JP7117128B2 - Sealant for liquid crystal display element, epoxy compound, method for producing epoxy compound, vertical conduction material, and liquid crystal display element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a sealant for liquid crystal display elements which is excellent in coatability, curability, and low liquid crystal contamination. The present invention also relates to an epoxy compound used in the liquid crystal display element sealant and a method for producing the epoxy compound. Furthermore, the present invention relates to a vertically conducting 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 to be used, a combination of light and heat curing type disclosed in Patent Documents 1 and 2 has been used. A liquid crystal dropping method called a dropping method using a sealant is used.
In the dropping method, first, a rectangular seal pattern is formed on one of the two electrode-attached substrates by dispensing. Next, liquid crystal droplets are dropped into the seal frame of the substrate while the sealant is not yet cured. After that, the liquid crystal display element is manufactured by heating for main curing. 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 miniaturization, narrowing of the frame of the liquid crystal display portion is mentioned. For example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as narrow frame design).
With such a narrow frame design, in the liquid crystal display element, the distance from the pixel area to the sealant is shortened, and there is a problem that display unevenness is likely to occur due to the liquid crystal being contaminated by the sealant. rice field.

JP-A-2001-133794 WO 02/092718

An object of the present invention is to provide a sealant for liquid crystal display elements which is excellent in applicability, curability, and low liquid crystal contamination. Another object of the present invention is to provide an epoxy compound used in the liquid crystal display element sealant and a method for producing the epoxy compound. A further object of the present invention is to provide a vertically conducting material and a liquid crystal display device using the sealant for a liquid crystal display device.

The present invention is a sealant for liquid crystal display elements containing a curable resin, wherein the curable resin is a sealant for liquid crystal display elements containing an epoxy compound having an aromatic hydroxyl group.
Also, the present invention is an epoxy compound having an aromatic hydroxyl group.
The present invention will be described in detail below.

As the curable resin used for the sealant for liquid crystal display elements, one containing an epoxy compound is usually used because of its excellent curability and adhesiveness. The present inventors have investigated the use of a highly polar epoxy compound as a curable resin in order to reduce the compatibility with liquid crystals and improve the liquid crystal contamination resistance of the sealant. However, when such a highly polar epoxy compound is used, there is a problem that the application properties of the sealant may deteriorate due to crystallization. Therefore, as a result of further intensive studies by the present inventors, it was found that by using an epoxy compound having a specific structure among highly polar epoxy compounds, excellent coating properties, curability, and low liquid crystal staining properties can be obtained for liquid crystal display devices. The inventors have found that a sealant can be obtained, and have completed the present invention.

The sealant for liquid crystal display elements of the present invention contains a curable resin.
The curable resin contains the epoxy compound of the present invention, that is, an epoxy compound having an aromatic hydroxyl group. By using the epoxy compound of the present invention, the sealant for liquid crystal display elements of the present invention is excellent in coatability, curability, and low liquid crystal contamination.
In addition, in this specification, the above-mentioned "aromatic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring. A hydrogen atom in the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, a nitro group, or the like.

The epoxy compound of the present invention preferably has a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (1-2). By containing a compound having a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (1-2) as the epoxy compound of the present invention, the liquid crystal display element seal of the present invention The agent is superior in coatability, curability, and low liquid crystal contamination.

The hydroxyl value (g/eq) of the epoxy compound of the present invention preferably has a lower limit of 120 and a preferred upper limit of 1,200. When the hydroxyl value of the epoxy compound of the present invention is 120 or more, the obtained sealing agent for liquid crystal display elements has excellent curability. When the hydroxyl value of the epoxy compound of the present invention is 1200 or less, the obtained sealing agent for liquid crystal display elements is excellent in low liquid crystal contamination. A more preferable lower limit of the hydroxyl value of the epoxy compound of the present invention is 140, and a more preferable upper limit thereof is 1,000.
In addition, in this specification, the above-mentioned "hydroxyl value" is a value measured based on JIS K0070.

