JP2006267964A - Sealing agent for liquid crystal display element, vertical conduction material, liquid crystal element, and method for manufacturing liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing agent for liquid crystal element preventimg the contamination of a liquid crystal by incorporating a ultraviolet absorber in the sealing agent containing thermosetting resin and performing a thermosetting by using heat generated by a ultraviolet irradiation so as to solve a conventional problem wherein the liquid crystal is contaminated in a long-term manufacturing process, and also to provide a vertical conduction materials, a liquid crystal display element and a method for manufacturing the liquid crystal display element. <P>SOLUTION: This sealing agent for liquid crystal display element contains the thermosetting resin, a thermosetting agent and/or a thermal polymerization initiator and the ultraviolet absorber. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a sealing agent for liquid crystal display elements, a vertical conduction material, a liquid crystal display element, and a method for manufacturing a liquid crystal display element that are cured by using heat generated by ultraviolet irradiation to prevent liquid crystal contamination.

In recent years, the manufacturing method of liquid crystal display elements such as liquid crystal display cells has been changed from a conventional vacuum injection method to a liquid crystal dropping method called a dropping method using a sealing agent made of a curable resin composition for the purpose of shortening tact time. It is changing. In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, if necessary, heating is performed during liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.

In connection with this, the sealing agent used for manufacture of a liquid crystal display element has changed from the thermosetting type to the light / heat combined curing type, and is disclosed in Patent Document 1, for example.
However, conventionally, the sealant is sometimes formed at a place where a light blocking member called a black matrix formed in the peripheral portion located outside the display area of the liquid crystal display element is formed. However, the light did not reach the sealant under the black matrix and could not be cured. In addition, although the sealant under the black matrix can be cured by heating after light irradiation, the uncured sealant continues to be in direct contact with the liquid crystal until it is thermally cured. There was a problem that the sealant component eluted from the sealant and contaminated the liquid crystal.
Furthermore, it is necessary to perform a heating process as a separate process, and the manufacturing process is complicated and takes a long time.

Japanese Patent Laid-Open No. 10-197880

The present invention provides a sealing agent for liquid crystal display elements, a vertical conduction material, a liquid crystal display element, and a method for manufacturing a liquid crystal display element, which are cured by using heat generated by ultraviolet irradiation to prevent liquid crystal contamination. Objective.

The sealing agent for liquid crystal display elements of this invention is a sealing agent for liquid crystal display elements containing a thermosetting resin, a thermosetting agent and / or a thermal polymerization initiator, and an ultraviolet absorber.
The present invention is described in detail below.

As a result of intensive studies, the inventors of the present invention have included an ultraviolet absorber in a sealing agent for liquid crystal display elements containing a thermosetting resin, and the ultraviolet absorber causes an exothermic reaction by irradiating with ultraviolet rays (UV). The present inventors have found that the sealing agent for liquid crystal display elements can be thermally cured by this heat, and have completed the present invention.

The sealing agent for liquid crystal display elements of this invention contains a ultraviolet absorber.
In the present specification, the ultraviolet absorber means a substance that generates heat by absorbing UV, and means a substance that can convert light energy into heat energy. The ultraviolet absorber serves as a heat source for thermosetting a thermosetting resin described later in the liquid crystal display element sealing agent of the present invention. That is, in the sealing agent for a liquid crystal display element of the present invention containing the ultraviolet absorber, the ultraviolet absorber that has absorbed UV by UV irradiation generates heat, and the thermosetting resin can be cured by this heat generation.

The ultraviolet absorber is not particularly limited, and examples thereof include organic pigments, inorganic pigments, organic dyes, 2-hydroxyphenylbenzotriazole derivatives, 2-hydroxybenzophenone derivatives, sacillylate derivatives, cyanoacrylate derivatives, etc. Since it is excellent in conversion of light energy into thermal energy, at least one selected from the group consisting of 2-hydroxyphenylbenzotriazole derivatives, 2-hydroxybenzophenone derivatives, and sacillylate derivatives is preferably used.

The content of the ultraviolet absorber is determined depending on the type of the ultraviolet absorber to be used. The lower limit of the molar extinction coefficient at 365 nm measured by the obtained sealing agent for liquid crystal display elements of the present invention in acetonitrile is 10 M ^−1. -It is preferable to contain so that an upper limit may become 100M < ^-1 > cm. The molar extinction coefficient is a parameter indicating the absorption of light energy. When the molar extinction coefficient is less than 10 M ⁻¹ · cm, sufficient performance as an ultraviolet absorber cannot be exhibited, and when it exceeds 100 M ⁻¹ · cm. The UV absorber may absorb UV too much and the sealing agent for liquid crystal display elements of the present invention may not be cured.
When manufacturing a liquid crystal display element, UV irradiation is performed in the process of hardening the sealing compound for liquid crystal display elements of this invention. Since the sealing agent for liquid crystal display elements of the present invention causes an exothermic reaction by this step, it can be cured by heat generation and the heating step after UV irradiation can be omitted.

