WO2021044842A1 - Sealing agent for liquid crystal display elements, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

A purpose of the present invention is to provide a sealing agent for liquid crystal display elements, said sealing agent having excellent storage stability, adhesiveness and low liquid crystal contamination properties. Another purpose of the present invention is to provide a vertical conduction material and a liquid crystal display element, each of which is obtained using the sealing agent for liquid crystal display elements. The present invention is a sealing agent for liquid crystal display elements, said sealing agent containing a thermosetting resin and a thermal curing agent, wherein: the thermal curing agent contains a hydrazide compound; and the hydrazide compound has a structure represented by formula (1-1) and a structure represented by formula (1-2). In formula (1-1), Ar represents an aromatic ring; and in formula (1-2), R¹ represents a hydrogen atom or a methyl group.

Description

Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element

The present invention relates to a sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. The present invention also relates to a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, dropping using a sealant as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening the 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-shaped seal pattern is formed on one of the two electrode-equipped substrates by dispensing. Next, in a state where the sealant is uncured, fine droplets of liquid crystal are dropped into the frame of the seal pattern, the other substrate is overlapped under vacuum, and then the sealant is cured to produce a liquid crystal display element. Currently, this dropping method is the mainstream method for manufacturing liquid crystal display elements.

By the way, in the present age when various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widespread, miniaturization of the devices is the most sought after issue. As a method of miniaturizing the device, a narrowing of the frame of the liquid crystal display unit can be mentioned. 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, the sealant is placed directly under the black matrix, so if the dropping method is performed, the light emitted when the sealant is photocured is blocked, and it is difficult for the light to reach the inside of the sealant. , The conventional sealant is insufficiently cured. When the sealant is not sufficiently cured in this way, there is a problem that the uncured sealant component elutes into the liquid crystal and easily causes liquid crystal contamination. In particular, in recent years, with the increasing polarity of liquid crystals, the sealant has been required to have further low liquid crystal contamination.

When it is difficult to photo-cure the sealant, it is considered that the sealant is cured by heating, and as a method for curing the sealant by heating, a thermosetting agent is added to the sealant. .. However, when a highly reactive thermosetting agent is used to improve the curability and adhesiveness of the sealant, the obtained sealant may be inferior in storage stability.

Japanese Unexamined Patent Publication No. 2001-133794 International Publication No. 02/092718

An object of the present invention is to provide a sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. Another object of the present invention is to provide a vertically conductive material and a liquid crystal display element using the sealant 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, wherein the thermosetting agent contains a hydrazide compound, and the hydrazide compound is represented by the following formula (1-1). It is a sealing agent for a liquid crystal display element having a structure to be formed and a structure represented by the following formula (1-2).

In formula (1-1), Ar is an aromatic ring, and in formula (1-2), R ¹ is a hydrogen atom or a methyl group.
The present invention will be described in detail below.

As a result of diligent studies, the present inventor has found that by using a thermosetting agent having a specific structure, a sealant for a liquid crystal display element having excellent storage stability, adhesiveness, and low liquid crystal contamination can be obtained. The present invention has been completed.

The sealant for a liquid crystal display element of the present invention contains a thermosetting agent.
The thermosetting agent contains a hydrazide compound.
The hydrazide compound has a structure represented by the above formula (1-1) and a structure represented by the above formula (1-2). Hereinafter, a hydrazide compound having a structure represented by the above formula (1-1) and a structure represented by the above formula (1-2) is also referred to as a “hydrazide compound according to the present invention”. By containing the hydrazide compound according to the present invention, the sealant for a liquid crystal display element of the present invention is excellent in all of storage stability, adhesiveness, and low liquid crystal contamination.

The following can be considered as the reason why the obtained sealant for a liquid crystal display element is excellent in storage stability, adhesiveness, and low liquid crystal contamination by using the hydrazide compound according to the present invention. ..
That is, it is considered that the storage stability can be improved because the softening point of the hydrazide compound can be controlled by having the structure represented by the above formula (1-1). Further, it is considered that the adhesiveness of the obtained sealant can be improved by having the structure represented by the above formula (1-2) containing the primary amino group. Further, it is considered that having these structures increases the molecular weight of the hydrazide compound, so that elution into the liquid crystal can be suppressed.

