JP2005031519A - Common transition material, liquid crystal panel, and manufacturing method of liquid crystal panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a common transition material capable of enhancing reliability of a liquid crystal panel, to provide the liquid crystal panel using the same and to provide a manufacturing method of the liquid crystal panel. <P>SOLUTION: The common transition material used for a common transition electrode provided between electrodes formed adjacently on respective inner sides of a pair of substrates opposed to each other contains a resin composition to be cured by light and heat and conductive particles and a non-conductive filler content is ≤10 pts.wt. to 100 pts.wt. resin composition to be cured by light and heat. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a common transition material used for a common transition electrode installed between electrodes of two substrates, a liquid crystal panel using the same, and a method for manufacturing a liquid crystal panel.

FIG. 8 shows a cross-sectional structure diagram of a conventional liquid crystal panel. In the conventional liquid crystal panel 400 shown in FIG. 8, the color filter substrate 405 and the array substrate 406 are disposed to face each other with the liquid crystal layer 411 interposed therebetween, and these substrates are bonded together with a sealant 412. Transparent electrodes 407 and 408 are respectively formed on the color filter substrate 405 and the array substrate 406 on the liquid crystal layer 411 side. Between the transparent electrodes 407 and 408, a common transition electrode 401 including conductive particles 403 and non-conductive fillers 404 in light or thermosetting resin 402 is provided.
Previously, external connection terminals were installed on both the color filter substrate 405 and the array substrate 406. However, in recent years, external connection terminals are installed only on the array substrate 406 side for reasons such as simplification of wiring. Therefore, when a current flows into the transparent electrode 408 of the array substrate 406, the current flows through the conductive particles 403 in the common transfer electrode 401 to the transparent electrode 407 of the color filter substrate 405.

A method of manufacturing such a conventional liquid crystal panel will be described below with reference to FIGS. First, as shown in FIG. 9, a color filter substrate 405 and an array substrate 406 are prepared, a common transfer electrode 401 is installed on the color filter substrate 405, and a sealant 412 is installed on the array substrate 406. Note that the color filter substrate 405 and the array substrate 406 are large, and a plurality of sealing agents 412 are formed on the array substrate 406. Here, as shown in FIG. 9, the sealant 412 formed on the array substrate 406 is not in a completely closed ring shape before the liquid crystal is injected, and one place of the sealant 412 is opened as a liquid crystal injection port. It is formed in a different shape.

Next, the color filter substrate 405 and the array substrate 406 are bonded together, and the sealant 412 and the common transfer electrode 401 are cured by heating or light irradiation. Thereafter, the substrate is divided into individual regions surrounded by the sealant 412 to obtain the bonded substrate 415 shown in FIGS. 10 and 11. Then, the bonded substrate 415 is accommodated in a vacuum apparatus, and both the inside and outside of the space surrounded by the sealant 412 are evacuated. In this state, as shown in FIG. 12, the liquid crystal inlet 416 is immersed in the liquid crystal 411a, and the inside of the vacuum apparatus is gradually returned to the atmospheric pressure. Then, the liquid crystal 411a is injected into this space due to the pressure difference inside and outside the space surrounded by the sealant 412 and the capillary phenomenon. Finally, as shown in FIG. 13, after the liquid crystal 411a is injected, the liquid crystal injection port is sealed with a sealing material 417, whereby the liquid crystal panel 400 is obtained.
However, in the liquid crystal panel obtained in this way, the electrical resistance between the electrodes often increases greatly, and the reliability may rapidly decrease.

Conventionally, a common transition electrode has been manufactured using a common transition material containing a resin curable by heat or a resin curable by light.
However, when a resin that is cured by heat is used, there is a problem that the reliability of the conductive connection is low because the common transition material expands or contracts when it is cured by heating. In addition, when a liquid crystal panel is manufactured by a dropping method in which a liquid crystal is dropped in a state where a sealant is uncured and the substrates are bonded together in recent years, the common transition material softens during heating. There are problems such as contamination of the liquid crystal and elution of the conductive material.
On the other hand, when a resin that is cured by light is used, there is no need for heating, so high connection reliability is obtained, but there is a portion that is not sufficiently irradiated with light as a shadow of the conductive powder or electrode. Is inevitable, and there is a problem that it cannot be completely cured at such sites.

An object of the present invention is to provide a common transition material capable of improving the reliability of a liquid crystal panel, a liquid crystal panel using the same, and a method for manufacturing the liquid crystal panel.

As a result of intensive studies, the inventors have found that the non-conductive filler contained in the common transition electrode has an increase in electrical resistance between the electrodes of the liquid crystal panel using the conventional common transition electrode.
Further, when a common transition material made of a resin that is cured by light and heat is used, it has been found that connection reliability is improved, and the present invention has been completed. In conventional common transition materials, in addition to conductive particles having a particle size corresponding to the distance between electrodes, a non-conductive filler is usually used to reduce the shrinkage of the resin due to heating during substrate bonding. 10-30 weight part is mix | blended with respect to 100 weight part of curable resin. However, as shown in FIG. 14, the non-conductive filler 404 is sandwiched between the conductive particles 403 and the electrode 407 or the electrode 408 when the substrates are bonded together, and this causes an electrical resistance between the electrodes. It is considered that the reliability of the liquid crystal panel is lowered.

The present invention relates to a common transition material used for a common transition electrode installed between electrodes formed adjacent to each other inside a pair of opposing substrates, a resin composition that is cured by light and heat, and It is a common transition material containing conductive particles and having a non-conductive filler content of 10 parts by weight or less based on 100 parts by weight of a resin composition that is cured by light and heat.
The present invention is described in detail below.

The common transfer material of the present invention contains a resin composition that is cured by light and heat and conductive particles.
In this specification, the resin composition that is cured by light and heat means a resin composition that is cured by both light irradiation and heating.
The resin composition curable by light and heat contains a resin curable by light and heat.

Examples of the resin curable by light and heat include a resin having at least one polymerizable functional group that reacts by irradiation with light and at least one functional group that reacts by heat in one molecule.
As such a resin, for example, a resin having at least one (meth) acryl group and epoxy group in one molecule is preferable. The resin composition containing such a resin can be a combination type of a photo-curing type and a thermo-curing type, and can be completely cured by thermo-curing after being temporarily fixed by photo-curing in advance. In addition to enabling high-precision and easy work, contamination of the liquid crystal can also be prevented.
In this specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

The resin having at least one (meth) acryl group and epoxy group in one molecule is not particularly limited, and examples thereof include (meth) acrylic acid-modified epoxy resins and urethane-modified (meth) acryl epoxy resins. Can be mentioned.

Examples of the (meth) acrylic acid-modified epoxy resin include novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, tris (hydroxyphenyl) alkyl type epoxy resin, and tetrakis (hydroxyphenyl) alkyl. A product obtained by partially (meth) acrylating a type epoxy resin or the like is preferable.
Examples of the epoxy resin used as a raw material for the (meth) acrylic acid-modified epoxy resin include, for example, a novolak type such as a phenol novolak type, a cresol novolak type, a biphenyl novolak type, a trisphenol novolak type, and a dicyclopentadiene novolak type. Examples of the bisphenol type include bisphenol A type, bisphenol F type, 2,2′-diallyl bisphenol A type, bisphenol S type, hydrogenated bisphenol type, and polyoxypropylene bisphenol A type.

