JP7112604B1 - Liquid crystal display element sealant, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a sealant for liquid crystal display elements which is excellent in storage stability, adhesiveness to alignment films, adhesiveness in high-temperature environments, 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 sealing compound for liquid crystal display elements containing a curable resin and a thermosetting agent, wherein the thermosetting agent does not have a cyclic structure and has at least one tertiary amino group in one molecule. and a compound having two or more hydrazide groups in one molecule.

Description

TECHNICAL FIELD The present invention relates to a sealant for liquid crystal display elements which is excellent in storage stability, adhesiveness to alignment films, adhesiveness in high-temperature environments, 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, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, dropping using a sealing agent as disclosed in Patent Documents 1 and 2 A liquid crystal dropping method called construction method is used.
In the dropping method, first, a frame-shaped seal pattern is formed on one of the two electrode-attached substrates by dispensing. Next, liquid crystal microdroplets are dropped into the frame of the seal pattern while the sealant is not yet cured, and the other substrate is superimposed under vacuum, and the sealant is cured to fabricate a liquid crystal display element. At present, this dripping 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 widely used, miniaturization of devices is the most demanded issue. As a method for downsizing the device, narrowing the frame of the liquid crystal display part is mentioned, and for example, the position of the seal part is arranged under the black matrix (hereinafter also referred to as narrow frame design).

JP-A-2001-133794 WO 02/092718

In the narrow frame design, the sealant is placed directly under the black matrix. The curing of the sealant is insufficient. Insufficient curing of the sealant causes the problem that the uncured sealant components are easily eluted into the liquid crystal to cause liquid crystal contamination. In particular, in recent years, as the polarity of liquid crystals has become higher, contamination of liquid crystals may occur even when using sealing agents that had no problems in the past. In narrow frame designs, the sealant is also placed on the alignment film, and liquid crystal display elements are required to have reliability in even harsher environments. There has been a demand for a sealant for liquid crystal display elements.

If it becomes difficult to photo-cure the sealant, it may be possible to cure the sealant by heating. 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 resulting sealant may have poor storage stability or cause liquid crystal contamination. was there.

An object of the present invention is to provide a sealant for liquid crystal display elements which is excellent in storage stability, adhesiveness to alignment films, adhesiveness in high-temperature environments, 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 1 is a sealant for liquid crystal display elements containing a curable resin and a thermosetting agent, wherein the thermosetting agent does not have a cyclic structure and has one or more tertiary amino groups in one molecule. and a compound having two or more hydrazide groups in one molecule.
Further, the present invention 2 is a sealing compound for a liquid crystal display element containing a curable resin and a thermosetting agent, wherein the thermosetting agent is a compound represented by the following formula (1) and a compound represented by the following formula (2) A sealant for a liquid crystal display element containing at least one selected from the group consisting of the compounds represented by

In formula (1), R ¹ represents an alkylene group having 1 to 4 carbon atoms, and R ² to R ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms.

In formula (2), R ¹ represents an alkylene group having 1 to 4 carbon atoms, and R ² to R ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms.

The present invention will be described in detail below.
Matters common to the liquid crystal display element sealing compound of the present invention 1 and the liquid crystal display element sealing compound of the present invention 2 are described as "the liquid crystal display element sealing compound of the present invention".

As a result of intensive studies by the present inventors, by using a thermosetting agent having a specific structure, a liquid crystal display that is excellent in storage stability, adhesion to alignment films, adhesion in high temperature environments, and low liquid crystal contamination. The inventors have found that a sealing compound for elements can be obtained, and have completed the present invention.

The sealant for liquid crystal display elements of the present invention contains a thermosetting agent.
In the present invention 1, the thermosetting agent is a compound having no cyclic structure and having one or more tertiary amino groups in one molecule and two or more hydrazide groups in one molecule (hereinafter referred to as "the present invention (Also referred to as "hydrazide compound according to 1").
By containing the hydrazide compound according to the present invention 1, the sealant for a liquid crystal display element of the present invention 1 has excellent storage stability, adhesion to alignment films, adhesion in high-temperature environments, and low liquid crystal contamination. It will be excellent for

Since the hydrazide compound according to the present invention 1 does not have a cyclic structure, steric hindrance during reaction is reduced and the reactivity with the curable resin is excellent.
In addition, the hydrazide compound according to the present invention 1 has one or more tertiary amino groups in one molecule, so that oxygen inhibition during radical reaction can be reduced, and photoradical reactivity and thermal radical reactivity can be reduced. become excellent.
In addition, the hydrazide compound according to the present invention 1 has two or more hydrazide groups in one molecule, so that it has excellent reactivity.

The hydrazide compound according to the present invention 1 is preferably a compound represented by the above formula (1), and most preferably ethylenediaminetetraacetic acid tetrahydrazide (a compound represented by the following formula (3)).
Among the hydrazide compounds according to the present invention 1, examples of hydrazide compounds other than the compound represented by the above formula (1) include nitrilotriacetic acid trihydrazide (compound represented by the following formula (4)).