The preferred lower limit of the number average molecular weight of the epoxy compound of the present invention is 200, and the preferred upper limit thereof is 3,000. When the number average molecular weight of the epoxy compound of the present invention is 200 or more, the obtained sealing agent for liquid crystal display elements is excellent in low liquid crystal contamination. When the epoxy compound of the present invention has a number average molecular weight of 3,000 or less, the obtained sealant for liquid crystal display elements has excellent applicability. A more preferable lower limit of the number average molecular weight of the epoxy compound of the present invention is 250, and a more preferable upper limit thereof is 2,500.
In addition, in this specification, the said "number average molecular weight" is a value which performs measurement using a tetrahydrofuran as a solvent by a gel permeation chromatography (GPC), 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).

The epoxy compound of the present invention can be obtained, for example, by epoxidizing a part of the aromatic hydroxyl groups of an aromatic compound having two or more aromatic hydroxyl groups in one molecule. A method for producing an epoxy compound of the present invention, comprising the step of epoxidizing a portion of the aromatic hydroxyl groups of an aromatic compound having two or more aromatic hydroxyl groups in one molecule. A method is also an aspect of the present invention.
In addition, in this specification, the above-mentioned "epoxidize" means to convert into an epoxy group or a group containing an epoxy group. Examples of the epoxy group-containing group include a glycidyloxy group.

Examples of the aromatic compound having two or more aromatic hydroxyl groups in one molecule include novolac type aromatic compounds, resorcinol, bisphenol A, bisphenol F, bisphenol E, 1,2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, phlorogricinol, leucoquinizarin and the like. Among them, novolak type aromatic compounds are preferable.
Examples of the novolak type aromatic compounds include phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins, and the like. Among them, phenol novolac resin is preferable.

Examples of methods for epoxidizing a portion of the aromatic hydroxyl groups include the following methods.
That is, first, an aromatic compound having two or more aromatic hydroxyl groups in one molecule, epichlorohydrin, tetra-n-butylammonium chloride, and dimethylsulfoxide are mixed. The amount of epichlorohydrin to be used is 1 to 10 times in molar amount the amount corresponding to the desired modification rate of the aromatic compound having two or more aromatic hydroxyl groups in one molecule. The amount of tetra-n-butylammonium chloride used is 0.0005 times the weight of epichlorohydrin. The amount of dimethylsulfoxide used is equal to the total weight of the aromatic compound having two or more aromatic hydroxyl groups in one molecule, epichlorohydrin, and tetra-n-butylammonium chloride.
Next, after heating the resulting mixture to 60°C, a 50% sodium hydroxide aqueous solution containing sodium hydroxide in an amount corresponding to the desired modification rate was gradually added dropwise, and the mixture was kept at 60°C after cooling. Allow to react for 3 hours. Thereafter, the reaction solution is cooled to room temperature, diluted with ethyl acetate of 9 times the weight of the reaction solution, and extracted and washed three times with 3% sodium chloride aqueous solution of 10 times the weight of the reaction solution. After drying the ethyl acetate solution after washing with magnesium sulfate, the aromatic compound having two or more aromatic hydroxyl groups in one molecule is removed from the aromatic compound by decompressing and vacuum drying with an evaporator. It is possible to obtain an epoxy compound by epoxidizing a part of the functional hydroxyl groups.

The curable resin may contain other curable resins in addition to the epoxy compound of the present invention as long as the object of the present invention is not impaired.
When the other curable resin is contained, the preferable lower limit of the content of the epoxy compound of the present invention in 100 parts by weight of the curable resin is 1 part by weight, and the preferable upper limit is 80 parts by weight. When the content of the epoxy compound of the present invention is within this range, the obtained sealing agent for liquid crystal display elements is excellent in curability and low liquid crystal contamination. A more preferable lower limit of the content of the epoxy compound of the present invention is 5 parts by weight, and a more preferable upper limit thereof is 70 parts by weight.

Examples of other curable resins include (meth)acrylic compounds and epoxy compounds other than the epoxy compound of the present invention.
In addition, in this specification, the above-mentioned "(meth)acryl" means acryl or methacryl, and the above-mentioned "(meth)acrylic compound" means a compound having a (meth)acryloyl group.

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 the molecule from the viewpoint of reactivity.
In addition, the above-mentioned "(meth)acryloyl" means acryloyl or methacryloyl. Moreover, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. Furthermore, the above-mentioned "epoxy (meth)acrylate" represents a compound obtained by reacting all epoxy groups in an epoxy compound with (meth)acrylic acid.

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, tri- or higher-functional 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.

