JP2014219589A - Sealing agent for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

Disclosed is a sealing agent for a liquid crystal dropping method which has excellent adhesion to an alignment film and hardly causes liquid crystal contamination. Moreover, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods are provided. A sealant for a liquid crystal dropping method comprising a curable resin, a polymerization initiator and / or a thermosetting agent, and a titanate coupling agent. [Selection figure] None

Description

The present invention relates to a sealing agent for a liquid crystal dropping method which has excellent adhesion to an alignment film and hardly causes liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.

A liquid crystal display element has a liquid crystal cell in which liquid crystal is sealed in a cell formed by applying a sealing agent to two substrates and bonding them together.
The liquid crystal display cell has two transparent substrates with electrodes facing each other at a predetermined interval, and the periphery thereof is sealed with a sealing agent to form a cell. The liquid crystal is injected into the liquid crystal and the liquid crystal injection port is sealed with a sealant or a sealant.

In recent years, a manufacturing method of a liquid crystal display element called a dripping method using a photocuring thermosetting combined sealant as disclosed in Patent Document 1 has also been studied.
In the dropping method, first, a frame-shaped seal pattern is formed on one of two transparent substrates with electrodes. Next, fine droplets of liquid crystal are applied dropwise over the entire surface of the transparent substrate seal pattern frame in an uncured state of the sealant, the other transparent substrate is stacked under reduced pressure, and the seal portion is irradiated with ultraviolet rays for temporary curing. After that, heating is performed to perform main curing, and a liquid crystal display element is manufactured.

In the conventional liquid crystal display element, the arrangement position of the sealing agent is mainly on an inorganic material such as glass or ITO, and the sealing agent is designed in consideration of the adhesive force to these inorganic materials. However, along with the recent expansion of applications of liquid crystal display devices, the narrowing of the frame of the liquid crystal display portion has progressed, and a substrate in which a sealant is disposed on the alignment film has been rapidly spreading. There was a problem that the adhesive strength to was insufficient.

JP 2001-133794 A

An object of the present invention is to provide a sealing agent for a liquid crystal dropping method which has excellent adhesion to an alignment film and hardly causes liquid crystal contamination. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods.

The present invention is a liquid crystal dropping method sealing agent containing a curable resin, a polymerization initiator and / or a thermosetting agent, and a titanate coupling agent.
The present invention is described in detail below.

As a result of diligent study, the present inventor has surprisingly found that by adding a titanate coupling agent to a sealing agent for liquid crystal dropping method, the adhesive force to the alignment film can be drastically improved. It came to complete.

The sealing agent for liquid crystal dropping method of the present invention contains a titanate coupling agent. By containing the titanate coupling agent, the sealing agent for liquid crystal dropping method of the present invention has excellent adhesion to the alignment film.

