JP4157896B2 - Sealant for liquid crystal dropping method, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing agent for a liquid crystal one-drop-fill method and a vertical conducting material having excellent adhesiveness to a substrate and causing no contamination of a liquid crystal in the manufacture of a liquid crystal display element. <P>SOLUTION: The sealing agent for a liquid crystal one-drop-fill method contains a (meta)acrylate compound having a structure represented by general formula (1), wherein the (meta)acrylate compound accounts for 10 to 70 wt.% of a curable resin component included in the agent. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

Since the present invention has excellent adhesion to a substrate in the production of a liquid crystal display element, the phenomenon of peeling between the substrate and the liquid crystal display is less likely to occur, and liquid crystal contamination is not caused. The present invention relates to a sealing agent for liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element, which are optimal for the manufacture of the element.

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

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

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

On the other hand, the manufacturing method of the liquid crystal display element called the dripping method using the sealing agent which consists of a photocurable thermosetting combined type resin composition is examined (for example, refer patent document 1). In the dropping method, first, a rectangular seal pattern is formed on one of the two transparent substrates with electrodes by screen printing. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with ultraviolet rays for temporary curing. Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.

However, such a liquid crystal dropping method can significantly reduce the liquid crystal introduction process time as compared with the vacuum injection method. On the other hand, since the sealing agent is in contact with the liquid crystal in an uncured state, the component of the sealing agent is There was a problem that it was easy to elute into the liquid crystal and caused liquid crystal contamination.
In order to solve such a problem, for example, a method of performing two-stage curing by ultraviolet rays and heating using a photocuring / thermosetting sealant is known. In such two-stage curing, the greater the proportion of the photocured sealant, the more the elution of the sealant component into the liquid crystal can be suppressed.

However, the sealing agent usually generates stress in the cured product when cured, resulting in poor adhesion to the substrate and poor adhesion. In particular, as shown in FIG. When a liquid crystal display element having a structure in which a substrate 21 on which a single-layer or multi-layer film 22 is formed and another substrate 23 are bonded via a sealant 20 and a liquid crystal 24 is sealed is manufactured by a dropping method, a cured seal is obtained. There was a problem that the adhesive force between the agent and the substrate (film) was lowered, and the peeling phenomenon became remarkable between them. FIG. 2 is a cross-sectional view schematically showing an example of a liquid crystal display element.
JP 2001-133794 A

In view of the above situation, the present invention has excellent adhesion to a substrate in the manufacture of a liquid crystal display element, and therefore does not easily peel off between the substrate and does not cause liquid crystal contamination. An object of the present invention is to provide a sealing agent for a liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element, which are optimal for manufacturing a liquid crystal display element with little unevenness.

This invention is a sealing compound for liquid crystal dropping methods containing the (meth) acrylate compound which has a structure represented by following General formula (1), Comprising: 10-70 weight% of the curable resin component to contain is said ( It is a sealing agent for liquid crystal dropping method which is a meth) acrylate compound.

一般式（１）中、Ｒ^１は、水素原子又はメチル基を表し、Ｘは、下記化学式（２）で表される群より選択される１種を表し、Ｙは、下記化学式（３）で表される群より選択される１種を表し、Ａは環状ラクトンの開環構造を表し、ｎは、１である。

In general formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents one selected from the group represented by the following chemical formula (2), and Y represents the following chemical formula (3). 1 represents one selected from the group represented, A represents a ring-opening structure of a cyclic lactone, and n is 1 .

以下に本発明を詳述する。

The present invention is described in detail below.

The present inventors have proposed the sealing agent for liquid crystal display elements using the curable resin composition containing an acrylated epoxy resin as a suitable sealing agent especially in the dropping method.
When such a curable resin composition is used, the sealing agent for liquid crystal display elements can be a combined type of photocuring and thermosetting, and the polarity of the contained resin is high, which is compatible with liquid crystals. Therefore, contamination of the liquid crystal can be effectively prevented. However, when a film such as an alignment film or a black matrix is formed on the surface of the substrate on which the sealing agent is formed, there is a problem that the adhesive force with the sealing agent is reduced after photocuring.
As a result of intensive studies, the present inventors have used a (meth) acrylate compound having a specific structure as a sealing agent for a liquid crystal dropping method, thereby forming a substrate such as a cured alignment film or a black matrix. It has been found that the adhesiveness to the surface can be excellent, and the present invention has been completed.

The sealing agent for liquid crystal dropping method of the present invention (hereinafter also simply referred to as the sealing agent of the present invention) contains a (meth) acrylate compound having a structure represented by the general formula (1).
In the general formula (1), X represents one selected from the group represented by the chemical formula (2), and Y represents one selected from the group represented by the chemical formula (3). And A represents a ring-opening structure of a cyclic lactone, and n is 0 or 1. Since the sealing agent of the present invention containing the (meth) acrylate compound having such a structure is excellent in adhesiveness to the substrate, the peeling phenomenon is unlikely to occur between the substrate and the liquid crystal is not contaminated. It is most suitable for manufacturing a liquid crystal display element with little color unevenness in liquid crystal display.
In the present specification, (meth) acrylate means acrylate or methacrylate.

If the said (meth) acrylate compound has a structure represented by the said General formula (1), it will not specifically limit as a structure of another part.
The (meth) acrylate compound preferably has a lactone-derived structure. Since the sealing agent of the present invention is excellent in flexibility, the adhesive force to the substrate surface is unlikely to decrease due to internal stress generated when it is cured, and the peeling phenomenon does not occur between the substrate and the substrate. In this case, n in A is 1 in the general formula (1).

The cyclic lactone is not particularly limited. For example, γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonalactone, γ-nonanolactone, γ-valerolactone, σ-valerolactone, β -Butyrolactone, γ-butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone and the like. These cyclic lactones may be used alone or in combination of two or more.
Among them, those in which the straight chain portion of the main skeleton has 5 to 7 carbon atoms when ring-opening are preferable.

The (meth) acrylate compound preferably has a segment in which three or more methylene groups are connected. As a result, the sealing agent of the present invention is excellent in flexibility, so that the adhesive force to the substrate surface is not easily lowered by the internal stress generated when it is cured, and the peeling phenomenon does not occur between the substrate and the substrate.