The sealing agent for liquid crystal display elements of this invention contains a thermosetting resin.
Although it does not specifically limit as such a thermosetting resin, Since it is excellent in reactivity, the compound which has a (meth) acryl group and / or an epoxy group is preferable.

The compound having the (meth) acrylic group is not particularly limited. For example, an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, or (meth) acrylic acid and an epoxy compound are reacted. Epoxy (meth) acrylate obtained by this, urethane (meth) acrylate obtained by making the (meth) acrylic acid derivative which has a hydroxyl group react with isocyanate, etc. are mentioned.

The ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited. Examples of monofunctional compounds include 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tet Hydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Rohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. It is done.

Examples of the bifunctional ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group include 1,4-butanediol di (meth) acrylate and 1,3-butane. Diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10 decanediol 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 (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, Tet Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol di Cyclopentadiene didi (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyl Roxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol (Meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene di (meth) acrylate.

Among the ester compounds obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group, those having three or more functional groups include, for example, pentaerythritol tri (meth) acrylate and trimethylolpropane tri (meth) acrylate. , Propylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol te La (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

The epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid and the epoxy compound is, for example, (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventionally known method. Obtained by reacting.

The epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited. For example, bisphenol A type epoxy resin such as Epicoat 828EL, Epicoat 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicoat 806, 2, such as bisphenol F type epoxy resin such as Epicoat 4004 (all manufactured by Japan Epoxy Resin Co., Ltd.), bisphenol S type epoxy resin such as Epicron EXA1514 (Dainippon Ink Co., Ltd.), RE-810NM (manufactured by Nippon Kayaku Co., Ltd.) 2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by Dainippon Ink), propylene oxide-added bisphenol A type epoxy resin such as EP-4000S (manufactured by Asahi Denka), EX Resorcinol type epoxy resin such as -201 (manufactured by Nagase ChemteX), biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin), sulfide type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei Co., Ltd.), Ether type epoxy resin such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.), dicyclopentadiene type epoxy resin such as EP-4088S (manufactured by Asahi Denka Co., Ltd.), Epicron HP4032, and Epicron EXA-4700 (all manufactured by Dainippon Ink and Company) Naphthalene type epoxy resins such as, Epoxylon N-770 (manufactured by Dainippon Ink), etc., phenol novolac type epoxy resins, Epicron N-670-EXP-S (manufactured by Dainippon Ink), etc. Epicron HP7200 (Dainippon Dicyclopentadiene novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.), Glycidylamine type epoxy resins such as Epicoat 630 (Japan Epoxy Resin), Epicron 430 (Dainippon Ink), TETRAD-X (Mitsubishi Gas Chemical), ZX-1542 (Toto Kasei), Epicron 726 (Manufactured by Dainippon Ink Co., Ltd.), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (manufactured by Nagase ChemteX Corporation), etc., alkyl polyol type epoxy resins, YR-450, YR-207 (all of which are Toto Kasei Co., Ltd.) Rubber) such as Epolide PB (Daicel Chemical) Type epoxy resin, glycidyl ester compound such as Denacol EX-147 (manufactured by Nagase ChemteX), bisphenol A type episulfide resin such as Epicoat YL-7000 (manufactured by Japan Epoxy Resin), other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.), EXA-7120 (manufactured by Dainippon Ink & Co.), TEPIC (Nissan Chemical Co., Ltd.) Manufactured) and the like.

Specifically, the epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid with the epoxy compound is, for example, 360 parts by weight of resorcinol type epoxy resin EX-201 (manufactured by Nagase ChemteX), polymerization It can be obtained by reacting 2 parts by weight of p-methoxyphenol as an inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid for 5 hours while stirring at 90 ° C. while feeding air.

Moreover, as a commercial item of the said epoxy (meth) acrylate, for example, Evecryl 3700, Evekrill 3600, Evekril 3701, Evekrill 3703, Evekrill 3200, Evekrill 3201, Evekrill 3412, Evekrill 860, Evekril RDX63182, Evekryl 6040, 3800 (all manufactured by Daicel UCB), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A Epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Poxyester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911 (any Also manufactured by Nagase ChemteX Corporation).

Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. It can be obtained by reacting 2 equivalents in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate used as a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, and 2,6-triene. 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 And tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate and the like.
Chain-extended isocyanates obtained by reaction of polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate A compound is also preferably used.

As the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative, for example, 2-hydroxyethyl (meth) Commercial products such as acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3- Mono (meth) acrylates of divalent alcohols such as butanediol, 1,4-butanediol and polyethylene glycol, mono (meth) acrylates or di (meth) of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin Acrylates, epoxy acrylates such as bisphenol A-modified epoxy acrylate.

Specifically, the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group includes, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor, As reaction catalysts, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate were added and reacted at 60 ° C. with stirring under reflux for 2 hours. Next, 51 parts by weight of 2-hydroxyethyl acrylate was added and air was fed. It can be obtained by reacting at 90 ° C. with stirring under reflux for 2 hours.

Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.), Evekril 230, Evekril 270, Evekril 4858, Evekril 8402, Evecryl 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecril 1290, Evecril 5129, Evecril 2102, Evecril 4827, Evecril 6700, Evecril 220, Evecryl 2220 (all manufactured by Daicel UCB) Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500
B (all manufactured by Negami Kogyo), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200, U-2061BA, U-10H, U- 122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA-306H, AI-600, UA-101T, UA- 101I, UA-306T, UA-306I, and the like.

The compound having the (meth) acrylic group may be a compound having one or more hydrogen-bonding functional groups in one molecule in order to suppress any elution of components into the liquid crystal before curing the sealant. preferable.

Examples of the hydrogen bonding functional group include an —OH group, —SH group, —NHR group (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof), —COOH group, —NHOH group. In addition, functional groups such as —NHCO—, —NH—, —CONHCO—, —NH—NH— and the like are present in the molecule, and in particular, an —OH group can be selected for ease of introduction. preferable.

Examples of the compound having one or more hydrogen bonding functional groups in one molecule and having a (meth) acryl group include the urethane (meth) acrylate and epoxy (meth) acrylate.

Examples of the compound having an epoxy group include an epichlorohydrin derivative, a cycloaliphatic epoxy resin, a compound obtained from a reaction between isocyanate and glycidol.

Examples of the epichlorohydrin derivative include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (all manufactured by Japan Epoxy Resin Co.), and bisphenols such as Epicoat 806 and Epicoat 4004 (all manufactured by Japan Epoxy Resin). F-type epoxy resin, bisphenol S-type epoxy resin such as Epicron EXA1514 (manufactured by Dainippon Ink), 2,2′-diallylbisphenol A-type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.), Epicron EXA7015 (large Resincinol type epoxy such as hydrogenated bisphenol type epoxy resin such as Nippon Ink Co., Ltd., propylene oxide added bisphenol A type epoxy resin such as EP-4000S (Asahi Denka Co., Ltd.), EX-201 (manufactured by Nagase ChemteX) Xylene resin, biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.), sulfide type epoxy resin such as YSLV-50TE (manufactured by Toto Kasei Co., Ltd.), ether type such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.) Epoxy resins, dicyclopentadiene type epoxy resins such as EP-4088S (Asahi Denka), naphthalene type epoxy resins such as Epicron HP4032, Epicron EXA-4700 (all manufactured by Dainippon Ink and Co.), Epicron N-770 (Large) Nihon Ink Co., Ltd.) phenol novolac type epoxy resin, Epicron N-670-EXP-S (Dainippon Ink Co., Ltd.) orthocresol novolak type epoxy resin, Epicron HP7200 (Dainippon Ink Co., Ltd.), etc. Pentadiene novolac epoxy tree , NC-3000P (Nippon Kayaku Co., Ltd.) and other biphenyl novolac type epoxy resins, ESN-165S (Toto Kasei Co., Ltd.) naphthalene phenol novolac type epoxy resin, Epicoat 630 (Japan Epoxy Resin Co., Ltd.), Epicron 430 ( Glycidylamine type epoxy resins such as Dainippon Ink Co., Ltd., TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.), ZX-1542 (Toto Kasei Co., Ltd.), Epicron 726 (Dainippon Ink Co., Ltd.), Epolite 80MFA (Kyoeisha Chemical Co., Ltd.) ), Denacol EX-611 (manufactured by Nagase ChemteX Corporation), etc., alkyl polyol type epoxy resins, YR-450, YR-207 (all manufactured by Toto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries), etc. Modified epoxy resin, Denacol EX-147 (Nagase Chemtech) Glycidyl ester compounds such as Epicoat YL-7000 (Japan Epoxy Resin Co., Ltd.), other bisphenol A type episulfide resins, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.), EXA-7120 (Dainippon Ink Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), and the like.