Examples of the titanate coupling agent include carboxylic acid type titanate coupling agents, phosphorous acid type titanate coupling agents, pyrophosphate type titanate coupling agents, amine titanate coupling agents, and alkylbenzenesulfonic acid type titanate coupling agents. Etc. Of these, an alkylbenzene sulfonic acid type titanate coupling agent is preferable because it has a linear alkyl group having a high affinity for the alignment film component.
Examples of the carboxylic acid type titanate coupling agent include isopropyl tri-n-stearoyl titanate, isopropyl diisostearoyl acryl titanate, isopropyl trioctanoyl titanate, isopropyl triisostearoyl titanate, dimethacrylethylene titanate, isostearoyl methacrylethylene titanate, Isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, dicumyl phenyloxyacetate titanate, isopropyl diisostearoyl cumyl phenyl titanate, diisostearoyl ethylene titanate, isopropyl distearoyl methacrylate titanate, isopropyl trimethacryl titanate, isopropyl triacryl H , Isopropyltrianthranyl titanate, diisopropyloxyacetate titanate, isostearoyl methacryloxyacetate titanate, isostearoyl acryloxyacetate titanate, dimethacryloxyacetate titanate, isopropyltricumylphenyl titanate, dicumylphenolate oxyacetate titanate, diacrylethylene titanate , Dianthranylethylene titanate, titanium methylphenoxide, titanium allyl acetoacetate triisopropoxide, titanium bis (triethanolamine) diisopropoxide, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium di Isopropoxide bis (tetramethylheptanedionate), titanium di Seo propoxide bis (ethylacetoacetate), titanium methacryloxyethyl acetoacetate triisopropoxide, titanium oxide bis (pentanedionate), di acryloxy acetate titanate, and the like.
Examples of the phosphorous acid type titanate coupling agent include tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, and tetra (2,2-diallyloxymethyl-1-butyl) bis. (Di-tridecyl) phosphite titanate, isopropyl tri (dioctyl phosphate) titanate, tetraisopropyl di (dilauroyl phosphite) titanate, di (dioctyl phosphate) oxyacetate titanate, di (dioctyl phosphate) ethylene titanate and the like.
Examples of the pyrophosphate-type titanate coupling agent include isopropyl dioctyl pyrophosphate titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tris (dioctyl). Pyrophosphate) ethylene titanate, isopropyl octyl, butyl pyrophosphate titanate, isopropyl di (butyl, methyl pyrophosphate) titanate, di (octyl, butyl pyrophosphate) oxyacetate titanate, di (butyl, methyl pyrophosphate) ethylene titanate It is done.
Examples of the amine titanate coupling agent include isopropyl tri (N-aminoethylaminoethyl) titanate, isopropyl 4-aminobenzenesulfonyldi (dodecylbenzenesulfonyl) titanate, isopropyldi (4-aminobenzoyl) isostearoyl titanate, Isopropyltri (N, N-dimethylethylamino) titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonyloxyacetate titanate, 4-aminobenzoylisostearoyloxyacetate titanate, 4-aminobenzenesulfonyldodecylbenzenesulfonylethylene titanate, 4-aminobenzoyl Examples thereof include isostearoyl ethylene titanate.
Examples of the alkylbenzene sulfonic acid type titanate compound include isopropyl tris (dodecylbenzenesulfonyl) titanate, isopropyl tris (decylbenzenesulfonyl) titanate, isopropyl tris (undecylbenzenesulfonyl) titanate, isopropyl tris (tridecylbenzenesulfonyl) titanate, Examples include isopropyl tris (tetradecylbenzenesulfonyl) titanate.
These titanate coupling agents may be used alone or in combination of two or more.

Examples of commercially available titanate coupling agents include KR-TTS (isopropyl triisostearoyl titanate), KR-46B (tetraoctylbis (ditridecyl phosphite) titanate), and KR-55 (tetra ( 2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate), KR-41B (tetraisopropyl bis (dioctyl phosphite) titanate), KR-38S (isopropyl tris (dioctyl borophosphate) titanate), KR-138S (bis (dioctyl bisphosphate) oxyacetate titanate), KR-238S (tris (dioctyl bisphosphate) ethylene titanate), 338X (isopropyl dioctyl bis pyrophos) Etochitaneto), KR-44 (isopropyl tri (N- aminoethyl) titanate), KR-9Sa (isopropyl tris (dodecylbenzene sulfonyl) titanate) (all include manufactured by Ajinomoto Fine-Techno Co., Ltd.).
Since these commercially available titanate coupling agents often contain a solvent, when using a titanate coupling agent containing a solvent, it is preferable to remove the solvent in advance.

The content of the titanate coupling agent is preferably 0.5 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. If the content of the titanate coupling agent is less than 0.5 parts by weight, the resulting liquid crystal dropping method sealing agent may have insufficient adhesion to the alignment film. When the content of the titanate coupling agent exceeds 10 parts by weight, the titanate coupling agent may elute into the liquid crystal in the liquid crystal display element, causing display unevenness and the like. A more preferred lower limit of the content of the titanate coupling agent is 2 parts by weight, a more preferred upper limit is 8 parts by weight, a still more preferred lower limit is 3 parts by weight, and a still more preferred upper limit is 5 parts by weight.

In addition to the titanate coupling agent, the sealing agent for liquid crystal dropping method of the present invention may contain a silane coupling agent as long as the object of the present invention is not impaired.
As the silane coupling agent, for example, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane and the like are preferably used. These silane coupling agents may be used alone or in combination of two or more.