The (meth) acrylate compound is preferably a polyfunctional (meth) acrylate compound having two or more (meth) acryl groups. When the (meth) acrylate compound is polyfunctional having two or more (meth) acryl groups, the cured product of the sealing agent of the present invention has excellent heat resistance and high reliability due to a high crosslinking density. It will be a thing.

In the sealing agent of the present invention, the (meth) acrylate compound having the structure represented by the general formula (1) can be obtained by, for example, a reaction represented by the following formula (4).

That is, carboxylic acid (C) is obtained by reacting (meth) acrylate (A) with cyclic anhydride (B). And the (meth) acrylate compound (E) which has a structure represented by the said General formula (1) is obtained by making carboxylic acid (C) and an epoxy compound (D) react.

In the (meth) acrylate (A), examples of X and A include the same as X and A in the structure represented by the general formula (1) of the (meth) acrylate compound.
The (meth) acrylate (A) preferably has a lactone-derived structure. When the (meth) acrylate (A) has a lactone-derived structure, the (meth) acrylate compound (E) to be synthesized has a lactone-derived structure. When the (meth) acrylate (A) has a lactone-derived structure, n in the A is 1.

Specific examples of the (meth) acrylate (A) having a structure derived from the lactone include, for example, caprolactone-2- (meth) acryloxyethyl, dicaprolactone-2- (meth) acryloxyethyl, aliphatic epoxy Examples thereof include acrylate (Ebecryl 111, Ebecryl 112, both manufactured by Daicel Setec Co., Ltd.), Epolite 1600 (manufactured by Kyoeisha Chemical Co., Ltd.) including a linear structure in which six methylene groups are connected.

The method for synthesizing the (meth) acrylate (A) having a structure derived from the lactone is not particularly limited, and may be a conventionally known method, for example, having a hydroxyl group such as 2-hydroxyethyl acrylate (meta ) A method in which an acrylic ester and the above cyclic lactone are mixed and heated to react.

In the cyclic anhydride (B), examples of Y include the same as Y in the structure represented by the general formula (1) of the (meth) acrylate compound.
Examples of such cyclic anhydride (B) include maleic anhydride, succinic anhydride, phthalic anhydride, citraconic anhydride, ricacid TH, ricacid HT-1, ricacid HH, ricacid HT-700, ricacid MH, ricacid MT. -500, Ricacid HNA, Ricacid HNA-100, Ricacid OSA, Ricacid DDSA (all of which are manufactured by Shin Nippon Chemical Co., Ltd.) and the like.

In the epoxy compound (D) of the above formula (4), m represents an integer of 1 or more. Such an epoxy compound (D) may be a monofunctional epoxy or a polyfunctional epoxy, and the structure thereof is not particularly limited as long as it is a compound having at least one epoxy group. That is, in the above formula (4), Z ′ constituting the epoxy compound (D) is not particularly limited, and includes any structure.

Specific examples of the epoxy compound (D) include, for example, Rika Resin L-100 (manufactured by Shin Nippon Chemical Co., Ltd.), EPICLON 520, and EPICLON 703 (all of which are manufactured by Dainippon Ink and Chemicals, Inc.). Examples thereof include n-butyl glycidyl ether, glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl and the like, and the number of carbon atoms constituting the main chain is preferably 10 or less. Among the polyfunctional epoxies, examples of the bifunctional epoxy include bisphenol types such as EPICLON EXA-850CRP (Dainippon Ink Chemical Co., Ltd.) and hydrogenated bisphenol types such as EPICLON EXA-7015 (Dainippon Ink Chemical Co., Ltd.). Ethylene glycol diglycidyl ether and the like, and examples of the tri- or higher functional epoxy include EPICLON 725 (Dainippon Ink Chemical Co., Ltd.). Examples of the bisphenol type and hydrogenated bisphenol type include A type, E type, and F type.

The epoxy compound (D) is preferably a bifunctional or higher functional epoxy compound having two or more epoxy groups. By using such an epoxy compound (D), the (meth) acrylate compound (E) to be synthesized can be a polyfunctional (meth) acrylate compound having two or more (meth) acryl groups described above. Specifically, by reacting 1 mol of the epoxy compound (D) with a carboxylic acid (C) having a number of moles corresponding to the number of epoxy groups of the epoxy compound (D), two or more (meth) acrylic compounds are reacted. A polyfunctional (meth) acrylate compound having a group is obtained. At this time, m in the said (meth) acrylate compound (E) becomes the same number as the number of the (meth) acryl groups of the said (meth) acrylate compound (E). The (meth) acrylate compound (E) is preferably tetrafunctional or higher.

Z in the (meth) acrylate compound (E) produced by such a method is not particularly limited. For example, the same structure as Z ′ constituting the epoxy compound (D) may be used. When Z ′ of the epoxy compound (D) contains one or more epoxy groups, a part or all of the epoxy groups in the Z ′ has a structure reacted with the carboxylic acid (C) or any acrylic acid. May be.

Specific examples of the (meth) acrylate compound (E) include KRM7856, Ebecryl 3708 (all of which are manufactured by Daicel Cytec Co., Ltd.).

When obtaining the said (meth) acrylate compound (E), it is preferable to use a catalyst for the purpose of obtaining sufficient reaction rate.
The catalyst is not particularly limited, and examples thereof include organic phosphine compounds such as triphenylphosphine, tertiary amines such as triethylamine and benzyldimethylamine, quaternary compounds such as trimethylammonium chloride, triethylbenzylammonium chloride, and trimethylammonium bromide. Examples include ammonium salts, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole, and organic metal salts such as chromium octenoate, cobalt octenoate, and chromium naphthenate. .
The minimum with the preferable addition amount of the said catalyst is 0.01 weight%, and an upper limit is 5.0 weight%. If it is less than 0.01% by weight, a sufficient reaction rate may not be obtained, and if it exceeds 5.0% by weight, various physical properties of the sealant of the present invention may be adversely affected. A more preferred lower limit is 0.05% by weight and an upper limit is 2.0% by weight.

Moreover, when obtaining the said (meth) acrylate compound (E), it is preferable to add a polymerization inhibitor in order to prevent superposition | polymerization of a (meth) acryl group.
The polymerization inhibitor is not particularly limited. For example, hydroquinone, hydroquinone monomethyl ether, phenothiazine p-t-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, p-benzoquinone, naphthoquinone. 2,5-diphenyl-p-benzoquinone, di-t-butyl-p-cresol, 2,5-di-t-butyl-4-methylphenol, p-methoxyphenol and the like.