Among the raw materials of the above (meth) acrylic acid-modified epoxy resin, for example, as a phenol novolak type, Epicron N-740, Epicron N-770, Epicron N-775 (above, Dainippon Ink and Chemicals, Inc.) Manufactured by the company), Epicoat 152, Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and examples of the cresol novolak type include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, and Epicron N. -680, Epicron N-695, Epicron N-665-EXP, Epicron N-672-EXP (above, manufactured by Dainippon Ink & Chemicals, Inc.) and the like.

The partially (meth) acrylated product of the epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It is possible to obtain an epoxy resin having a desired acrylation rate by appropriately changing the blending amount of the epoxy resin and (meth) acrylic acid.

The urethane-modified (meth) acrylic epoxy resin is obtained by the following method, for example. That is, a method of reacting a polyol with a bifunctional or higher isocyanate and further reacting a (meth) acryl monomer having a hydroxyl group and glycidol; a (meth) acryl having a hydroxyl group in a bifunctional or higher isocyanate without using a polyol It can be produced by a method in which a monomer or glycidol is reacted; a method in which glycidol is reacted with a (meth) acrylate having an isocyanate group. Specifically, for example, first, 1 mol of trimethylolpropane and 3 mol of isophorone diisocyanate are reacted under a tin-based catalyst, and an isocyanate group remaining in the obtained compound and hydroxyethyl acrylate which is an acrylic monomer having a hydroxyl group and It can be produced by reacting with glycidol which is an epoxy having a hydroxyl group.

It does not specifically limit as said polyol, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane, (poly) propylene glycol etc. are mentioned.
The isocyanate is not particularly limited as long as it is bifunctional or higher. For example, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate , Tris (isocyanatephenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate, etc. I can get lost.

The (meth) acrylic monomer having a hydroxyl group is not particularly limited, and examples of the monomer having one hydroxyl group in the molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Examples of the monomer having two or more hydroxyl groups in the molecule include epoxy (meth) acrylates such as bisphenol A-modified epoxy (meth) acrylate. These may be used alone or in combination of two or more.

In the case where the resin composition cured by light and heat is mainly composed of a resin having at least one (meth) acryl group and epoxy group in one molecule, the epoxy group, (meth) acryl group, The blending ratio of acryl: epoxy is preferably from 4: 6 to 9: 1. When the equivalent ratio of (meth) acrylic groups is less than 4, the photoreactivity decreases, and not only the initial temporary curing is lost even when irradiated with light, but the elution into the liquid crystal may increase. If it exceeds 9, it may be insufficient in terms of adhesion and moisture permeability. More preferably, it is 5: 5 to 8: 2.

The resin having at least one (meth) acryl group and epoxy group in one molecule preferably has a hydroxyl group and / or a urethane bond from the viewpoint of reducing compatibility with liquid crystal and eliminating contamination.
The compound having at least one (meth) acryl group and epoxy group in one molecule is at least one selected from a biphenyl skeleton, a naphthalene skeleton, a bisphenol skeleton, and a partial (meth) acrylate of a novolac type epoxy resin. It preferably has two molecular skeletons. Thereby, heat resistance improves.

The number average molecular weight of the resin having at least one (meth) acryl group and epoxy group in one molecule is preferably 300 or more. If it is less than 300, it may elute into the liquid crystal and disturb the alignment. The number average molecular weight is preferably 3000 or less. If it exceeds 3000, it may be difficult to adjust the viscosity.

When the infrared absorption spectrum is measured after curing the resin composition that is cured by light and heat, each of which contains a resin having at least one (meth) acryl group and epoxy group in one molecule, (meth) acryl is measured. An absorption peak of a carbonyl group derived from the group is observed. Moreover, when the hydroxyl group derived from an epoxy group and an epoxy group exists, the absorption peak can also be observed.

The resin composition curable by light and heat may contain a resin curable by light or a resin curable by heat.
The resin that is cured by light is not particularly limited, and examples thereof include (meth) acrylic resins and unsaturated polyester resins having a polymerizable functional group that reacts by light irradiation such as a (meth) acrylic group. These resins may be used alone or in combination of two or more.

As the resin having the (meth) acrylic group, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters can be used.
Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl acrylate, diethylene glycol monoethyl ether acrylate, isobornyl acrylate, 3-methoxybutyl acrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, Examples include 2-methacryloyloxyethyl-2-hydroxylpropyl phthalate.
Examples of the bifunctional (meth) acrylic acid esters include ethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and polytetra Methylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane di (meth) acrylate, etc. Is mentioned.
Examples of the trifunctional or higher functional (meth) acrylic acid esters include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate. , Tri (2-acryloyloxyethyl) phosphate, tetramethylolmethane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, triallyl isocyanurate and derivatives thereof. These (meth) acrylic acid esters may be used alone or in combination of two or more.

The resin curable by heat is not particularly limited, and examples thereof include a resin having a functional group that reacts with heat such as a cyclic ether group such as an epoxy group or an oxetane group.
Examples of such a resin that is cured by heating include unsaturated polyester resins, epoxy acrylate resins, and epoxy resins. These resins may be used alone or in combination of two or more.

Examples of the resin having an epoxy group include an orthocresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a bisphenol A type epoxy resin, an alkyl substituted bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and an alkyl substituted bisphenol F type. Examples thereof include epoxy resins, bisphenol S type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins.

The resin composition that is cured by light and heat preferably contains a photopolymerization initiator, a curing agent, and a silane coupling agent.
The photopolymerization initiator is not particularly limited as long as it can polymerize the curable compound component by light irradiation, but preferably has a reactive double bond and a photoreaction start part. Such a photopolymerization initiator can give sufficient reactivity when blended in the resin composition cured by light and heat, and 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. However, when the reactive double bond is used as a photopolymerization initiator of the common transfer material of the present invention, it has high reactivity. Thus, (meth) acrylic residues are preferred. By having such a reactive double bond, the weather resistance is improved when blended with the common transition material.

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, it may be eluted into the liquid crystal before curing when blended with a common transition material.

In the benzoin (ether) compounds, the reactive double bond and hydroxyl group and / or 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 photopolymerization initiator, the residue is reduced and the amount of outgas can be reduced.

In the formula, R represents hydrogen or 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 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 photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, phenyl-2-hydroxy-2-propyl A ketone etc. can be used alone or in combination of two or more.

A preferable lower limit of the blending amount of the photopolymerization initiator is 0.1 part by weight with respect to 100 parts by weight of the resin cured by light and heat, and a preferable upper limit is 10 parts by weight. 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 curing agent is for reacting and crosslinking epoxy groups and acrylic groups, which are thermosetting functional groups in a resin that is cured by light and heat by heating, and is cured by light and heat after curing. It has the role of improving the adhesiveness and moisture resistance of the resin composition. As the curing 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 a curing agent 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-dihydroxymethylimidazole, etc. Examples include imidazole derivatives, modified aliphatic polyamines, tetrahydrophthalic anhydride, acid anhydrides such as ethylene glycol-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.