Examples of the cycloaliphatic epoxy resin include Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, EHPE (all manufactured by Daicel Chemical Industries), and the like.

The compound obtained from the reaction between the isocyanate and glycidol can be obtained, for example, by reacting a compound having two isocyanate groups with 2 equivalents of glycidol in the presence of a catalytic amount of a tin compound.

Examples of the isocyanate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), and hydrogenated MDI. , Polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethyl Examples include xylene diisocyanate and 1,6,10-undecane triisocyanate.
In addition, chain-extended isocyanates obtained by reaction of polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate A compound is also preferably used.

Specific examples of the method for synthesizing the compound obtained from the reaction between the isocyanate and glycidol include, for example, 134 parts by weight of trimethylolpropane, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate. And then reacted for 2 hours with stirring under reflux at 60 ° C., and then added with 222 parts by weight of glycidol and allowed to react for 2 hours with stirring under reflux at 90 ° C. while feeding air.

It does not specifically limit as a compound which has the said (meth) acryl group and an epoxy group, For example, the compound which has 1 or more each of (meth) acryl groups and epoxy groups in 1 molecule is mentioned.

The compound having one or more (meth) acryl groups and epoxy groups in one molecule is obtained by, for example, reacting an epoxy group of a part of a compound having two or more epoxy groups with (meth) acrylic acid. The compound obtained by making the compound obtained and the (meth) acrylic acid derivative and glycidol which have a hydroxyl group react with bifunctional or more isocyanate is mentioned.

The compound obtained by reacting a part of the epoxy groups of the compound having two or more epoxy groups with (meth) acrylic acid is, for example, a basic catalyst obtained by reacting an epoxy resin and (meth) acrylic acid according to a conventional method. It can be obtained by reacting in the presence of

Examples of the epoxy resin used as a raw material of the compound obtained by reacting a part of the epoxy groups having two or more epoxy groups with (meth) acrylic acid include, for example, Epicoat 828EL and Epicoat 1004 (both Japan Epoxy Bisphenol A type epoxy resin such as Resin Co., Ltd., Bisphenol F type epoxy resin such as Epicoat 806 and Epicoat 4004 (both manufactured by Japan Epoxy Resin Co., Ltd.), and Bisphenol S type epoxy resin such as Epicron EXA1514 (Dainippon Ink Co., Ltd.) 2,2′-diallyl bisphenol A type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol type epoxy resin such as Epicron EXA7015 (manufactured by Dainippon Ink and Chemicals), EP-4000S (Asahi Denka Co., Ltd.) Made) Pyrene oxide-added bisphenol A type epoxy resin, resorcinol type epoxy resin such as EX-201 (manufactured by Nagase ChemteX), biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin), YSLV-50TE (Tohto Kasei) Sulfur type epoxy resins such as YSLV-80DE (manufactured by Tohto Kasei Co., Ltd.), dicyclopentadiene type epoxy resins such as EP-4088S (Asahi Denka Co., Ltd.), Epicron HP4032, Epicron EXA- Naphthalene type epoxy resin such as 4700 (all manufactured by Dainippon Ink), phenol novolac type epoxy resin such as Epicron N-770 (manufactured by Dainippon Ink), Epicron N-670-EXP-S (manufactured by Dainippon Ink Co., Ltd.) ) Ortho-cresol Borac type epoxy resin, dicyclopentadiene novolac type epoxy resin such as Epicron HP7200 (manufactured by Dainippon Ink and Co., Ltd.), biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.), ESN-165S (manufactured by Tohto Kasei Co., Ltd.) ) And other glycidylamine type epoxy resins such as Epicoat 630 (Japan Epoxy Resin), Epicron 430 (Dainippon Ink), TETRAD-X (Mitsubishi Gas Chemical), ZX- 1542 (manufactured by Tohto Kasei Co., Ltd.), Epicron 726 (manufactured by Dainippon Ink & Co., Ltd.), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (manufactured by Nagase ChemteX Corporation), and the like, YR-450 , YR-207 (East Tokyo) Kasei Co., Ltd.), rubber-modified epoxy resins such as Epolide PB (manufactured by Daicel Chemical Industries), glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX), Epicoat YL-7000 (manufactured by Japan Epoxy Resins Co., Ltd.), etc. Bisphenol A type episulfide resin, other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 (all manufactured by Japan Epoxy Resin), EXA-7120 (Dainippon Ink Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), etc. are mentioned.