Moreover, it is preferable to perform reaction with the said carboxylic acid (C) and an epoxy compound (D) until an acid value becomes 2 mgKOH or less. When it exceeds 2 mgKOH, a large amount of carboxylic acid (C) is still present, and the amount of (meth) acrylate compound (E) is insufficient.
The reaction is preferably performed until the oxirane oxygen concentration becomes 1% or less. If it exceeds 1%, a large amount of the epoxy compound (D) still exists and the amount of the (meth) acrylate compound (E) is insufficient.
In addition, it is preferable to perform the said reaction, measuring an acid value and an oxirane oxygen concentration by methods, such as a titration method.

In the sealing agent of the present invention, the lower limit of the amount of the (meth) acrylate compound in the curable resin component contained is 10% by weight, and the upper limit is 70% by weight. If it is less than 10% by weight, the residual stress of the cured product of the sealing agent of the present invention cannot be sufficiently relaxed, and the adhesion between the substrates of the produced liquid crystal display element becomes insufficient. If it exceeds 70% by weight, the cured product of the sealing agent of the present invention increases the adhesion between the substrates of the liquid crystal display device to be produced in order to disperse the residual stress, but the workability such as the dispensing property of the sealing agent of the present invention. Will be very bad.

The sealing agent of the present invention may further contain other curable resin in addition to the (meth) acrylate compound having the structure represented by the general formula (1). The curable resin is not particularly limited, and examples of the reactive functional group include those having a (meth) acryloyl group, a cyclic ether such as an epoxy group or an oxetanyl group, and a styryl group. Specific examples include (meth) acrylic acid esters, partial epoxy (meth) acrylate resins, and epoxy resins.

Examples of the (meth) acrylic acid ester include an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, and an epoxy obtained by reacting (meth) acrylic acid with an epoxy compound ( Examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylates and isocyanates with (meth) acrylic acid derivatives having a hydroxyl group.

The ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited. Examples of monofunctional compounds include 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth) acrylate. 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tet Hydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) Acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, -octafluoropentyl (meth) acrylate, imide (Meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Rohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) ) Acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl Roxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, etc. It is done.

Examples of the bifunctional compound include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9. -Nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Pyrene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene didi (meth) acrylate, 1,3-butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, poly Ether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene geo Distearate (meth) acrylate.

Examples of the tri- or higher functional group include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (meth). Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin Li (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.

The epoxy (meth) acrylate obtained by reacting the (meth) acrylic acid with an epoxy compound is not particularly limited. For example, an epoxy resin and (meth) acrylic acid are present in the presence of a basic catalyst according to a conventional method. What is obtained by reacting under is mentioned.

The epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate is not particularly limited, and examples of commercially available products include bisphenols such as Epicoat 828EL and Epicoat 1004 (both manufactured by Japan Epoxy Resin Co., Ltd.). Type A epoxy resin; Bisphenol F type epoxy resin such as Epicoat 806, Epicoat 4004 (all manufactured by Japan Epoxy Resin Co., Ltd.), Epicron 830CRP (manufactured by Dainippon Ink and Chemicals); Bisphenol such as Epicron EXA1514 (manufactured by Dainippon Ink Co., Ltd.) S-type epoxy resin; 2,2′-diallylbisphenol A-type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.); Hydrogenated bisphenol-type epoxy resin such as Epicron EXA7015 (manufactured by Dainippon Ink and Co., Ltd.); EP-4000 Propylene oxide-added bisphenol A type epoxy resin such as Asahi Denka Co .; Resorcinol type epoxy resin such as EX-201 (manufactured by Nagase ChemteX); Biphenyl type epoxy such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.) Resin; Sulfide type epoxy resin such as YSLV-50TE (manufactured by Tohto Kasei); Ether type epoxy resin such as YSLV-80DE (manufactured by Tohto Kasei); Dicyclopentadiene type epoxy such as EP-4088S (manufactured by Asahi Denka) Resin; Naphthalene type epoxy resin such as Epicron HP4032 and Epicron EXA-4700 (both manufactured by Dainippon Ink and Co.); Phenol novolac type epoxy resin such as Epicron N-770 (manufactured by Dainippon Ink and Company); Epicron N-670-EXP -S (Dainippon Ink Co., Ltd. Orthocresol novolac type epoxy resins such as: Epicyclone HP7200 (manufactured by Dainippon Ink and Co., Ltd.); Dicyclopentadiene novolac type epoxy resins such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); Naphthalene phenol novolak type epoxy resin such as Toto Kasei Co., Ltd .; Glycidylamine type epoxy such as Epicoat 630 (Japan Epoxy Resin), Epicron 430 (Dainippon Ink Co.), TETRAD-X (Mitsubishi Gas Chemical Co., Ltd.) Resins: Alkyl polyol type epoxy resins such as ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiklon 726 (manufactured by Dainippon Ink and Chemicals), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611, (manufactured by Nagase ChemteX) YR-450, YR -207 (both manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical Industries), etc .; rubber-modified epoxy resins; glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX Corporation); Epicoat YL-7000 (Japan) Bisphenol A type episulfide resin such as Epoxy Resin Co .; other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031 and Epicoat 1032 (all Japan) Epoxy resin), EXA-7120 (Dainippon Ink), TEPIC (Nissan Chemical) and the like.

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

Moreover, as a commercial item of the said epoxy (meth) acrylate, for example, Evecryl 3700, Evekril 3600, Evekril 3701, Evekril 3703, Evekrill 3200, Evekrill 3201, Evekrill 3600, Evekrill 3702, Evekrill 3412, Evekril 860, Evekril RDX63182, 6040, Evecryl 3800 (all manufactured by Daicel Cytec), 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 Tell 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).

Examples of the urethane (meth) acrylate obtained by reacting the above isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.

It does not specifically limit as isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, For example, isophorone diisocyanate, 2, 4-tolylene diisocyanate, 2 , 6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, Xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) Ofosufeto, tetramethyl xylene diisocyanate, 1,6,10- undecene country isocyanate.

Moreover, it does not specifically limit as isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group, For example, ethylene glycol, glycerol, sorbitol, a trimethylol propane It is also possible to use chain-extended isocyanate compounds obtained by reaction of polyols such as (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.

