. The hydroxyl group-containing hydrazide compound that is the origin of the hydroxyl group-containing hydrazide compound residue in the feature (a) is a compound having a hydroxyl group and two or more hydrazide groups in one molecule, and
The sealing compound for liquid crystal display elements according to claim 1, wherein the isocyanate compound that is the origin of the isocyanate compound residue in the feature (b) is a compound having two or more isocyanate groups in one molecule. The sealing compound for liquid crystal display elements according to claim 1 or 2, wherein the content of the compound (A) in 100 parts by weight of the curable resin is 0.1 parts by weight or more and 20 parts by weight or less. A vertical conduction material comprising the liquid crystal display element sealing agent according to claim 1, 2 or 3 and conductive fine particles. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2, or 3, or the vertical conduction material according to claim 4.