Specific examples of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, a phenol novolac type epoxy resin (Dow Chemical Co., Ltd .: D E.N.431) 1000 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid, while stirring and refluxing at 90 ° C. It can be obtained by reacting for a period of time (in this case 50% partially acrylated).

Among the compounds obtained by reacting a part of the epoxy groups having two or more epoxy groups with (meth) acrylic acid, a commercially available product is, for example, Evecryl 1561 (manufactured by Daicel UC Corporation). It is done.

The compound obtained by reacting the (meth) acrylic acid derivative having a hydroxyl group with the bifunctional or higher isocyanate and glycidol is, for example, (meth) acrylic acid having a hydroxyl group with respect to 1 equivalent of the compound having two isocyanate groups. One equivalent each of the derivative and glycidol can be obtained by reacting in the presence of a catalytic amount of a tin compound.

Examples of the bifunctional or higher isocyanate used as a raw material for the compound obtained by reacting the bifunctional or higher isocyanate with a (meth) acrylic acid derivative having a hydroxyl group and glycidol include, for example, isophorone diisocyanate and 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 phenol) ) Thiophosphate, tetramethylxylene diisocyanate, 1,6,10- undecene country isocyanate.

Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for a compound obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative and glycidol with the bifunctional or higher functional isocyanate, include 2-hydroxyethyl (meth). Commercial products such as acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3- Mono (meth) acrylates of divalent alcohols such as butanediol, 1,4-butanediol and polyethylene glycol, mono (meth) acrylates or di (meth) of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin. ) Acrylates, epoxy acrylates such as bisphenol A-modified epoxy acrylate.

Specific examples of the compound obtained by reacting the above-mentioned bifunctional or higher isocyanate with a (meth) acrylic acid derivative having a hydroxyl group and glycidol include, for example, 134 parts by weight of trimethylolpropane, and 0.2% by weight of BHT as a polymerization initiator. Part, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate as reaction catalysts were added and reacted at 60 ° C. with stirring under reflux for 2 hours, then 25.5 parts by weight of 2-hydroxyethyl acrylate and glycidol 111 It can be obtained by adding parts by weight and reacting at 90 ° C. with refluxing for 2 hours while feeding air.

Since the curable resin reduces the uncured residue at the time of curing, it is preferable to select a compound having two or more reactive groups in one molecule.

The sealing agent for liquid crystal display elements of the present invention contains a thermosetting agent and / or a thermal polymerization initiator.
The thermosetting agent is not particularly limited, and examples thereof include heat addition polymerization type curing agents such as amine compounds, polyhydric phenol compounds, and acid anhydrides.

The amine compound represents a compound having one or more primary to tertiary amino groups in the molecule. For example, aromatic amines such as metaphenylenediamine and diaminodiphenylmethane, 2-methylimidazole, 1, Imidazole compounds such as 2-dimethylimidazole and 1-cyanoethyl-2-methylimidazole, imidazoline compounds such as 2-methylimidazoline, dihydrazide compounds such as sebacic acid dihydrazide and isophthalic acid dihydrazide, Amicure PN-23, Amicure MY-24 (Ajinomoto) Amine adducts such as fine techno), and dicyandiamide.

The polyhydric phenol compound is not particularly limited, and examples thereof include polyphenol compounds such as EpiCure 170 and EpiCure YL6065 (both manufactured by Japan Epoxy Resin Co., Ltd.), and novolac type phenol resins such as EpiCure MP402FPI (produced by Japan Epoxy Resin Co., Ltd.). Can be mentioned.

Examples of the acid anhydride include epicure YH-306, YH-307 (both manufactured by Japan Epoxy Resin Co., Ltd.) and the like.

Further, as the thermosetting agent, a dihydrazide compound is also preferably used in that it is excellent in low-temperature curability and storage stability.
Such thermosetting agents may be used alone or in combination.

The thermal polymerization initiator means a compound that generates radical species by heat (hereinafter also referred to as a thermal radical generator). The thermal polymerization initiator is not particularly limited. For example, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, etc. Organic peroxide initiators, azo initiators such as azonitriles, azoesters and azoamides.
Such thermal polymerization initiators may be used alone or in combination.

The sealing agent for liquid crystal display elements of the present invention may further contain a photopolymerization initiator.
In this case, among the thermosetting resins described above, any resin that can be cured by radicals can be cured by a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize a curable compound component by light irradiation. For example, acetophenone compound, benzophenone compound, benzoin compound, benzoin ether compound, acylphosphine oxide compound, thioxanthone compound, etc. Is mentioned. Examples of such compounds include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone.
These may be used alone or in combination of two or more.