The (meth) acrylic acid derivative having a hydroxyl group, which is a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative, is not particularly limited. For example, 2-hydroxy Commercial products such as ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, Mono (meth) acrylates of trivalent alcohols such as mono (meth) acrylates of divalent alcohols such as 1,3-butanediol, 1,4-butanediol and polyethylene glycol, trimethylolethane, trimethylolpropane and glycerin Or di (meth) acrylate, epoxy acrylates such as bisphenol A-modified epoxy acrylate.

Specific examples of urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative include, for example, 134 parts by weight of trimethylolpropane, and 0.2 part by weight of BHT as a polymerization inhibitor. Then, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate were added as reaction catalysts, and the mixture was reacted at 60 ° C. with stirring under reflux for 2 hours. Then, 51 parts by weight of 2-hydroxyethyl acrylate was added, and air was fed. The mixture can be obtained by reacting at 90 ° C. with stirring under reflux for 2 hours.

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, Evecryl 8402, Evecryl 8804, Evecril 8803, Evecril 8807, Evecril 9260, Evecril 1290, Evecril 5842, Evecril 210, Evecril 4827, Evecril 6700, Evecril 220, Evecril 2220 -9000H, Art Resin UN-9000A, Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin UN-3320H , Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Kogyo Co., Ltd.), U-122P, U-108A, U-340P, U-4HA, U-6HA, U-324A, U-15HA, UA -5201P, UA-W2A, U-1084A, U-6LPA, U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA, UA-7200 , U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), AH-600, AT-600, UA-306H AI-600, UA-101T, UA-101I, UA-306T, UA-306I, and the like.

Examples of the partial epoxy (meth) acrylate resin include a compound obtained by reacting a partial epoxy group of a compound having two or more epoxy groups with (meth) acrylic acid, or a hydroxyl group in a bifunctional or higher isocyanate. And (meth) acrylic acid derivatives having a compound and a compound obtained by reacting glycidol.

Examples of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, an epoxy resin and (meth) acrylic acid in a basic manner according to a conventional method. What is obtained by reacting in presence of a catalyst is mentioned.
At this time, as a compounding quantity of the said epoxy resin and (meth) acrylic acid, Preferably, the minimum of carboxylic acid is 0.1 equivalent with respect to 1 equivalent of epoxy groups, and an upper limit is 0.5 equivalent, More preferably The lower limit of carboxylic acid is 0.2 equivalent and the upper limit is 0.4 equivalent with respect to 1 equivalent of epoxy group.

As an epoxy compound that is a raw material of a compound obtained by reacting a part of the epoxy group of the compound having two or more epoxy groups with (meth) acrylic acid, for example, the above-described epoxy (meth) acrylate is synthesized. The thing similar to the epoxy compound used as the raw material for doing is mentioned.

Specific examples of the compound obtained by reacting a part of the epoxy group having two or more epoxy groups with (meth) acrylic acid include, for example, a phenol novolac type epoxy resin (manufactured by Dow Chemical Company): DEN 431) 1000 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 200 parts by weight of acrylic acid while stirring at 90 ° C. while refluxing. It can be obtained by reacting for 5 hours (in this case 50% partially acrylated).

Among the compounds obtained by reacting a part of the epoxy groups having two or more epoxy groups with (meth) acrylic acid, a commercially available product is, for example, Evecryl 1561 (Daicel Cytec).

The compound obtained by reacting the (meth) acrylic acid derivative having a hydroxyl group with the bifunctional or higher isocyanate and glycidol is, for example, (meth) acrylic acid having a hydroxyl group with respect to 1 equivalent of the compound having two isocyanate groups. One equivalent each of the derivative and glycidol can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.

The bifunctional or higher isocyanate used as a raw material of the compound obtained by reacting the (meth) acrylic acid derivative having a hydroxyl group with the bifunctional or higher isocyanate and glycidol is not particularly limited. The thing similar to the isocyanate used as the raw material of the urethane (meth) acrylate obtained by making the (meth) acrylic acid derivative which has it react is mentioned.

The (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of a compound obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative and a glycidol with a bifunctional or higher isocyanate, is not particularly limited. The same thing as the (meth) acrylic acid derivative which has a hydroxyl group used as the raw material of the urethane (meth) acrylate obtained by making the said isocyanate react with the (meth) acrylic acid derivative which has a hydroxyl group is mentioned.

Specific examples of the compound obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with a bifunctional or higher isocyanate and glycidol include, for example, 134 parts by weight of trimethylolpropane, and BHT0.2 as a polymerization initiator. Parts by weight, 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate as reaction catalysts were added and reacted at 60 ° C. with stirring under reflux for 2 hours, followed by 25.5 parts by weight of 2-hydroxyethyl acrylate and glycidol It can be obtained by adding 111 parts by weight and reacting at 90 ° C. while refluxing for 2 hours while feeding air.

The epoxy resin is not particularly limited, and examples thereof include epichlorohydrin derivatives, cycloaliphatic epoxy resins, compounds obtained from the reaction of isocyanate and glycidol, and the like.