When an acrylic acid-modified epoxy resin is used as the resin having at least one (meth) acryl group and epoxy group in one molecule, the reactivity of the acrylic epoxy resin changes more than its structure, and the urethane modification In the case of an epoxy resin, it is excellent in storage stability even when a highly reactive curing agent is used, but in the case of a (meth) acrylic acid-modified epoxy resin, the reactivity is high and the melting point is 100 ° C. or higher. A curing agent having low reactivity is preferred from the viewpoint of storage stability.

The preferable lower limit of the blending amount of the curing agent is 5 parts by weight with respect to 100 parts by weight of the resin cured by light and heat, and the preferable upper limit is 60 parts by weight. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 50 parts by weight. Outside the above range, the adhesiveness and chemical resistance of the cured product may be lowered, and the liquid crystal characteristics may be deteriorated in a high temperature and high humidity operation test.
Further, as the curing agent, when a coating curing agent in which the surface of the solid curing agent particle is coated with fine particles is used, the resin composition that cures by light and heat is very high storage even as a one-component type. Since stability is obtained, it is particularly suitable.

The silane coupling agent mainly serves as an adhesion aid for favorably bonding the common transition material and the liquid crystal display element substrate. In the case where the common transition material 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, it may be used in a method of treating the surface of a non-conductive filler with a silane coupling agent.

As said silane compound, what has at least 1 functional group shown by the following A group and at least 1 functional group shown by the following B group is suitable.

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

By using the silane compound having such a structure as a silane coupling agent, the resin composition that is cured by light and heat can improve the adhesion to the substrate, and has a functional group represented by Group B. Through the chemical bonding of the silane compound with the resin that is cured by the light and heat, the outflow into the liquid crystal can be prevented.
In addition, when the resin composition hardened | cured with the said light and a heat | fever mix | blends such a silane coupling agent, heat processing are performed after a silane coupling agent mixing | blending. By the heat treatment, the silane compound is chemically bonded to the resin that is cured by the light and heat through the functional group represented by the group B. The heat treatment is preferably performed by stirring the resin mixture in order to increase the reaction efficiency. The stirring method is not particularly limited, and examples thereof include a general method such as rotating a stirrer or stirring blade with a motor or the like. The preferable lower limit of the temperature of the heat treatment is 30 ° C., and the preferable upper limit is 70 ° C. When the temperature is lower than 30 ° C., the reaction between the silane compound and the curable resin may not occur sufficiently, and when the temperature exceeds 70 ° C., curing by heat may start. A more preferable lower limit is 40 ° C., and a more preferable upper limit is 60 ° C. The preferable lower limit of the heat treatment time is 1 hour, and the preferable upper limit is 2 hours. If it is less than 1 hour, all functional groups in the silane compound may not react and unreacted substances may remain. The residual ratio of at least one functional group represented by the group B after the heat treatment is 10% or less. If it exceeds 10%, it reacts with the resin component during storage to increase the viscosity, or it flows out into the liquid crystal and becomes contaminated. The residual ratio of at least one functional group represented by Group B can be determined from the relative ratio of the peak intensity of various functional groups in the silane compound and the peak intensity after heat treatment by ¹ H-NMR measurement. it can.

As the silane coupling agent, an imidazole silane compound having a structure in which an imidazole skeleton and an alkoxysilyl group are bonded via a spacer group is also suitable. The imidazole structure shows almost no reactivity with the above resin cured by light and heat at a storage temperature of about room temperature. However, the imidazole structure exhibits reactivity with a resin cured by light and heat when the temperature is applied. A resin composition that is cured by light and heat, which contains a simple silane coupling agent, has excellent adhesive strength and storage stability, has a very low outgassing amount, and does not easily dissolve into liquid crystals. It will have both.

Examples of the imidazole silane compound include those represented by the following general formula (3) or the following general formula (4).

In formula, R < ¹ > -R < ⁵ > represents a hydrocarbon group, hydrogen, or a hydroxymethyl group each independently. Among these, R ¹ and R ⁵ are each independently preferably a hydrocarbon group having 1 to 5 carbon atoms, hydrogen, a hydroxymethyl group or the like, and more preferably a hydrogen group or a methyl group from the viewpoint of ease of synthesis. , Vinyl group, hydroxymethyl group and the like. R ² is preferably a hydrocarbon group having 1 to 20 carbon atoms, hydrogen, or a hydroxymethyl group, and more preferably hydrogen, a methyl group, an ethyl group, an undecyl group, or a heptadecyl group for ease of synthesis. And a phenyl group. Furthermore, R ³ and R ⁴ are each independently preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen, a methyl group, an ethyl group, or the like in view of ease of synthesis.
In the formula, -SP- is a spacer group composed of a linear alkyl group or a branched alkyl group into which an ester group, ether group, carbonate group, urethane group, amide group, sulfone group, ketone group, alkylene group or the like may be introduced. Represents. Of these, urethane groups are preferably introduced from the viewpoint of reducing elution into the liquid crystal. Further, from the viewpoint of reducing elution into the liquid crystal, it is preferable that part of the hydrogen atoms in the spacer group is substituted with a highly polar functional group. Examples of such substituents include halogen atoms. , Hydroxyl group, mercapto group, carboxyl group, amino group and the like. Furthermore, the spacer group represented by -SP- preferably has 1 to 20 atoms constituting the main chain of the spacer group. If it is less than 1, the boiling point tends to decrease and it is likely to cause outgassing, and liquid crystal contamination is likely to occur. If it exceeds 20, the viscosity becomes high and becomes difficult to handle, and the amount of addition is reduced because the alkoxysilane equivalent becomes small. If it is not increased, the effect may be difficult to appear. More preferably, it is 3-10.

Specific examples of the compound represented by the general formula (3) or the general formula (4) include a compound represented by the following formula (5) or the following formula (6).

Examples of the method for producing the compound represented by the above formula (5) include a method of reacting 2,4-dimethylimidazole with γ-glycidoxypropyltrimethoxysilane. Moreover, as a manufacturing method of the compound represented by the said Formula (6), the method etc. with which 2-phenyl-3-methyl-5-hydroxymethylimidazole and (gamma) -isocyanatopropyltrimethoxysilane are made to react are mentioned, for example. .

The preferable lower limit of the compounding amount of the imidazolesilane compound in the resin composition cured by light and heat is 0.1 part by weight with respect to 100 parts by weight of the resin, and the preferable upper limit is 15 parts by weight. When the amount is less than 0.1 part by weight, sufficient adhesive strength may not be exhibited. When the amount exceeds 15 parts by weight, storage stability may be deteriorated.

Although it does not specifically limit as a method of manufacturing the resin composition hardened | cured by the said light and heat, At least the process 1 which makes an ion-adsorbing solid and the resin composition hardened | cured by light and heat contact, and an ion-adsorbing solid, A method having the step 2 of separating the resin composition that is cured by light and heat is preferable.

The ion-adsorptive solid is not particularly limited as long as it is capable of adsorbing ionic impurities present in the adhesive, and for example, those composed of a compound represented by the following general formula (7) preferable.

