TWI766068B - Liquid crystal display element sealing compound, vertical conduction material, and liquid crystal display element - Google Patents

Abstract

An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in curability to long-wavelength light, and can suppress the generation|occurence|production of a foreign material. Moreover, the objective of this invention is to provide the up-down conduction material and liquid crystal display element using this sealing compound for liquid crystal display elements.

The present invention relates to a sealing agent for liquid crystal display elements, which contains a curable resin, a photopolymerization initiator and a maleimide compound, and the extinction coefficient of the photopolymerization initiator at a wavelength of 430 nm is 0.8×10 ² mL /g‧cm or more.

Description

Liquid crystal display element sealing compound, vertical conduction material, and liquid crystal display element

The present invention relates to a sealing compound for liquid crystal display elements which is excellent in curability to long-wavelength light and can suppress the generation of foreign matter. Moreover, this invention relates to the up-down conduction material and liquid crystal display element using this sealing compound for liquid crystal display elements.

In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display unit, the methods disclosed in Patent Document 1 and Patent Document 2 have been used from the viewpoints of shortening tact time and optimizing the amount of liquid crystal used. The liquid crystal dropping method called the dropping method of the photothermal combined use hardening sealant.

In the dropping method, first, a frame-shaped sealing pattern is formed by dispensing on one of the two transparent substrates with electrodes. Next, droplets of liquid crystal are dropped into the entire frame of the transparent substrate in a state where the sealant is not cured, another transparent substrate is immediately bonded, and the sealing portion is irradiated with light such as ultraviolet rays to perform pre-curing. Then, it heats at the time of liquid crystal annealing, and it hardens|cures substantially, and manufactures a liquid crystal display element. If the substrates are bonded under reduced pressure, a liquid crystal display element can be produced with extremely high efficiency, and at present, the dropping method is the mainstream of the liquid crystal display element production method.

In addition, in the modern age when various mobile devices with liquid crystal panels, such as mobile phones and portable game consoles, are popularized, the miniaturization of devices is the most urgent issue. As a method for miniaturization of the device, there can be mentioned the narrowing of the frame of the liquid crystal display portion, for example, the step of arranging the position of the sealing portion below the black matrix (hereinafter, also referred to as narrow frame design).

However, in the narrow frame design, since the encapsulant is disposed directly under the black matrix, if the dripping method is performed, the light irradiated when the encapsulant is photocured is blocked, and the light does not reach the inside of the encapsulant. The problem that hardening becomes insufficient. Therefore, if the curing of the sealant is insufficient, the uncured sealant component is eluted into the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in the problem of liquid crystal contamination.

Moreover, as a method of photohardening a sealing compound normally, it irradiates an ultraviolet-ray, but in a liquid-crystal dropping method, since a sealing compound is hardened after dripping a liquid crystal, there exists a problem that a liquid crystal is degraded by ultraviolet-ray irradiation. In order to prevent the deterioration of the liquid crystal caused by ultraviolet rays, it is considered that a photopolymerization initiator excellent in reactivity to long-wavelength light is blended, and photohardening is performed by long-wavelength light passing through a cut filter or the like. However, in the case of using such a photopolymerization initiator, there are problems such as the following: the sealing agent is partially cured by a small amount of light before the photocuring step, and foreign matter is generated.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2001-133794

Patent Document 2: International Publication No. 02/092718

An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in curability to long-wavelength light, and can suppress the generation|occurence|production of a foreign material. Moreover, the objective of this invention is to provide the up-down conduction material and liquid crystal display element using this sealing compound for liquid crystal display elements.

The present invention relates to a sealing agent for liquid crystal display elements, which contains a curable resin, a photopolymerization initiator and a maleimide compound, and the extinction coefficient of the photopolymerization initiator at a wavelength of 430 nm is 0.8×10 ² mL /g‧cm or more.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention have surprisingly found that by blending a maleimide compound in a sealant, even if a photopolymerization initiator excellent in reactivity to long-wavelength light is used, it is possible to suppress the effects of light The sealing compound for liquid crystal display elements which generate|occur|produce the foreign material by local hardening of a sealing compound before a hardening process has completed this invention.

The sealing compound for liquid crystal display elements of this invention contains a photopolymerization initiator.

The extinction coefficient of the above-mentioned photopolymerization initiator at a wavelength of 430 nm is 0.8×10 ² mL/g·cm or more. Hereinafter, the photopolymerization initiator whose extinction coefficient at a wavelength of 430 nm is 0.8×10 ² mL/g·cm or more is also referred to as the “photopolymerization initiator of the present invention”.

Since the extinction coefficient of the photopolymerization initiator of the present invention at a wavelength of 430 nm is 0.8×10 ² mL/g·cm or more, the sealing compound for liquid crystal display elements of the present invention is excellent in curability to long-wavelength light. The preferred lower limit of the extinction coefficient of the photopolymerization initiator of the present invention at a wavelength of 430 nm is 1.0×10 ² mL/g·cm.

