JP3826144B2 - Curable resin composition for liquid crystal display element, sealing agent for liquid crystal dropping method, material for vertical conduction and liquid crystal display element - Google Patents

Description

The present invention can produce a high-quality liquid crystal display element that hardly causes liquid crystal contamination and has little color unevenness even when used as a sealing agent for a liquid crystal dropping method in the production of a liquid crystal display element by the dropping method. The present invention relates to a curable resin composition for a liquid crystal display element, a sealing agent for a liquid crystal dropping method, a material for vertical conduction, and a liquid crystal display element.

Conventionally, a liquid crystal display element such as a liquid crystal display cell forms a cell by facing two transparent substrates with electrodes facing each other at a predetermined interval and sealing the periphery with a sealing agent made of a curable resin composition. However, it was produced by injecting liquid crystal into the cell from a liquid crystal injection port provided in a part thereof, and sealing the liquid crystal injection port with a sealing agent or a sealing agent.

In this method, first, a seal pattern provided with a liquid crystal injection port using a thermosetting sealant is formed on one of two transparent substrates with electrodes by screen printing, and prebaked at 60 to 100 ° C. Dry the solvent in the sealant. Next, alignment is performed with the two substrates facing each other with a spacer interposed therebetween, and the gap in the vicinity of the seal is adjusted by performing hot pressing at 110 to 220 ° C. for 10 to 90 minutes, and then at 110 to 220 ° C. in an oven. Heat for 10 to 120 minutes to fully cure the sealant. Next, liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.

However, according to this manufacturing method, the positional displacement, gap variation, decrease in adhesion between the sealing agent and the substrate, etc. occur due to thermal strain; residual solvent thermally expands to generate bubbles, resulting in cap variation and seal path. The seal curing time is long; the prebaking process is complicated; the usable time of the sealant is short due to the volatilization of the solvent; and it takes time to inject liquid crystal. In particular, in a large liquid crystal display device in recent years, it takes a very long time to inject liquid crystal.

On the other hand, a manufacturing method of a liquid crystal display element called a dripping method using a photocuring / thermosetting sealant has been studied. In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by a dispenser. 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, 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. In the future, this dripping method is expected to become the mainstream of liquid crystal display manufacturing methods.

As a sealing agent for a liquid crystal dropping method used in such a dropping method, an epoxy resin is generally used as a thermosetting component because high adhesiveness is obtained (for example, Patent Document 1). However, the liquid crystal display device manufactured by the dropping method has a problem that display defects such as uneven color are likely to occur due to disordered alignment of the liquid crystal. This is presumably because, in the dropping method, the liquid crystal dropping method sealing agent in an uncured state directly touches the liquid crystal in the process.
In recent years, liquid crystals for liquid crystal display elements have become low-polarity liquid crystals in terms of low-voltage driving, and in particular, the demand for prevention of liquid crystal contamination by liquid crystal dripping method sealing agents has become stricter. However, there has been a demand for a liquid crystal dropping method sealing agent that does not contaminate the liquid crystal even when it is present.

JP 2001-133794 A

In view of the above situation, the present invention provides a liquid crystal display element with a high quality image that hardly causes liquid crystal contamination and has little color unevenness even when used as a sealing agent for a liquid crystal dropping method in the manufacture of a liquid crystal display element by a dropping method. It aims at providing the curable resin composition for liquid crystal display elements which can be manufactured, the sealing compound for liquid crystal dropping methods, the material for up-and-down conduction, and a liquid crystal display element.

This invention is a curable resin composition for liquid crystal display elements containing the epoxy resin whose softening point is 50 degreeC or more, (meth) acrylic resin, a thermosetting agent, and radical photopolymerization initiator.
The present invention is described in detail below.

