JP2011141576A - Curable resin composition for one drop fill, sealant for one drop fill, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for One Drop Fill, a sealant for One Drop Fill, which is used for manufacturing a liquid crystal display element by one drop fill as a sealant for one drop fill, and prevents deformation or breakage in a sealant pattern even when a liquid crystal cell produced by bonding substrates under reduced pressure is taken out in a normal pressure environment, and to provide a vertical conduction material and the liquid crystal display element. <P>SOLUTION: The curable resin composition for one drop fill contains a curable resin and a solid component, wherein the total blended amount of the solid component is 60 to 90 pts.wt. based on 100 pts.wt. of the curable resin, and the solid component has an inorganic filler of 40 to 60 pts.wt. based on 100 pts.wt. of the curable resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention is a case where a liquid crystal cell produced by laminating a substrate under reduced pressure is taken out in a normal pressure environment when used as a sealing agent for a liquid crystal dropping method and for manufacturing a liquid crystal display element by the dropping method. Further, the present invention relates to a curable resin composition for a liquid crystal dropping method, a sealing agent for a liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element, in which the sealant pattern is not deformed or broken.

In recent years, electronic devices such as liquid crystal display elements, electronic components, and the like are required to have higher performance and higher quality.
In a liquid crystal display element, usually, two transparent substrates on which an alignment film is formed are bonded together via a sealing agent formed near the outer periphery thereof, and a space formed by these two transparent substrates and the sealing agent. It has a structure in which a liquid crystal material is enclosed.

In the liquid crystal display element having such a structure, the alignment film plays a role of controlling the alignment of directors of liquid crystal molecules, but in recent years, such an alignment film tends to have hydrophobicity.

In recent years, a method for manufacturing a liquid crystal display element such as a liquid crystal display cell is a liquid crystal dropping method called a dropping method using a sealant made of a photocurable resin composition from a conventional vacuum injection method for the purpose of shortening tact time. (See, for example, Patent Document 1). 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 onto the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid to produce a liquid crystal cell. Curing is performed. Thereafter, if necessary, heating is performed during liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the process of manufacturing a liquid crystal cell by bonding substrates is performed under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method has become the mainstream method for manufacturing liquid crystal display elements. ing.

In addition, when manufacturing liquid crystal display elements by the dripping method, liquid crystal display elements are not manufactured one by one, but a plurality of liquid crystal display element units are manufactured between large substrates in order to improve productivity. A method of manufacturing a plurality of liquid crystal display elements at a time by separating and cutting them is generally performed. In such a method of manufacturing a plurality of liquid crystal display elements at a time, a plurality of liquid crystal cells are manufactured by bonding large substrates together under reduced pressure, but the cell gap is kept uniform around the edge of the large substrate. A dummy seal pattern is formed.

However, in the manufacture of a liquid crystal display element by a conventional dripping method, when a liquid crystal cell produced by bonding substrates together under reduced pressure is taken out under a normal pressure environment, the pressure difference between the inner side and the outer side of the sealing agent causes The pattern sometimes deformed or broke down. In particular, in the method of manufacturing a plurality of liquid crystal display elements at once, the space between the main seal portion of the liquid crystal cell manufactured under reduced pressure and the dummy seal is in a reduced pressure state. As a result, a large pressure difference is generated between the inside and the outside of the cell, and the dummy seal is easily broken. Further, the main seal portion that encloses the liquid crystal inside the dummy seal is also broken and the liquid crystal leaks. there were.
Except for dummy seals, if the sealant is left uncured after vacuum bonding, the uncured sealant cannot withstand the negative pressure of the liquid crystal, and the pattern of this sealant is deformed. There was a thing.

JP 2001-133794 A

In view of the above situation, the present invention provides a sealing agent for a liquid crystal dropping method, and when used for manufacturing a liquid crystal display element by the dropping method, takes out a liquid crystal cell produced by laminating substrates under reduced pressure in a normal pressure environment. It is an object to provide a curable resin composition for a liquid crystal dropping method, a sealing agent for a liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element that does not cause deformation or breakage of the sealing agent pattern even in the case of And

The present invention is a curable resin composition for a liquid crystal dropping method containing a curable resin and a solid component, and the total blending amount of the solid component is 60 to 90 weights with respect to 100 parts by weight of the curable resin. The solid component is a curable resin composition for a liquid crystal dropping method containing an inorganic filler of 40 to 60 parts by weight with respect to 100 parts by weight of the curable resin.
The present invention is described in detail below.