Examples of epoxy compounds that are raw materials for synthesizing the epoxy (meth)acrylate include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and 2,2′-diallylbisphenol A type epoxy compounds. , hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol Novolak-type epoxy compounds, ortho-cresol novolac-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolak-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds , glycidyl ester compounds, and the like.

Examples of commercially available bisphenol A type epoxy compounds include jER828EL, jER1004 (both manufactured by Mitsubishi Chemical Corporation), Epiclon 850CRP (manufactured by DIC Corporation), and the like.
Examples of commercially available bisphenol F-type epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available bisphenol S-type epoxy compounds include Epiclon EXA1514 (manufactured by DIC Corporation).
Examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy compounds include Epiclon EXA7015 (manufactured by DIC Corporation).
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
Commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene-type epoxy compounds include Epiclon HP4032 and Epiclon EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenolic novolac type epoxy compounds include Epiclon N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolac type epoxy compounds include Epiclon N-670-EXP-S (manufactured by DIC Corporation).
Examples of commercially available dicyclopentadiene novolac type epoxy compounds include Epiclon HP7200 (manufactured by DIC Corporation).
Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Commercially available naphthalenephenol novolac type epoxy compounds include, for example, ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), Epiclon 430 (manufactured by DIC Corporation), and TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.).
Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX-611. (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available rubber-modified epoxy compounds include YR-450 and YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and Epolead PB (manufactured by Daicel Corporation).
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 & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, jER1032 (any Mitsubishi Chemical Co., Ltd.), EXA-7120 (DIC Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), and the like.

Commercially available epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Allnex, 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, 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.

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 the isocyanate compound 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(isocyanatophenyl) thiophosphate, tetramethylxylylene isocyanate, 1,6,11-undecane triisocyanate, and the like.

As the isocyanate compound, 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, 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.

Examples of the other epoxy compounds include epoxy compounds that serve as raw materials for synthesizing the above-described epoxy (meth)acrylates, partially (meth)acryl-modified epoxy compounds, and the like.
In the present specification, the partially (meth)acrylic-modified epoxy compound is obtained by reacting a partial epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid. means a compound having an epoxy group and a (meth)acryloyl group.

The sealant for liquid crystal display elements of the present invention preferably contains a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among them, organic acid hydrazides are preferably used.
The thermosetting agents may be used alone, or two or more of them may be used in combination.

Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.

The content of the thermosetting agent has a preferable lower limit of 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is within this range, the obtained sealing compound for liquid crystal display elements can be made more excellent in thermosetting properties without deteriorating the applicability and the like. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may contain a polymerization initiator.
Examples of the polymerization initiator include radical polymerization initiators and cationic polymerization initiators.

As the radical polymerization initiator, a photoradical polymerization initiator that generates radicals by light irradiation or a thermal radical polymerization initiator that generates radicals by heating can be used.

Examples of the radical photopolymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone.
The radical photopolymerization initiators may be used alone, or two or more of them may be used in combination.

Examples of commercially available radical photopolymerization initiators include radical photopolymerization initiators manufactured by IGM Resins, radical photopolymerization initiators manufactured by Tokyo Chemical Industry Co., Ltd., and the like.
Examples of photoradical polymerization initiators manufactured by IGM Resins include Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 651, Omnirad 819, Omnirad 907, Omnirad 2959, Omnirad OXE01, and Lucirin TPO.
Examples of the radical photopolymerization initiator manufactured by Tokyo Kasei Kogyo Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

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 polymeric azo compound (hereinafter also referred to as a "polymeric azo initiator" is more preferable.
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.

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.
Examples of commercially available polymeric azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). be done.
Examples of non-polymeric azo initiators include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).

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

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

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts; organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes; are mentioned.

Commercially available photo cationic polymerization initiators include, for example, Adeka Optomer SP-150 and Adeka Optomer SP-170 (both manufactured by ADEKA).

The content of the polymerization initiator has a preferable lower limit of 0.01 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 polymerization initiator is within this range, the obtained sealing compound for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination. A more preferable lower limit to the content of the polymerization initiator is 0.1 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, further improving adhesiveness due to stress dispersion effect, improving coefficient of linear expansion, improving moisture resistance of the cured product, and the like. preferable.