The curable resin composition for a liquid crystal display element of the present invention contains an epoxy resin having a softening point of 50 ° C. or higher, a (meth) acrylic resin, a thermosetting agent, and a radical photopolymerization initiator.
As a result of intensive studies, the inventors of the present invention have contaminated the liquid crystal when a liquid crystal display element is produced by the dropping method or the like, mainly due to the liquid epoxy resin contained in the sealing agent for the liquid crystal dropping method. I found out. That is, in the manufacturing method of the liquid crystal display device by the dropping method, a slight time lag occurs between the start of heating in the main curing process until the epoxy resin is completely cured. It was found that this leaked to the liquid crystal. As a result of further studies, it has been found that if an epoxy resin having a softening point of 50 ° C. or higher is used instead of the liquid epoxy resin, such liquid crystal contamination can be suppressed to a minimum, and the present invention has been completed.

In this specification, the softening point means the temperature at which the sample begins to soften and hangs down when the sample is heated under specified conditions. For example, in JIS K 7234 “Testing method for softening point of epoxy resin”. It can be measured accordingly.

When the softening point of the contained epoxy resin is less than 50 ° C., the liquid crystal display element of the present invention is used as a sealing agent for the liquid crystal dropping method, and the liquid crystal display element is produced by the dropping method. In some liquid crystal display elements, uneven color due to contamination of the liquid crystal by epoxy resin may be observed. Preferably it is 75 degreeC or more. Although it does not specifically limit as an upper limit of a softening point, It is preferable that it is 120 degrees C or less. When it exceeds 120 degreeC, the workability | operativity at the time of mixing with another structural component may fall.

The epoxy resin having a softening point of 50 ° C. or higher is not particularly limited as long as it has the above-mentioned softening point. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, orthocresol Examples include novolac type epoxy resins, dicyclo novolac type epoxy resins, biphenyl novolac type epoxy resins, naphthalene novolac type epoxy resins, bisphenol A type epoxy resins, isocyanate-modified resins, hydrogenated bisphenol A type epoxy resins, and the like. Among them, a novolac type epoxy resin is preferable because the epoxy equivalent is small and the adhesion reliability is high.
These epoxy resins having a softening point of 50 ° C. or higher may be used alone or in combination of two or more.

The epoxy resin having a softening point of 50 ° C. or higher preferably has a weight average molecular weight of 600 or higher. If it is less than 600, the outflow to the liquid crystal may not be sufficiently suppressed.

Of these epoxy resins having a softening point of 50 ° C. or higher, those commercially available include, for example, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004 (above, manufactured by JER) for bisphenol A type epoxy resin; Epicoat 4004P and Epicoat 4007P (above, manufactured by JER) for F type epoxy resins; EPPN-201-L (made by Nippon Kayaku Co., Ltd.), N-770, N-775 (above, Dainippon Ink) for phenol novolac type epoxy resins. EOCN-1020, EOCN-102S, EOCN-4500 (above, Nippon Kayaku Co., Ltd.), N-660, N-667, N-673 (above, Dainippon Ink, Inc.) Made by dicyclo novolac type epoxy resin XD-1000L (manufactured by Nippon Kayaku Co., Ltd.); NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) for biphenyl novolac type epoxy resin; NC-7000L (manufactured by Nippon Kayaku Co., Ltd.), ESN-165, ESN for naphthalene novolac type epoxy resin -195, ESN-355, ESN-375 (above, manufactured by Tohto Kasei Co., Ltd.); XAC4151 (Asahi Kasei Co., Ltd.) for bisphenol A type epoxy resin isocyanate-modified resin; ST-5080 (Tohto Kasei Co., Ltd.) for hydrogenated bisphenol A type epoxy resin Other epoxy resins include EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 1031S (manufactured by JER), and the like.

The curable resin composition for a liquid crystal display element of the present invention contains a (meth) acrylic resin. By containing the (meth) acrylic resin, the curable resin composition for a liquid crystal display element of the present invention becomes a photothermal combination type that can be cured by irradiation with light or by heating, in particular. It is suitable as a sealing agent for liquid crystal dropping method used for the dropping method.