Examples of the epichlorohydrin derivative include bisphenol A type epoxy resins such as Epicoat 828EL and Epicoat 1004 (all manufactured by Japan Epoxy Resin Co.), and bisphenols such as Epicoat 806 and Epicoat 4004 (all manufactured by Japan Epoxy Resin). F-type epoxy resin, bisphenol S-type epoxy resin such as Epicron EXA1514 (manufactured by Dainippon Ink), 2,2′-diallylbisphenol A-type epoxy resin such as RE-810NM (manufactured by Nippon Kayaku Co., Ltd.), Epicron EXA7015 (large Resincinol-type epoxy resins such as hydrogenated bisphenol-type epoxy resins such as Nippon Ink Co., Ltd., propylene oxide-added bisphenol A-type epoxy resins such as EP-4000S (manufactured by Asahi Denka Co., Ltd.), and EX-201 (manufactured by Nagase ChemteX Corporation). Xylene resin, biphenyl type epoxy resin such as Epicoat YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.), sulfide type epoxy resin such as YSLV-50TE (manufactured by Toto Kasei Co., Ltd.), ether type such as YSLV-80DE (manufactured by Toto Kasei Co., Ltd.) Epoxy resins, dicyclopentadiene type epoxy resins such as EP-4088S (Asahi Denka Co.), naphthalene type epoxy resins such as Epicron HP4032, Epicron EXA-4700 (all manufactured by Dainippon Ink and Co.), Epicron N-770 (Large) Nihon Ink Co., Ltd.) phenol novolac type epoxy resin, Epicron N-670-EXP-S (Dainippon Ink Co., Ltd.) orthocresol novolak type epoxy resin, Epicron HP7200 (Dainippon Ink Co., Ltd.), etc. Pentadiene novolac epoxy Oil, 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.), Epicron 430 (Manufactured by Dainippon Ink Co., Ltd.), glycidylamine type epoxy resins such as TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Inc.), ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiklon 726 (manufactured by Dainippon Ink Co., Ltd.), Epolite 80MFA (Kyoeisha Chemical), Denacol EX-611 (manufactured by Nagase ChemteX), etc., alkyl polyol type epoxy resins, YR-450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.), Epolide PB (manufactured by Daicel Chemical) Rubber-modified epoxy resin, Denacol EX-147 (Nagase Chemtech) Glycidyl ester compounds such as Epicote YL-7000 (manufactured by Japan Epoxy Resin), other YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Tohto 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.

Moreover, although it does not specifically limit as said cycloaliphatic epoxy resin, As a commercial item, Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, EHPE (all are Daicel Chemical Co., Ltd.) etc. are mentioned, for example.

The compound obtained from the reaction between the isocyanate and glycidol is not particularly limited. For example, it can be obtained by reacting a compound having two isocyanate groups in the presence of a tin compound using 2 equivalents of glycidol as a catalyst. it can.

The isocyanate is not particularly limited. 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 (isocyanatophenyl) thiophosphate And tetramethylxylene diisocyanate, 1,6,10-undecane triisocyanate and the like.

Examples of the isocyanate include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate. The resulting chain-extended isocyanate compound can also be used.

Specific examples of the method for synthesizing the compound obtained from the reaction between the isocyanate and glycidol include, for example, 134 parts by weight of trimethylolpropane, 0.01 part by weight of dibutyltin dilaurate as a reaction catalyst, and 666 parts by weight of isophorone diisocyanate. And then reacting at 60 ° C. with reflux stirring for 2 hours, and then adding 222 parts by weight of glycidol and reacting at 90 ° C. with reflux stirring for 2 hours while feeding air.

In the sealing agent of the present invention, the curable resin is preferably a compound having two or more reactive groups in one molecule in order to reduce the uncured residue at the time of curing.

Moreover, in order to further suppress the elution of components into the liquid crystal before curing of the sealing agent of the present invention, the curable resin preferably has at least one hydrogen bonding functional group in one molecule.

The hydrogen-bonding functional group is not particularly limited, and examples thereof include an —OH group, —SH group, —NHR group (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof), —COOH group. , Functional groups such as —NHOH group, and residues such as —NHCO—, —NH—, —CONHCO—, —NH—NH—, etc. present in the molecule. An OH group is preferred.

The sealing agent of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited. For example, benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, KR-02 (Light Chemical Company) Etc.) can be suitably used. These photoinitiators may be used independently and may use 2 or more types together.

Examples of commercially available photopolymerization initiators include Irgacure 907, Irgacure 819, Irgacure 651, Irgacure 369 (all of which are manufactured by Ciba Specialty Chemicals), benzoin methyl ether, and benzoin. Examples include ethyl ether, benzoin isopropyl ether, and lucillin TPO (manufactured by BASF Japan). Among these, Irgacure 907, Irgacure 651, BIPE, and Lucillin TPO preferably have a molar extinction coefficient at 350 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ or more.

As content of the said photoinitiator, a minimum is 0.1 weight part with respect to a total of 100 weight part of the (meth) acrylate compound and curable resin which have a structure represented by General formula (1) mentioned above. The upper limit is 10 parts by weight. If the amount is less than 0.1 parts by weight, the ability of initiating photopolymerization is insufficient, and the above-described effects of the present invention cannot be obtained. If the amount exceeds 10 parts by weight, a large amount of unreacted radical polymerization initiator remains. The weather resistance of the sealing agent of the invention is deteriorated. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 5 parts by weight.

In addition to the above photopolymerization initiator, the sealant of the present invention may further contain a radical polymerization initiator that generates active radicals when irradiated with light.

The radical polymerization initiator preferably has a lower limit of the molar extinction coefficient at 350 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ and an upper limit of 100,000 M ⁻¹ · cm ⁻¹ . When it is less than 100 M ⁻¹ · cm ⁻¹ , there is a case where the shielding portion in a portion where the irradiation of ultraviolet rays is shielded by a black matrix (BM) or the like cannot be cured quickly and sufficiently. If it exceeds 100,000 M ⁻¹ · cm ⁻¹ , the surface of the portion that is directly irradiated when irradiated with ultraviolet rays is cured first, and the interior cannot be sufficiently cured. The part that is shielded from ultraviolet rays may not be cured. A more preferred lower limit is ^{200M -1} · ^cm -1, more preferred upper limit is 10,000 ^{M -1} · ^cm -1, still more preferred lower limit ^{300M -1} · ^cm -1, still more preferred upper limit ^3000M -1 · cm ^{- 1} .

The radical polymerization initiator preferably has a molar extinction coefficient at 450 nm measured in acetonitrile of 100 M ⁻¹ · cm ⁻¹ or less. If it exceeds 100 M ⁻¹ · cm ⁻¹ , active radicals are generated by light having a wavelength in the visible light range, and handling becomes very poor.

In the present specification, the molar extinction coefficient is ε (M ⁻¹ · cm ⁻¹ ) defined by the Lambert-Beer formula for the acetonitrile solution containing the radical polymerization initiator shown in the following formula (1). Means the value of

In the above formula (1), I is the intensity of transmitted light, I _o is the intensity of transmitted light of the acetonitrile pure solvent, c is the molar concentration (M), d is the thickness (cm) of the solution layer, and log (I _o / I) represents absorbance.

The radical polymerization initiator is not particularly limited as long as it satisfies the molar extinction coefficient. For example, the radical polymerization initiator has a radical polymerization initiation group such as a carbonyl group, a sulfur-containing group, an azo group, or an organic peroxide-containing group. Among them, a group having a structure represented by the following general formulas (5) to (8) is preferable.