Although it does not specifically limit as content of the said photoinitiator, A preferable minimum is 0.1 weight part with respect to 100 weight part of said thermosetting resins, and a preferable upper limit is 10 weight part. If the amount is less than 0.1 parts by weight, curing may be insufficient. If the amount exceeds 10 parts by weight, the photopolymerization initiator may remain and may contaminate the liquid crystal. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 5 parts by weight.

It is preferable that the sealing compound for liquid crystal display elements of the present invention further contains a silane coupling agent. The silane coupling agent mainly serves as an adhesion aid for favorably bonding the sealing agent for liquid crystal display elements and the liquid crystal display element substrate.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. It is done.
These silane compounds may be used alone or in combination of two or more.

Although it does not specifically limit as content of the said silane coupling agent, A preferable minimum is 0.1 weight part with respect to 100 weight part of said thermosetting resins, and a preferable upper limit is 10 weight part.
When the amount is less than 0.1 parts by weight, the performance as a silane coupling agent may not be sufficiently exerted. When the amount exceeds 10 parts by weight, the silane coupling agent may be eluted into the liquid crystal and the display quality may be deteriorated. . A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 5 parts by weight.

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

The filler is not particularly limited, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, Examples include inorganic fillers such as glass beads, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.

Although it does not specifically limit as content of the said filler, A preferable minimum is 1 weight part with respect to 100 weight part of said thermosetting resins, and a preferable upper limit is 100 weight part. When the amount is less than 1 part by weight, the performance as a filler may not be sufficiently exhibited, and when the amount exceeds 100 parts by weight, handling properties such as the drawability of the sealant may be deteriorated. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 50 parts by weight.

It does not specifically limit as a method of manufacturing the sealing compound for liquid crystal display elements of this invention, It mix | blends with the said thermosetting resin, a thermosetting agent, and / or a thermal-polymerization initiator, and an ultraviolet absorber as needed. And a method of mixing the additive with a conventionally known method.

Moreover, a vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the light-shielding sealing agent of this invention. By using such a vertical conduction material, the electrodes of the transparent substrate can be conductively connected without contaminating the liquid crystal.
The vertical conduction material containing the light-shielding sealant for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.

The conductive fine particles are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.

The liquid crystal display element which uses the sealing compound for liquid crystal display elements of this invention and / or the vertical conduction material of this invention is also one of this invention.

When manufacturing the liquid crystal display element of this invention, as mentioned above, UV irradiation is performed as a process of hardening the sealing compound for liquid crystal display elements of this invention. Since the sealing agent for liquid crystal display elements of the present invention causes an exothermic reaction by this step, it can be cured by heat generation and the heating step after UV irradiation can be omitted. Thereby, shortening of manufacturing time, reduction of energy, etc. can be expected. Such a method for producing a liquid crystal display element of the present invention is also one aspect of the present invention. That is, it is a method for manufacturing a liquid crystal display element of the present invention, which is a method for manufacturing a liquid crystal display element in which ultraviolet rays are irradiated to generate heat from an ultraviolet absorber to thermoset a thermosetting resin.
Moreover, when the liquid crystal display element of this invention contains a photoinitiator and also has photocurability in addition to thermosetting, it can be made to photocure and thermoset by irradiating with an ultraviolet-ray. Thereby, liquid crystal contamination can be further reduced.
The UV irradiation is preferably performed at an irradiation intensity of 80 mW / cm ² or more for 30 seconds or more in order to efficiently generate heat.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements which performed thermosetting using the heat | fever which generate | occur | produced by ultraviolet irradiation, and prevented liquid-crystal contamination, the vertical conduction material, a liquid crystal display element, and the manufacturing method of a liquid crystal display element are provided. be able to.

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

(1) Synthesis of thermosetting resin The following (1a) and (1b) were synthesized as thermosetting resins.
(1a) Synthesis of epoxy acrylate 120 g of EX-201 (resorcinol type epoxy resin) was dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine was added to this solution to obtain a uniform solution. To this solution, 70 g of acrylic acid was added dropwise over 2 hours with stirring under reflux, followed by further stirring under reflux for 8 hours. Next, by removing toluene, epoxy (meth) acrylate (EX-201 completely modified product: viscosity 60 Pa) in which all epoxy groups were converted to acryloyl groups was obtained.