In addition, the preferred upper limit of the extinction coefficient of the photopolymerization initiator of the present invention at a wavelength of 430 nm is 1.0×10 ⁴ mL/g·cm.

In addition, the said extinction coefficient can be measured using a spectrophotometer after dissolving the compound to be measured in a solvent so that the density|concentration may become 0.1 mg/mL.

The above-mentioned solvent is not particularly limited as long as it dissolves the compound to be measured and does not absorb light at the absorption wavelength to be measured, and examples thereof include acetonitrile, methanol, and the like.

The photopolymerization initiator of the present invention is preferably a compound having a structure represented by the following formula (1) from the viewpoint of being excellent in reactivity to long-wavelength light, more preferably one molecule of this formula The compound of the structure represented by (1) is more preferably a compound represented by the following formula (2-1) and/or a compound represented by the following formula (2-2).

In formula (1), * is a bonding position.

In formulas (2-1) and (2-2), R is a structure derived from a monofunctional epoxy compound. In formula (2-1), m is an integer of 1 to 5.

-9-酮與單官能環氧化合物攪拌6~72小時一面進行反應之方法等。 As a method for producing the compound represented by the above (2-1), for example, in the presence of an alkaline catalyst, 2-(carboxymethoxy)-9H- sulfur

- A method of reacting 9-ketone and a monofunctional epoxy compound while stirring for 6 to 72 hours.

-9-酮與單官能環氧化合物攪拌6~72小時一面進行反應之方法等。 Moreover, as a method for producing the compound represented by the above (2-2), for example, in the presence of an alkaline catalyst, 2-hydroxy-9H-sulfur is added under the conditions of 80°C or higher and 130°C or lower.

- A method of reacting 9-ketone and a monofunctional epoxy compound while stirring for 6 to 72 hours.

-9-酮及2-羥基-9H-硫

-9-酮亦稱為「原料9-氧硫

衍生物」。 Below, 2-(carboxymethoxy)-9H-thio

-9-keto and 2-hydroxy-9H-thio

-9-ketone is also known as "raw material 9-oxysulfur

derivative".

It is preferable that the said monofunctional epoxy compound is an aromatic ring which has at least 1 or more of C1 or more substituents, or an aliphatic ring which has at least 1 or more C1 or more substituents.

Examples of the above-mentioned aromatic ring or the above-mentioned aliphatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring, a norbornene ring, a tricyclic ring At least one hydrogen atom in an aromatic ring such as a cyclodecane ring or an aliphatic ring is substituted with a substituent having 1 or more carbon atoms.

The substituent having 1 or more carbon atoms may be linear or branched. When the substituent having 1 or more carbon atoms is linear, it is preferably 6 or more carbon atoms, more preferably 10 or more carbon atoms. When the substituent having 1 or more carbon atoms is branched, it is preferably 4 or more carbon atoms. Moreover, it is preferable that the carbon number of the C1 or more substituent which the said aromatic ring or the said aliphatic ring has is the number which becomes the following 300 or less of the molecular weight of the said monofunctional epoxy compound.

An alkyl group is preferable as a C1 or more substituent which the said aromatic ring or the said aliphatic ring has.

As the above-mentioned monofunctional epoxy compound, for example, alkyl phenyl glycidyl ether, tosylate having glycidyl group, 2-epoxy-4-vinylcyclohexane, methacrylic acid 3, 4-Epoxy cyclohexyl methyl ester, etc.

As said alkyl phenyl glycidyl ether, for example, o-methyl phenyl glycidyl ether, m-methyl phenyl glycidyl ether, p-methyl phenyl glycidyl ether, p-tertiary butyl Phenyl glycidyl ether, etc.

Among the above-mentioned monofunctional epoxy compounds, for example, a monofunctional epoxy compound manufactured by Nagase Kasei Co., Ltd., a monofunctional epoxy compound manufactured by Adeka Co., Ltd., a monofunctional epoxy compound manufactured by Mitsubishi Chemical Corporation, Monofunctional epoxy compound manufactured by Tokyo Chemical Industry Co., Ltd., monofunctional epoxy compound manufactured by Daicel Corporation, etc.

Denacol EX-146 etc. are mentioned as a monofunctional epoxy compound manufactured by the said Nagase Chemical Co., Ltd., for example.

As a monofunctional epoxy compound by the said ADEKA company, ED-509S, ED-509E, ED-529 etc. are mentioned, for example.

As a monofunctional epoxy compound by the said Mitsubishi Chemical Corporation, YED-122 etc. are mentioned, for example.