The (meth) acrylic resin is not particularly limited, and examples thereof include polyester acrylate, epoxy acrylate, and urethane acrylate. Of these, epoxy acrylate and urethane acrylate are preferable.

Further, as the (meth) acrylic resin, an epoxy / (meth) acrylic resin having at least one epoxy group and (meth) acrylic group in one molecule can be suitably used.
The epoxy / (meth) acrylic resin is not particularly limited. For example, a (meth) acrylic acid-modified epoxy resin, a urethane-modified (meth) acrylic epoxy resin, and the like have a hydrogen-bonding functional group and are eluted into a liquid crystal. This is preferable because of a small amount.
Examples of the (meth) acrylic acid-modified epoxy resin include novolak type epoxy resins, bisphenol type epoxy resins; biphenyl type epoxy resins, naphthalene type epoxy resins, tris (hydroxyphenyl) alkyl type epoxy resins, and tetrakis (hydroxyphenyl) alkyl. A product obtained by partially (meth) acrylating a type epoxy resin or the like is preferable.

The hydrogen bonding functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bonding properties, for example, —OH group, —NH ₂ group, —NHR group (R is aromatic, aliphatic, etc. Hydrocarbon, or a derivative thereof), —COOH group, —CONH ₂ group, —NHOH group, etc., —NHCO— bond, —NH— bond, —CONHCO— bond, —NH—NH— present in the molecule Examples thereof include a group having a residue such as a bond. Of these, a hydroxyl group and / or a urethane group are preferred.

The curable resin composition for a liquid crystal display element of the present invention contains a thermosetting agent.
The said thermosetting agent is for making the epoxy group and (meth) acryl group in the curable resin composition for liquid crystal display elements react by heating, and making it bridge | crosslink, The curable resin composition for liquid crystal display elements after hardening It has the role of improving the adhesion and moisture resistance of objects. As the thermosetting agent, a latent curing agent having a melting point of 100 ° C. or higher is preferably used. When a curing agent having a melting point of 100 ° C. or lower is used, the storage stability may be remarkably deteriorated.

Examples of such thermosetting agents include hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2- (2-Methyl-1-imidazolyl) ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, N, N′-bis (2-methyl -1-imidazolylethyl) urea, N, N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethyl Imidazole derivatives such as imidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol Examples thereof include acid anhydrides such as bis (anhydrotrimellitate), addition products of various amines and epoxy resins, and the like. These may be used alone or in combination of two or more.

As the thermosetting agent, a coating curing agent in which the surface of solid curing agent particles is coated with fine particles is also suitable. If such a coating curing agent is used, a curable resin composition for a liquid crystal display element having high storage stability can be obtained even if a thermosetting agent is blended in advance.

The curable resin composition for a liquid crystal display element of the present invention contains a radical photopolymerization initiator.
Although it does not specifically limit as said radical photopolymerization initiator, What has a reactive double bond and a photoreaction start part is suitable. If such a radical photopolymerization initiator is used, sufficient reactivity can be imparted to the curable resin composition for a liquid crystal display element of the present invention, and it does not elute into the liquid crystal and contaminate the liquid crystal. . Of these, benzoin (ether) compounds having a reactive double bond and a hydroxyl group and / or a urethane bond are preferred. The benzoin (ether) compounds represent benzoins and benzoin ethers.

Examples of the reactive double bond include residues such as an allyl group, a vinyl ether group, and a (meth) acryl group, and a (meth) acryl residue is preferable because of its high reactivity. By having such a reactive double bond, the weather resistance of the curable resin composition for a liquid crystal display element of the present invention is improved.

The said benzoin (ether) type compound should just have any one of a hydroxyl group and a urethane bond, and may have both. If the benzoin (ether) compound has neither a hydroxyl group nor a urethane bond, it may elute into the liquid crystal.