_{X m Y n (Z p O} q) W r · sH 2 O (7)

In the formula, X represents Na ⁺ , K ⁺ or Ca ²⁺ , Y represents Mg ²⁺ , Fe ²⁺ , Al ³⁺ , Fe ³⁺ , Ti ⁴⁺ or Mn ²⁺ , Z represents Si ⁴⁺ , Al ³⁺ , W represents OH ⁻ , Cl ⁻ , F ⁻ , and CO ₃ ²⁻ are represented. m, n, p, q, r, and s represent an integer of 0 or more. Moreover, it is preferable that m, n, p, q, r, and s satisfy | fill following formula (8).

            2q + ra = ma + na + pa (8)

In the formula, ra, ma, na, and pa represent values obtained by multiplying r, m, n, and p, respectively, by the charge of the ion of the general formula (7).

As said ion-adsorptive solid, what contains an aluminum element is preferable, and what contains ^{Al3 +} is more preferable. The content of Al ^3+, of the ion atomic number of combined Y and Z in the formula (7), it is preferable 5 to 80 mol% is ^{Al 3+.} If it is less than 5 mol%, the amount of ion adsorption may be low, and if it exceeds 80 mol%, Al ³⁺ may be easily dissolved.

As the ion-adsorptive solid, a layered inorganic compound is preferably used. The layered inorganic compound has a laminated structural unit having a certain property and has a gap structure, so that it has high designability and function-imparting property, and has unique properties and functions such as two-dimensional physical properties and ion exchange. It is what you have. By using such a layered inorganic compound, metal atoms existing between the layers of the layered inorganic compound can capture ionic impurities. Moreover, since it has a layered structure, it is difficult for the ionic impurities that have been trapped and adsorbed at one end to be re-eluted.

The layered inorganic compound is preferably a layered silicate mineral.
Examples of the layered silicate mineral include hydrotalcite group compounds, serpentine-kaolin group compounds, talc pyrophyllite group compounds, smectite group compounds, vermiculite group compounds, mica groups, interlayer-deficient mica compounds, and brittle mica. Group compounds, chlorite group compounds, mixed layer minerals, diatomaceous earth, aluminum silicate and the like, preferably hydrotalcite group compounds and serpentine-kaolin group compounds. Among these, those having an aluminum element amount in the above range are more preferable, and hydrotalcite group compounds and serpentine-kaolin group compounds having an aluminum element amount in the above range are more preferable. The layered silicate mineral may be a naturally produced product or a synthesized product. These layered silicate minerals may be used alone or in combination of two or more.

As the hydrotalcite compound is preferably one represented by the following general formula (9), among _{others, Mg 6 Al 2 (OH)} 16 CO 3 · 4H 2 O are preferred.

Mg _n1 Al _n2 (OH) _r1 (CO ₃ ) _r2 · sH ₂ O (9)

In the formula, n1, n2, r1, and r2 represent integers of 1 or more, and satisfy the relationship of n = n1 + n2 and r = r1 + r2 in the relationship with the general formula (7) and the general formula (8).

Examples of the serpentine-kaolin group compounds include lizardite, burcerin, amesite, cronsteite, nepoite, keriaite, fraponite, brindriaite, kaolinite, dickite, nacrite, halosite (plate-like), audinite Etc.
Examples of the talc pyrophyllite group compound include talc, willemsite, kerolite, pimelite, pyrophyllite, ferripyrophyllite and the like.
Examples of the smectite group compound include saponinite, hectorite, saconite, stevensite, swinholderite, montmorillonite, beidellite, nontronite, and bolcon score.

Examples of the vermiculite group compound include 3 octahedral vermiculite, 2 octahedral vermiculite, and the like.
Examples of the mica group compound include biotite, phlogopite, iron mica, yeast knight, siderophyllite tetraferri iron mica, scale mica, polyriccionite, muscovite, celadonite, iron ceradonite, iron aluminoceradone. Stones, aluminoceradone stones, abrasive mica, soda mica and the like.
Examples of the interlaminar defect type mica compound include a dioctahedral type (illite, sea green stone, bramerlite), a trioctahedral type (wonnesite), and the like.
Examples of the brittle mica group compounds include clintonite, kinoshita, bidet mica, ananda stone, and pearl mica.
Examples of the chlorite group compounds include clinochlore, chamosite, penantite, nimite, bailicroa, dombasite, kukeaite, and suedoite.
Examples of the mixed layer mineral include collensite, hydrobiotite, arietite, crucareite, rectolite, tosudite, dodrite, lnjanglite, salioite and the like.

The ion-adsorptive solid is preferably a granular solid so that it can be easily separated after contact with a resin composition that is cured by light and heat. Further, the shape of the ion-adsorbing solid is not particularly limited, and its particle size is preferably small for the purpose of increasing the chance of contact with the ionic impurities to be recovered, but it becomes a problem such as clogging during filtration. Therefore, it is preferably 2 μm or more.

In the method for producing a resin composition that is cured by light and heat using the ion-adsorptive solid, the step 1 of contacting the ion-adsorptive solid and the resin composition that is cured by light and heat, and the ion-adsorptive property The process 2 which isolate | separates solid and a photocurable resin composition or a thermosetting resin composition is performed.

In the step 1, the method for bringing the ion-adsorbing solid into contact with the resin composition that is cured by light and heat is not particularly limited, and for example, mixing is performed using a stirrer, a planetary stirrer, a primary mixer, or the like. Method: A method in which an ion-adsorbing solid is packed in a column and a resin composition that is cured by light and heat is passed through the column. Moreover, in process 1, it is preferable to contact an ion-adsorptive solid and the resin composition hardened | cured with light and heat, heating at 40-100 degreeC. When the temperature is lower than 40 ° C., the surface activity of the ion-exchange solid is hardly increased, and ionic impurities may not be easily removed. If the temperature exceeds 100 ° C., the resin composition that is cured by light and heat that is the target may be thickened. More preferably, it is 60-80 degreeC. When the ion-adsorbing solid is brought into contact with the resin composition that is cured by light and heat by a mixing method, the addition amount of the ion-adsorbing solid can be appropriately selected depending on the amount and type of ionic impurities. The preferred lower limit is 2 parts by weight and the preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the resin composition cured by light and heat. If the amount is less than 2 parts by weight, the ability to adsorb ionic impurities may be insufficient and the effect may not be obtained. If the amount exceeds 20 parts by weight, not only the ion-adsorbing solid is wasted, but also the mixture. Filtration may take time due to the increased viscosity. The lower limit is more preferably 7 parts by weight, and the upper limit is more preferably 15 parts by weight.

In the step 2, the method for separating the ion-adsorbing solid from the resin composition that is cured by light and heat is not particularly limited, and examples thereof include filtration and centrifugation.

In the method for producing a resin composition that is cured by light and heat using the ion adsorbing solid, the ion adsorbing solid is recovered after mixing the ion adsorbing solid and the resin composition that is cured by light and heat. It is preferable to remove ionic impurities by purification. If the ion-adsorbing solid is not recovered and left as it is, the purified ionic impurities may be eluted again in a weather resistance test such as high temperature and high humidity.

The resin composition curable by light and heat produced by the method of producing a resin composition curable by light and heat using the ion adsorbing solid is sodium ion, potassium ion, chlorine ion, acrylic acid, methacrylic. Ionic impurities such as acids are removed, and these can be prevented from flowing into the liquid crystal.

