JP5919073B2 - Liquid crystal dropping method sealing agent, vertical conduction material, and liquid crystal display element - Google Patents

Description

The present invention relates to a sealant for a liquid crystal dropping method having excellent adhesiveness, low moisture permeability of a cured product, and hardly causing liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.

In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. Such a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.

In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing. . Thereafter, heating is performed at the time of 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, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.

Usually, the curable resin used for the sealant for the dripping method can be a combined type of photocuring and heat curing, and since it has high polarity and low compatibility with liquid crystals, it is effective in contaminating liquid crystals. Therefore, epoxy (meth) acrylate having a hydroxyl group is used. However, since the hydrophilicity of the curable resin is increased by having a hydroxyl group, the moisture permeability of the cured sealant is increased. When the liquid crystal display element is driven after being exposed to high temperature and high humidity, the liquid crystal display element There has been a problem that reliability is lowered, such as display defects such as color unevenness which were not produced at the time of production.
In order to reduce the moisture permeability of the cured product of the sealant, it is conceivable to use an inorganic filler, but in order to sufficiently reduce the moisture permeability of the cured product of the sealant, it is necessary to add a large amount of inorganic filler. However, when a large amount of an inorganic filler is added, there is a problem that the adhesiveness of the sealing agent is lowered.

JP 2001-133794 A International Publication No. 02/092718 Pamphlet

An object of the present invention is to provide a sealing agent for a liquid crystal dropping method, which has excellent adhesiveness and has low moisture permeability of a cured product 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 are manufactured using 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 silane coupling agent, wherein the silane coupling agent is 2- (3, 4-Epoxycyclohexyl) ethyltrimethoxysilane is a sealing agent for liquid crystal dropping method.

The present inventor, by blending 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as a silane coupling agent, has excellent adhesion and low moisture permeability of the cured product, causing liquid crystal contamination. The present inventors have found that a sealing agent for a liquid crystal dropping method with almost no slag can be obtained and completed the present invention.

The sealing agent for liquid crystal dropping method of the present invention contains a silane coupling agent.
The silane coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. By containing 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane as the silane coupling agent, the liquid crystal dropping method sealing agent of the present invention has excellent adhesiveness and low moisture permeability of the cured product. It will be a thing.

The content of the silane coupling agent is preferably 0.1 parts by weight and preferably 10 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 containing the silane coupling agent cannot be sufficiently obtained, and the resulting sealant is inferior in moisture resistance of the cured product. It may become. When the content of the silane coupling agent exceeds 10 parts by weight, the silane coupling agent may contaminate the liquid crystal, or the obtained cured product of the liquid crystal dropping method sealing agent may have poor moisture resistance. Sometimes. The minimum with more preferable content of the said silane coupling agent is 1 weight part, and a more preferable upper limit is 5 weight part.

The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin preferably contains (meth) acrylate having an isocyanuric skeleton and / or (meth) acrylate having a dicyclopentadiene skeleton. By containing the (meth) acrylate having the isocyanuric skeleton and / or the (meth) acrylate having the dicyclopentadiene skeleton, the sealing agent for liquid crystal dropping method of the present invention is particularly excellent in moisture resistance of the cured product. Become.

Examples of the (meth) acrylate having an isocyanuric skeleton include ethoxylated isocyanuric triacrylate, ethoxylated isocyanuric trimethacrylate, caprolactone-modified ethoxylated isocyanuric triacrylate, caprolactone-modified ethoxylated isocyanuric trimethacrylate, and the like. Of these, ethoxylated isocyanuric triacrylate is preferable because the cured product has excellent moisture resistance and good curability.

Examples of the (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Of these, tricyclodecane dimethanol diacrylate is preferred because of good adhesion.

The content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is preferably 0.1 parts by weight and preferably has a preferable upper limit with respect to 100 parts by weight of the entire curable resin. 30 parts by weight. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is less than 0.1 parts by weight, the moisture resistance of the cured product of the liquid crystal dropping method sealing agent is improved. The effect may not be fully exhibited. When the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton exceeds 30 parts by weight, the liquid crystal contamination may be increased. The more preferable lower limit of the content of the (meth) acrylate having the isocyanuric skeleton and the (meth) acrylate having the dicyclopentadiene skeleton is 1 part by weight, and the more preferable upper limit is 20 parts by weight.