An inorganic filler or an organic filler can be used as the filler.
Examples of inorganic fillers 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 serves as an adhesion assistant for good adhesion between the sealing agent and the substrate.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the 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.
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 adhesiveness 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, as the radical photopolymerization initiator or the cationic photopolymerization initiator, by using the one capable of initiating the reaction by light having a wavelength (370 nm or more and 450 nm or less) at which the transmittance of the titanium black becomes high, the present invention can be achieved. It is possible to further increase the photocurability of the sealant for liquid crystal display elements. 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 sealing agent for a liquid crystal display element of the present invention, for example, a curable resin and a heat Examples thereof include a method of mixing a curing agent, a polymerization initiator, and an additive such as a silane coupling agent.

The liquid crystal display element sealant of the present invention preferably has a lower limit of 50,000 mPa·s and a preferred upper limit of viscosity measured at 25° C. and 1 rpm using an E-type viscometer. When the viscosity is within this range, it becomes more excellent in coatability. A more preferable lower limit of the viscosity is 100,000 mPa·s, and a more preferable upper limit is 800,000 mPa·s.

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 the liquid crystal display element sealant of the present invention and conductive fine particles is also one aspect of the present invention.

As the conductive fine particles, a metal ball, a resin fine particle having a conductive metal layer formed on its surface, or 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 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 by applying the sealant for a liquid crystal display element of the present invention to a substrate by screen printing, dispenser coating, or the like is performed. 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 uncured, 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 coating property, curability, and low-liquid-crystal contamination property can be provided. Moreover, according to this invention, the manufacturing method of the epoxy compound used for this sealing compound for liquid crystal display elements, and this epoxy compound can be provided. Furthermore, 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 to these Examples.

(Preparation of epoxy compound A having an aromatic hydroxyl group)
Novolac type phenolic resin (manufactured by Meiwa Kasei Co., Ltd., "DL-75") 53.5 parts by weight, epichlorohydrin 74.0 parts by weight, tetra-n-butylammonium chloride 0.030 parts by weight, and dimethyl sulfoxide 127 0.53 parts by weight were mixed. Next, after heating the resulting mixture to 60° C., 20.0 parts by weight of a 50% aqueous sodium hydroxide solution was gradually added dropwise (aromatic hydroxyl group: epichlorohydrin: sodium hydroxide=1:1. 6:0.5 (molar ratio)). After cooling to room temperature, the reaction solution was diluted with 2476 parts by weight of ethyl acetate and extracted and washed three times with 2751 parts by weight of a 3% sodium chloride aqueous solution. After drying the ethyl acetate solution after washing with magnesium sulfate, the epoxy compound A having an aromatic hydroxyl group was obtained by performing decompression and vacuum drying with an evaporator.
By ¹ H-NMR, GPC, and FT-IR analysis, the epoxy compound A having the aromatic hydroxyl group is represented by the structural unit represented by the above formula (1-1) and the above formula (1-2). It was confirmed that it has a structural unit that is The modification rate of epoxy groups was 49%. Further, the hydroxyl value of epoxy compound A having an aromatic hydroxyl group was 265 as measured according to JIS K0070. Furthermore, the number average molecular weight of epoxy compound A having an aromatic hydroxyl group was 625 as measured by GPC.

(Preparation of epoxy compound B having an aromatic hydroxyl group)
Epoxy compound B having an aromatic hydroxyl group was prepared in the same manner as in "(Preparation of epoxy compound A having an aromatic hydroxyl group)" except that the amount of the 50% aqueous sodium hydroxide solution added was changed to 12.0 parts by weight. got
By ¹ H-NMR, GPC, and FT-IR analysis, the epoxy compound B having the aromatic hydroxyl group is represented by the structural unit represented by the above formula (1-1) and the above formula (1-2). It was confirmed that it has a structural unit that is The modification rate of epoxy groups was 29%. Further, the hydroxyl value of epoxy compound B having an aromatic hydroxyl group was 182 as measured according to JIS K0070. Furthermore, the number average molecular weight of epoxy compound B having an aromatic hydroxyl group was 564 as measured by GPC.