The common transition material of the present invention contains conductive particles.
Examples of the conductive particles include metal particles, those obtained by subjecting resin particles to metal plating, or mixtures thereof. Among them, the resin particles plated with gold can have excellent conductivity and the reliability of the liquid crystal panel can be further improved, and the manufacturing cost can be reduced as compared with the case of using gold particles. .
In the present specification, the material having conductivity means that the material is a 1 cm square cube, and the electric resistance value is less than 10Ω, preferably 2Ω or less, when a voltage is applied to both end faces. Means.

The preferable lower limit of the diameter of the conductive particles is 100% of the distance between the electrodes formed on the substrate, and the preferable upper limit is 150%. Within this range, the conductive particles and the electrode formed on the substrate can be sufficiently brought into contact with each other, so that the electrical resistance between the electrodes tends to be further lowered, and the reliability of the liquid crystal panel is increased. More improved. A more preferred lower limit is 105%, and a more preferred upper limit is 110%.
Also, in this case, a preferable lower limit of the compression elastic modulus of the conductive particles is 2000N / mm ^2, the upper limit is preferably 7000N / mm ^2. Within this range, since the balance between the pressure applied from the electrode to the conductive particles and the repulsive force applied from the conductive particles to the electrode is excellent, the electrode and the conductive particles can be sufficiently brought into contact with each other. Therefore, the electrical resistance between the electrodes can be further reduced, and the reliability of the liquid crystal panel can be further improved. The lower limit is more preferably 3000N / mm ^2, and more preferable upper limit is 4000 N / mm ^2.

The conductive particles may have a protrusion protruding outward from the surface. FIG. 2 shows a schematic cross-sectional view of an example of a common transition electrode using a common transition material including conductive particles on which the protrusions are formed. As shown in FIG. 2, a plurality of protrusions 209 formed on the common transition electrode 201 are formed on the surface of the conductive particles 203, and the protrusions 209 protrude toward the outside of the conductive particles 203. With the above-described configuration of the conductive particles, a plurality of protrusions 209 can come into contact with the electrode 207 or the electrode 208 as shown in FIG. 2, so that the conductivity between the electrode 207 and the electrode 208 is improved. In addition, the reliability of the liquid crystal panel can be improved.

The preferable lower limit of the height of the protrusion is 0.05% of the average particle diameter of the conductive particles, and the preferable upper limit is 5%. If it is less than 0.05%, the protrusions are too short and the effect of forming the protrusions may not be sufficiently obtained, and the reliability of the liquid crystal panel may not be improved. If it exceeds 5.0%, the protrusions are formed on the substrate. Since the conductive particles cannot be sufficiently brought into contact with the electrodes, the reliability of the liquid crystal panel may be lowered. The height of the protrusion means the distance h from the surface S in contact with the surface of the conductive particle 203 to the longest height of the protrusion 209 shown in FIG.

The conductive particles having the protrusions can be prepared by a conventionally known method. For example, a method of forming irregularities on the surface of resin particles and performing metal plating on the irregular surface, a surface of a conductive substance such as metal And the like, and a method of coating with a conductive material having a smaller size than this conductive material.

A preferable lower limit of the compounding amount of the conductive particles is 0.2 parts by weight with respect to 100 parts by weight of the resin composition cured by light and heat, and a preferable upper limit is 5 parts by weight. If the amount is less than 0.2 parts by weight, current conduction between the electrodes cannot be sufficiently achieved, and the reliability of the liquid crystal panel may be lowered. If the amount exceeds 5 parts by weight, the number of contacts between the conductive particles However, the number of contact points of the conductive particles is greatly reduced by the thermal shock when the liquid crystal panel is aged, so that the electrical resistance between the electrodes formed on the substrate is higher than before aging. There is.

The common transition material of the present invention preferably further contains conductive fine particles having an average particle diameter smaller than that of the conductive particles.
FIG. 4 shows a schematic cross-sectional view of an example of the common transition material of the present invention including the conductive fine particles. As shown in FIG. 4, the conductive fine particles 310 are contained in the common transition material 301 together with the conductive particles 303. With such a configuration, a plurality of conductive fine particles 310 can come into contact with the electrode 307 or the electrode 308 as shown in FIG. 4, so that the conductivity between the electrode 307 and the electrode 308 is improved, and the liquid crystal The reliability of the panel can be improved.
Further, by adding such conductive fine particles, the viscosity of the common transition material of the present invention can be adjusted, and further, the linear expansion before and after curing is suppressed, and the blending amount of the nonconductive filler is at least. , Heat shrinkage and the like can be suppressed.

The preferable lower limit of the average particle diameter of the conductive fine particles is 0.05% of the average particle diameter of the conductive particles, and the preferable upper limit is 20%. If it is less than 0.05%, the conductive fine particles are too small, and thus the effect of adding the conductive fine particles may not be sufficiently obtained. If it exceeds 20%, the electrical resistance between the electrodes formed on the substrate is low. On the contrary, it may rise.

A preferable lower limit of the compounding amount of the conductive fine particles is 1 part by weight with respect to 100 parts by weight of the resin composition cured by light and heat, and a preferable upper limit is 100 parts by weight. If the amount is less than 1 part by weight, the amount of conductive fine particles interposed between the conductive particles and the electrode placed on the substrate may be insufficient, and the reliability improvement effect of the liquid crystal panel may not be obtained. On the other hand, the viscosity may increase significantly or the liquid crystal may be contaminated with conductive fine particles. A more preferred lower limit is 10 parts by weight, and a more preferred upper limit is 20 parts by weight.

In the common transition material of the present invention, the content of the nonconductive filler is 10 parts by weight or less with respect to 100 parts by weight of the resin composition that is cured by light and heat. If it exceeds 10 parts by weight, the electrical resistance between the common transition electrode and the electrode installed on the substrate will be significantly increased, and the reliability of the liquid crystal panel will be drastically reduced. More preferably, no non-conductive filler is contained. More preferably, it is 1 part by weight or less.
In the common transition material of the present invention, there is hardly any influence such as resin shrinkage due to the reduction of the non-conductive filler. This is because the conductive connection reliability is improved by the conductive particles having a particle diameter corresponding to the distance between the electrodes, the protrusions suitably provided on the conductive particles, and the conductive fine particles suitably blended. It is believed that there is.
Examples of the nonconductive filler include calcium carbonate, barium sulfate, alumina, silica, talc, magnesium oxide, and zinc oxide.

The common transition material of the present invention may further contain a conventionally known additive as required.

A schematic conceptual diagram of a preferred example of a common transition electrode using the common transition material of the present invention is shown in FIG. In FIG. 1, a common transition electrode 101 has a configuration in which conductive particles 103 are included in a resin composition 102 that is cured by light and heat, and a nonconductive filler such as an inorganic filler is not included. . When the common transition electrode as shown in FIG. 1 is used, a non-conductive filler such as an inorganic filler is not sandwiched between the electrode and the conductive particles as in the prior art. The sex can be further improved.