In the general formulas (5) to (8), R ² , R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a hydroxyl group, or an alkoxyl group having 1 to 6 carbon atoms. , (Meth) acrylic group, phenyl group,

Represents an aromatic ring which may have an alkyl group having 1 to 6 carbon atoms or a halogen group.

Among these, a group having a structure represented by the general formula (5) is more preferable from the viewpoint of the generation efficiency of active radicals.

The radical polymerization initiator preferably contains a hydrogen bonding functional group.
The hydrogen bonding functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bonding properties, for example, OH group, NH ₂ group, NHR group (R is an aromatic or aliphatic hydrocarbon) And COOH groups, CONH ₂ groups, NHOH groups, and the like, and groups having residues such as NHCO bonds, NH bonds, CONHCO bonds, and NH—NH bonds in the molecule.
By having such a hydrogen bonding functional group, even when the uncured sealing agent of the present invention is in contact with the liquid crystal, the radical polymerization initiator is less likely to elute and liquid crystal contamination is less likely to occur.

The radical polymerization initiator preferably further has a reactive functional group capable of reacting with and binding to the curable resin.
The reactive functional group is not particularly limited as long as it is a functional group that can be bonded to the curable resin by a polymerization reaction, and examples thereof include cyclic ether groups such as epoxy groups and oxetanyl groups, (meth) acrylic groups, styryl groups, and the like. Can be mentioned. Of these, a (meth) acryl group or an epoxy group is preferred.
By having such a reactive functional group in the molecule, the radical polymerization initiator itself is fixed by forming a copolymer with the curable resin. Is not eluted into the liquid crystal, and is not outgassed by heating during liquid crystal realignment.

The sealing agent of the present invention may contain a thermosetting agent.
The thermosetting agent reacts and crosslinks the (meth) acrylic group of the (meth) acrylate compound having the structure represented by the general formula (1) by heating, and has an adhesive property after curing. , Has the role of improving moisture resistance.

Examples of such a thermosetting 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- Imidazole derivatives such as dihydroxymethylimidazole, modified aliphatic polyamines, tetrahydrophthalic anhydride, ethylene glycol Acid anhydrides such as Korubisu (anhydrotrimellitate), addition products such as the various amines and epoxy resins. These may be used alone or in combination of two or more. Of these, hydrazide compounds are preferably used.

As the thermosetting agent, a latent curing agent having a melting point of 100 ° C. or higher is preferably used. When a curing agent having a melting point of 100 ° C. or lower is used, the storage stability may be remarkably deteriorated.

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

The minimum with the preferable compounding quantity of the said thermosetting agent is 1 weight part with respect to a total of 100 weight part of the (meth) acrylate compound and curable resin which have a structure represented by the said General formula (1), and a preferable upper limit is 60. Parts by weight. If it is out of this range, the adhesiveness of the cured product is lowered, and the liquid crystal characteristic deterioration in the high temperature and high humidity operation test may be accelerated. A more preferred lower limit is 5 parts by weight, and a more preferred upper limit is 50 parts by weight.

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

The sealing agent of the present invention may contain a filler for the purpose of improving the adhesiveness due to the stress dispersion effect and improving the linear expansion coefficient. The filler is not particularly limited, for example, talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, diatomaceous earth, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, Magnesium hydroxide, aluminum hydroxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminum nitride and other inorganic fillers, polyester fine particles, polyurethane fine particles, vinyl heavy Organic fillers such as coalesced fine particles and acrylic polymer fine particles can be mentioned.

The sealing agent of the present invention further includes a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting thixotropy, a spacer such as polymer beads for adjusting the panel gap, and 3-P-chlorophenyl, if necessary. A curing accelerator such as -1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives may be contained.

The sealing agent of the present invention is, for example, mixed with the above-described curable resin, radical polymerization initiator and additives blended as necessary by a conventionally known method using three rolls, and uniformly dispersed. Methods and the like. At this time, in order to remove ionic impurities, it may be brought into contact with an ion-adsorbing solid such as a layered silicate mineral.

Since the sealing agent of the present invention is excellent in adhesion to a substrate in the production of a liquid crystal display element, the phenomenon of peeling between the substrate and the liquid crystal is unlikely to occur, and liquid crystal contamination is not caused. It can be suitably used for the production of a few liquid crystal display elements.

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

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 method for producing a liquid crystal display element using the sealing agent of the present invention and / or the vertical conducting material of the present invention is not particularly limited, and for example, it can be produced by the following method.
First, a rectangular seal pattern is formed on one of two transparent substrates with electrodes such as an ITO thin film by screen printing, dispenser application or the like using the sealing agent of the present invention and / or the vertical conduction material of the present invention. Next, fine droplets of liquid crystal are dropped and applied to the entire surface of the transparent substrate frame in an uncured state of the sealant, and the other transparent substrate is immediately overlaid and cured by irradiating the seal portion with ultraviolet rays. When the sealant or the like of the present invention has thermosetting properties, it is further cured by heating in an oven at 100 to 200 ° C. for 1 hour to complete the curing, thereby producing a liquid crystal display element.
A liquid crystal display element using the sealing agent of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
Furthermore, the manufacturing method of the liquid crystal display element of the present invention, that is, at least one of the two transparent substrates with electrodes is coated with the sealing agent of the present invention and / or the vertical conduction material of the present invention to form a seal pattern. In the process, the liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate with the sealant and / or the vertical conducting material of the present invention in an uncured state, and the other transparent substrate is immediately overlapped to form a seal portion. A method for producing a liquid crystal display element having a step of curing by irradiating with ultraviolet rays is also one aspect of the present invention.

According to the present invention, in the manufacture of a liquid crystal display element, the adhesiveness to the substrate is excellent, so that the peeling phenomenon between the substrate and the liquid crystal display device hardly occurs, and liquid crystal contamination is not caused. It is possible to provide a sealing agent for liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element that are optimal for manufacturing a liquid crystal display element.

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

(Synthesis of curable resin (A))
To the reaction flask, 116 parts by weight of 2-hydroxyethyl acrylate, 0.3 part by weight of p-methoxyphenol and 148 parts by weight of phthalic anhydride were added as a polymerization inhibitor, heated to 90 ° C. with a mantle heater, and stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added, and the resulting mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin (A).