The curable resin composition for liquid crystal dropping method of the present invention (hereinafter also referred to as curable resin composition of the present invention) contains a curable resin.
As said curable resin, when using the curable resin composition of this invention for the sealing agent for dripping method, reaction is started by light and heat, and it is curable resin which has an unsaturated double bond which can carry out polymerization hardening. Preferably there is.
The curable resin having an unsaturated double bond is not particularly limited as long as the reaction is initiated by light and heat. For example, a vinyl group, an allyl group, a cinnamoyl group, a cinnamylidene group, a maleimide group, (meta ) A resin having an acryl group or the like is mentioned, and a resin having a (meth) acryl group is preferable from the viewpoint of reactivity. In addition, in this specification, a (meth) acryl group means an acryl group or a methacryl group.

As said (meth) acrylic acid ester, the ester compound obtained by making the compound which has a hydroxyl group react with (meth) acrylic acid, the epoxy (meth) obtained by making (meth) acrylic acid and an epoxy compound react. Examples thereof include urethane (meth) acrylate obtained by reacting acrylate and isocyanate with a (meth) acrylic acid derivative having a hydroxyl group.

The sealing agent using the curable resin composition of the present invention is used for manufacturing a liquid crystal display element by a dropping method, and since the uncured sealing agent is in direct contact with the liquid crystal, the liquid crystal is contaminated by the sealing agent and the display quality is improved. Often gives a problem. Accordingly, the curable resin constituting the sealing agent is preferably incompatible with liquid crystal, and specifically, the epoxy (meth) acrylate or urethane (meth) acrylate is preferable.

Examples of commercially available products of the epoxy (meth) acrylate include Evecryl 3700, Evekril 3600, Evekril 3701, Evekril 3703, Evekril 3200, Evekrill 3201, Evekril 3600, Evekril 3412, Evekril 860, Evekryl RDX63182, Evecril 3800 (all manufactured by Daicel UCB), EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), Epoxy ester M -600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, 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 (all manufactured by Nagase ChemteX Corporation).
In addition to these, for example, a part of an epoxy compound modified with (meth) acrylic acid may be used as the epoxy (meth) acrylate.

Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, and M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858, Evekril 8402, Evecryl 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecril 1290, Evecril 5129, Evecril 2102, Evecril 4827, Evecril 6700, Evecril 220, Evecril 2220 (all manufactured by Daicel UCB) 9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320HB, Ar 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 and the like.

Moreover, the epoxy resin may be added to the curable resin composition of this invention. When the said epoxy resin is added, the sealing agent using the curable resin composition of this invention can be made into the combined use type of photocuring and thermosetting.

The epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (all manufactured by Japan Epoxy Resin); Epicoat 806 and Epicoat 4004 (all manufactured by Japan Epoxy Resin). Bisphenol F type epoxy resin; Bisphenol S type epoxy resin such as Epicron EXA1514 (manufactured by Dainippon Ink &Co.); 2,2′-diallylbisphenol A type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); Epicron EXA7015 ( Hydrogenated bisphenol type epoxy resin such as Dainippon Ink Co., Ltd .; Propylene oxide-added bisphenol A type epoxy resin such as EP-4000S (Asahi Denka Co.); Resorcinol type such as EX-201 (manufactured by Nagase ChemteX) Poxy resin; Biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin); Sulfide type epoxy resin such as YSLV-50TE (manufactured by Toto Kasei); Ether type such as YSLV-80DE (manufactured by Toto Kasei) Epoxy resin; Dicyclopentadiene type epoxy resin such as EP-4088S (Asahi Denka); Naphthalene type epoxy resin such as Epicron HP4032, Epicron EXA-4700 (both manufactured by Dainippon Ink and Co.); Epicron N-770 (Large) Phenol novolac type epoxy resins such as Nippon Ink Co .; orthocresol novolac type epoxy resins such as Epicron N-670-EXP-S (Dainippon Ink Co.); dicyclo such as Epicron HP7200 (Dainippon Ink Co., Ltd.) Pentadiene novolac type epoxy Resin; biphenyl novolac type epoxy resin such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); naphthalene phenol novolac type epoxy resin such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.); Epicoat 630 (manufactured by Japan Epoxy Resin Co., Ltd.) (Manufactured by Dainippon Ink, Inc.), glycidylamine type epoxy resins such as TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.); Alkyl polyol type epoxy resin such as Denacor EX-611 (manufactured by Nagase ChemteX); YR-450, YR-207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical) Rubber-modified epoxy resin; Denacol EX-147 (Nagase Chemte A glycidyl ester compound such as Epicote YL-7000 (manufactured by Japan Epoxy Resin Co., Ltd.); other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Toto Kasei Co., Ltd.), XAC4151 (made by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all made by Japan Epoxy Resin Co., Ltd.), EXA-7120 (Dainippon Ink Co., Ltd.), TEPIC (Nissan Chemical Co., Ltd.), etc. are mentioned.