Examples of the method for producing the hydrazide compound according to the present invention 1 include the following methods.
First, ethylenediaminetetraacetic acid and sulfuric acid are dissolved in methanol, refluxed at 90° C., neutralized with sodium hydroxide and esterified. Next, the resulting ester is dissolved in an aqueous solution of magnesium sulfate and ethyl acetate, and the mixture is separated, dissolved in methanol, hydrazine is added, and the mixture is stirred to form a hydrazide. Then, after repeating concentration under reduced pressure, the product is washed with methanol and dried in a vacuum to obtain ethylenediaminetetraacetic acid tetrahydrazide as the hydrazide compound according to the first aspect of the present invention.

The content of the hydrazide compound according to the present invention 1 has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 10.0 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 1 is 0.5 parts by weight or more with respect to 100 parts by weight of the curable resin, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the hydrazide compound according to the present invention 1 is 10.0 parts by weight or less with respect to 100 parts by weight of the curable resin, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance. becomes. The lower limit of the content of the hydrazide compound according to the present invention 1 is more preferably 1.5 parts by weight, the upper limit is more preferably 5.0 parts by weight, and the lower limit is still more preferably 2.0 parts by weight, relative to 100 parts by weight of the curable resin. A preferred upper limit is 3.5 parts by weight.
Further, when an epoxy compound described later is contained as the curable resin, the preferable lower limit of the content of the hydrazide compound according to the present invention 1 to 1 equivalent of the epoxy compound is 0.1 equivalent, and the preferable upper limit is 0.4 equivalent. . When the content of the hydrazide compound according to the present invention 1 is 0.1 equivalent or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the hydrazide compound according to the present invention 1 is 0.4 equivalent or less relative to 1 equivalent of the epoxy compound, the resulting sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance. A more preferable lower limit of the content of the hydrazide compound according to the present invention 1 to 1 equivalent of the epoxy compound is 0.2 equivalents, and a more preferable upper limit thereof is 0.35 equivalents.

In the present invention 2, the thermosetting agent is at least one selected from the group consisting of the compounds represented by the above formula (1) and the compounds represented by the above formula (2) (hereinafter referred to as "invention 2 (also referred to as "such hydrazide compounds").
By containing the hydrazide compound according to the second aspect of the present invention, the sealant for liquid crystal display elements of the second aspect of the present invention has all of the storage stability, adhesiveness to alignment films, adhesiveness in high-temperature environments, and low liquid crystal contamination. It will be better.

Ethylenediaminetetraacetic acid tetrahydrazide is preferable as the compound represented by the above formula (1).
As the compound represented by the above formula (2), ethylenediaminetetraacetic acid trihydrazide (compound represented by the following formula (5)) is preferable.

The content of the hydrazide compound according to the present invention 2 has a preferable lower limit of 0.5 parts by weight and a preferable upper limit of 10.0 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 2 is 0.5 parts by weight or more with respect to 100 parts by weight of the curable resin, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. When the content of the hydrazide compound according to the present invention 2 is 10.0 parts by weight or less per 100 parts by weight of the curable resin, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance. becomes. A more preferable lower limit of the content of the hydrazide compound according to the present invention 2 to 100 parts by weight of the curable resin is 1.5 parts by weight, a more preferable upper limit is 5.0 parts by weight, and a further preferable lower limit is 2.0 parts by weight. A preferred upper limit is 3.5 parts by weight.
Further, when the epoxy compound described later is contained as the curable resin, the preferable lower limit of the content of the hydrazide compound according to the present invention 2 to 1 equivalent of the epoxy compound is 0.1 equivalent, and the preferable upper limit is 0.4 equivalent. . When the content of the hydrazide compound according to the present invention 2 is 0.1 equivalent or more relative to 1 equivalent of the epoxy compound, the obtained sealing agent for liquid crystal display elements has excellent curability and adhesiveness. By setting the content of the hydrazide compound according to the present invention 2 to 1 equivalent of the epoxy compound to 0.4 equivalent or less, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and low liquid crystal contamination resistance. A more preferable lower limit of the content of the hydrazide compound according to the present invention 2 to 1 equivalent of the epoxy compound is 0.2 equivalents, and a more preferable upper limit thereof is 0.35 equivalents.

The sealant for a liquid crystal display element of the present invention may contain other thermosetting agents in addition to the hydrazide compound according to the first aspect of the present invention or the hydrazide compound according to the second aspect of the present invention, as long as the object of the present invention is not impaired. good.
Examples of other thermosetting agents include organic acid hydrazides other than the hydrazide compound according to the first aspect of the invention and the hydrazide compound according to the second aspect of the invention, imidazole derivatives, amine compounds, polyhydric phenolic compounds, acid anhydrides, and amine adducts. compounds, urea adduct compounds, and the like.
Among them, from the viewpoint of storage stability and adhesion after exposure to a high temperature and high humidity environment, the thermosetting agent is selected from the group consisting of an amine adduct compound and a urea adduct compound as the other thermosetting agent. preferably contains at least one

When an epoxy compound to be described later is contained as the curable resin, the preferable lower limit of the content of at least one selected from the group consisting of the amine adduct compound and the urea adduct compound with respect to 1 equivalent of the epoxy compound is 0.3 equivalents, preferably The upper limit is 0.8 equivalents. By setting the content of at least one selected from the group consisting of the amine adduct compound and the urea adduct compound to 1 equivalent of the epoxy compound to be 0.3 equivalents or more, the obtained sealing agent for a liquid crystal display element has excellent curability and It becomes a thing excellent by adhesiveness. When the content of at least one selected from the group consisting of the amine adduct compound and the urea adduct compound per equivalent of the epoxy compound is 0.8 equivalent or less, the obtained sealing agent for a liquid crystal display element has storage stability and Adhesiveness after exposure to a high-temperature and high-humidity environment is more excellent.