The curable resin preferably contains an epoxy (meth) acrylate.
In the present specification, (meth) acrylate means acrylate or methacrylate. Moreover, in this specification, the said epoxy (meth) acrylate represents the compound which made all the epoxy groups in an epoxy resin react with (meth) acrylic acid.
The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventional method. Among these, an epoxy methacrylate resin is preferable because the cured product has excellent moisture resistance.
In addition, in this specification, (meth) acryl means acryl or methacryl.

The epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallylbisphenol 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 epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin Naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.

As what is marketed among the said bisphenol A type epoxy resin, Epicoat 828EL, Epicoat 1004 (all are the Mitsubishi Chemical company make), Epiklon 850 (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 Tohto Kasei Co., Ltd.) etc. are mentioned, for example.
As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Tohto Kasei 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 Tohto Kasei 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 Toto Kasei), Epicron 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 ( Nagase ChemteX Corporation).
Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Tohto Kasei 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.
As what is marketed among the said bisphenol A type | mold episulfide resin, Epicoat YL-7000 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
Other commercially available epoxy resins include, for example, 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 ( These include Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation), and the like.

Examples of commercially available epoxy (meth) acrylates include, for example, Evecryl 860, Evekril 3200, Evekril 3201, Ebekrill 3412, Evekril 3600, Evekrill 3700, Evekril 3701, Evekril 3703, Evekril 3800, Evekril 3040. , 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 30 2A, 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 sealing agent for liquid crystal dropping method of the present invention may contain an epoxy resin as a curable resin.
As said epoxy resin, if it is resin to which the epoxy group was provided, it can be used without a limitation, The epoxy resin used as a raw material for synthesize | combining the said epoxy (meth) acrylate etc. can be used.

Moreover, you may contain a partial (meth) acryl modified epoxy resin as said epoxy resin.
In the present specification, the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule. In the present specification, the above (meth) acryloyloxy group means an acryloyloxy group or a methacryloyloxy group.
The partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy group of a part of an epoxy resin having two or more epoxy groups with (meth) acrylic acid.

The upper limit with the preferable ratio of the epoxy group with respect to the total amount of the (meth) acryloyloxy group and an epoxy group in the said whole curable resin is 50 mol%. When the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there. A more preferable upper limit of the ratio of the epoxy group is 20 mol%.

The sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent.
The polymerization initiator is not particularly limited. For example, a radical polymerization initiator that generates radicals by irradiation or heating with light such as ultraviolet rays, or irradiation or heating with light such as ultraviolet rays. And cationic polymerization initiators that generate cations. As the polymerization initiator, an appropriate one is selected depending on the kind of the curable resin.

Among the radical polymerization initiators, examples of the photo radical polymerization initiator that generates radicals when irradiated with light include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime esters. A compound, a benzoin ether compound, thioxanthone, or the like can be preferably used.
Examples of commercially available photo radical polymerization initiators include Irgacure 184, Irgacure 369, Irgacure 379, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure 2959, Irgacure OXE01, and Lucyrin TPO (all of which are BASF). Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all of which are manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, Irgacure 651, Irgacure 907, benzoin isopropyl ether, and Lucillin TPO are preferable because of their wide absorption wavelength range. These radical photopolymerization initiators may be used alone or in combination of two or more.

Among the above radical polymerization initiators, thermal radical polymerization initiators that generate radicals by heat are not particularly limited, and examples thereof include peroxides and azo compounds. Examples of commercially available ones include perbutyl O and perhexyl O. Perbutyl PV (all manufactured by NOF Corporation), V-30, V-501, V-601, VPE-0201 (all manufactured by Wako Pure Chemical Industries, Ltd.) and the like. These thermal radical polymerization initiators may be used alone or in combination of two or more.