The curable resin composition of the present invention contains a solid component.
The solid component is not particularly limited, and examples thereof include solid components used in applications such as inorganic fillers, organic fillers such as resin fine particles, gelling agents, curing accelerators, and thermosetting agents. Of these, inorganic fillers are preferred from the viewpoint of excellent thermal stability such as heat resistance and mechanical stability.

The inorganic 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, water Examples thereof include magnesium oxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite activated clay, and aluminum nitride.

When the solid component contains the inorganic filler, the blending amount is not particularly limited, but a preferable lower limit is 40 parts by weight and a preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the curable resin. When the amount is less than 40 parts by weight, the performance as an inorganic filler such as thermal stability and mechanical stability may not be sufficiently exhibited. When the amount exceeds 60 parts by weight, the adhesiveness may be significantly reduced. is there.

The resin fine particles are not particularly limited, and examples thereof include acrylic fine particles such as polymethyl methacrylate and butyl acrylate, and rubber fine particles such as butadiene-nitrile.

The gelling agent is not particularly limited, and examples thereof include a copolymer of methacrylic acid and an alkyl compound, and a sugar compound such as dibenzylidene sorbitol. Among such gelling agents, commercially available ones include, for example, ZEON F-320, ZEON F-301, ZEON F-340 (all of which are manufactured by ZEON CORPORATION), Gel All D, Gel All MD ( As described above, all of them are manufactured by Shin Nippon Chemical Co., Ltd.).

The thermosetting agent is for reacting and crosslinking the unsaturated double bond or epoxy group in the curable resin having the unsaturated double bond by heating, and the adhesiveness of the cured product after curing. , Has the role of improving moisture resistance.
Although it does not specifically limit as said thermosetting agent, When using the curable resin composition of this invention as a sealing agent for dripping construction method, in order to harden at the curing temperature of 100-120 degreeC, it becomes low temperature reactivity. It is preferable to contain an excellent amine and / or thiol group. Such a thermosetting agent is not particularly limited, and examples of those containing an amine and / or thiol group include 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], adipic acid dihydrazide, and the like. Organic acid dihydrazide compounds; 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-imidazoline-2-thiol, 2-2′-thio Imidazole compounds such as di-ethanethiol, acid anhydride, addition products such as the various amines and epoxy resins. These may be used independently and 2 or more types may be used together.

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 light-shielding sealing agent having high storage stability can be obtained even if a thermosetting agent is blended in advance.

Although it does not specifically limit as content of the said thermosetting agent, A preferable minimum is 1 weight part with respect to 100 weight part of curable resins which have the said unsaturated double bond, and a preferable upper limit is 8 weight part. If the amount is less than 1 part by weight, the curable resin composition of the present invention may not be provided with sufficient thermosetting property. If the amount exceeds 8 parts by weight, the curable resin composition of the present invention is sealed for a liquid crystal dropping method. When used as an agent, an unreacted thermosetting agent may elute into the liquid crystal phase or affect physical properties such as moisture resistance reliability.

The total amount of the solid component is such that the lower limit is 60 parts by weight and the upper limit is 90 parts by weight with respect to 100 parts by weight of the curable resin having an unsaturated double bond. When it was less than 60 parts by weight, the curable resin composition of the present invention was used as a sealing agent for a liquid crystal dropping method, and a liquid crystal display device was produced by a dropping method using the sealing agent for a liquid crystal dropping method. When the liquid crystal cell is taken out under normal pressure, the sealant pattern is deformed or broken. When the amount exceeds 90 parts by weight, the viscosity of the curable resin composition of the present invention becomes too high and workability deteriorates, and when the curable resin composition of the present invention is used as a sealing agent for liquid crystal dropping method, dispensing is performed. Coating by is difficult. A preferred lower limit is 70 parts by weight and a preferred upper limit is 80 parts by weight.