In the benzoin (ether) compound, the reactive double bond and the hydroxyl group and / or the urethane bond may be located at any part of the benzoin (ether) skeleton, and are represented by the following general formula (1). Those having a molecular skeleton are preferred. If a compound having such a molecular skeleton is used as a radical photopolymerization initiator, the amount of residue is reduced and the amount of outgas can be reduced.

式中、Ｒは水素、炭素数４以下の脂肪族炭化水素残鎖を表す。Ｒが炭素数４を超える脂肪族炭化水素残鎖であると、光ラジカル重合開始剤を配合したときの保存安定性は増加するものの、置換基の立体障害により反応性が低下することがある。

In the formula, R represents hydrogen or a residual aliphatic hydrocarbon chain having 4 or less carbon atoms. When R is a residual aliphatic hydrocarbon chain having more than 4 carbon atoms, the storage stability when a radical photopolymerization initiator is added increases, but the reactivity may decrease due to steric hindrance of the substituent.

Examples of benzoin (ether) compounds having a molecular skeleton represented by general formula (1) include compounds represented by the following general formula (2).

式中、Ｒは水素又は炭素数４以下の脂肪族炭化水素残基を表し、Ｘは炭素数１３以下の２官能イソシアネート誘導体の残基を表し、Ｙは炭素数４以下の脂肪族炭化水素残基又は残基を構成する炭素と酸素の原子数比が３以下の残基を表す。Ｘが炭素数１３を超える２官能イソシアネート誘導体の残基であると、液晶に溶解しやすくなることがあり、Ｙが炭素数４を超える脂肪族炭化水素基又は炭素と酸素の原子数比が３を超える残基であると、液晶に溶解しやすくなることがある。

In the formula, R represents hydrogen or an aliphatic hydrocarbon residue having 4 or less carbon atoms, X represents a residue of a bifunctional isocyanate derivative having 13 or less carbon atoms, and Y represents an aliphatic hydrocarbon residue having 4 or less carbon atoms. This represents a residue having an atomic ratio of carbon and oxygen constituting a group or residue of 3 or less. When X is a residue of a bifunctional isocyanate derivative having more than 13 carbon atoms, it may be easily dissolved in the liquid crystal, and Y may be an aliphatic hydrocarbon group having more than 4 carbon atoms or an atomic ratio of carbon to oxygen of 3 If the residue exceeds 50, it may be easily dissolved in the liquid crystal.

Other examples of the photo radical polymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. These radical photopolymerization initiators may be used alone or in combination of two or more.

In the curable resin composition for a liquid crystal display element of the present invention, the preferable lower limit of the amount of the epoxy resin in the total amount of 100 parts by weight of the epoxy resin and the (meth) acrylic resin is 5 parts by weight, and the preferable upper limit is 70 parts by weight. It is. If it is less than 5 parts by weight, the adhesiveness may be inferior, and if it exceeds 70 parts by weight, the liquid crystal may be contaminated. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 40 parts by weight.
In the curable resin composition for a liquid crystal display element of the present invention, the preferable lower limit of the amount of the thermosetting agent with respect to 100 parts by weight of the total amount of the epoxy resin and the (meth) acrylic resin is 3 parts by weight, and the preferable upper limit is 40 parts by weight. It is. If it is less than 3 parts by weight, the curability may be insufficient, and if it exceeds 40 parts by weight, the reliability may be lowered. A more preferred lower limit is 4 parts by weight, and a more preferred upper limit is 20 parts by weight.
In the curable resin composition for a liquid crystal display element of the present invention, the preferable lower limit of the amount of the radical photopolymerization initiator added relative to 100 parts by weight of the total amount of the epoxy resin and the (meth) acrylic resin is 0.1 part by weight, and the preferable upper limit. Is 20 parts by weight. If it is less than 0.1 part by weight, the curability may be insufficient, and if it exceeds 20 parts by weight, the liquid crystal may be contaminated. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 5 parts by weight.