The cationic polymerization initiator is not particularly limited, and examples thereof include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.
Examples of commercially available cationic polymerization initiators include optomer SP-150, optomer SP-151, optomer SP-170, optomer SP-171 (all manufactured by ADEKA), UVE-1014 (general electronics). Irgacure 261 (BASF Japan), Sun-Aid SI-60L, Sun-Aid SI-80L, UVI-6990 (Union Carbide), BBI-103, MPI-103, TPS-103, MDS-103, DTS -103, NAT-103, NDS-103 (all manufactured by Midori Chemical Co., Ltd.), Sun-Aid SI-100L (all manufactured by Sanshin Chemical Industry Co., Ltd.), CI-2064, CI-2639, CI-2624, CI-2481 ( All are made by Nippon Soda Co., Ltd.), RHODOR SIL PHOTOINITIATOR 2074 (manufactured by Rhone-Poulenc), CD-1012 (manufactured by Sartomer) and the like. These cationic polymerization initiators may be used alone or in combination of two or more. Further, if necessary, a sensitizer such as anthracene or thioxanthone may be used in combination.

Although content of the said polymerization initiator is not specifically limited, A preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of said curable resins. When the content of the polymerization initiator is less than 0.1 parts by weight, polymerization of the resulting sealant may not sufficiently proceed. When content of the said polymerization initiator exceeds 10 weight part, many unreacted polymerization initiators remain and the weather resistance of the sealing agent obtained may worsen. The minimum with more preferable content of the said polymerization initiator is 1 weight part, and a more preferable upper limit is 5 weight part.

The said thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, solid organic acid hydrazide is preferably used.

The solid organic acid hydrazide is not particularly limited, and examples thereof include 1,3-bis [hydrazinocarboethyl-5-isopropylhydantoin], sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. Examples of commercially available products include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), and the like.

The sealing agent for liquid crystal dropping method of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the coefficient of linear expansion, and further improving the moisture resistance of the cured product. preferable.
The filler is not particularly limited. For example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, hydroxide Inorganic fillers such as magnesium, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. Of organic fillers.

Although content of the said filler is not specifically limited, A preferable minimum is 5 weight part and a preferable upper limit is 40 weight part with respect to 100 weight part of said curable resins. If the content of the filler is less than 5 parts by weight, the effect of blending the filler may not be sufficiently obtained. When content of the said filler exceeds 40 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness or drawing property. A more preferable lower limit of the content of the filler is 10 parts by weight, and a more preferable upper limit is 35 parts by weight.

The liquid crystal dropping method sealing agent of the present invention further includes a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, and 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea, an antifoamer, a leveling agent, and a polymerization inhibitor.

The method for producing the sealant for the liquid crystal dropping method of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three roll, And a method of mixing a polymerization initiator and / or a thermosetting agent, a silane coupling agent, and an additive to be added as necessary.

A vertical conduction material can be manufactured by mix | blending electroconductive fine particles with the sealing compound for liquid crystal dropping methods of this invention. Such a 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.

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 using the sealing compound for liquid crystal dropping method of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in adhesiveness, and the moisture permeability of hardened | cured material is low, and hardly causes liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using 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.

(Examples 1-13, Comparative Examples 1-3)
In accordance with the blending ratio described in Table 1, each material was mixed using a planetary stirrer (“Shinky Netaro” manufactured by Shinky), and then further mixed using three rolls. To 13 and Comparative Examples 1 to 3 were prepared.

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

(1) Adhesiveness 1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is added to the sealing agents obtained in Examples and Comparative Examples, and two pieces of alkali glass test pieces with ITO film are included. (30 × 40 mm) was finely dropped on one side and the other glass test piece was bonded in a cross shape to this, and irradiated with 3000 mJ / cm ² ultraviolet rays with a metal halide lamp, and then at 120 ° C. for 60 minutes. An adhesion test piece was obtained by heating. About the obtained adhesion test piece, the tension test (5 mm / sec) was done with the chuck | zipper arranged up and down. The case where the value obtained by dividing the obtained measured value (kgf) by the cross-sectional area (cm ² ) of seal application is 20 kgf / cm ² or more is “◯”, and is 10 kgf / cm ² or more and less than 20 kgf / cm ² Was evaluated as “×” when “Δ” was less than 10 kgf / cm ² .

(2) Adhesion after PCT Adhesion test piece prepared in the same manner as “(1) Adhesion” was subjected to a pressure cooker test (121 ° C., 100% RH, 0.2 MPa) for 24 hours to obtain an adhesion test piece after PCT. Got. Next, the obtained post-PCT adhesion test piece was subjected to a tensile test (5 mm / sec) using a vertically arranged chuck. The case where the value obtained by dividing the obtained measured value (kgf) by the cross-sectional area (cm ² ) of seal application is 20 kgf / cm ² or more is “◯”, and is 10 kgf / cm ² or more and less than 20 kgf / cm ² Was evaluated as “×” when “Δ” was less than 10 kgf / cm ² .