In the hydrazide compound according to the present invention, the preferable lower limit of the ratio of the structure represented by the above formula (1-1) is 5 mol%, and the preferable upper limit is 95 mol%. When the ratio of the structure represented by the above formula (1-1) is 5 mol% or more, the obtained sealant for a liquid crystal display element becomes more excellent in storage stability. When the ratio of the structure represented by the above formula (1-1) is 95 mol% or less, the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness. The more preferable lower limit of the ratio of the structure represented by the above formula (1-1) is 10 mol%, the more preferable upper limit is 90 mol%, and the further preferable upper limit is 50 mol%.

In the hydrazide compound according to the present invention, the preferable lower limit of the ratio of the structure represented by the above formula (1-2) is 5 mol%, and the preferable upper limit is 95 mol%. When the ratio of the structure represented by the above formula (1-2) is 5 mol% or more, the obtained sealant for the liquid crystal display element becomes more excellent in adhesiveness. When the ratio of the structure represented by the above formula (1-2) is 95 mol% or less, the obtained sealant for a liquid crystal display element becomes more excellent in storage stability. The more preferable lower limit of the ratio of the structure represented by the above formula (1-2) is 10 mol%, the more preferable upper limit is 90 mol%, and the further preferable lower limit is 50 mol%.

The hydrazide compound according to the present invention may have other structures in addition to the structure represented by the above formula (1-1) and the structure represented by the above formula (1-2).
The hydrazide compound according to the present invention preferably has a structure represented by the following formula (2) as the above-mentioned other structure. By having the structure represented by the following formula (2), the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness.

In the formula (2), R ² is a hydrogen atom or a methyl group, R ³ is an −C (= O) OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms). -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.

The hydrazide compound according to the present invention has a preferable lower limit of 2000 and a preferable upper limit of 200,000 in weight average molecular weight. When the weight average molecular weight is 2000 or more, the obtained sealant for a liquid crystal display element becomes more excellent in low liquid crystal contamination. When the weight average molecular weight is 200,000 or less, the obtained sealant for a liquid crystal display element becomes more excellent in handleability. The more preferable lower limit of the weight average molecular weight is 4000, and the more preferable upper limit is 100,000.
In the present specification, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).

The preferable lower limit of the softening point of the hydrazide compound according to the present invention is 65 ° C., and the preferable upper limit is 200 ° C. When the softening point of the hydrazide compound according to the present invention is 65 ° C. or higher, the obtained sealant for a liquid crystal display element becomes more excellent in storage stability. When the softening point of the hydrazide compound according to the present invention is 200 ° C. or lower, the obtained sealant for a liquid crystal display element becomes more excellent in adhesiveness. The more preferable lower limit of the softening point of the hydrazide compound according to the present invention is 90 ° C., and the more preferable upper limit is 160 ° C.
The softening point can be determined by the ring-and-ball method according to JIS K 2207.

Examples of the method for producing the hydrazide compound according to the present invention include the following methods.
That is, first, the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2) are dissolved in a solvent such as tetrahydrofuran, and the polymerization of azobisisobutyronitrile or the like is started. In the presence of the agent, the reaction is carried out by heating and stirring while substituting nitrogen. After concentrating the obtained reaction product, it is reprecipitated in an ethanol solution to obtain an intermediate polymer compound. The obtained intermediate polymer compound and hydrazine hydrate are dissolved in a solvent such as tetrahydrofuran and reacted under reflux. After completion of the reaction, the hydrazide compound according to the present invention can be obtained by concentrating and separating the solid matter.
Further, in addition to the compound represented by the following formula (3-1) and the compound represented by the following formula (3-2), a compound represented by the following formula (4) may be used.

In formula (3-1), Ar is an aromatic ring, in formula (3-2), R ¹ is a hydrogen atom or a methyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms. is there.