(Synthesis of curable resin (B))
Place 116 parts by weight of 2-hydroxyethyl acrylate and 217 parts by weight of β-propiolactone in a reaction flask, add 0.3 part by weight of p-methoxyphenol as a polymerization inhibitor, and heat to 90 ° C. with a mantle heater for 5 hours. Stir. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added, and the resulting mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin (B).

(Synthesis of curable resin (C))
Place 116 parts by weight of 2-hydroxyethyl acrylate and 340 parts by weight of 7-butyl-2-oxepanone in a reaction flask, add 0.3 part by weight of p-methoxyphenol as a polymerization inhibitor, and heat to 90 ° C. with a mantle heater. Stir for 5 hours. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added, and the resulting mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin (C).

(Synthesis of curable resin (D))
To the reaction flask, 144 parts by weight of 4-hydroxybutyl acrylate, 0.3 part by weight of p-methoxyphenol and 148 parts by weight of phthalic anhydride were added as a polymerization inhibitor, heated to 90 ° C. with a mantle heater, and stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added and stirred at 90 ° C. for 5 hours to obtain a curable resin (D).

(Synthesis of curable resin (E))
In a reaction flask, 144 parts by weight of 4-hydroxybutyl acrylate and 217 parts by weight of β-propiolactone are added, 0.3 parts by weight of p-methoxyphenol is added as a polymerization inhibitor, heated to 90 ° C. with a mantle heater, and stirred for 5 hours. did. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added and stirred at 90 ° C. for 5 hours to obtain a curable resin (E).

(Synthesis of curable resin (F))
In a reaction flask, 144 parts by weight of 4-hydroxybutyl acrylate and 340 parts by weight of 7-butyl-2-oxepanone are added, 0.3 part by weight of p-methoxyphenol is added as a polymerization inhibitor, and heated to 90 ° C. with a mantle heater. Stir for 5 hours. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added, and the resulting mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin (F).

(Synthesis of curable resin (G))
In a reaction flask, 144 parts by weight of 4-hydroxybutyl acrylate and 680 parts by weight of 7-butyl-2-oxepanone are added, 0.3 parts by weight of p-methoxyphenol is added as a polymerization inhibitor, and heated to 90 ° C. with a mantle heater. Stir for 5 hours. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 170 parts by weight of bisphenol A diglycidyl ether was added and stirred at 90 ° C. for 5 hours to obtain a curable resin (G).

(Synthesis of curable resin (H))
In a reaction flask, 144 parts by weight of 4-hydroxybutyl acrylate and 340 parts by weight of 7-butyl-2-oxepanone are added, 0.3 part by weight of p-methoxyphenol is added as a polymerization inhibitor, and heated to 90 ° C. with a mantle heater. Stir for 5 hours. To the stirred product, 148 parts by weight of phthalic anhydride was added and further stirred for 5 hours.
Subsequently, 150 parts by weight of glycidyl phenyl ether was added, and the resulting mixture was stirred at 90 ° C. for 5 hours to obtain a curable resin (H).

(Synthesis of curable resin (I))
A reaction flask was charged with 72 parts by weight of acrylic acid and 312 parts by weight of bisphenol F diglycidyl ether, 0.3 parts by weight of p-methoxyphenol as a polymerization inhibitor, 0.3 parts by weight of triethylamine as a reaction catalyst, and a mantle heater. The mixture was heated to 90 ° C. and stirred for 5 hours to obtain a curable resin (I) in which one epoxy group remained.

(Example 1)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the curable resin (A) synthesized, 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700), were synthesized. 30 parts by weight of curable resin (B), 1 part by weight of silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a three-roll ceramic roll to obtain sealant A.

(Example 2)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the curable resin (B) synthesized, 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700), were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant B.

(Example 3)
3 parts by weight of a photoinitiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the curable resin (C) synthesized, 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700), were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant B.

Example 4
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the curable resin (D) synthesized, 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700), were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant D.

(Example 5)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the synthesized curable resin (E), 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700) were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant E.

(Example 6)
3 parts by weight of a photoinitiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the synthesized curable resin (F), 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec, EB3700), were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant F.

(Example 7)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the synthesized curable resin (G), 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec Co., Ltd., EB3700), were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a three ceramic roll to obtain sealant G.

(Example 8)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 20 parts by weight of the synthesized curable resin (H), 10 parts by weight of a bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec, EB3700) were synthesized. 30 parts by weight of curable resin (I), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatechs, SO-C1), and a thermosetting agent (Ajinomoto Fine Techno) VDH), 3.5 parts by weight, was blended and stirred with a planetary stirrer, and then uniformly dispersed with a ceramic three roll to obtain sealant H.

Example 9
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., Ltd., KR-02), 20 parts by weight of an epoxy acrylate having a long chain methylene group (manufactured by Daicel Cytec Co., Ltd., KRM7856), a bisphenol A type epoxy acrylate resin (Daicel UCB) Manufactured, EB3700) 10 parts by weight, synthesized curable resin (I) 30 parts by weight, silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) 1 part by weight, silica (manufactured by Admatechs, SO-C1) 15 parts by weight And 3.5 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., adipic acid dihydrazide), and after stirring with a planetary stirrer, uniformly disperse with a ceramic three roll to obtain a sealing agent I. Obtained.

(Example 10)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 30 parts by weight of an epoxy acrylate having a long chain methylene group (manufactured by Daicel Cytec, KRM7856), 30 parts by weight of the curable resin (I) synthesized, Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) 1 part by weight, silica (manufactured by Admatechs Corporation, SO-C1) 15 parts by weight, and thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., adipic acid dihydrazide) 3.5 parts by weight The components were blended and stirred with a planetary stirrer, and then uniformly dispersed with a three ceramic roll to obtain a sealing agent J.

(Example 11)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 40 parts by weight of an epoxy acrylate having a long chain methylene group (manufactured by Daicel Cytec Co., Ltd., KRM7856), 20 parts by weight of the curable resin (I) synthesized, Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403) 1 part by weight, silica (manufactured by Admatechs Corporation, SO-C1) 15 parts by weight, and thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., adipic acid dihydrazide) 2.3 weights After mixing the parts, the mixture was stirred with a planetary stirrer, and then uniformly dispersed with a three ceramic roll to obtain a sealant K.