The resin composition that is cured by light and heat used in the common transition material of the present invention preferably has a volume resistance of 1 × 10 ¹³ Ω · cm or more after curing. If it is less than 1 × 10 ¹³ Ω · cm, it means that the common transition material contains ionic impurities, and the ionic impurities are eluted into the liquid crystal when energized, affecting the liquid crystal driving voltage, It may cause display unevenness.

The common transition material of the present invention preferably has a dielectric constant (relative dielectric constant) of 3 or more at 100 kHz after curing. The dielectric constant of the liquid crystal is usually 10 for ε _// (parallel) and about 3.5 for ε _⊥ (vertical). Therefore, when the dielectric constant is less than 3, the common transition material of the present invention is contained in the liquid crystal. Elution may affect the liquid crystal drive voltage and cause display unevenness.

In the common transition material 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. If it is less than 80 ° C., it may be inferior in moisture resistance (high temperature and humidity resistance), and if it exceeds 150 ° C., it may become too rigid and inferior in adhesion to the substrate. A more preferable lower limit is 95 ° C., and a more preferable upper limit is 140 ° C.
In addition, the said glass transition temperature is the value measured on conditions with a temperature increase rate of 5 degree-C / min and a frequency of 10 Hz by DMA method. 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 resin composition that is cured by light and heat has a preferable lower limit of 50 ° C. and a preferable upper limit of 120 ° C. after curing.

The common transition material of the present invention preferably has an extraction water ion conductivity of 50 μS / cm or less before curing. If it exceeds 50 μS / cm, it means that the common transition material of the present invention contains ionic impurities, and the ionic impurities are eluted into the liquid crystal, affecting the liquid crystal driving voltage and causing display unevenness. It becomes. More preferably, it is 30 μS / cm or less.
The extracted water ion conductivity is determined by dissolving the resin composition cured by light and heat in a solvent, extracting the solution with pure water, and measuring the conductivity of the pure water with a conductivity meter (for example, Horiba, Ltd.). It can be obtained by measuring using ES-12 or the like manufactured by the company.

The common transition material of the present invention preferably has a resistivity before curing of 1.0 × 10 ^{6 to} 1.0 × 10 ¹⁰ Ω · cm. If it is less than 1.0 × 10 ⁶ Ω · cm, when these are eluted into the liquid crystal, the liquid crystal driving voltage is affected, causing display unevenness. If it exceeds 1.0 × 10 ¹⁰ Ω · cm, elution into the liquid crystal may increase or adhesion to the substrate may be poor.

When the position of the common transfer material and the peripheral sealant is close, the peripheral sealant may spread during bonding. At this time, if the viscosity of the common transition material before curing is low, the common transition material may be swept away and conduction may be insufficient. Accordingly, the common transition material of the present invention preferably has a viscosity before curing higher than the viscosity before curing of the peripheral sealing agent provided around the common transition material.
In the common transition material of the present invention, the preferable lower limit of the viscosity before curing is 100,000 mPa · s, and the preferable upper limit is 800,000 mPa · s. If the viscosity before curing is within this range, pressure can be sufficiently applied between the substrates on which the electrodes are formed, so that the electrodes and the conductive particles can be sufficiently brought into contact with each other. The reliability of the liquid crystal panel can be further improved.
In order to obtain a common transition material having such a viscosity, the viscosity of the resin composition cured by light and heat before curing is preferably 90% or more of the viscosity of the peripheral sealant.

The method for producing the common transition material of the present invention is not particularly limited. For example, the resin composition, the conductive particles, and the like that are cured by light and heat are weighed so as to have a predetermined blending amount, and these are rolled. The method of mixing with a mixer etc. is mentioned.

By using the common transition electrode made of the common transition material of the present invention, a liquid crystal panel with extremely high reliability can be obtained.
The first substrate, the second substrate installed through the liquid crystal layer with respect to the first substrate, and the liquid crystal layer installed between the first substrate and the second substrate. A liquid crystal panel including a sealant, comprising the common transition material of the present invention between an electrode formed on the liquid crystal layer side of the first substrate and an electrode formed on the liquid crystal layer side of the second substrate A liquid crystal panel provided with a common transition electrode is also one aspect of the present invention.

A schematic cross-sectional view of an example of the liquid crystal panel of the present invention is shown in FIG.
In FIG. 5, a liquid crystal panel 100 according to the present invention includes a first substrate 105 and a second substrate 106 which are disposed to face each other with a liquid crystal layer 111 interposed therebetween. A transparent electrode 107 and a transparent electrode 108 are respectively formed on 106, and a sealing agent 112 is formed so as to surround the liquid crystal layer 111. Further, the common transition electrode 101 is disposed inside the sealing agent 112, that is, on the liquid crystal layer 111 side of the sealing agent 112.

Since the liquid crystal panel of the present invention has a configuration in which the common transition electrode 101 made of the common transition material of the present invention is installed between the transparent electrode 107 and the transparent electrode 108, the liquid crystal panel contains a large amount of non-conductive filler. The reliability is significantly improved compared to the conventional liquid crystal panel using the common transition electrode.

Here, as the first substrate 105 and the second substrate 106, conventionally known substrates can be used, and examples thereof include a glass substrate and a silicon substrate. In addition to the transparent electrode 107, the transparent electrode 108, the sealant 112, and the common transition electrode 101, for example, a color filter, a black matrix, a polarizing plate, and the like are installed on the first substrate 105 and the second substrate 106. Can be done. Furthermore, switching elements such as TFT (Thin Film Transistor) and MIM (Metal Insulator Metal) can be installed.

In addition, as the transparent electrode 107 and the transparent electrode 108 installed on the first and second substrates, for example, an ITO (indium tin oxide) film, a SnO ₂ (tin oxide) film, or the like can be used. The common transition electrode 101 can also be installed outside the sealing agent 112, that is, on the side of the sealing agent 112 that is not on the liquid crystal layer 111 side. In addition, the photocurable resin used for the common transition electrode 101 and the resin used for the sealant 112 may be the same type of resin component or different types of resin components.

As the liquid crystal constituting the liquid crystal layer 111, a conventionally known liquid crystal can be used. For example, a TN (Twisted Nematic) liquid crystal, an STN (Super Twisted Nematic) liquid crystal, a TSTN (Triple super Twisted Nematic) liquid crystal, or an FSTN (Film supra) Twisted Nematic) liquid crystal and the like.

The liquid crystal panel of the present invention is suitably used for, for example, a mobile phone, a personal computer, a word processor, a television, an electronic notebook, a digital camera, a video camera, a projector, a calculator, a clock, a stereo, a car navigation, a microwave oven, a facsimile machine, and a copy machine. It is done.

The method for producing the liquid crystal panel of the present invention is not particularly limited, but a step of forming a common transition electrode made of the common transition material of the present invention on at least one upper surface of a pair of substrates, and a sealing agent on at least one upper surface of the substrate A step of forming a plurality of closed frame bodies, a step of injecting liquid crystal by dropping liquid crystal into each of the plurality of closed frame bodies, a step of bonding a pair of substrates, and a step of curing a sealing agent Is preferred.
Such a method for producing the liquid crystal panel of the present invention is also one aspect of the present invention.