In formula (4), R ² is a hydrogen atom or a methyl group, R ³ is a -C (= O) OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms). -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.

Regarding the content of the hydrazide compound according to the present invention, the preferable lower limit is 1 part by weight and the preferable upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the hydrazide compound according to the present invention is 1 part by weight or more, the obtained sealant for a liquid crystal display element becomes excellent in curability and adhesiveness. When the content of the hydrazide compound according to the present invention is 20 parts by weight or less, the obtained sealant for a liquid crystal display element becomes excellent in storage stability and low liquid crystal contamination. The more preferable lower limit of the content of the hydrazide compound according to the present invention is 2 parts by weight, and the more preferable upper limit is 15 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain other heat-curing agents in addition to the hydrazide compound according to the present invention as long as the object of the present invention is not impaired.
Examples of the heat-curing agent include organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenol compound, acid anhydride and the like.

The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type epoxy resin. , Propoxy 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 type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compound, etc. Be done.

Examples of commercially available bisphenol A type epoxy resins include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
Examples of commercially available bisphenol F type epoxy resins include jER806, jER4004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (manufactured by DIC Corporation), and the like.
Examples of commercially available bisphenol E-type epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals, Inc.) and the like.
Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation) and the like.
Among the above 2,2'-diallyl bisphenol A type epoxy resins, commercially available ones include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy resins include EPICLON EXA-7015 (manufactured by DIC Corporation) and the like.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available naphthalene-type epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenol novolac type epoxy resins include EPICLON N-770 (manufactured by DIC Corporation) and the like.
Examples of commercially available orthocresol novolac type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
Examples of commercially available dicyclopentadiene novolac type epoxy resins include EPICLON HP-7200 (manufactured by DIC Corporation) and the like.
Examples of commercially available biphenyl novolac type epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like.
Among the above alkyl polyol type epoxy resins, commercially available ones include, for example, ZX-1542 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), EPICLON726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-. 611 (manufactured by Nagase ChemteX Corporation) and the like can be mentioned.
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 Co., Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
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 Corporation), 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 partially (meth) acrylic-modified epoxy resin is also preferably used.
In the present specification, the partial (meth) acrylic-modified epoxy resin can be obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups with (meth) acrylic acid. It means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in the molecule.
In the present specification, the above-mentioned "(meth) acrylic" means acrylic or methacrylic, and the above-mentioned "(meth) acryloyl" means acryloyl or methacryloyl.

Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE1561 and KRM8287 (both manufactured by Daicel Ornex).

Further, the curable resin may contain a (meth) acrylic 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. Further, 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 above-mentioned "(meth) acrylic compound" means a compound having a (meth) acryloyl group. Further, the above-mentioned "(meth) acrylate" means acrylate or methacrylate, and the above-mentioned "epoxy (meth) acrylate" is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid. Represents that.

Among the above (meth) acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 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-hydroxybutyl (meth) acrylate, cyclohexyl ( Meta) 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, tetrahydrofurfuryl (meth) acrylate, ethylcarbi Thor (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, Imid (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2-( Examples thereof include 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, and glycidyl (meth) acrylate.

Examples of the bifunctional one among the above (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Diol di (meth) acrylate, 1,9-nonane diol di (meth) acrylate, 1,10-decane diol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meta) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol 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 dicyclopentadienyldi (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonatediol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, those having trifunctionality or higher include, for example, trimetyl propanetri (meth) acrylate, ethylene oxide-added trimethyl propanetri (meth) acrylate, and propylene oxide-added trimethyl propanetri (meth) acrylate. Meta) acrylate, caprolactone-modified trimethylol propantri (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, Examples thereof include tris (meth) acryloyloxyethyl phosphate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 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 the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate, the same epoxy compound as the above-mentioned epoxy compound can be used as the curable resin contained in the sealant for a liquid crystal display element of the present invention.