The sealant for liquid crystal display elements of the present invention contains a curable resin.
The curable resin preferably contains an epoxy compound.
Examples of the epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallylbisphenol A type epoxy resin, 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 novolak type epoxy resin, ortho cresol Novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalenephenol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, etc. be done.

Commercially available bisphenol A type epoxy resins include, for example, jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON850 (manufactured by DIC Corporation), and the like.
Commercially available bisphenol F type epoxy resins include, for example, jER806, jER4004 (both manufactured by Mitsubishi Chemical Corporation) and EPICLON EXA-830CRP (manufactured by DIC Corporation).
Examples of commercially available bisphenol E type epoxy resins include Epomic R710 (manufactured by Mitsui Chemicals, Inc.).
Examples of commercially available bisphenol S-type epoxy resins include EPICLON EXA-1514 (manufactured by DIC Corporation).
Commercially available 2,2'-diallylbisphenol A type epoxy resins include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available hydrogenated bisphenol type epoxy resins include, for example, EPICLON EXA-7015 (manufactured by DIC Corporation).
Commercially available propylene oxide-added bisphenol A type epoxy resins include, for example, EP-4000S (manufactured by ADEKA).
Commercially available resorcinol-type epoxy resins include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
Commercially available biphenyl-type epoxy resins include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Commercially available sulfide-type epoxy resins include, for example, 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.).
Commercially available dicyclopentadiene type epoxy resins include, for example, EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene-type epoxy resins include EPICLON HP-4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Commercially available phenolic novolac epoxy resins include, for example, EPICLON N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolak type epoxy resins include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
Commercially available dicyclopentadiene novolac type epoxy resins include, for example, EPICLON HP-7200 (manufactured by DIC Corporation).
Commercially available biphenyl novolak type epoxy resins include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available naphthalene phenol novolak type epoxy resins include, for example, ESN-165S (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available glycidylamine epoxy resins include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.).
Commercially available alkyl polyol type epoxy resins include, for example, ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available rubber-modified epoxy resins include YR-450 and YR-207 (both manufactured by Nippon Steel Chemical & Materials) and Epolead PB (manufactured by Daicel).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include 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), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.

Partially (meth)acrylic-modified epoxy resins are also suitably used as the epoxy compound.
In this specification, the partially (meth)acrylic-modified epoxy resin is 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 addition, in this specification, the above-mentioned "(meth)acryl" means acryl or methacryl, and the above-mentioned "(meth)acryloyl" means acryloyl or methacryloyl.

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

Moreover, the curable resin may contain a (meth)acrylic compound.
Examples of the (meth)acrylic compound include (meth)acrylic acid ester compounds, epoxy (meth)acrylates, and urethane (meth)acrylates. Among them, epoxy (meth)acrylate is preferred. The (meth)acrylic compound preferably has two or more (meth)acryloyl groups in one molecule from the viewpoint of reactivity.
In addition, in this specification, the said "(meth)acrylic compound" means the compound which has a (meth)acryloyl group. Further, the above "(meth)acrylate" means acrylate or methacrylate, and the above "epoxy(meth)acrylate" is a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid. represents

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 ( 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, methoxypolyethyleneglycol (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbi tall (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imido (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-( meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate and the like.

Among the above (meth)acrylic acid ester compounds, bifunctional ones include, 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 (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol 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 , dimethyloldicyclopentadienyl 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 di(meth)acrylate and the like.

Further, among the above (meth)acrylic acid ester compounds, trifunctional or higher ones 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 and the like.

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 serving as a raw material for synthesizing the epoxy (meth)acrylate, the same epoxy compound as the curable resin contained in the liquid crystal display element sealant of the present invention can be used.

Among the epoxy (meth)acrylates that are commercially available, for example, epoxy (meth)acrylate manufactured by Daicel Ornex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( Meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, epoxy (meth) acrylate manufactured by KSM, and the like.
上記ダイセル・オルネクス社製のエポキシ（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３７０８、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬ ＲＤＸ６３１８２、ＫＲＭ９３１２等が挙げられる。
Examples of epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical 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, for example, 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.
Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.
Examples of epoxy (meth)acrylates manufactured by KSM include BAEA-100.

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

Examples of isocyanate compounds that are raw materials for the urethane (meth)acrylate include 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-undecane triisocyanate, and the like.

In addition, as the isocyanate compound that is a raw material for the urethane (meth)acrylate, a chain-extended isocyanate compound obtained by reacting a polyol with an excessive amount of an isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and the like.