The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 20 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited. When content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination. The minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.

The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin preferably has an epoxy group and / or a (meth) acryloyl group.
Examples of the curable resin having an epoxy group (hereinafter also referred to as epoxy resin) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac Type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthalenephenol Examples include novolac type epoxy resins, glycidyl amine type epoxy resins, alkyl polyol type epoxy resins, rubber-modified epoxy resins, and glycidyl ester compounds.

As what is marketed among the said bisphenol A type epoxy resins, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850-S (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy resins, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said propylene oxide addition bisphenol A type epoxy resins, EP-4000S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said resorcinol type epoxy resins, EX-201 (made by Nagase ChemteX Corporation) etc. are mentioned, for example.
As what is marketed among the said biphenyl type epoxy resins, Epicoat YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
As what is marketed among the said sulfide type epoxy resins, YSLV-50TE (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene type epoxy resins, EP-4088S (made by ADEKA) etc. are mentioned, for example.
As what is marketed among the said naphthalene type | mold epoxy resins, Epicron HP4032, Epicron EXA-4700 (all are the products made from DIC) etc. are mentioned, for example.
As what is marketed among the said phenol novolak-type epoxy resins, Epicron N-770 (made by DIC Corporation) etc. are mentioned, for example.
As what is marketed among the said ortho cresol novolak-type epoxy resins, Epicron N-670-EXP-S (made by DIC) etc. are mentioned, for example.
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
As what is marketed among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said naphthalene phenol novolak-type epoxy resins, ESN-165S (made by Nippon Steel Chemical Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said glycidylamine type epoxy resins, Epicoat 630 (made by Mitsubishi Chemical Corporation), Epicron 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Co., Inc.) etc. are mentioned, for example.
Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel Chemical Co., Ltd.), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX- 611 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (all manufactured by Nippon Steel Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries, Ltd.), and the like.
As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase ChemteX Corporation) etc. is mentioned, for example.
Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031, and Epicoat. 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.

Examples of the curable resin having a (meth) acryloyl group (hereinafter also referred to as (meth) acrylic resin) include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and (meth) acrylic. Examples include epoxy (meth) acrylate obtained by reacting an acid with an epoxy compound, urethane (meth) acrylate obtained by reacting an isocyanate with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferred from the standpoint of ease of synthesis.
In the present specification, the above (meth) acryloyl group means an acryloyl group or a methacryloyl group, and the above (meth) acryl means acryl or methacryl. Moreover, the said (meth) acrylate means an acrylate or a methacrylate, The said epoxy (meth) acrylate means what all the epoxy groups of the epoxy compound reacted with (meth) acrylic acid.

Examples of monofunctional compounds among the ester compounds include 2-hydroxyethyl (meth) acrylate, 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, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl cal Tall (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene 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, cyclohexyl (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) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2- Examples thereof include hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate and the like.

Examples of the bifunctional one of the ester compounds include 1,4-butanediol di (meth) acrylate, 1,3-butanediol 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, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (me ) 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 dicyclopentadienyl di (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) acryloyloxypropyl (meth) acrylate, carbonate diol di ( (Meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate Polybutadiene di (meth) acrylate.

Examples of the ester compound having three or more functional groups include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and 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 tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide De additional glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

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

As an epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, the thing similar to the epoxy resin mentioned above can be used.

Specific examples of the epoxy (meth) acrylate include, for example, 360 parts by weight of a resorcinol type epoxy resin (manufactured by Nagase ChemteX Corporation, “EX-201”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, and a reaction catalyst. Resorcinol-type epoxy acrylate can be obtained by reacting 2 parts by weight of triethylamine and 210 parts by weight of acrylic acid at 90 ° C. while refluxing and stirring for 5 hours.

Examples of commercially available epoxy (meth) acrylates include, for example, Evecryl 860, Evekril 3200, Evekril 3201, Evekryl 3412, Evekril 3600, Evekril 3700, Evekrill 3703, Evekril 3703, Evekril 3800, Evekril 6040. , Evacryl RDX63182 (all manufactured by Daicel Cytec), EA-1010, EA-1020, EA-5323, EA-5520, 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 3 02A, Epoxy ester 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 (Both manufactured by Nagase ChemteX Corporation).