Here, although the solid component is contained also in the curable resin composition used for the conventional sealing agent for liquid crystal dropping method, the content is about 50 parts by weight with respect to 100 parts by weight of the curable resin. There were few compared with the curable resin composition of this invention. Therefore, when the liquid crystal display element is manufactured by the dropping method using the conventional sealing agent for liquid crystal dropping method, when the liquid crystal cell produced under the reduced pressure environment is taken out under the normal pressure environment, the inside and outside of the sealing agent pattern The seal pattern easily deformed due to the pressure difference and broke down. In particular, when a method of manufacturing a plurality of liquid crystal display elements at a time using a large substrate is performed by the dropping method, the space between the dummy seal and the main seal portion is in a reduced pressure state, so that the device is manufactured in a reduced pressure environment. When the liquid crystal cell was taken out under a normal environment, the dummy seal was easily deformed and broken.
On the other hand, the curable resin composition of the present invention has a large amount of solid components and has a high viscosity. Therefore, the curable resin composition is used as a sealing agent for a liquid crystal dropping method and uses a large substrate by the dropping method. Even when a method of manufacturing a plurality of liquid crystal display elements at a time is performed, the seal pattern is hardly deformed when the liquid crystal cell manufactured under a reduced pressure environment is taken out under a normal pressure environment, and it is broken. Does not occur.

The curable resin composition of the present invention may further contain a photopolymerization initiator, a silane coupling agent, and the like.
The photopolymerization initiator is not particularly limited as long as it can polymerize the curable resin having an unsaturated double bond by light irradiation, but preferably has a reactive double bond and a photoreaction start part. It is. Such a photopolymerization initiator can give sufficient reactivity when blended in the curable resin composition of the present invention, and the curable resin composition of the present invention as a sealing agent for liquid crystal dropping method. When used, 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. In the present specification, 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. When used as a photopolymerization initiator of the curable resin composition of the present invention, the reactive double bond is reactive. A (meth) acrylic residue is preferred because of its height. By having such a reactive double bond, the weather resistance is improved when blended with the curable resin composition of the present invention.

The said benzoin (ether) type compound should just have any one of a hydroxyl group and a urethane bond, and may have both. When the benzoin (ether) compound has neither a hydroxyl group nor a urethane bond, when the curable resin composition of the present invention is used as a sealant for a liquid crystal dropping method, it elutes into the liquid crystal before curing. May end up.

In the benzoin (ether) compounds, the reactive double bond and the hydroxyl group and / or urethane bond may be located at any part of the benzoin (ether) skeleton, but 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 photopolymerization initiator, the residue is reduced and the amount of outgas can be reduced.

In formula (1), R represents hydrogen and a residual aliphatic hydrocarbon chain having 4 or less carbon atoms. When R is an aliphatic hydrocarbon residual chain having more than 4 carbon atoms, the storage stability when a 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).

In formula (2), 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 group having 4 or less carbon atoms. It represents a hydrocarbon residue or a residue having an atomic ratio of carbon and oxygen constituting the residue of 3 or less. When X is a residue of a bifunctional isocyanate derivative having more than 13 carbon atoms, when the curable resin composition of the present invention is used as a sealing agent for liquid crystal dropping method, it may be easily dissolved in liquid crystal. When the curable resin composition of the present invention is used as a sealant for a liquid crystal dropping method, an aliphatic hydrocarbon residue having a carbon number of 4 or a residue having an atomic ratio of carbon to oxygen of more than 3 is used for a liquid crystal dropping method. May be easily dissolved.

Other examples of the photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, phenyl-2-hydroxy-2-phenyl Propyl ketone or the like can be used. These photoinitiators may be used independently and may use 2 or more types together.

As a compounding quantity of the said photoinitiator, a preferable minimum is 0.1 weight part with respect to 100 weight part of curable resins which have the said unsaturated double bond, and a preferable upper limit is 10 weight part. If it is less than 0.1 parts by weight, the ability to initiate photopolymerization may be insufficient and the effect may not be obtained. If it exceeds 10 parts by weight, a large amount of unreacted photopolymerization initiator may remain, Weather resistance may deteriorate. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 5 parts by weight.

The silane coupling agent mainly serves as an adhesion aid for favorably bonding the curable resin composition of the present invention and a glass substrate or the like. In the case where the curable resin composition of the present invention contains a small amount of non-conductive filler for the purpose of improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, etc., the non-conductive filler and the resin In order to improve the interaction with the silane, it may be used in a method of treating the surface of the non-conductive filler with a silane coupling agent.