(1b) Synthesis of a novolak-type epoxy resin obtained by reacting a part of an epoxy group with acrylic acid 190 g of phenol novolak-type epoxy resin N-770 (manufactured by Dainippon Ink) was dissolved in 500 mL of toluene, and triphenylphosphine 0 was added to this solution. 0.1 g was added to obtain a uniform solution. To this solution, 35 g of acrylic acid was added dropwise with stirring under reflux over 2 hours, followed by further stirring under reflux for 6 hours. Next, novolak-type solid modified epoxy resin (hereinafter, also referred to as partially modified resin) in which 50 mol% of epoxy groups reacted with (meth) acrylic acid was obtained by removing toluene. The modification rate was measured by a method in which the resin was dissolved in a hydrochloric acid-dioxane solution and the amount of hydrochloric acid consumed by the epoxy group was titrated with KOH.

Example 1
20 parts by weight of epoxy acrylate produced in (1a), 80 parts by weight of partially modified resin produced in (1b), 3 parts by weight of SEESORB 701 (manufactured by Sipro Kasei Co., Ltd.), Amicure VDH (Ajinomoto) as a thermosetting resin 16 parts by weight of Fine Techno Co., Ltd., 0.5 parts by weight of perbutyl O (Nippon Yushi Co., Ltd.), 30 parts by weight of SO-C1 (manufactured by Admatechs) as filler, and KBM- as a silane coupling agent 2 parts by weight of 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., Aritori Nertaro), and then mixed using three rolls to produce a sealing agent for liquid crystal display elements. did.
Next, the obtained sealing agent for liquid crystal display elements was applied to a black matrix and a substrate with a transparent electrode with a dispenser so as to draw a rectangular frame.
Subsequently, liquid crystal (Chisso Corp .; JC-5004LA) droplets were applied to the entire surface of the transparent substrate, and another substrate with a transparent electrode (without a black matrix) was immediately placed on top of the substrate with the matrix. Then, ultraviolet rays were irradiated at 100 mW / cm ² for 30 seconds using a high-pressure mercury lamp on the seal part. At this time, the line width of the squeezed liquid crystal display element sealant was about 1.2 mm, and 0.3 mm was drawn so as to overlap the black matrix. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour to obtain a liquid crystal display element.

(Example 2)
50 parts by weight of the epoxy acrylate produced in (1a), 50 parts by weight of the partially modified resin produced in (1b), 3 parts by weight of SEESORB 701 (manufactured by Sipro Kasei Co., Ltd.), and Amicure VDH (Ajinomoto) as the thermosetting resin Finetechno) 10 parts by weight, Perbutyl O (Nippon Yushi Co., Ltd.) 0.5 parts, SO-C1 (manufactured by Admatechs) 30 parts by weight, and silane coupling agent KBM- 2 parts by weight of 403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., Aritori Nertaro), and then mixed using three rolls to produce a sealing agent for liquid crystal display elements. did.
Thereafter, a liquid crystal display element was obtained by the same operation as in Example 1.

(Example 3)
100 parts by weight of epoxy acrylate produced in (1a), 3 parts by weight of SEESORB 701 (manufactured by Sipro Kasei Co., Ltd.) as an ultraviolet absorber, 0.5 parts by weight of perbutyl O (manufactured by NOF Corporation) as a thermosetting resin, and as a filler 30 parts by weight of SO-C1 (manufactured by Admatechs) and 2 parts by weight of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent were used with a planetary stirrer (manufactured by Shinky, Nertaro Awatori). After mixing, a sealant for a liquid crystal display element was produced by further mixing using three rolls.
Thereafter, a liquid crystal display element was obtained by the same operation as in Example 1.

Example 4
50 parts by weight of epoxy acrylate prepared in (1a), 80 parts by weight of partially modified resin prepared in (1b), 1 part by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and SEESORB 701 as an ultraviolet absorber 3 parts by weight (manufactured by Sipro Kasei Co., Ltd.), 10 parts by weight Amicure VDH (manufactured by Ajinomoto Fine Techno Co., Ltd.) as a thermosetting resin, 0.5 parts by weight perbutyl O (manufactured by NOF Corporation), and SO-C1 as a filler After mixing 30 parts by weight (manufactured by Admatechs Co., Ltd.) and 2 parts by weight of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent using a planetary stirrer (manufactured by Shinky Co., Ltd., Kentaro Awatori) Furthermore, the sealing agent for liquid crystal display elements was manufactured by mixing using 3 rolls.
Thereafter, a liquid crystal display element was obtained by the same operation as in Example 1.