(Preparation of epoxy compound C having an aromatic hydroxyl group)
Epoxy compound C having an aromatic hydroxyl group was prepared in the same manner as in "(Preparation of epoxy compound A having an aromatic hydroxyl group)" except that the amount of the 50% aqueous sodium hydroxide solution added was changed to 34.0 parts by weight. got
By ¹ H-NMR, GPC, and FT-IR analysis, the epoxy compound C having the aromatic hydroxyl group is represented by the structural unit represented by the above formula (1-1) and the above formula (1-2). It was confirmed that it has a structural unit that is The modification rate of epoxy groups was 83%. Moreover, the hydroxyl value of epoxy compound C having an aromatic hydroxyl group was 915, measured according to JIS K0070. Furthermore, the number average molecular weight of epoxy compound C having an aromatic hydroxyl group was 690 as measured by GPC.

(Preparation of phenol novolak type epoxy resin)
A phenol novolak epoxy resin was obtained in the same manner as in the above "(Preparation of epoxy compound A having an aromatic hydroxyl group)" except that the amount of the 50% sodium hydroxide aqueous solution added was changed to 48.0 parts by weight.
According to ¹ H-NMR, GPC, and FT-IR analysis, the phenol novolac epoxy resin has a structural unit represented by the above formula (1-1) and is represented by the above formula (1-2). It was confirmed that it does not have a structural unit that Also, the number average molecular weight of the phenol novolak type epoxy resin measured by GPC was 706.

(Preparation of biphenyl-type epoxy compound D having an alcoholic hydroxyl group)
46.5 parts by weight of 4,4'-biphenol, 1.2 parts by weight of triphenylphosphine and 500 parts by weight of toluene were mixed. After heating the resulting mixed solution to 120° C., 188 parts by weight of a tetramethylbiphenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “YX4000H”) was added and reacted at 120° C. for 6 hours. After that, toluene was distilled off to obtain a biphenyl-type epoxy compound D having an alcoholic hydroxyl group.
It was confirmed by ¹ H-NMR, GPC, and FT-IR analysis that the biphenyl-type epoxy compound D did not have an aromatic hydroxyl group. The modification rate of epoxy groups was 49%. Moreover, the hydroxyl value of the biphenyl-type epoxy compound D measured according to JIS K0070 was 335. Furthermore, the number average molecular weight of the biphenyl type epoxy compound D measured by GPC was 670.

(Examples 1 to 5, Comparative Examples 1 to 3)
According to the compounding ratio shown in Table 1, each material was stirred with a planetary stirrer (manufactured by Thinky Co., Ltd., "Awatori Mixer"), and then uniformly mixed with a ceramic 3-roll. 5 and Comparative Examples 1 to 3 were obtained as sealants for liquid crystal display elements.
Since the epoxy compounds A to C having an aromatic hydroxyl group contain raw materials and by-products, the content of the epoxy compound having an aromatic hydroxyl group in 100 parts by weight of the curable resin is shown in Table 1. .

<Evaluation>
Each sealant for liquid crystal display elements obtained in Examples and Comparative Examples was evaluated as follows. Table 1 shows the results.

(viscosity)
The viscosities of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples were measured at 25° C. and 1 rpm using an E-type viscometer (manufactured by Brookfield, "DV-III").

(Applicability)
Using a dispenser (manufactured by Musashi Engineering, "SHOTMASTER 300"), each liquid crystal display element sealant obtained in Examples and Comparative Examples was applied onto a glass substrate. When applying with a dispense nozzle of 400 μm, a nozzle gap of 30 μm, and a fixed dispensing pressure of 300 kPa, “○” indicates that there was no fading or sagging. The applicability was evaluated as "Δ" and "x" when the coating was cut off or could not be applied at all.

(Curability)
Each liquid crystal display element sealant obtained in Examples and Comparative Examples was applied on a glass substrate to a thickness of about 5 μm, and then glass substrates of the same size were superimposed to prepare a test piece. Next, the obtained test piece was irradiated with ultraviolet rays of 3000 mJ/cm ² using a metal halide lamp, and then heated at 120° C. for 60 minutes to cure the sealant. Using an infrared spectrometer (manufactured by BIORAD, "FTS3000"), the change rate (decrease rate) of the peak area derived from the acryloyl group after light irradiation and the change rate (decrease rate) of the peak area derived from the epoxy group after heat curing ) was measured.
"○" when the reduction rate of the peak area derived from the acryloyl group after light irradiation was 95% or more, "△" when it was 90% or more and less than 95%, and " when it was less than 90%. The curability was evaluated as x. In addition, when the reduction rate of the peak area derived from the epoxy group after heat curing was 70% or more, "○", when it was 60% or more and less than 70%, "Δ", when it was less than 60% The curability was evaluated as "×".