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

Examples of commercially available urethane (meth) acrylates include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. 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)acrylates manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210 and M-1600.
上記ダイセル・オルネクス社製のウレタン（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ２２２０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０等がmentioned.
Examples of the urethane (meth)acrylates manufactured by Negami Kogyo Co., Ltd. include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN- 7100, Artresin UN-9000A, Artresin UN-9000H and the like.
The urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include, for example, 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. be done.

When the curable resin contains the (meth)acrylic compound in addition to the epoxy compound, or when the partially (meth)acryl-modified epoxy compound is contained, the epoxy group in the curable resin and the (meth) It is preferable that the ratio of (meth)acryloyl groups in the total amount of acryloyl groups is 30 mol % or more and 95 mol % or less. When the ratio of the (meth)acryloyl group is within this range, the obtained sealant for a liquid crystal display element has excellent 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 —OH group, —NH— group, or —NH ₂ group.

It is preferable that the sealant for a liquid crystal display element of the present invention further contains a photoradical polymerization initiator.
Examples of the radical photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Specific examples of the photoradical polymerization initiator include compounds represented by the following formula (6), 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-1-butanone, 2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1, 2-diphenylethan-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- benzoyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.
The radical photopolymerization initiators may be used alone, or two or more of them may be used in combination.

As for the content of the radical photopolymerization initiator, a preferable lower limit is 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 radical photopolymerization initiator is within this range, the resulting sealing compound for liquid crystal display elements is excellent in storage stability and photocurability while suppressing liquid crystal contamination. A more preferable lower limit to the content of the radical photopolymerization initiator is 1 part by weight, and a more preferable upper limit is 7 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
Examples of the thermal radical polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, from the viewpoint of suppressing liquid crystal contamination, an initiator composed of an azo compound (hereinafter also referred to as an "azo initiator") is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as a "polymer azo initiator") is preferable. Also referred to as "initiator") is more preferred.
The thermal radical polymerization initiators may be used alone, or two or more of them may be used in combination.
As used herein, the term "polymeric azo compound" means a compound having an azo group, generating a radical capable of curing a (meth)acryloyl group by heat, and having a number average molecular weight of 300 or more. do.

A preferable lower limit of the number average molecular weight of the above high-molecular azo compound is 1,000, and a preferable upper limit thereof is 300,000. When the number-average molecular weight of the high-molecular-weight azo compound is within this range, it can be easily mixed with the curable resin while preventing adverse effects on the liquid crystal. The lower limit of the number average molecular weight of the high-molecular azo compound is more preferably 5,000, the upper limit is 100,000, the lower limit is still more preferably 10,000, and the upper limit is still more preferably 90,000.
In addition, in this specification, the said number average molecular weight is a value which measures by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and is calculated|required by polystyrene conversion. Examples of a column for measuring the number average molecular weight by GPC in terms of polystyrene 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, one having a polyethylene oxide structure is preferred.
Specific examples of the high-molecular 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.
Commercially available polymeric azo initiators include, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and the like. mentioned.
Examples of non-polymeric azo initiators include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

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

The content of the thermal radical polymerization initiator has a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 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 within this range, the obtained sealing compound for liquid crystal display elements is excellent in storage stability and thermosetting property while suppressing liquid crystal contamination. A more preferable lower limit to the content of the thermal radical polymerization initiator is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

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

An inorganic filler or an organic filler can be used as the filler.
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, acrylic polymer fine particles, and the like.
The above fillers may be used alone, or two or more of them may be used in combination.

A preferable lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 10 parts by weight, and a preferable upper limit thereof is 70 parts by weight. When the content of the filler is within this range, the effect of improving adhesiveness and the like is excellent without deteriorating coatability and the like. A more preferable lower limit of the filler content is 20 parts by weight, and a more preferable upper limit thereof is 60 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may contain a silane coupling agent. The silane coupling agent mainly functions as an adhesion assistant for good adhesion between the liquid crystal display element sealing compound 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 adhesiveness 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. Among them, 3-glycidoxypropyltrimethoxysilane is preferred.
The silane coupling agents may be used alone, or two or more of them may be used in combination.

A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the liquid crystal display element sealing compound of the present invention is 0.1 parts by weight, and a preferable upper limit thereof is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving adhesion while suppressing the occurrence of liquid crystal contamination is more excellent. A more preferable lower limit to the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

The sealant for liquid crystal display elements of the present invention may contain a light shielding agent. By containing the light shielding agent, the sealant for liquid crystal display elements 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, and resin-coated carbon black. Among them, titanium black is preferable.

Titanium black is a substance that exhibits a higher transmittance for light in the vicinity of the ultraviolet region, particularly light with a wavelength of 370 nm or more and 450 nm or less, than average transmittance for light with a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting a light-shielding property to the sealing agent for a liquid crystal display element of the present invention by sufficiently shielding light of wavelengths in the visible light region, while transmitting light of wavelengths in the vicinity of the ultraviolet region. It is a light-shielding agent with Therefore, by using, as the photoradical polymerization initiator, one capable of initiating the reaction by light of 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 On the other hand, as the light shielding agent contained in the sealing compound for liquid crystal display elements of the present invention, a substance with high insulating properties is preferable, and titanium black is also suitable as the light shielding agent with high insulating properties.
The above titanium black preferably has an optical density (OD value) per 1 μm of 3 or more, more preferably 4 or more. The higher the light shielding property of the titanium black, the better. Although there is no particular upper limit for the OD value of the titanium black, it is usually 5 or less.