The curable resin composition for a liquid crystal display element of the present invention may contain a silane coupling agent. By containing the silane coupling agent, when the curable resin composition for a liquid crystal display element of the present invention is used as a sealing agent for a liquid crystal element, the adhesion between the sealing agent and the transparent substrate can be improved.
The silane coupling agent is not particularly limited, but is excellent in adhesion improvement effect with a transparent substrate and the like, and can be prevented from flowing into the liquid crystal material by chemically bonding with a curable resin. Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc., or a structure in which the imidazole skeleton and alkoxysilyl group are bonded via a spacer group What consists of an imidazole silane compound which has this, etc. are used suitably. These silane coupling agents may be used alone or in combination of two or more.

The curable resin composition for a liquid crystal display element 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, silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, gypsum, calcium silicate , Talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, and other inorganic fillers.

It does not specifically limit as a method to manufacture the curable resin composition for liquid crystal display elements of this invention, The said softening point is 50 degreeC or more, the epoxy resin, (meth) acrylic resin, a thermosetting agent, radical photopolymerization initiator And a method of mixing additives, etc., which are added as necessary, by a conventionally known method. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.

Since the curable resin composition for a liquid crystal display element of the present invention has the above-described configuration, even when used as a sealing agent for a liquid crystal dropping method, liquid crystal contamination is unlikely to occur, and high-quality images with little color unevenness are obtained. A liquid crystal display element can be manufactured. In particular, even when there is a step in which the uncured liquid crystal dropping method sealing agent and the liquid crystal come into contact as in the dropping method, liquid crystal contamination can be suppressed.
The sealing agent for a liquid crystal dropping method comprising the curable resin composition for a liquid crystal display element of the present invention is also one aspect of the present invention.

In the sealing agent for liquid crystal dropping method of the present invention, the preferable lower limit of the glass transition temperature after curing is 80 ° C., and the preferable upper limit is 150 ° C. When it is less than 80 ° C., when the liquid crystal display element is produced using the liquid crystal dropping method sealing agent of the present invention, it may be inferior in moisture resistance (high temperature and high humidity resistance). It may be inferior in adhesion to the substrate.
The glass transition temperature is a value measured by a DMA method under conditions of a temperature rising rate of 5 ° C./min and a frequency of 10 Hz. However, since measurement of the glass transition temperature by the DMA method requires a large amount of sample, when only a small amount of sample is obtained, it is preferable to perform the measurement at a temperature increase rate of 10 ° C./min by the DSC method. . In general, the glass transition temperature measured by the DSC method is about 30 ° C. lower than the glass transition temperature measured by the DMA method. Therefore, when the glass transition temperature is measured by the DSC method, the preferred lower limit of the glass transition temperature after curing of the sealant for liquid crystal dropping method of the present invention is 50 ° C., and the preferred upper limit is 120 ° C.

A material for vertical conduction can be produced by blending conductive fine particles with the curable resin composition for a liquid crystal display element of the present invention and / or the sealing agent for a liquid crystal dropping method of the present invention. If such a material for vertical conduction is used, the electrodes of the transparent substrate can be conductively connected without contaminating the liquid crystal.
The material for vertical conduction containing the curable resin composition for liquid crystal display elements of the present invention and / or 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 agent for liquid crystal dropping method of the present invention and / or the material for vertical conduction of the present invention is also one aspect of the present invention.

According to the present invention, it is possible to produce a liquid crystal display element having a high-quality image that hardly causes liquid crystal contamination and has little color unevenness even when used as a sealing agent for a liquid crystal dropping method in the production of a liquid crystal display element by a dropping method. It is possible to provide a curable resin composition for a liquid crystal display element, a sealing agent for a liquid crystal dropping method, a material for vertical conduction, and a liquid crystal display element.

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 1-8, Comparative Examples 1-2)
After mixing the materials in the amounts shown in Table 1 using a planetary stirrer, they are further mixed using three rolls to prepare a curable resin composition for a liquid crystal display device, which is used for a liquid crystal dropping method. A sealant was used.