Among the above-mentioned epoxy (meth) acrylates, commercially available ones include, for example, epoxy (meth) acrylate manufactured by Daicel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and epoxy (meth) acrylate manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylate manufactured by Daicel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3701
Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
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, and epoxy ester 1600A. Examples thereof include epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, and epoxy ester 400EA.
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 urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with respect to an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate compound used as a raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4. '-Diisocyanate (MDI), hydrogenated MDI, polypeptide MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantryisocyanate and the like can be mentioned.

Further, as the isocyanate compound which is a raw material of the urethane (meth) acrylate, a chain-extended isocyanate compound obtained by reacting a polyol with 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 dihydric alcohol, mono (meth) acrylate of trihydric alcohol, and di (meth) acrylate. , Epoxy (meth) acrylate and the like.
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 trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol A type epoxy acrylate and the like.

Among the above urethane (meth) acrylates, commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic 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 Industry 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, and Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like can be mentioned.
Examples of the urethane (meth) 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, and the like. 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- Examples thereof include 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, and UA-W2A.
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. Be done.

When the curable resin contains the (meth) acrylic compound in addition to the epoxy compound, or when the partial (meth) acrylic-modified epoxy compound is contained, the epoxy group and the (meth) in the curable resin It is preferable that the ratio of the (meth) acryloyl group in the total with the acryloyl group is 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the sealant for the liquid crystal display element obtained is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.

The curable resin preferably has hydrogen-bonding units such as _{-OH group, -NH- group, and -NH 2} group from the viewpoint of further suppressing liquid crystal contamination.

The sealant for a liquid crystal display element of the present invention preferably further contains a photoradical polymerization initiator.
Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenyl 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) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-Hydroxy-2-methyl-1-propane-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime), 2,4,6-trimethyl Examples thereof include benzoyldiphenylphosphine oxide.
The photoradical polymerization initiator may be used alone or in combination of two or more.

The content of the photoradical polymerization initiator is preferably 0.5 parts by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the photoradical polymerization initiator is in this range, the obtained sealant for a liquid crystal display element is excellent in storage stability and photocurability while suppressing liquid crystal contamination. The more preferable lower limit of the content of the photoradical polymerization initiator is 1 part by weight, and the more preferable upper limit is 7 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a thermal radical polymerization initiator.
Examples of the thermal radical polymerization initiator include those composed of an azo compound, an organic peroxide, or the like. Among them, an initiator composed of an azo compound (hereinafter, also referred to as “azo initiator”) is preferable from the viewpoint of suppressing liquid crystal contamination, and an initiator composed of a polymer azo compound (hereinafter, “polymer azo”) is preferable. Also referred to as "initiator") is more preferred.
The thermal radical polymerization initiator may be used alone or in combination of two or more.
In the present specification, the above-mentioned "polymer azo compound" means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth) acryloyl group by heat. 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 in this range, it can be easily mixed with 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 further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.
In the present specification, the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. 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 a polycondensate 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 and the like.
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 Fujifilm Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.

Regarding the content of the thermal radical polymerization initiator, the preferable lower limit is 0.1 parts by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermal radical polymerization initiator is in this range, the obtained sealant for a liquid crystal display element is excellent in storage stability and thermosetting property while suppressing liquid crystal contamination. The more preferable lower limit of the content of the thermal radical polymerization initiator is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness by the stress dispersion effect, improving the coefficient of linear expansion, improving the moisture resistance of the cured product, and the like.

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, active white 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, acrylic polymer fine particles, and the like.
The above-mentioned filler may be used alone or in combination of two or more.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element 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 in this range, the effect of improving the adhesiveness and the like is excellent without deteriorating the coatability and the like. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a silane coupling agent. The silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering a sealant for a liquid crystal display element and a substrate or the like.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness with the substrate and the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
The silane coupling agent may be used alone or in combination of two or more.

The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness while suppressing the occurrence of liquid crystal contamination becomes more excellent. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black and the like. Of these, titanium black is preferable.