As the monofunctional epoxy compound manufactured by the above-mentioned Tokyo Chemical Industry Co., Ltd., glycidyl 2-methoxyphenyl ether, 1-methyl-1, 2- epoxycyclohexane, etc. are mentioned, for example.

As a monofunctional epoxy compound manufactured by the said Daicel company, Celloxide 2000, Cyclomer M100, etc. are mentioned, for example.

From the viewpoint of the compatibility between the photopolymerization initiator of the present invention and the curable resin, the molecular weight of the monofunctional epoxy compound is preferably 300 or less.

衍生物與上述單官能環氧化合物進行反應時之使用比率，較佳為以莫耳比計，原料9-氧硫

衍生物：單官能環氧化合物=1：1~10：1。藉由上述原料9-氧硫

衍生物與上述單官能環氧化合物之使用比率為該範圍，可以高產率製造上述式(2-1)表示之化合物或上述式(2-2)表示之化合物。 As the above-mentioned raw material 9-oxosulfur

The use ratio of the derivative when reacting with the above-mentioned monofunctional epoxy compound is preferably in molar ratio, the raw material 9-oxysulfur

Derivatives: monofunctional epoxy compounds = 1:1~10:1. By the above-mentioned raw material 9-oxosulfur

When the use ratio of the derivative to the above-mentioned monofunctional epoxy compound is in this range, the compound represented by the above formula (2-1) or the compound represented by the above formula (2-2) can be produced in high yield.

衍生物與上述單官能環氧化合物進行反應時使用之鹼性觸媒，較佳為三價有機磷酸化合物及/或胺化合物。 As the above-mentioned raw material 9-oxosulfur

The basic catalyst used when the derivative reacts with the above-mentioned monofunctional epoxy compound is preferably a trivalent organic phosphoric acid compound and/or an amine compound.

Specific examples of the basic catalyst include triphenylphosphine, triethylamine, tripropylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, triethylamine Methylcetylammonium bromide, tetrabutylammonium bromide, trimethylbutylphosphonium bromide, tetrabutylphosphonium bromide, etc. Among them, triphenylphosphine is preferable.

In addition, the above-mentioned basic catalyst may be supported by a polymer, and may be used in the form of a polymer-supported basic catalyst.

Examples of the photopolymerization initiator of the present invention other than the compound having the structure represented by the above formula (1) include bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and the like.

The content of the photopolymerization initiator of the present invention is 100 parts by weight in total of the curable resin and the maleimide compound, the preferred lower limit is 0.1 parts by weight, and the preferred upper limit is 20 parts by weight. By making content of the photopolymerization initiator of this invention 0.1 weight part or more, the sealing compound for liquid crystal display elements obtained becomes the thing which is more excellent in hardenability with respect to the light of a long wavelength. By making content of the photopolymerization initiator of this invention 20 weight part or less, the sealing compound for liquid crystal display elements obtained becomes the thing which is more excellent in the effect of suppressing generation|occurrence|production of a foreign material. The more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.2 parts by weight, and the more preferable lower limit is 0.3 parts by weight, and the more preferable lower limit is 0.5 parts by weight, and the more preferable lower limit is 1 part by weight. The more preferable upper limit of the content of the photopolymerization initiator of the present invention is 10 parts by weight, and the further preferable upper limit is 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a thermal polymerization initiator in the range which does not inhibit the objective of this invention.

As said thermal polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, a polymer azo initiator composed of a polymer azo compound is preferable.

In addition, in this specification, the above-mentioned "polymer azo compound" means having an azo group and generating a radical which can harden (meth)acryloyloxy groups by heat and has a number-average molecular weight of 300 or more. compound.

The preferable lower limit of the number average molecular weight of the above-mentioned polymer azo compound is 1,000, and the preferable upper limit is 300,000. By making the number average molecular weight of the said polymer azo compound into this range, liquid crystal contamination can be suppressed, and it can mix easily with a curable resin. A more preferable lower limit of the number average molecular weight of the polymer azo compound is 5,000, a more preferable upper limit is 100,000, a further preferable lower limit is 10,000, and a further preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is the value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC), using tetrahydrofuran as a solvent. As a column for measuring the number average molecular weight in terms of polystyrene by GPC, Shodex LF-804 (manufactured by Showa Denko Co., Ltd.) and the like can be mentioned, for example.

As said high molecular azo compound, the thing which has the structure which several units, such as a polyalkylene oxide (polyalkylene oxide) and a polydimethylsiloxane are bonded via an azo group, is mentioned, for example.

As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group, those having a polyethylene oxide structure are preferred.

As said polymer azo compound, the polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation polymer of nitrogen bis (4-cyanovaleric acid) and polydimethylsiloxane with terminal amine group, etc.

Among the above-mentioned high molecular azo compounds, for example, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like can be mentioned.