The above titanium black exerts a sufficient effect even if it is not surface-treated, but it can also be used when the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxide. Surface-treated titanium blacks, such as those coated with inorganic components such as zirconium and magnesium oxide, can also be used. Among them, those treated with an organic component are preferable because they can further improve the insulating properties.
Further, the liquid crystal display device manufactured using the sealing agent for a liquid crystal display device of the present invention in which the above-described titanium black is blended as a light shielding agent has sufficient light shielding properties, so that light does not leak out and has high contrast. A liquid crystal display element having excellent image display quality can be realized.

Commercially available titanium blacks include, for example, titanium black manufactured by Mitsubishi Materials Corporation, titanium black manufactured by Ako Kasei Co., Ltd., and the like.
Examples of 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 Tilak D and the like.

The specific surface area of the titanium black has a preferred lower limit of 13 m ² /g, a preferred upper limit of 30 m ² /g, a more preferred lower limit of 15 m ² /g, and a more preferred upper limit of 25 m ² /g.
The preferred lower limit of the volume resistivity of titanium black is 0.5 Ω·cm, the preferred upper limit is 3 Ω·cm, the more preferred lower limit is 1 Ω·cm, and the more preferred upper limit is 2.5 Ω·cm.

The primary particle size of the light shielding agent is not particularly limited as long as it is equal to or smaller than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5000 nm. When the primary particle size of the light shielding agent is within this range, the obtained sealing agent for liquid crystal display elements can be made more excellent in light shielding properties without deteriorating the applicability or the like. The primary particle size of the light shielding agent has a more preferable lower limit of 5 nm, a more preferable upper limit of 200 nm, a still more preferable lower limit of 10 nm, and a still more preferable upper limit of 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).

A preferable lower limit of the content of the light shielding agent in 100 parts by weight of the liquid crystal display element sealing compound of the present invention is 5 parts by weight, and a preferable upper limit thereof is 80 parts by weight. When the content of the light-shielding agent is within this range, the obtained sealant for liquid crystal display elements exhibits excellent light-shielding properties without significantly deteriorating the adhesiveness, strength after curing, and drawability. 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 still more preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.

The sealant for liquid crystal display elements of the present invention may further contain, if necessary, stress relaxation agents, reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents, polymerization inhibitors, and the like. It may contain an agent.

As a method for producing the liquid crystal display element sealing compound of the present invention, for example, a mixer is used to mix a curable resin, a thermosetting agent, and a photoradical polymerization initiator to be added as necessary. and the like.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and three rolls.

In the liquid crystal display device sealant of the present invention, it is preferable that the adhesive strength of the cured product to polyimide at 25°C is 50% or more of the adhesive strength to glass at 25°C. Since the adhesive strength of the cured product to polyimide at 25° C. is 50% or more of the adhesive strength to glass at 25° C., the sealant for a liquid crystal display element of the present invention is suitably used for a liquid crystal display element with a narrow frame design. It becomes possible. More preferably, the adhesive strength of the cured product to polyimide at 25°C is 70% or more of the adhesive strength to glass at 25°C.
As used herein, the above-mentioned "adhesive strength to polyimide" refers to a test piece obtained by bonding two glass substrates having a polyimide alignment film through a sealing agent and then curing the sealing agent, using a tension gauge. It is obtained as an adhesive strength measured using Further, in this specification, the above-mentioned "adhesive force to glass" is measured using a tension gauge on a test piece obtained by bonding two glass substrates via a sealing agent and then curing the sealing agent. It is obtained as the adhesive strength to be used. The sealing agent is cured by irradiating the sealing agent with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp and then heating the sealing agent at 120° C. for 1 hour.

In the liquid crystal display device sealant of the present invention, it is preferable that the adhesive strength of the cured product to glass at 80°C is 30% or more of the adhesive strength to glass at 25°C. Since the adhesive strength to glass at 80° C. of the cured product is 30% or more of the adhesive strength to glass at 25° C., the sealant for a liquid crystal display element of the present invention is a liquid crystal that requires reliability in severe environments. It can be suitably used for a display element. More preferably, the adhesive strength of the cured product to glass at 80°C is 40% or more of the adhesive strength to glass at 25°C.