The titanium black is a substance having a higher transmittance for light in the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting light-shielding property to the sealant for a liquid crystal display element of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. It is a light-shielding agent. Therefore, by using the photoradical polymerization initiator that can initiate the reaction with light having a wavelength that increases the transmittance of the titanium black, the photocurability of the sealant for a liquid crystal display element of the present invention is further increased. Can be made to. On the other hand, as the light-shielding agent contained in the sealant for a liquid crystal display element of the present invention, a substance having high insulating properties is preferable, and titanium black is also preferable as the light-shielding agent having high insulating properties.
The titanium black has an optical density (OD value) per μm of preferably 3 or more, and more preferably 4 or more. The higher the light-shielding property of the titanium black, the better, and the OD value of the titanium black has no particular preferable upper limit, but is usually 5 or less.

The above titanium black exerts 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, or oxidation. Surface-treated titanium black, such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
Further, the liquid crystal display element manufactured by using the sealant for the liquid crystal display element of the present invention containing the above titanium black as a light shielding agent has sufficient light shielding properties, so that there is no light leakage and the contrast is high. A liquid crystal display element having excellent image display quality can be realized.

Examples of commercially available titanium blacks 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, 13MC, 13RN, 14MC and the like.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.

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

The primary particle size of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, but the preferable lower limit is 1 nm and the preferable upper limit is 5000 nm. When the primary particle size of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the coatability of the obtained sealant for the liquid crystal display element. The more preferable lower limit of the primary particle size of the light-shielding agent is 5 nm, the more preferable upper limit is 200 nm, the further preferable lower limit is 10 nm, and the further preferable upper limit is 100 nm.
The primary particle size of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element 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, the adhesiveness of the obtained sealant for a liquid crystal display element, the strength after curing, and the drawability are not significantly deteriorated, and more excellent light-shielding property is exhibited. be able to. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.

The sealant for a liquid crystal display element of the present invention further contains a stress relaxation agent, a reactive diluent, a rocking agent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor and the like, if necessary. The agent may be contained.

As a method for producing the sealant for a liquid crystal display element of the present invention, for example, a curable resin, a thermosetting agent, a thermal radical polymerization initiator added as needed, and the like are mixed using a mixer. The method of doing this can be mentioned.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

By blending conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertically conductive material can be produced. Such a vertically conductive material containing the sealant for a liquid crystal display element of the present invention and conductive fine particles is also one of the present inventions.

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

A liquid crystal display element made of the sealant for a liquid crystal display element of the present invention or the vertically conductive material of the present invention is also one of the present inventions.

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.
Further, when the liquid crystal display element of the present invention is manufactured, the coating width of the sealant for the liquid crystal display element of the present invention is preferably 1 mm or less.

The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
Examples of the method for manufacturing 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 a substrate by screen printing, applying a dispenser, or the like to the sealant for a liquid crystal display element of the present invention is performed. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, fine droplets of liquid crystal are dropped and applied to the entire surface of the frame of the seal pattern, and a step of immediately superimposing another substrate is performed. After that, a liquid crystal display element can be obtained by a method of heating and curing the sealant. Further, before the step of heating and curing the sealant, a step of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealant may be performed.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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

(Synthesis of Compound A)
208.3 g (2.0 mol) of styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer. ) 172.1 g (2.0 mol) was dissolved in 300 mL of tetrahydrofuran. 16.4 g (0.1 mol) of azobisisobutyronitrile was added to the obtained solution as a polymerization initiator, and the mixture was stirred at 80 ° C. for 1 hour while substituting with nitrogen for reaction. The obtained reaction product was concentrated and then reprecipitated in an ethanol solution to obtain an intermediate polymer compound.
The intermediate polymer compound obtained in a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 200 mL of tetrahydrofuran and under reflux. The reaction was carried out for 3 hours. After completion of the reaction, the compound A was obtained by concentrating and separating the solid matter.
¹ Compound A obtained by 1 H-NMR, MS, and FT-IR is represented by the structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} confirmed. Further, the obtained compound A had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound A was 15,000, and the softening point was 130 ° C.