(Adhesiveness)
1% by weight of a silica spacer (manufactured by Sekisui Chemical Co., Ltd., "SI-H055") was added to each liquid crystal display element sealing agent obtained in Examples and Comparative Examples, and two glass substrates with an ITO thin film (30 ×40 mm). Another ITO thin film-coated glass substrate was attached to this in a cross shape, irradiated with ultraviolet rays of 3000 mJ/cm ² with a metal halide lamp, and then heated at 120° C. for 60 minutes to obtain an adhesive test piece. A tensile test (5 mm/sec) was performed on the obtained adhesive test piece with chucks arranged vertically. When the value obtained by dividing the obtained measured value (kgf) by the seal application cross-sectional area (cm ² ) was ^2.8 kgf/cm ² or more, "○" The adhesiveness was evaluated as “Δ” when it was less than cm ² and as “×” when it was less than 2.2 kgf/cm ² .

(low liquid crystal contamination)
1% by weight of a silica spacer (manufactured by Sekisui Chemical Co., Ltd., "SI-H055") was added to each liquid crystal display element sealant obtained in Examples and Comparative Examples, and defoaming treatment was performed to remove the After removing the foam, it was filled into a syringe for dispensing (manufactured by Musashi Engineering Co., Ltd., "PSY-10E") and defoamed again. Next, using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER 300"), a sealant was applied to one of the two ITO thin film-coated glass substrates so as to draw a frame. Subsequently, microdroplets of TN liquid crystal (manufactured by Chisso, "JC-5001LA") are dropped and applied in the frame of the sealant by a liquid crystal dropping device, and the other glass substrate with the ITO thin film is superimposed and placed in a vacuum bonding device. The two substrates were bonded together under a reduced pressure of 5 Pa. The cells after bonding were irradiated with ultraviolet rays of 3000 mJ/cm ² using a metal halide lamp, and then heated at 120° C. for 60 minutes to cure the sealant, thereby obtaining a liquid crystal display element. After the obtained liquid crystal display element was stored in an environment of 80° C. and 90% RH for 72 hours, it was driven with a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed. "○" indicates that no display unevenness was observed, "△" indicates that display unevenness was observed in the peripheral part of the liquid crystal display element, and the display unevenness spread not only to the peripheral part of the liquid crystal display element but also to the central part. The low liquid crystal contamination resistance was evaluated by setting the case where the liquid crystal contamination was low as "x".

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in coating property, curability, and low-liquid-crystal contamination property can be provided. Moreover, according to this invention, the manufacturing method of the epoxy compound used for this sealing compound for liquid crystal display elements, and this epoxy compound can be provided. Furthermore, 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 (9)

A sealant for a liquid crystal display element containing a curable resin,
The curable resin contains an epoxy compound having an aromatic hydroxyl group,
The epoxy compound having an aromatic hydroxyl group has a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (1-2), and has a hydroxyl value of 120 to 1200. is below
A sealant for a liquid crystal display device, characterized by:

2. The sealant for liquid crystal display elements according to claim 1 , wherein the epoxy compound having an aromatic hydroxyl group has a number average molecular weight of 200 or more and 3000 or less. 3. The sealing compound for a liquid crystal display element according to claim 1 , wherein the content of said epoxy compound having an aromatic hydroxyl group in 100 parts by weight of said curable resin is 1 part by weight or more and 80 parts by weight or less. An epoxy compound having a structural unit represented by the following formula (1-1) and a structural unit represented by the following formula (1-2), and having a hydroxyl value of 120 or more and 1200 or less .

5. The epoxy compound according to claim 4 , which has a number average molecular weight of 200 or more and 3,000 or less. A method for producing the epoxy compound according to claim 4 or 5 ,
A method for producing an epoxy compound, comprising the step of epoxidizing a part of the aromatic hydroxyl groups of an aromatic compound having two or more aromatic hydroxyl groups in one molecule. 7. The method for producing an epoxy compound according to claim 6 , wherein the aromatic compound having two or more aromatic hydroxyl groups in one molecule is a novolac type aromatic compound. 4. A vertically conducting material comprising the liquid crystal display element sealant according to claim 1, 2 or 3 and conductive fine particles. 9. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2 or 3 or the vertically conductive material according to claim 8 .