The urethane (meth) acrylate is obtained, for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of a compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Can do.

As an isocyanate used as the raw material of the urethane (meth) acrylate, for example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4 ′ -Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (Isocyanate phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate Etc. The.

In addition, as an isocyanate that is a raw material of the urethane (meth) acrylate, polyols such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like Chain-extended isocyanate compounds obtained by reaction with excess isocyanate can also be used.

Examples of the (meth) acrylic acid derivative having a hydroxyl group that is a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Commercial products such as acrylate and 2-hydroxybutyl (meth) acrylate, and divalent alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol Mono (meth) acrylate, trimethylol ethane, trimethylol propane, mono (meth) acrylate or di (meth) acrylate of trivalent alcohol such as glycerin, epoxy acrylate such as bisphenol A modified epoxy acrylate, etc. It is below.

Specifically, the urethane (meth) acrylate includes, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate. The mixture can be reacted at 60 ° C. for 2 hours with stirring under reflux, then 51 parts by weight of 2-hydroxyethyl acrylate is added, and the mixture is reacted at 90 ° C. with stirring under reflux for 2 hours while feeding air.

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, and Evekril 4858. , Evecril 8402, Evecril 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecryl 1290, Evecril 5129, Evecril 4842, Evecril 4827, Evecril 4827, Evecril 6700, Evecril 220, Evecryl 22B Resin UN-9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-33 0HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), 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 (all manufactured by Kyoeisha Chemical Co., Ltd.) It is.

The (meth) acrylic resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, and —NH ₂ group from the viewpoint of suppressing adverse effects on the liquid crystal.
The (meth) acrylic resin preferably has 2 to 3 (meth) acryloyl groups in the molecule because of its high reactivity.

Examples of the curable resin having an epoxy group and a (meth) acryloyl group include partial (meth) acryl modification obtained by reacting a part of the epoxy group of a compound having two or more epoxy groups with (meth) acrylic acid. An epoxy resin etc. are mentioned.

The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. Specifically, for example, 190 g of phenol novolac type epoxy resin N-770 (manufactured by DIC) is dissolved in 500 mL of toluene, 0.1 g of triphenylphosphine is added to this solution to obtain a uniform solution, and 35 g of acrylic acid is added to this solution. Was added dropwise for 2 hours under reflux stirring, and further reflux stirring was performed for 6 hours. Next, by removing toluene, a partially acrylic modified phenol novolac type epoxy resin in which 50 mol% of the epoxy groups reacted with acrylic acid was removed. Can be obtained (in this case 50% partially acrylic modified).

As what is marketed among the said partial (meth) acryl modified epoxy resins, UVACURE1561 (made by Daicel Cytec) is mentioned, for example.

The preferable lower limit of {number of moles of (meth) acryloyl group} / {number of moles of (meth) acryloyl group + number of moles of epoxy group} in the curable resin in the sealant for liquid crystal dropping method of the present invention is 0.5. The preferred upper limit is 0.9. When the {number of moles of (meth) acryloyl group} / {number of moles of (meth) acryloyl group + number of moles of epoxy group} in the curable resin is less than 0.5, the obtained sealing agent for liquid crystal dropping method is obtained. It may contaminate the liquid crystal and cause uneven color in the display element. When {number of moles of (meth) acryloyl group} / {number of moles of (meth) acryloyl group + number of moles of epoxy group} in the curable resin exceeds 0.9, the display element is reliable in a high-temperature and high-humidity environment. May decrease. The more preferred lower limit of {number of moles of (meth) acryloyl group} / {number of moles of (meth) acryloyl group + number of moles of epoxy group} in the curable resin is 0.7, and the more preferred upper limit is 0.85. .

The sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent.
Examples of the polymerization initiator include photo radical polymerization initiators for reacting (meth) acryloyl groups with light such as ultraviolet rays, thermal radical polymerization initiators for reacting (meth) acryloyl groups with heat, and epoxy groups with photo And a cationic photopolymerization initiator for reacting an epoxy group with heat, and the like, which are appropriately selected depending on the curable resin used and the application.

Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like.
Examples of commercially available photo radical polymerization initiators include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACUREO XE01, and Lucirin TPO (all manufactured by BASF 30 from KAS, JASF 30). SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.

When using the said radical photopolymerization initiator, as for content of the said radical photopolymerization initiator, a preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of curable resin. If the content of the photo radical polymerization initiator is less than 0.1 parts by weight, the liquid crystal dropping method sealing agent of the present invention may not be sufficiently photocured. When the content of the radical photopolymerization initiator exceeds 10 parts by weight, the storage stability may be lowered.

Examples of the thermal radical polymerization initiator include peroxides and azo compounds.
Examples of commercially available thermal radical polymerization initiators include perbutyl O, perhexyl O, perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, and VPE-0201. , VPE-0401, VPE-0601 (both manufactured by Wako Pure Chemical Industries, Ltd.) and the like.

When using the said thermal radical polymerization initiator, as for content of the said thermal radical polymerization initiator, a preferable minimum is 0.01 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 10 weight part. When the content of the thermal radical polymerization initiator is less than 0.01 parts by weight, the liquid crystal dropping method sealing agent of the present invention may not be sufficiently cured. When content of the said thermal radical polymerization initiator exceeds 10 weight part, storage stability may fall.

As said photocationic polymerization initiator, aromatic diazonium salt, aromatic iodonium salt, aromatic sulfonium salt etc. are mentioned, for example.
Examples of commercially available photocationic polymerization initiators include Adekaoptomer SP-150 and Adekaoptomer SP-170 (both manufactured by ADEKA).

When using the said cationic photopolymerization initiator, as for content of the said cationic photopolymerization initiator, a preferable minimum is 0.1 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 10 weight part. When the content of the photocationic polymerization initiator is less than 0.1 parts by weight, the sealing agent for liquid crystal dropping method of the present invention may not be sufficiently photocured. If the content of the cationic photopolymerization initiator exceeds 10 parts by weight, the storage stability may be lowered.

Examples of the thermal cationic polymerization initiator include various onium salts such as a quaternary ammonium salt, a phosphonium salt, and a sulfonium salt.

Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl. -N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyl Trifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-die -N- (4- methoxybenzyl) preparative Luigi hexafluoroantimonate and the like.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, and diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate and the like.

Examples of commercially available thermal cationic polymerization initiators include Adeka Opton CP-66, Adeka Opton CP-77 (all manufactured by ADEKA), Sun-Aid SI-60L, Sun-Aid SI-80L, and Sun-Aid SI-100L ( Any of them may be Sanshin Chemical Co., Ltd.), CI series (Nihon Soda Co., Ltd.),

When using the said thermal cationic polymerization initiator, as for content of the said thermal cationic polymerization initiator, a preferable minimum is 0.1 weight part with respect to 100 weight part of whole curable resin, and a preferable upper limit is 10 weight part. When the content of the thermal cationic polymerization initiator is less than 0.1 part by weight, the sealing agent for liquid crystal dropping method of the present invention may not be sufficiently cured. When content of the said thermal cationic polymerization initiator exceeds 10 weight part, storage stability may fall.

Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.

Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like. For example, SDH, MDH (all manufactured by Nippon Finechem Co., Ltd.), ADH (manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.) Etc.

When using the said thermosetting agent, as for content of the said thermosetting agent, a preferable minimum is 1 weight part with respect to 100 weight part of curable resin, and a preferable upper limit is 50 weight part. When the content of the thermosetting agent is less than 1 part by weight, the sealing agent for liquid crystal dropping method of the present invention may not be sufficiently cured. When the content of the thermal epoxy thermosetting agent exceeds 50 parts by weight, the viscosity of the sealing agent for liquid crystal dropping method of the present invention is increased, which may impair applicability and the like. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.

The sealing agent for liquid crystal dropping method of the present invention may contain an inorganic filler. The said inorganic filler has effects, such as an adhesive improvement by a stress dispersion | distribution effect, and an improvement of a linear expansion coefficient.
Examples of the inorganic filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, and water. Examples thereof include aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, and aluminum nitride. These inorganic fillers may be used alone or in combination of two or more.