The preferred upper limit of the storage elastic modulus at 25° C. of the cured product of the liquid crystal display element sealant of the present invention is 3.5 GPa. When the storage elastic modulus of the cured product at 25° C. is 3.5 GPa or less, the sealant for liquid crystal display elements of the present invention is superior in adhesiveness to alignment films. A more preferable upper limit of the storage elastic modulus at 25°C of the cured product is 3.0 GPa.
From the standpoint of reliability when the adherends are bonded together, the preferable lower limit of the storage elastic modulus at 25° C. of the cured product is 0.1 GPa, and the more preferable lower limit is 1.0 GPa.
The cured product for measuring the storage elastic modulus was cured by heating at 120° C. for 1 hour after irradiating ultraviolet rays (wavelength: 365 nm) of 100 mW/cm ² for 30 seconds using a metal halide lamp as the sealant. things are used. Further, the cured product means a cured sealant used for bonding and sealing substrates and the like in a liquid crystal display element.
In addition, the storage elastic modulus was measured using a dynamic viscoelasticity measuring device (for example, "DVA-200" manufactured by IT Keisoku Kogyo Co., Ltd.) in a tensile mode, a test piece width of 5 mm, a thickness of 0.35 mm, and a grip width of 25 mm. , a heating rate of 10° C./min, and a frequency of 5 Hz.

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

As the conductive fine particles, for example, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, and the like can be used. Among them, the one in which a 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 using the sealant for a liquid crystal display element of the present invention or the vertically conductive material of the present invention is also one aspect of the present invention.
The sealant for liquid crystal display elements of the present invention has low compatibility with liquid crystal molecules having polar groups. The effect of suppressing display defects is more pronounced than with conventional sealants. That is, the liquid crystal display element of the present invention preferably uses liquid crystal containing liquid crystal molecules having polar groups.
Polar groups of the liquid crystal molecules include, for example, 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, it is preferable that the width of the frame portion around the liquid crystal display section is 2 mm or less.
Moreover, it is preferable that the coating width of the sealant for a liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.

The sealing compound for liquid crystal display elements of the present invention can be suitably used for manufacturing liquid crystal display elements by the 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 with a dispenser, or the like, is performed with the sealant for a liquid crystal display element of the present invention. Next, a step of applying liquid crystal microdroplets to the entire surface of the frame of the seal pattern while the sealant for a liquid crystal display element of the present invention is in an uncured state, and immediately superimposing another substrate is performed. After that, a liquid crystal display element can be obtained by a method of performing a step of heating and curing the sealant. Moreover, before the step of heating and curing the sealant, a step of temporarily curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays may be performed.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in the storage stability, the adhesiveness with respect to an alignment film, the adhesiveness in a high temperature environment, and the low liquid-crystal contamination property can be provided. 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.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples.

(Synthesis of ethylenediaminetetraacetic acid tetrahydrazide)
Using a 50 mL eggplant-shaped flask, 10.0 g of ethylenediaminetetraacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.36 g of sulfuric acid were added to 30 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 12 hours under a nitrogen atmosphere. After refluxing and reacting, methanol was distilled off under reduced pressure. Next, the obtained reaction solution was dissolved in 100 mL of ethyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and extracted once with 100 mL of saturated magnesium sulfate 1 N NaOH aqueous solution. Tetramethyl ethylenediaminetetraacetate was obtained. Furthermore, using a 50 mL eggplant-shaped flask, 3.5 g of tetramethyl ethylenediaminetetraacetate and 8.01 g of hydrazine monohydrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to 10 mL of methanol, and the temperature was adjusted to 40° C. under a nitrogen atmosphere. The reaction was allowed to proceed for 8 hours. Using a Kiriyama funnel, the precipitate was collected by filtration, washed with methanol, and then vacuum-dried to obtain ethylenediaminetetraacetic acid tetrahydrazide (compound represented by the above formula (3)).
The structure of the obtained ethylenediaminetetraacetic acid tetrahydrazide was confirmed by ¹ H-NMR, GC-MS and FT-IR.

(Synthesis of ethylenediaminetetraacetic acid trihydrazide)
Ethylenediaminetetraacetic acid trihydrazide (the above A compound represented by formula (5)) was obtained.
The structure of the obtained ethylenediaminetetraacetic acid trihydrazide was confirmed by ¹ H-NMR, GC-MS and FT-IR.

(Synthesis of nitrilotriacetic acid trihydrazide)
Using a 50 mL eggplant-shaped flask, 6.51 g of nitrilotriacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.36 g of sulfuric acid were added to 30 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the mixture was stirred for 12 hours under a nitrogen atmosphere. After refluxing and reacting, methanol was distilled off under reduced pressure. Next, the obtained reaction solution was dissolved in 100 mL of ethyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and extracted once with 100 mL of saturated magnesium sulfate 1 N NaOH aqueous solution. Trimethyl nitrilotriacetate is obtained. Furthermore, using a 50 mL eggplant-shaped flask, 3.5 g of trimethyl nitrilotriacetate and 8.01 g of hydrazine monohydrate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were added to 10 mL of methanol, and the mixture was heated at 40 ° C. under a nitrogen atmosphere. reacted over time. Using a Kiriyama funnel, the precipitate was collected by filtration, washed with methanol, and then vacuum-dried to obtain nitrilotriacetic acid trihydrazide (compound represented by formula (4) above).
The structure of the obtained nitrilotriacetic acid trihydrazide was confirmed by ¹ H-NMR, GC-MS and FT-IR.