As said silane coupling agent, what has at least 1 functional group shown by A group in the following general formula and at least 1 functional group shown by the following B group is suitable.

Specifically, examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-isocyanatopropyltrimethoxysilane. Can be mentioned. These silane compounds may be used alone or in combination of two or more.

By using as a silane coupling agent having such a structure, the curable resin composition of the present invention can improve adhesion to a substrate or the like.

The curable resin composition of the present invention further includes a reactive diluent for adjusting viscosity, a thixotropic agent for adjusting thixotropy, spacers such as polymer beads for panel gap adjustment, if necessary, It may contain a curing accelerator such as p-chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.

The curable resin composition of the present invention has a preferred lower limit of 300 Pa · s and a preferred upper limit of 450 Pa · s when measured at 25 ° C. and 1.0 rpm using an E-type viscometer. The curable resin composition of the present invention is used as a sealant for a liquid crystal dropping method, and the sealant for a liquid crystal dropping method is used for a main seal and a dummy seal in a method of manufacturing a plurality of liquid crystal display elements by the dropping method described above at one time. If this occurs, the dummy seal may break due to the pressure difference between the outside and inside via the dummy seal after the large substrates are vacuum-bonded together, or the seal formed on the inside may break. Furthermore, stringing may occur during coating, and the seal width may be uneven. When it exceeds 450 Pa · s, workability may be deteriorated, and when the curable resin composition of the present invention is used as a sealant for a liquid crystal dropping method, coating by dispensing may be difficult.

In the curable resin composition of the present invention, the volume resistivity of the cured body is preferably 10 ⁷ Ω · cm or more. If it is less than 10 ⁷ Ω · cm, the insulating property of the curable resin composition of the present invention after curing deteriorates, and the liquid crystal display element produced using the curable resin composition of the present invention as a sealing agent for liquid crystal dropping method May be short-circuited.

The method for producing the curable resin composition of the present invention is not particularly limited, and the curable resin having an unsaturated double bond and a solid component, and the photopolymerization initiator and the silane cup, which are blended as necessary. Examples include a method of mixing a predetermined amount of a ring agent or the like by a conventionally known method. At this time, in order to remove the ionic impurities contained, it may be brought into contact with an ion-adsorbing solid.

The curable resin composition of the present invention has a higher solid content and higher viscosity than conventional curable resin compositions. Therefore, the curable resin composition is used as a sealing agent for a dropping method, and a liquid crystal display by a dropping method. Even when the element is manufactured, when the substrates are bonded together in a vacuum environment and then taken out in a normal pressure environment, the seal pattern hardly deforms and does not break.
Such a sealing agent for liquid crystal dropping method using the curable resin composition of the present invention is also one aspect of the present invention.

Moreover, 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. If such a vertical conduction material is used, the electrodes of the transparent substrate can be conductively connected even in the case of a fine pattern.
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.

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.

According to the present invention, when a liquid crystal cell produced by bonding substrates together under reduced pressure is used as a sealant for a liquid crystal dropping method and used for manufacturing a liquid crystal display element by the dropping method, Even if it exists, it can provide the curable resin composition for liquid crystal dropping methods, the sealing agent for liquid crystal dropping methods, a vertical conduction material, and a liquid crystal display element which a deformation | transformation and destruction do not arise in a sealing agent pattern.

Hereinafter, embodiments of 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 acrylic acid-modified phenol novolac epoxy resin)
1000 parts by weight of a liquid phenol novolac type epoxy resin (manufactured by Dow Chemical Co .: DEN 431), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, 200 parts by weight of acrylic acid Was allowed to react for 5 hours while stirring at 90 ° C. while feeding air.
In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd .: Siritin V85) An acrylic acid-modified phenol novolac epoxy resin (50% partially acrylated product) was obtained.

Example 1
As curable resin, 30 parts by weight of bisphenol A type epoxy acrylate (Daicel UCB: EB3700) and 20 parts by weight of urethane acrylate resin (Daicel UCB: EB4858), and the partial acrylic acid obtained earlier. After 50 parts by weight of a modified phenol novolac epoxy resin (50% partially acrylate) was mixed and stirred with a planetary stirrer, 1 part by weight of a photoinitiator (manufactured by Light Chemical Co .; KR-02) was dissolved by heating.
As resin fine particles, 25 parts by weight of methacrylic acid-alkyl copolymer fine particles (manufactured by Nippon Zeon Co., Ltd .: F-325), 45 parts by weight of spherical silica (manufactured by Admatechs: SO-C2), thermosetting agent (manufactured by Otsuka Chemical Co., Ltd .: ADH) 6 parts by weight and 1 part by weight of a silane coupling agent (manufactured by Chisso: S510) are mixed and stirred with a planetary stirrer, and then dispersed with a ceramic three-roll mill to form a curable resin composition. Obtained. This curable resin composition was used as a sealing agent for liquid crystal dropping method.