The content of the inorganic filler is such that a preferred lower limit is 5 parts by weight and a preferred upper limit is 70 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the inorganic filler is less than 5 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited. When content of the said inorganic filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability | paintability may worsen. The minimum with more preferable content of the said inorganic filler is 10 weight part, and a more preferable upper limit is 60 weight part.

The sealing agent for liquid crystal dropping method of the present invention contains organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc., in addition to the above-mentioned inorganic fillers, as long as the object of the present invention is not impaired. May be.

The sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent. By containing the said light shielding agent, the sealing compound for liquid crystal dropping methods of this invention can be used suitably as a light shielding sealing agent.

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

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

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

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

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

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is not more 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 5 μm. When the primary particle size of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5 μm, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated. The more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.

The preferable lower limit of the content of the light-shielding agent is 5% by weight and the preferable upper limit is 80% by weight with respect to the entire sealing agent for liquid crystal dropping method of the present invention. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent is more than 80% by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered. The more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.

The sealing agent for the liquid crystal dropping method of the present invention further includes a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting the thixotropy, a spacer such as a polymer bead for adjusting the panel gap, if necessary. Other known additives such as a curing accelerator such as -P-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, and a polymerization inhibitor may be contained.

Examples of the method for producing the sealant for the liquid crystal dropping method of the present invention include, for example, a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, a three-roll mixer, etc. Examples include a method of mixing an agent and / or a thermosetting agent, a titanate coupling agent, a silane coupling agent added if necessary, and the like.

A vertical conduction material can be produced by blending conductive fine particles with the sealant for the liquid crystal dropping method of the present invention. If such a vertical conduction material is used, the electrodes can be reliably conductively connected.
The vertical conduction material containing the sealing agent for liquid crystal dropping method of the present invention and conductive fine particles is also one aspect of the present invention.

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

The liquid crystal display element using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
As a method for producing the liquid crystal display device of the present invention, for example, the liquid crystal dropping method sealing agent of the present invention is applied to one of substrates having an electrode such as an ITO thin film and an alignment film by screen printing, dispenser coating, or the like. , A step of forming a rectangular seal pattern, a step of applying a liquid crystal microdrop on the entire surface of the frame of the seal pattern, and a step of superposing the other substrate under a vacuum, the liquid crystal dropping method sealing agent of the present invention with ultraviolet rays, etc. And the like. The method includes a step of temporarily curing the sealing agent by irradiating the light and a step of heating and temporarily curing the temporarily cured sealing agent.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in the adhesiveness to alignment film and hardly causes liquid-crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.

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

(Synthesis of epoxy methacrylate (curable resin 1))
1000 parts by weight of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, “Epicoat 828EL”, epoxy equivalent 190), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 905 methacrylic acid The mixture was stirred at reflux while feeding air at 90 ° C. and reacted for 5 hours. 100 parts by weight of the resulting product was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin ("Siritin V85" manufactured by Hoffman Mineral Co.) in order to adsorb ionic impurities in the reaction product. Then, a curable resin 1 was obtained as an epoxy methacrylate.

(Synthesis of partially methacryl-modified epoxy resin (curable resin 2))
1000 parts by weight of a bisphenol A type epoxy resin (“Epicoat 828EL”, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 453 methacrylic acid The mixture was stirred at reflux while feeding air at 90 ° C. and reacted for 5 hours. 100 parts by weight of the resulting product was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral, Siritin V85) to adsorb ionic impurities in the reaction product, Curable resin 2 was obtained as a 50% partially methacryl-modified epoxy resin.