(Synthesis of Compound B)
Compound B was obtained as the hydrazide compound according to the present invention in the same manner as in the above "(Synthesis of compound A)" except that the stirring time when stirring at 80 ° C. while substituting with nitrogen was changed to 4 hours.
The ^{compound B obtained by 1} H-NMR, MS, and FT-IR has a structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure represented by (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} It was confirmed. Further, the obtained compound B had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound B was 70,000, and the softening point was 147 ° C.

(Synthesis of Compound C)
Compound C was obtained as the hydrazide compound according to the present invention in the same manner as in the above "(Synthesis of compound A)" except that the stirring time when stirring at 80 ° C. while substituting with nitrogen was changed to 0.5 hours. ..
The ^{compound C obtained by 1} H-NMR, MS, and FT-IR has a structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure represented by (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} It was confirmed. Further, the obtained compound C had a structure represented by the above formula (1-1) in an amount of 50 mol%. Further, the weight average molecular weight of the obtained compound C was 3000, and the softening point was 92 ° C.

(Synthesis of Compound D)
The compounding amount of styrene was changed to 416.6 g (4.0 mol), the compounded amount of methyl acrylate was changed to 86.0 g (1.0 mol), and the compounded amount of hydrazine hydrate was 60 g (1. Compound D was obtained as the hydrazine compound according to the present invention in the same manner as in the above "(Synthesis of compound A)" except that it was changed to 2 mol).
The ^{compound D obtained by 1} H-NMR, MS, and FT-IR has a structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure represented by (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} It was confirmed. Further, the obtained compound D had 80 mol% of the structure represented by the above formula (1-1). Further, the weight average molecular weight of the obtained compound D was 25,000, and the softening point was 156 ° C.

(Synthesis of compound E)
The compounding amount of styrene was changed to 494.7 g (4.75 mol), the compounding amount of methyl acrylate was changed to 21.5 g (0.25 mol), and the compounding amount of hydrazine hydrate was 20 g (0. Compound E was obtained as the hydrazine compound according to the present invention in the same manner as in the above "(Synthesis of compound A)" except that it was changed to 4 mol).
The ^{compound E obtained by 1} H-NMR, MS, and FT-IR has a structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure represented by (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} It was confirmed. Further, the obtained compound E had 95 mol% of the structure represented by the above formula (1-1). Further, the weight average molecular weight of the obtained compound E was 24,000, and the softening point was 200 ° C.

(Synthesis of Compound F)
The compounding amount of styrene was changed to 26.0 g (0.25 mol), the compounding amount of methyl acrylate was changed to 408.7 g (4.75 mol), and the compounding amount of hydrazine hydrate was 275 g (5. Compound F was obtained as the hydrazine compound according to the present invention in the same manner as in the above "(Synthesis of compound A)" except that it was changed to 5 mol).
The ^{compound F obtained by 1} H-NMR, MS, and FT-IR has a structure represented by the above formula (1-1) (Ar is a phenyl group) and the above formula (1-2). It is a compound having a structure represented by (R ¹ is a hydrogen atom) and a structure represented by the above formula (2) (R ² is a hydrogen atom and R ³ is -C (= O) OCH _{3 groups).} It was confirmed. Further, the obtained compound F had a structure represented by the above formula (1-1) in an amount of 5 mol%. Further, the weight average molecular weight of the obtained compound F was 16000, and the softening point was 69 ° C.

(Synthesis of compound G)
Methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 86.1 g (1.0 mol) and 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer. 116.1 g (1.0 mol) was dissolved in 150 mL of tetrahydrofuran. Azobisisobutyronitrile (16.4 g (0.1 mol)) was added to the obtained solution as a polymerization initiator, and the mixture was reacted by stirring at 80 ° C. for 2 hours while substituting nitrogen. The obtained reaction product was concentrated and then reprecipitated in an ethanol solution to obtain an intermediate polymer compound.
The intermediate polymer compound obtained in a three-necked flask equipped with a reflux condenser, a thermometer, and a stirrer and 113 g (2.3 mol) of hydrazine hydrate were dissolved in 100 mL of methanol and 10 mL of water. The reaction was carried out under reflux for 3 hours. After completion of the reaction, the compound G was obtained by concentrating and separating the solid matter.
¹ It was confirmed by 1 H-NMR, MS and FT-IR that the obtained compound G was a compound represented by the following formula (5). The weight average molecular weight of the obtained compound G was 12000, and the softening point was 64 ° C.