(Synthesis of iminodiacetic acid dihydrazide)
Using a 50 mL eggplant-shaped flask, N-methylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) 25 mL, diethyl iminodiacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.46 g and hydrazine monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd. ) was added and reacted at 40° C. for 8 hours under a nitrogen atmosphere. Using a Kiriyama funnel, the precipitate was collected by filtration, washed with methanol, and vacuum-dried to obtain iminodiacetic acid dihydrazide.
The structure of the resulting iminodiacetic acid dihydrazide was confirmed by ¹ H-NMR, GC-MS and FT-IR.

(Synthesis of 2,5-pyridinedicarboxylic acid dihydrazide)
Except for changing 9.46 g of diethyl iminodiacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) to 11.16 g of diethyl 2,5-pyridinedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), the above “(Synthesis of iminodiacetic acid dihydrazide) 2,5-pyridinedicarboxylic acid dihydrazide was obtained in the same manner as described above.
The structure of the obtained 2,5-pyridinedicarboxylic acid dihydrazide was confirmed by ¹ H-NMR, GC-MS and FT-IR.

(Synthesis of compound represented by formula (6))
5 parts by weight of N-ethylcarbazole, 2.81 parts by weight of 2,5-thiophenedicarboxylic acid dichloride, and 3.76 parts by weight of aluminum chloride were added to 40 mL of dichloromethane and stirred overnight at room temperature. 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added to the obtained reaction solution, and the mixture was further stirred at room temperature for 4 hours. After the resulting reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and concentrated to give product (A1).
3 parts by weight of the obtained product (A1), 0.76 parts by weight of hydroxylammonium chloride, and 0.86 parts by weight of pyridine were added to 30 mL of ethanol and stirred under reflux for 10 hours. The resulting reaction solution was poured into ice water and then filtered. After the filtrate was washed with water, it was dissolved in ethyl acetate, dried with anhydrous magnesium sulfate and concentrated to obtain the product (B1).
After 1.5 parts by weight of the obtained product (B1) was dissolved in 25 parts by weight of N,N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. 0.78 parts by weight of triethylamine was added dropwise to the resulting solution while cooling to 10° C. or lower, and the mixture was stirred at room temperature for 4 hours. The resulting reaction solution was poured into water and then filtered. The filtrate was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane:hexane=2:1) to obtain the compound represented by the above formula (6).
The structure of the obtained compound represented by formula (6) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

(Examples 1 , 3 to 16 , Reference Example 2 , Comparative Examples 1 to 12)
According to the compounding ratios shown in Tables 1 to 4, each material was mixed using a planetary stirrer (manufactured by Thinky Co., Ltd., "Awatori Mixer"), and then further mixed using three rolls. Sealants for liquid crystal display elements of Examples 1 , 3 to 16 , Reference Example 2 , and Comparative Examples 1 to 12 were prepared.

<Evaluation>
The sealants for liquid crystal display elements obtained in Examples , Reference Examples, and Comparative Examples were evaluated as follows. The results are shown in Tables 1-4.

(Storage stability)
The initial viscosities immediately after production and the viscosities after storage at 25° C. for 6 days after production were measured for each sealing compound for liquid crystal display elements obtained in Examples , Reference Examples, and Comparative Examples. (Viscosity after storage) / (initial viscosity) is defined as the viscosity increase rate, and the viscosity increase rate is less than 1.2 "◎", and 1.2 or more and less than 1.4 "○" , 1.4 or more and less than 2.0 were evaluated as "Δ", and those with 2.0 or more were evaluated as "×".
The viscosity of the liquid crystal display element sealant was measured using an E-type viscometer (“DV-III” manufactured by BROOK FIELD) at 25° C. and a rotational speed of 1.0 rpm.

(storage modulus)
Each sealant for liquid crystal display elements obtained in Examples , Reference Examples, and Comparative Examples was irradiated with ultraviolet rays (wavelength: 365 nm) at 100 mW/cm ² for 30 seconds using a metal halide lamp, and then at 120° C. for 1 hour. A cured product was obtained by heating.
Using a dynamic viscoelasticity measuring device, the storage modulus at 25°C of the obtained cured product was measured under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a gripping width of 25 mm, a heating rate of 10°C/min, and a frequency of 5 Hz. was measured. Also, the temperature of the maximum value of the loss tangent (tan δ) was determined as the glass transition temperature. DVA-200 (manufactured by IT Keisoku Co., Ltd.) was used as the dynamic viscoelasticity measuring device.