Example 1
As a curable resin, 58 parts by weight of curable resin 1 and 42 parts by weight of curable resin 2 were mixed in predetermined containers, mixed and stirred with a planetary stirrer, and then isopropyl tris (dodecyl) as a titanate coupling agent. Benzenesulfonyl) titanate (manufactured by Ajinomoto Fine Techno Co., Ltd., “KR-9SA”) (3.0 parts by weight) was mixed and stirred, and the solvent was removed by heating at 120 ° C. in a vacuum oven with a vacuum degree of 5.0 Torr. Into the obtained mixture, 1.7 parts by weight of a radical photopolymerization initiator (BASF Japan, “Irgacure 651”) was blended and dissolved by heating at 80 ° C., and γ-glycidoxy as a silane coupling agent. 1.5 parts by weight of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone, “KBM-403”) is mixed and stirred, and silica (manufactured by Admatechs, “SO-C2”, average particle diameter 0.6 μm) as an inorganic filler. , Aspect ratio 1.0) 42 parts by weight and 5.0 parts by weight of malonic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., “MDH”) as a thermosetting agent were mixed and stirred, and then dispersed in a ceramic three roll mill. By doing so, the sealing agent for liquid crystal dropping method of Example 1 was obtained.

(Examples 2 to 14 and Comparative Example 1)
Except having used each material according to the compounding ratio described in Table 1, the sealing agent for liquid crystal dropping methods of Examples 2-14 and the comparative example 1 was prepared like Example 1. FIG.
The thermal radical polymerization initiator used in Example 9 was blended simultaneously with the photo radical polymerization initiator.

<Evaluation>
The following evaluation was performed about the sealing agent for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Table 1.

(1) Adhesiveness to alignment film The silica spacer (manufactured by Sekisui Chemical Co., Ltd., “SI-H055”) is blended in the sealing agent for liquid crystal dropping method obtained in Examples and Comparative Examples, so as to be 1% by weight, A metal halide lamp is obtained by minutely dropping one of two non-alkali glasses with an alignment film for VA (30 × 40 mm) and pasting the other non-alkali glass with an alignment film for VA in a cross shape. After irradiating with 3000 mJ / cm ^{2 of} ultraviolet rays, an adhesive test piece was obtained by heating at 120 ° C. for 60 minutes. About the obtained adhesion test piece, the tension test (5 mm / sec) was done with the chuck | zipper arranged up and down. The value obtained by dividing the measured value (kgf) by the seal application cross-sectional area (cm ² ) was 0 kgf / cm ² or more and less than 10 kgf / cm ² was “x”, 10 kgf / cm ² or more and less than 20 kgf / cm ² The adhesiveness to the alignment film was evaluated with “Δ” as the case and “◯” as the case where it was 20 kgf / cm ² or more.

(2) Dispensing syringes (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.) were used as liquid crystal dropping method sealants obtained in Examples and Comparative Examples of liquid crystal display elements that were driven after being stored at high temperature and high humidity. )) And subjected to defoaming treatment. Next, two transparent electrode substrates with an ITO thin film coated with an alignment film for VA on the surface are prepared, and a rectangular frame is drawn on one transparent electrode substrate using a dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”). A sealant was applied in the same manner. Subsequently, fine droplets of VA liquid crystal were dropped and applied with a liquid crystal dropping device, and the other transparent electrode substrate was bonded under reduced pressure with a vacuum laminating device. The cells after bonding were irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, then heated in an oven at 120 ° C. for 60 minutes to thermally cure the sealing agent, and five liquid crystal display elements for each sealing agent. Produced. The obtained liquid crystal display element was stored for 36 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the periphery of the halftone sealant was visually observed. The case where no color unevenness was observed at all around the sealant part was evaluated as “◯”, the case where slightly light color unevenness was observed as “Δ”, and the case where clear dark color unevenness was observed as “X”.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in the adhesiveness to alignment film and hardly causes liquid-crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal dropping methods can be provided.

Claims (6)

A sealing agent for a liquid crystal dropping method comprising a curable resin, a polymerization initiator and / or a thermosetting agent, and a titanate coupling agent. The sealant for a liquid crystal dropping method according to claim 1, wherein the titanate coupling agent is an alkylbenzenesulfonic acid type titanate coupling agent. The content of the titanate coupling agent is 0.5 to 10 parts by weight with respect to 100 parts by weight of the curable resin. The sealing agent for liquid crystal dropping method according to claim 1 or 2. 4. The sealing agent for liquid crystal dropping method according to claim 1, wherein the curable resin has an epoxy group and / or a (meth) acryloyl group. A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, or 4, and conductive fine particles. A liquid crystal display element manufactured using the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, or 4, or the vertical conduction material according to claim 5.