In formula (5), m and n are repetition numbers.

(Examples 1 to 10, Comparative Examples 1 to 3)
According to the compounding ratios shown in Tables 1 and 2, each material is mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., "Awatori Rentaro"), and then further mixed using three rolls. Sealing agents for each liquid crystal display element of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared.

<Evaluation>
The following evaluations were performed on the sealants for each liquid crystal display element obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Storage stability)
For each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples, the initial viscosity immediately after production and the viscosity after storage at 25 ° C. for 1 week after production were measured. (Viscosity after storage) / (Initial viscosity) is defined as the thickening rate, and the thickening rate of less than 1.1 is "◎", and the thickening rate of 1.1 or more and less than 1.5 is "○". , 1.5 or more and less than 2.0 was evaluated as "Δ", and 2.0 or more was evaluated as "x" to evaluate the storage stability.
The viscosity of the sealant for the liquid crystal display element was measured using an E-type viscometer (“DV-III” manufactured by BROOK FIELD) at 25 ° C. under the condition of a rotation speed of 1.0 rpm.

(Adhesiveness)
The sealant for each liquid crystal display element obtained in Examples and Comparative Examples was filled in a syringe for dispensing (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) and defoamed. Dispens the sealant for the liquid crystal display element after defoaming treatment 30 mm inward from the edge of the glass substrate (150 mm x 150 mm) with a dispenser (Musashi Engineering Co., Ltd., "SHOTMASTER300"), and another glass substrate (110 mm x 110 mm). ) Were overlapped and pasted together under vacuum. A high-pressure mercury lamp is used to ^{irradiate 100 mW / cm 2} ultraviolet rays for 30 seconds to temporarily cure the sealant for the liquid crystal display element, and then heat at 120 ° C. for 1 hour to thermally cure the sealant for the liquid crystal display element. An adhesion test piece was obtained. When the edge of the substrate of the obtained adhesive test piece is pushed in at a speed of 5 mm / min using a metal rod having a radius of 5 mm, the strength (kgf) at the time of panel peeling is measured, and the adhesive strength (kg / kg /) is measured. cm) was calculated.
"◎" when the adhesive strength is 3.5 kg / cm or more, "○" when the adhesive strength is 3.0 kg / cm or more and less than 3.5 kg / cm, and the adhesive strength is 2.0 kg / cm. The adhesiveness was evaluated as "Δ" when the amount was less than 3.0 kg / cm and "x" when the adhesive strength was less than 2.0 kg / cm.

(Low liquid crystal contamination (NI point))
0.1 g of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples and 1 g of liquid crystal (“4-pentyl-4-biphenylcarbonitrile” manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the sample bottle. This sample bottle was placed in an oven at 120 ° C. for 1 hour, then allowed to stand to return to 25 ° C., and then the liquid crystal portion was taken out and filtered through a 0.2 μm filter to prepare a liquid crystal sample for evaluation. 10 mg of the obtained liquid crystal sample for evaluation was enclosed in an aluminum sample pan, and a differential scanning calorimeter (“DSC-Q100” manufactured by TA instrument) was used to obtain an NI point at a heating rate of 5 ° C./min. The measurement was performed. In addition, 10 mg of the liquid crystal which had not contacted with the sealant for a liquid crystal display element was sealed in an aluminum sample pan, and the result of measuring the NI point under the condition of a heating rate of 5 ° C./min was used as a blank.
When the difference between the NI point measured by the evaluation liquid crystal sample and the NI point of the blank is -2 ° C or higher, it is "◎", when it is -3 ° C or higher and lower than -2 ° C, it is "○",- The low liquid crystal contamination was evaluated as "Δ" when the temperature was 5 ° C. or higher and lower than -3 ° C. and "x" when the temperature was lower than -5 ° C.