(Comparative Example 1)
As curable resin, 30 parts by weight of bisphenol A type epoxy acrylate (Daicel UCB: EB3700), 20 parts by weight of urethane acrylate resin (Daicel UCB: EB4858), partially acrylic acid-modified phenol novolac epoxy resin ( 50 parts by weight of 50% partially acrylated product was mixed and stirred with a planetary stirrer, and then 1 part by weight of a photoinitiator (manufactured by Light Chemical Co., Ltd .; KR-02) was dissolved by heating.
45 parts by weight of spherical silica (manufactured by Admatechs: SO-C2), 6 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical: ADH), and 1 part by weight of a silane coupling agent (manufactured by Chisso: S510) are blended. After mixing and stirring with a type stirrer, the mixture was dispersed with a ceramic three roll mill to obtain a curable resin composition. This curable resin composition was used as a sealing agent for liquid crystal dropping method.

(Comparative Example 2)
As curable resin, 30 parts by weight of bisphenol A type epoxy acrylate (Daicel UCB: EB3700), 20 parts by weight of urethane acrylate resin (Daicel UCB: EB4858), partially acrylic acid-modified phenol novolac epoxy resin ( 50 parts by weight of 50% partially acrylated product was mixed and stirred with a planetary stirrer, and then 1 part by weight of a photoinitiator (manufactured by Light Chemical Co., Ltd .; KR-02) was dissolved by heating.
As resin fine particles, 25 parts by weight of methacrylic acid-alkyl copolymer fine particles (manufactured by Nippon Zeon Co., Ltd .: F-325), 25 parts by weight of spherical silica (manufactured by Admatechs: SO-C2), thermosetting agent (manufactured by Otsuka Chemical Co., Ltd .: ADH) 6 parts by weight and 1 part by weight of a silane coupling agent (manufactured by Chisso: S510) are mixed and stirred with a planetary stirrer, and then dispersed with a ceramic three-roll mill to obtain a curable resin composition. Obtained. This curable resin composition was used as a sealing agent for liquid crystal dropping method.

(Evaluation)
The sealing agent for liquid crystal dropping method prepared in Example 1 and Comparative Examples 1 and 2 was evaluated by the following method.

After filling and defoaming the liquid crystal dropping method sealing agent prepared in Example 1 and Comparative Examples 1 and 2 in a syringe, it was applied with a dispenser so as to draw a square on a glass substrate with ITO coated with an alignment film. .
Next, an appropriate amount of liquid crystal (manufactured by Chisso Co., Ltd., JC-5004LA) is dropped in a seal frame and placed in a vacuum bonding apparatus, and the other substrate is stacked under a vacuum of 50 Pa, and then 10 minutes. The seal shape after being left was visually observed. The results are shown in Table 1. In Table 1, “O” indicates that the seal shape did not change, and “X” indicates that a part of the seal portion broke down and the liquid crystal leaked.

According to the present invention, when a liquid crystal cell produced by bonding substrates together under reduced pressure is used as a sealant for a liquid crystal dropping method and used for manufacturing a liquid crystal display element by the dropping method, Even if it exists, it can provide the curable resin composition for liquid crystal dropping methods, the sealing agent for liquid crystal dropping methods, a vertical conduction material, and a liquid crystal display element which a deformation | transformation and destruction do not arise in a sealing agent pattern.

Claims (4)

A curable resin composition for a liquid crystal dropping method containing a curable resin and a solid component, wherein the total amount of the solid component is 60 to 90 parts by weight with respect to 100 parts by weight of the curable resin, The said solid component contains the inorganic filler used as 40-60 weight part with respect to 100 weight part of curable resin, The curable resin composition for liquid crystal dropping methods characterized by the above-mentioned. A sealing agent for liquid crystal dropping method comprising the curable resin composition for liquid crystal dropping method according to claim 1. A vertical conduction material comprising the curable resin composition for liquid crystal dropping method according to claim 1 and conductive fine particles. A liquid crystal display device comprising the sealing agent for liquid crystal dropping method according to claim 2 and / or the vertical conduction material according to claim 3.