(Comparative Example 1)
50 parts by weight of epoxy acrylate produced in (1a), 50 parts by weight of partially modified resin produced in (1b), 10 parts by weight of Amicure VDH (manufactured by Ajinomoto Fine Techno Co.) as thermosetting resin, and perbutyl O (Nippon Yushi) 0.5 parts by weight), 30 parts by weight of SO-C1 (manufactured by Admatechs) as a filler, and 2 parts by weight of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent A sealant for a liquid crystal display element was manufactured by mixing using a three-roller after mixing using Shintaro Co., Ltd. (Nentaro Awatori).
Thereafter, a liquid crystal display element was obtained by the same operation as in Example 1.

(Comparative Example 2)
50 parts by weight of epoxy acrylate produced in (1a), 50 parts by weight of partially modified resin produced in (1b), 1 part by weight of Irgacure 184 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, and Amicure as a thermosetting resin 10 parts by weight of VDH (manufactured by Ajinomoto Fine-Techno Co., Ltd.), 0.5 parts by weight of perbutyl O (manufactured by NOF Corporation), 30 parts by weight of SO-C1 (manufactured by Admatechs) as a filler, and a silane coupling agent 2 parts by weight of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., Nertaro Awatori), and further mixed using three rolls to obtain a seal for a liquid crystal display element An agent was produced.
Thereafter, a liquid crystal display element was obtained by the same operation as in Example 1.

<Evaluation>
The following evaluation was performed about the sealing compound for liquid crystal display elements and liquid crystal display element which were obtained in Examples 1-4 and Comparative Examples 1-2. The results are shown in Table 1.

(1) Measurement of molar extinction coefficient of sealant for liquid crystal display element Seal for liquid crystal display element using acetonitrile for ultraviolet absorption spectrum (manufactured by Dojin Chemical Co., Ltd.) so that the sample concentration becomes 1.0 × 10 ⁻⁴ M. An agent solution was prepared, placed in a quartz cell having an optical path length (1 cm), and absorbance at 365 nm was measured using a spectrophotometer (UV-2450, manufactured by Shimadzu Corporation). The molar extinction coefficient was a value obtained by dividing the measured absorbance by the molar concentration (M) of the solution and the thickness (cm) of the cell.

(2) Reaction rate measurement of sealing agent for liquid crystal display element Two glasses of the liquid crystal display element before liquid crystal annealing were peeled off, and the curing rate of the seal portion was measured. The measurement was performed at two locations, a portion directly irradiated with UV light (UV irradiated portion) and a portion where UV light was shielded by the black matrix (UV light shielding portion). The measurement of reaction rate is performed using microscopic IR, converted peak acrylic groups peaks 810 cm ^-1, each of the reaction rate from the reduction rate of the peak of 910 cm ^-1 as a peak of the epoxy group (%) .

(3) Observation of unevenness of liquid crystal display element The obtained liquid crystal display element was visually observed for color unevenness generated in the liquid crystal around the seal portion, and evaluated in the following four stages.
◎ (No color irregularity)
○ (There is almost no uneven color)
△ (There are some uneven colors)
× (There is considerable color unevenness)
The observation was performed immediately after the liquid crystal display element was manufactured and after storage for 100 hours in an 80 ° C. environment.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements which performed thermosetting using the heat | fever which generate | occur | produced by ultraviolet irradiation, and prevented liquid-crystal contamination, the vertical conduction material, a liquid crystal display element, and the manufacturing method of a liquid crystal display element are provided. be able to.

Claims (6)

A sealing agent for a liquid crystal display element, comprising a thermosetting resin, a thermosetting agent and / or a thermal polymerization initiator, and an ultraviolet absorber. The sealing agent for liquid crystal display elements according to claim ¹ , wherein the molar extinction coefficient at 365 nm measured in acetonitrile is 10 to 100 M ⁻¹ · cm ⁻¹ . 3. The liquid crystal display element according to claim 1, wherein the ultraviolet absorber is at least one selected from the group consisting of a 2-hydroxyphenylbenzotriazole derivative, a 2-hydroxybenzophenone derivative, and a sacillylate derivative. Sealing agent. A vertical conduction material comprising the sealing agent for a liquid crystal display element according to claim 1, 2 or 3 and conductive fine particles. A liquid crystal display element comprising the sealant for a liquid crystal display element according to claim 1, 2 or 3, and / or the vertical conduction material according to claim 4. 6. A method for manufacturing a liquid crystal display element according to claim 5, wherein the thermosetting resin is thermally cured by irradiating ultraviolet rays to cause the ultraviolet absorber to generate heat.