(Comparative Example 1)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 30 parts by weight of bisphenol A type epoxy acrylate resin (manufactured by Daicel Cytec, EB3700), 30 parts by weight of the curable resin (I) synthesized, silane cup 1 part by weight of a ring agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), 15 parts by weight of silica (manufactured by Admatex, SO-C1), and 3.5 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., adipic acid dihydrazide) After blending and stirring with a planetary stirrer, a sealing agent L was obtained by uniformly dispersing with a ceramic three roll.

(Comparative Example 2)
3 parts by weight of a photopolymerization initiator (manufactured by Light Chemical Co., KR-02), 60 parts by weight of the synthesized epoxy acrylate (A), 1 part by weight of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403), silica (Admatex Corporation) 15 parts by weight manufactured by SO-C1) and 3.5 parts by weight of a thermosetting agent (manufactured by Otsuka Chemical Co., Ltd., adipic acid dihydrazide) were mixed and stirred with a planetary stirrer, and then with a ceramic three roll The sealing agent M was obtained by uniformly dispersing.

(Evaluation)
The following evaluation was performed using each sealing agent obtained in Examples 1 to 11 and Comparative Examples 1 and 2.

(Production of liquid crystal panel)
1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., Micropearl SI-H050, 5 μm) is dispersed in 100 parts by weight of each obtained sealant, and defoamed with a centrifugal defoamer (Awatron AW-1). As a sealing agent for a liquid crystal dropping method, it was applied to one of two alignment films and a substrate with a transparent electrode by a dispenser so that the line width of the sealing agent was 1 mm.
Subsequently, liquid droplets (manufactured by Chisso Co., Ltd., JC-5004LA) are dropped onto the entire surface of the sealing agent frame of the substrate with the transparent electrode, and the other color filter substrate with the transparent electrode is immediately pasted together. The film was temporarily cured by irradiation at 100 mW / cm ² for 30 seconds using a metal halide lamp. A main curing was performed by heating at 120 ° C. for 1 hour to prepare a liquid crystal display panel.

(Sealant dispensing evaluation (workability evaluation))
For each of the sealing agents obtained in Examples 1 to 11 and Comparative Examples 1 and 2, 20 liquid crystal panels each having a syringe discharge pressure of 300 kPa, a nozzle gap of 42 μm, a coating speed of 80 mm / sec, and a nozzle diameter of 0.4 mmφ were used. The number of defective panels due to disconnection was counted. The results are shown in Table 1. The evaluation was performed in the following four stages according to the number of defective panels.
◎: Number of defective panels 0: Number of defective panels 1-2: Δ: Number of defective panels 3-5 x: Number of defective panels 5 or more

(Liquid crystal panel evaluation (color unevenness evaluation))
About each obtained liquid crystal display panel, the liquid crystal orientation disorder in the sealant vicinity immediately after display panel preparation was confirmed visually. The alignment disorder was judged from the color unevenness of the display portion, and the evaluation was performed in the following four stages according to the degree of the color unevenness. The results are shown in Table 1. Note that liquid crystal panels with evaluations of ◎ and ○ are at a level where there is no problem in practical use.
◎: No color unevenness ○: Color unevenness is slightly △: Color unevenness is slightly ×: Color unevenness is considerable

(Multilayer substrate adhesion evaluation)
As shown in FIG. 1, the sealant 10 obtained in Examples 1 to 11 and Comparative Examples 1 and 2 is dispensed on a glass substrate 13 (90 mm × 90 mm) 30 mm inside from the end, and polyimide, ITO is used as the film 12. A glass substrate 11 (70 mm × 70 mm) on which chromium, a resin black matrix, and carbon were formed was stacked and bonded together under vacuum. Ultraviolet rays (100 mW / cm ² , 3000 mJ) were irradiated, followed by heating at 120 ° C. for 1 hour to cure the sealant, thereby obtaining an adhesion test piece.
When the edge part of the board | substrate of the produced adhesion test piece panel was pushed in at a speed | rate of 5 mm / min using the metal cylinder with a radius of 5 mm, the intensity | strength in case panel peeling occurred was measured and the peeling state was observed. The evaluation results are shown in Table 1.
In addition, when the glass substrate was cracked before the panel peeling occurred due to the strong adhesion of the sealing agent, the substrate was cracked. Further, as shown in FIG. 1, the peeling state is shown as “peeling A” when the glass substrate-film is peeled, and “peeling B” when the glass substrate-glass substrate is peeled off.

According to the present invention, in the manufacture of a liquid crystal display element, the adhesiveness to the substrate is excellent, so that the peeling phenomenon between the substrate and the liquid crystal display device hardly occurs, and liquid crystal contamination is not caused. It is possible to provide a sealing agent for a liquid crystal dropping method, a vertical conduction material, and a liquid crystal display element that are optimal for manufacturing a liquid crystal display element.

It is explanatory drawing which shows the evaluation method of the liquid crystal display element manufactured by the Example and the comparative example. It is sectional drawing which shows an example of a liquid crystal display element typically.

Explanation of symbols

10, 20 Sealing agent 11, 13 Glass substrate 12, 22 Film 21, 23 Substrate 24 Liquid crystal

Claims (5)

A sealing agent for liquid crystal dropping method comprising a (meth) acrylate compound having a structure represented by the following general formula (1), wherein 10 to 70% by weight of the curable resin component contained is the (meth) acrylate compound And the (meth) acrylate compound has a structure derived from a lactone.

In general formula (1), R ¹ represents a hydrogen atom or a methyl group, X represents one selected from the group represented by the following chemical formula (2), and Y represents the following chemical formula (3). 1 represents one selected from the group represented, A represents a ring-opening structure of a cyclic lactone, and n is 1 .

The sealing agent for liquid crystal dropping method according to claim 1, wherein the (meth) acrylate compound has a segment in which three or more methylene groups are connected. 3. The sealing agent for liquid crystal dropping method according to claim 1, wherein the (meth) acrylate compound is a polyfunctional (meth) acrylate compound having two or more (meth) acryl groups. A vertical conduction material comprising the sealing agent for liquid crystal dropping method according to claim 1, 2 or 3, and conductive fine particles. A liquid crystal display element comprising the sealing agent for a liquid crystal dropping method according to claim 1, 2 or 3, and / or the vertical conduction material according to claim 4.

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