After filling and defoaming the obtained sealing agent for liquid crystal dropping method in a syringe, drawing on one of the two glass substrates with transparent electrodes treated with an alignment film using a dispenser, it matches the volume in the seal frame An amount of liquid crystal (manufactured by Chisso Corporation, JC-5004LA) was divided into several times and dropped in fine droplets. In addition, on the electrode part of the other glass substrate, the obtained sealing agent for liquid crystal dropping method and conductive particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl AULB-206, average particle size 6.0 to 6.2 μm) and The material for vertical conduction prepared by mixing was applied. Thereafter, these two substrates are bonded together in vacuum, irradiated with ultraviolet rays at a strength of 100 mW / cm ² for 30 seconds using a metal halide lamp, and further heated at 120 ° C. for 1 hour to produce a liquid crystal display element. did.

(Evaluation)
The obtained sealing agent for liquid crystal dropping method and liquid crystal display element were evaluated by the following methods. The results are shown in Table 1.

(1) Evaluation of Adhesive Strength of Sealant for Liquid Crystal Drop Method 3 parts by weight of silica (“Micropearl SI” manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 5 μm per 100 parts by weight of sealant for liquid crystal drop method Dispersed with a stirrer to obtain a uniform liquid, the obtained sealant is a 20 mm × 50 mm × 1.1 mmt size glass plate (Corning Corp., 1737) superimposed in a cross shape, with a diameter of about A sealant was applied to a 4 mm circle. Using a metal halide lamp, ultraviolet rays were irradiated at an intensity of 100 mW / cm ² for 30 seconds, and then heated at 120 ° C. for 1 hour to obtain an adhesion test piece.
About the obtained adhesion test piece, the adhesive strength was measured using the autograph (made by Shimadzu Corp.).

(2) Evaluation of panel display 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 according to the following criteria.
◎: No color unevenness is observed at all ○: Color unevenness is hardly recognized Δ: Some color unevenness is recognized ×: Color unevenness is considerably recognized

(3) Evaluation of panel display unevenness of liquid crystal display element after aging The obtained liquid crystal display element was aged by leaving it at 80 ° C. for 100 hours in a state where a DC voltage of 5 V was applied. Color unevenness generated in the liquid crystal around the seal portion after aging was visually observed and evaluated according to the following criteria.
◎: No color unevenness is observed at all ○: Color unevenness is hardly recognized Δ: Some color unevenness is recognized ×: Color unevenness is considerably recognized

According to the present invention, it is possible to produce a liquid crystal display element having a high-quality image that hardly causes liquid crystal contamination and has little color unevenness even when used as a sealing agent for a liquid crystal dropping method in the production of a liquid crystal display element by a dropping method. It is possible to provide a curable resin composition for a liquid crystal display element, a sealing agent for a liquid crystal dropping method, a material for vertical conduction, and a liquid crystal display element.

Claims (4)

Liquid crystal dropping containing an uncured epoxy resin , an uncured (meth) acrylic acid-modified epoxy resin in which all epoxy groups in the molecule are modified with (meth) acrylic acid , a thermosetting agent, and a radical photopolymerization initiator A sealing agent for construction methods,
The uncured epoxy resin consists only of a softening point of 50 ° C. or higher,
The uncured epoxy resin occupies a total amount of 100 parts by weight of the uncured epoxy resin and the uncured (meth) acrylic acid modified epoxy resin in which all the epoxy groups in the molecule are modified with (meth) acrylic acid. The compounding quantity of 5-70 weight part, The sealing compound for liquid crystal dropping methods characterized by the above-mentioned. 2. The sealing agent for liquid crystal dropping method according to claim 1, wherein the uncured epoxy resin is a novolak type epoxy resin. A material for vertical conduction comprising the sealing agent for liquid crystal dropping method according to claim 1 or 2 and conductive fine particles. A liquid crystal display element comprising the sealing agent for liquid crystal dropping method according to claim 1 and / or the material for vertical conduction according to claim 3.