In the liquid crystal panel manufacturing method of the present invention, the liquid crystal is injected by dropping the liquid crystal 111a into a sealant 112 formed in a closed frame body having no liquid crystal injection port, for example, as shown in FIG. Therefore, since it takes a long time to inject liquid crystal before the bonded substrate is divided as shown in FIG. 6, the liquid crystal is divided into a plurality of bonded substrates as in the prior art. There is no need to inject liquid crystal for each bonded substrate. Therefore, according to the method for manufacturing a liquid crystal panel of the present invention, the production efficiency of the liquid crystal panel can be dramatically improved. Here, examples of the method for dropping the liquid crystal include a method of applying by a dispenser and a method of applying by ink jet.

In the liquid crystal panel manufacturing method of the present invention, as a method of forming a common transition electrode or a method of forming a sealing agent on a closed frame, for example, a method of applying on a substrate using a dispenser, or a method of screen printing on a substrate. Examples include a printing method.

For example, as shown in FIG. 7, the common transfer electrode 101 is formed on the substrate 106 on which the sealing agent 112 into which the liquid crystal 111a is injected is formed. A method of covering the substrate 105 from above and pressurizing between the substrates 105 and 106 may be used. In addition, after pressurizing the substrate, the sealing agent 112 and the common transition electrode 101 are cured by irradiating and heating the sealing agent 112 and the common transition material electrode 101 with light of, for example, about 3000 to 5000 mJ.
The sealing agent 112 and the common transition electrode 101 may be formed on different substrates, or may be formed on the same substrate.

ADVANTAGE OF THE INVENTION According to this invention, the common transition material which can improve the reliability of a liquid crystal panel, a liquid crystal panel using the same, and the manufacturing method of the liquid crystal panel 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 1-18, Comparative Example 1)
(1) Production of resin curable by light and heat 1000 parts by weight of liquid phenol novolac type epoxy resin (DOW Chemical Co., DEN 431), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, reaction As a catalyst, 2 parts by weight of triethylamine and 200 parts by weight of acrylic acid were stirred at 90 ° C. while air was fed and reacted for 5 hours. In order to adsorb ionic impurities during the reaction, 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), and acrylic acid. A phenol novolac epoxy resin (50% partially acrylated product) was obtained.

Meanwhile, 1440 parts by weight of liquid polyoxyalkylene bisphenol A diglycidyl ether (EP4000S, manufactured by Asahi Denka Kogyo Co., Ltd.), 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 The mixture was stirred at 90 ° C. while feeding air and reacted for 5 hours. In order to adsorb ionic impurities during the reaction, 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), and acrylic acid. A modified propylene oxide bisphenol A phenol novolac epoxy resin (50% partially acrylated product) was obtained.

(2) Preparation of common transition material A photopolymerization initiator and a thermosetting agent are added to a resin that is cured by light and heat so as to have the composition shown in Tables 1 to 5, and these are mixed by three rolls. The conductive particles and, if necessary, conductive fine particles and inorganic filler were added and kneaded using a vacuum centrifugal stirring method so that the average distribution amount of the conductive particles in the resin was 50 ± 5 particles / mm ² . .

In Examples 1 to 10 and Examples 15 to 18, resin particles plated with gold (Micropearl AU-20625 manufactured by Sekisui Chemical Co., Ltd., average particle diameter 6.25 to 6.45 μm) were used as the conductive particles. .
In Examples 11 to 14, resin particles (micropearl AULB-206 manufactured by Sekisui Chemical Co., Ltd., average particle diameter of 6.0 to 6.2 μm) plated with gold were used as the conductive particles. Although the electroconductive particle used in Examples 11-14 has a protrusion, this protrusion was produced as follows. First, silver powder having an average particle diameter of 0.2 μm (trade name “Silcoat Ag · CG” manufactured by Fukuda Metals Co., Ltd.) was immersed in a sufficient amount of acetone and dispersed by applying ultrasonic vibration. To this, 3% silane coupling (trade name “TSC-6350” manufactured by Toshiba Silicon Co., Ltd.) and an epoxy curing agent (trade name “Curesol 2M2” manufactured by Shikoku Kasei Co., Ltd.) were added and dissolved. Further, 50% epoxy resin (manufactured by Yuka Shell Co., Ltd., trade name “Epoxy Epicoat-1001”) was added and mixed, and the above resin particles were added and mixed, and acetone was volatilized as it was. Here, the mixing ratio of the silver powder, the silane coupling aqueous solution, and the epoxy curing agent was 129: 4: 9. Next, this was vacuum-dried at room temperature, made into single particles with a ball mill, and then heated at 150 ° C. for 10 minutes to produce protrusions.

Tin oxide (Ishihara Sangyo Co., Ltd., “SN-100P”, average particle size 0.2 μm) is used as the conductive fine particles, and silica (Admafine Co., Ltd., “SO-C1”, average particle size distribution 2 μm) is used as the inorganic filler. As a photopolymerization initiator, phenyl 2-hydroxy-2-propyl ketone (Ciba Geigy, “Darocur 1173”) is used as a thermosetting agent, and organic acid dihydrazide (Ajinomoto Co., “Amicure-VDH”) is used. Using.

(3) Production of liquid crystal panel A liquid crystal panel was produced as follows.
First, both the array substrate and the color filter substrate are processed from the cleaning process to the rubbing process, and an in-plane spacer (trade name “SP” manufactured by Sekisui Chemical Co., Ltd. is applied to the array substrate subjected to this process by a dry spraying method. −2045AS ”, spacer diameter 4.5 μm, fixed type) was sprayed and heated at 120 ° C. for 15 minutes, and then the common transition material was applied by a dispenser. The coating conditions at this time were a nitrogen discharge pressure of 0.3 MPa, a discharge time of 0.06 seconds, and a dispenser nozzle inner diameter of 0.24 mm. Under these conditions, coating was performed on an electrode of about 900 μm square so that the coating diameter was 250 to 300 μm and the height was within 25 μm.

Next, on the color filter substrate, a photothermal combined curing type epoxy resin (manufactured by Kyoritsu Chemical Industry Co., Ltd., trade name “World Lock D70-F3”) is used as a sealant to form a closed frame with a line width of 120 μm ± 20 μm by a dispenser. Then, the liquid crystal was injected into the sealant by dropping the liquid crystal.

Finally, the array substrate and the color filter substrate were bonded together in a vacuum of 6.5 × 10 ⁻¹ Pa, and then pressed at atmospheric pressure. The pressed substrate was irradiated with light at 4000 mJ, and then heated at 120 ° C. for 60 minutes. Finally, each cell was divided to obtain a liquid crystal panel.

(Evaluation)
The liquid crystal panel was evaluated by measuring the electrical resistance between the electrodes of the liquid crystal panel produced in Examples 1 to 18 and Comparative Example 1, and calculating the ratio of the liquid crystal panel through which the current flowed.
The results are shown in Tables 1-5.

(1) Electrical resistance measurement method Electrical resistance is measured because the terminals for connecting the liquid crystal panel and the external signal driver exist around the liquid crystal panel, and the resistance between the electrodes of each sample was measured using it. . The electrical resistance between the electrodes was measured in two cases immediately after the liquid crystal panel was produced and after aging for 500 hours at a temperature of 60 ° C. and a humidity of 95%.