(Adhesiveness)
Spacer particles having an average particle diameter of 4 μm (“Micropearl SP-2050” manufactured by Sekisui Chemical Co., Ltd.) per 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples , Reference Examples, and Comparative Examples. The weight parts were evenly dispersed by means of a planetary stirrer. A very small amount of a liquid crystal display element sealing agent in which spacer particles were dispersed was applied to the center of a glass substrate (20 mm×45 mm×0.7 mm in thickness), and a glass substrate of the same type was placed thereon. Spread the liquid crystal display element sealing agent, irradiate 100 mW/cm ² ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp, and then heat at 120 ° C. for 1 hour to cure the liquid crystal display element sealing agent, Adhesion specimens were obtained. A glass substrate having a polyimide alignment film for TN (manufactured by Nissan Chemical Industries, Ltd., "SE6414") instead of the glass substrate (hereinafter also referred to as "substrate with polyimide alignment film") was similarly obtained. .
The adhesive strength (adhesive force) was measured for each adhesive test piece obtained using a tension gauge. The adhesive strength was measured at 25°C for the adhesive test piece prepared using the substrate with the polyimide alignment film, and at 25°C and 80°C for the adhesive test piece prepared using the glass substrate. Further, a high temperature and high humidity test was performed by exposing the adhesion test piece prepared using the glass substrate to PCT conditions (121° C., 100% RH, 2 atm) for 24 hours. The adhesive strength (adhesive strength) of the adhesive test piece after the high temperature and high humidity test was also measured at 25°C using a tension gauge, and the obtained adhesive strength was taken as the adhesive strength to glass after 24 hours of PCT.

(low liquid crystal contamination)
1 part by weight of spacer fine particles having an average particle diameter of 7 μm (manufactured by Sekisui Chemical Co., Ltd., "Micropearl SI-H050") is added to 100 parts by weight of each sealing agent for liquid crystal display elements obtained in Examples , Reference Examples, and Comparative Examples. was dispersed, filled in a syringe, and defoamed with a centrifugal deaerator (AWATRON AW-1). Using a dispenser, the sealant for liquid crystal display elements after defoaming treatment is applied to two alignment films and 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 on one side of the substrate with ITO. At this time, the discharge pressure was adjusted so that the line width of the liquid crystal display element sealant was about 1.0 mm. Subsequently, microdroplets of liquid crystal (manufactured by Tokyo Kasei Kogyo Co., Ltd., "4-pentyl-4-biphenylcarbonitrile") are dropped onto the entire frame of the liquid crystal display element sealing agent of the substrate coated with the liquid crystal display element sealing agent. After coating and leaving for 2 hours, the other substrate was bonded together under vacuum. After the panel was allowed to stand still for 15 minutes after bonding, the liquid crystal display element sealing agent portion was irradiated with ultraviolet rays of 100 mW/cm ² for 30 seconds using a metal halide lamp to temporarily cure the liquid crystal display element sealing agent. Next, the composition was heated at 120° C. for 1 hour for final curing, thereby producing a liquid crystal display device.
The obtained liquid crystal display element was checked for liquid crystal alignment disorder (display unevenness) near the seal using a polarizing microscope (manufactured by Keyence Corporation, "VHX-5000"). Orientation disorder was judged from the color unevenness of the display area. If no display unevenness was observed on the liquid crystal display element, a "○" was given. The low liquid crystal contamination resistance was evaluated as "Δ" when the display was uneven, and as "x" when the display unevenness occurred over the entire seal peripheral portion.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in the storage stability, the adhesiveness with respect to an alignment film, the adhesiveness in a high temperature environment, and the low liquid-crystal contamination property can be provided. 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 (10)

A sealant for a liquid crystal display element containing a curable resin and a thermosetting agent,
The thermosetting agent contains at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2). .

In formula (1), R ¹ represents an alkylene group having 1 to 4 carbon atoms, and R ² to R ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms.

In formula (2), R ¹ represents an alkylene group having 1 to 4 carbon atoms, and R ² to R ⁵ each independently represent an alkylene group having 1 to 4 carbon atoms. 2. The sealing compound for a liquid crystal display element according to claim 1 , wherein said thermosetting agent further contains at least one selected from the group consisting of amine adduct compounds and urea adduct compounds. 3. The sealing compound for liquid crystal display elements according to claim 1 , wherein the curable resin contains an epoxy compound. The content of at least one selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) relative to 1 equivalent of the epoxy compound is 0.1 equivalent or more and 0.4 4. The sealing compound for liquid crystal display elements according to claim 3 , which has an equivalent weight or less. The curable resin contains an epoxy compound,
3. The sealing compound for a liquid crystal display element according to claim 2 , wherein the content of at least one selected from the group consisting of the amine adduct compound and the urea adduct compound per equivalent of the epoxy compound is 0.3 equivalent or more and 0.8 equivalent or less. . 6. The sealant for liquid crystal display elements according to claim 1, 2, 3, 4 or 5 , wherein the adhesive strength to polyimide at 25° C. of the cured product of said sealant for liquid crystal display elements is 50% or more of the adhesive strength to glass at 25° C. agent. 7. The liquid crystal display element according to claim 1, 2, 3, 4, 5 or 6 , wherein the adhesive strength to glass at 80[deg.] C. of the cured product of said sealant for liquid crystal display elements is 30% or more of the adhesive strength to glass at 25[deg.] C. sealant. 8. The sealant for liquid crystal display elements according to claim 1, wherein the cured product of said sealant for liquid crystal display elements has a storage elastic modulus at 25[deg.] C. of 3.5 GPa or less. 9. A vertically conducting material comprising the liquid crystal display element sealant according to claim 1, 2, 3, 4, 5, 6, 7 or 8 and conductive fine particles. 10. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2, 3, 4, 5, 6, 7 or 8 or the vertically conductive material according to claim 9 .