(Display performance of liquid crystal display element)
1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") having an average particle diameter of 5 μm was dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and a syringe was used. And defoamed with a centrifugal defoamer (Awatron AW-1). Using a dispenser, the sealant for the liquid crystal display element after the defoaming treatment is applied to the two alignment films under the conditions of a nozzle diameter of 0.4 mmφ, a nozzle gap of 42 μm, a syringe discharge pressure of 100 to 400 kPa, and a coating speed of 60 mm / sec. It was applied in a frame shape to one of the substrates with ITO. At this time, the discharge pressure was adjusted so that the line width of the sealant for the liquid crystal display element was about 1.5 mm. Subsequently, fine droplets of liquid crystal (“4-pentyl-4-biphenylcarbonitrile” manufactured by Tokyo Chemical Industry Co., Ltd.) are dropped on the entire surface of the liquid crystal display element sealant on the substrate coated with the liquid crystal display element sealant. It was applied and the other substrate was bonded under vacuum. Immediately after the bonding, the sealant for the liquid crystal display element was temporarily cured by irradiating the ^{sealant portion for the liquid crystal display element with ultraviolet rays of 100 mW / cm 2 for 30 seconds using a metal halide lamp.} Then, it was heated at 120 ° C. for 1 hour to perform main curing to prepare a liquid crystal display element.
Three liquid crystal display elements were produced for each of the liquid crystal display element sealants obtained in Examples and Comparative Examples, and for each of the obtained liquid crystal display elements, the vicinity of the liquid crystal display element sealant immediately after the liquid crystal display element was produced. The liquid crystal alignment disorder was visually confirmed. Orientation disorder is judged from the color unevenness of the display part, and when no display unevenness is seen in the peripheral part of the liquid crystal display element, "◎", when a slightly light display unevenness is seen, "○", it is clear and dark. The display performance of the liquid crystal display element was evaluated as "Δ" when there was display unevenness and as "x" when the clear dark display unevenness spread not only to the peripheral part but also to the central part.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element, which is excellent in storage stability, adhesiveness, and low liquid crystal contamination. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

Claims (8)

1. A sealant for a liquid crystal display element containing a curable resin and a thermosetting agent.
   The thermosetting agent contains a hydrazide compound and contains.
   The hydrazide compound is a sealant for a liquid crystal display element, which has a structure represented by the following formula (1-1) and a structure represented by the following formula (1-2).
   

   

   In formula (1-1), Ar is an aromatic ring, and in formula (1-2), R ¹ is a hydrogen atom or a methyl group.
2. The sealant for a liquid crystal display element according to claim 1, wherein the hydrazide compound has a structure represented by the formula (1-1) in an amount of 5 mol% or more and 95 mol% or less.
3. The sealant for a liquid crystal display element according to claim 1 or 2, wherein the hydrazide compound further has a structure represented by the following formula (2).
   

   

   In the formula (2), R ² is a hydrogen atom or a methyl group, R ³ is an −C (= O) OR ⁴ group (R ⁴ is a hydrogen atom or an alkyl group having 1 or more and 10 or less carbon atoms). -CN group, -OR ⁵ group (R ⁵ is an alkyl group having 1 to 10 carbon atoms), or a hydrogen atom.
4. The sealant for a liquid crystal display element according to claim 1, 2 or 3, wherein the hydrazide compound has a weight average molecular weight of 2000 or more and 200,000 or less.
5. The sealant for a liquid crystal display element according to claim 1, 2, 3 or 4, wherein the hydrazide compound has a softening point of 65 ° C. or higher and 200 ° C. or lower.
6. The sealant for a liquid crystal display element according to claim 1, 2, 3, 4 or 5, further comprising a photoradical polymerization initiator.
7. A vertically conductive material containing the sealant for a liquid crystal display element according to claim 1, 2, 3, 4, 5 or 6, and conductive fine particles.
8. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2, 3, 4, 5 or 6, or the vertically conductive material according to claim 7.