(2) Reliability of liquid crystal panel The reliability of the liquid crystal panel was evaluated by the following formula.
(Reliability of liquid crystal panel) = (Number of liquid crystal panels through which current flows) / (Total number of liquid crystal panels on which electrical resistance was measured)

(Evaluation results)
As shown in Tables 1 to 5, the liquid crystal panels produced in Examples 1 to 18 had a significantly lower electrical resistance than the liquid crystal panel produced in Comparative Example 1, and were greatly superior in the reliability of the liquid crystal panel. Moreover, it turned out that the liquid crystal panel produced in Examples 1-18 does not change so much before and after aging as a whole, and is excellent also in durability.

In addition, as shown in Table 1, the liquid crystal panels produced in Examples 1 to 3 using a common transition material having a viscosity before curing in the range of 100,000 to 800,000 mPa · s are resin before curing. There was a tendency to be more reliable than the liquid crystal panel produced in Example 4 using a resin composition whose viscosity was not within that range.
Moreover, as shown in Table 2, the liquid crystal panel produced in Example 5 using the common transition material in which the blending amount of the conductive particles is in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the resin is In addition, the liquid crystal panel produced in Example 6 using the common transition material in which the blending amount of the conductive particles is not within the range is more reliable, and the electrical resistance after aging is higher than that of the liquid crystal panel produced in Example 7. Tended to be lower.

Moreover, as shown in Table 3, the common transition material in which the average particle diameter of the conductive particles is in the range of 100 to 110% of the distance between the electrodes and the compression modulus is in the range of 2000 to 7000 N / mm ^2. The liquid crystal panel produced in Example 8 using a lower electrical resistance than the liquid crystal panel produced in Example 9 using a common transition material in which the compressive elastic modulus of the conductive particles is not within the range. There was a tendency to be more reliable than the liquid crystal panel produced in the above.

In addition, as shown in Table 4, the liquid crystal panel produced in Example 11 using conductive particles having a protrusion height in the range of 0.05 to 5% of the average particle diameter has a protrusion height in the range. There was a tendency to be more reliable than the liquid crystal panel produced in Example 13 using conductive particles not included. Moreover, the liquid crystal panel produced in Example 12 using the conductive particles having the projection height within the above range is the liquid crystal panel produced in Example 14 using the conductive particles having the projection height not within the above range. It tended to be more reliable than.

Moreover, as shown in Table 5, the liquid crystal panel produced in Example 15 using the common transition material in which the blending amount of the conductive fine particles is in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the resin is There was a tendency to be more reliable than the liquid crystal panel produced in Example 17 using a common transition material in which the blending amount of the conductive fine particles was not within the range. In addition, the liquid crystal panel manufactured in Example 16 using the common transition material in which the blending amount of the conductive fine particles is in the above range is an example using the common transition material in which the blending amount of the conductive fine particles is not in the above range. The change in electrical resistance before aging tended to be less than that of the liquid crystal panel produced in No. 18.

ADVANTAGE OF THE INVENTION According to this invention, the common transition material which can improve the reliability of a liquid crystal panel, a liquid crystal panel using the same, and the manufacturing method of the liquid crystal panel can be provided.

It is a typical expanded sectional view of an example of the common transition material of this invention. It is a typical expanded sectional view of an example of the common transition material of this invention when a processus | protrusion is formed in the surface of electroconductive particle. It is a typical expanded sectional view which shows the height of the processus | protrusion formed in the surface of electroconductive particle. It is a typical expanded sectional view of an example of the common transition material of this invention which added electroconductive fine particles. It is typical sectional drawing of an example of the liquid crystal panel of this invention. It is the typical conceptual diagram which showed an example of the liquid crystal dropping process used for this invention. It is the typical concept figure which showed an example of the board | substrate bonding process used for this invention. It is sectional drawing of the conventional liquid crystal panel. It is the conceptual diagram which showed the conventional board | substrate bonding process. It is a top view of the conventional bonded substrate. It is a perspective view of the conventional bonded substrate. It is a conceptual diagram showing a conventional liquid crystal injection process. It is a top view of the conventional liquid crystal panel. It is an expanded sectional view of the conventional common transition electrode.

Explanation of symbols

100, 400 Liquid crystal panel 101, 201, 301, 401 Common transition electrode 102, 402 Resin 103, 203, 303, 403 Conductive particle 404 Non-conductive filler 105, 106, 405, 406 Substrate 107, 108, 207, 208, 307, 308, 407, 408 Electrode 209 Protrusion 310 Conductive fine particles 111, 411 Liquid crystal layer 111a, 411a Liquid crystal 112, 412 Sealing agent 416 Liquid crystal inlet 417 Sealing material

Claims (15)

A common transition material used for a common transition electrode placed between electrodes formed adjacent to each other inside a pair of opposing substrates, a resin composition that is cured by light and heat, and conductive particles And a non-conductive filler content is 10 parts by weight or less based on 100 parts by weight of the resin composition that is cured by light and heat. The common transfer material according to claim 1, wherein the viscosity before curing is higher than the viscosity before curing of a peripheral sealing agent provided around the periphery. The common transition material according to claim 1, wherein the viscosity before curing is 100,000 to 800,000 mPa · s. The common transition material according to claim 1, wherein the extracted water ion conductivity is 50 μS / cm or less before curing. 5. The common transition material according to claim 1, wherein the resin curable by light and heat has at least one (meth) acryl group and epoxy group in one molecule. 6. The common transition material according to claim 1, wherein the diameter of the conductive particles is 100 to 150% of the distance between the electrodes formed on the substrate. The common transition material according to claim 1, 2, 3, 4, 5 or 6, wherein the conductive particles have protrusions protruding outward from the surface. The common transition material according to claim 7, wherein the height of the protrusion is 0.05 to 5% of the average particle diameter of the conductive particles. Conductive particles, common transfer material according to claim 7 or 8, wherein the compression modulus of 2000~7000N / mm ^2. The blending amount of the conductive particles is 0.2 to 5 parts by weight with respect to 100 parts by weight of the resin composition that is cured by light and heat. The common transition material according to claim 7, 8, or 9. The common transition material according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, further comprising conductive fine particles having an average particle diameter smaller than that of the conductive particles. The common transition material according to claim 11, wherein the diameter of the conductive fine particles is 0.05 to 20% of the diameter of the conductive particles. 13. The common transition material according to claim 11, wherein the content of the conductive fine particles is 1 to 100 parts by weight with respect to 100 parts by weight of the resin composition cured by light and heat. A first substrate, a second substrate disposed with respect to the first substrate via a liquid crystal layer, and the liquid crystal layer is surrounded between the first substrate and the second substrate. A liquid crystal panel including a sealant disposed between the electrode formed on the liquid crystal layer side of the first substrate and the electrode formed on the liquid crystal layer side of the second substrate. 14. A liquid crystal panel comprising a common transition electrode made of a common transition material according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13. A step of forming a common transition electrode made of the common transition material according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 on at least one upper surface of a pair of substrates. When,
Forming a plurality of closing frames as sealing agents on at least one upper surface of the substrate;
Injecting liquid crystal by dropping liquid crystal into each of the plurality of closed frames; and
Bonding the pair of substrates together;
And a step of curing the sealing agent.

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