(3) Moisture resistance of cured product The sealants obtained in the Examples and Comparative Examples were applied to a smooth release film with a coater to a thickness of 200 to 300 μm, and then 3000 mJ / cm ^{2 with} a metal halide lamp. After irradiating with ultraviolet rays, the cured film for moisture permeability measurement was obtained by heating at 120 ° C. for 60 minutes. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture proof packaging materials (cup method), and the obtained cured film for moisture permeability measurement was attached, and the temperature was 80 ° C. and the humidity was 90% RH. The moisture permeability was measured by putting it in a high-temperature and high-humidity oven. The case where the obtained moisture permeability value is less than 60 g / m ² · 24 hr is “◯”, and the case where it is 60 g / m ² · 24 hr or more and less than 80 g / m ² · 24 hr is “Δ”, 80 g / m ^The case where it was ² · 24 hours or more was evaluated as “x”.

(4) Liquid crystal contamination (color unevenness)
The obtained sealing agent for liquid crystal dropping method was applied to a substrate on which a transparent electrode and an alignment film were formed with a dispenser so as to draw a square frame. Subsequently, a fine droplet of liquid crystal (“JC-5004LA” manufactured by Chisso Corporation) is dropped onto the entire surface of the transparent base frame, and a substrate on which another transparent electrode and an alignment film are formed is superposed in a vacuum, and vacuum is applied. After the release, the outer frame seal portion was irradiated with 100 mW / cm ² ultraviolet rays for 30 seconds using a high-pressure mercury lamp. Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour, and the liquid crystal dropping method sealing agent was thermally cured to obtain a liquid crystal display element. About the obtained liquid crystal display element, the color nonuniformity which arose in the liquid crystal around the light-shielding sealant for liquid crystal display elements was observed visually. As a result, “◎” indicates that there is no color unevenness, “◯” indicates that there is almost no color unevenness, “△” indicates that there is slight color unevenness, and “×” indicates that there is considerable color unevenness. ".

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal dropping methods which is excellent in adhesiveness, and the moisture permeability of hardened | cured material is low, and hardly causes liquid crystal contamination can be provided. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.

Claims (10)

A liquid crystal dropping method sealing agent containing a curable resin, a polymerization initiator and / or a thermosetting agent, and a silane coupling agent,
The curable resin contains an epoxy (meth) acrylate and / or a partial (meth) acryl-modified epoxy resin,
The said silane coupling agent is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. The sealing agent for liquid crystal dropping method according to claim 1, further comprising a polymerization initiator and a thermosetting agent. The sealing agent for liquid crystal dropping method according to claim 1 or 2, wherein the polymerization initiator is a radical polymerization initiator. 4. The liquid crystal dropping method sealing agent according to claim 1 , wherein the content of the silane coupling agent is 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable resin. The curable resin contains a (meth) acrylate having an isocyanuric skeleton and / or a (meth) acrylate having a dicyclopentadiene skeleton, 5. The liquid crystal dropping method seal according to claim 1, 2, 3 or 4 Agent. The curable resin contains a (meth) acrylate having an isocyanuric skeleton,
The sealing agent for liquid crystal dropping method according to claim 5, wherein the (meth) acrylate having an isocyanuric skeleton is ethoxylated isocyanuric triacrylate. The curable resin contains a (meth) acrylate having a dicyclopentadiene skeleton,
The sealing agent for liquid crystal dropping method according to claim 5 or 6, wherein the (meth) acrylate having a dicyclopentadiene skeleton is tricyclodecane dimethanol diacrylate. Claims having (meth) acrylate and dicyclopentadiene skeleton having an isocyanuric skeleton content of the (meth) acrylate, relative to the total 100 parts by weight of the curable resin, characterized in that 0.1 to 30 parts by weight Item 8. A sealing agent for liquid crystal dropping method according to item 5, 6 or 7 . A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2, 3, 4, 5, 6, 7 or 8 , 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, 4, 5, 6, 7 or 8 , and / or the vertical conduction material according to claim 9. .