Moreover, as an azo compound which is not a polymer, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) etc. are mentioned, for example.

As the above-mentioned organic peroxide, for example, ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, ester peroxide, diacyl peroxide, Peroxydicarbonate, etc.

The content of the above-mentioned thermal polymerization initiator is preferably 0.05 parts by weight and the upper limit is preferably 10 parts by weight relative to 100 parts by weight of the total of the curable resin and the maleimide compound. By making content of the said thermal polymerization initiator 0.05 weight part or more, the sealing compound for liquid crystal display elements of this invention becomes the thing which is more excellent in thermosetting property. By making content of the said thermal polymerization initiator 10 weight part or less, the sealing compound for liquid crystal display elements of this invention becomes the thing which is more excellent in low liquid crystal contamination property or storage stability. A more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferable upper limit is 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention contains curable resin.

As described below, in the present invention, the maleimide compound is not included in the aforementioned curable resin.

The said curable resin preferably contains a (meth)acrylic compound.

As said (meth)acrylic compound, (meth)acrylate compound, epoxy (meth)acrylate, (meth)acrylate urethane, etc. are mentioned, for example. Among them, epoxy (meth)acrylate is preferred. Moreover, it is preferable that the said (meth)acrylic acid compound has the point which has high reactivity in a molecule|numerator of 2 or more (meth)acryloyl groups.

In addition, in this specification, the above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryloyl group, and the above-mentioned "(meth)acrylic acid compound" means a compound having a (meth)acryloyl group. group) Acryloyl" means acryl or methacryloyl. In addition, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. Furthermore, the said "epoxy (meth)acrylate" shows the compound which made all the epoxy groups in an epoxy compound react with (meth)acrylic acid.

Examples of monofunctional ones among the above-mentioned (meth)acrylate compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate. Esters, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , isononyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, cyclohexyl (meth)acrylate, ( Isobornyl meth)acrylate, dicyclopentenyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxy (meth)acrylate ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H (meth)acrylate -Octafluoropentyl ester, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(methyl) succinate ) Acryloyloxyethyl ester, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate, 2-hydroxypropyl phthalate, phosphoric acid 2-(meth)acryloyloxyethyl ester, glycidyl (meth)acrylate, etc.

Moreover, as a bifunctional thing among the said (meth)acrylate compounds, 1, 3- butanediol di(meth)acrylate, 1, 4- butanediol di(meth)acrylate are mentioned, for example , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate (meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2 -Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol Alcohol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloyloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone glycol di(meth)acrylate, polybutadiene glycol di(meth)acrylate, etc.

Moreover, as the above-mentioned (meth)acrylate compound, trimethylolpropane tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(methyl) are mentioned, for example. ) Acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanurate Acid tri(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, neotaerythritol tri(meth)acrylate, phosphate tri[(methyl) ) Acryloyloxyethyl] ester, bis(trimethylolpropane)tetra(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipivalerythritol penta(meth)acrylate , Dipionaerythritol hexa(meth)acrylate, etc.

As said epoxy (meth)acrylate, what obtained by making an epoxy compound and (meth)acrylic acid react in the presence of a basic catalyst in accordance with a conventional method, etc. are mentioned, for example.

As the epoxy compound used as a raw material for synthesizing the above epoxy (meth)acrylate, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2 ,2'-Diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type ring Oxygen compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolak type epoxy compound, o-cresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthol novolak type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound Compounds, rubber-modified epoxy compounds, glycidyl ester compounds, etc.

As what is marketed among the said bisphenol A type epoxy compounds, jER 828EL, jER 1004 (all are made by Mitsubishi Chemical Corporation), Epiclon 850CRP (made by DIC Corporation), etc. are mentioned, for example.

As what is marketed among the said bisphenol F type epoxy compounds, jER 806, jER 4004 (all are made by Mitsubishi Chemical Corporation), etc. are mentioned, for example.

As what is marketed among the said bisphenol S type epoxy compounds, Epiclon EXA1514 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said 2,2'- diallyl bisphenol A type epoxy compounds, RE-810NM (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said hydrogenated bisphenol type epoxy compounds, Epiclon EXA7015 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said propylene oxide addition bisphenol A type epoxy compounds, EP-4000S (made by ADEKA company) etc. are mentioned, for example.

As what is marketed among the said resorcinol type epoxy compounds, EX-201 (made by Nagase Chemical Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said biphenyl type epoxy compounds, jER YX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.

As what is marketed among the said sulfide type epoxy compounds, YSLV-50TE (made by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said diphenyl ether type epoxy compounds, YSLV-80DE (made by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said dicyclopentadiene type epoxy compounds, EP-4088S (made by ADEKA company) etc. are mentioned, for example.

As what is marketed among the said naphthalene type epoxy compounds, Epiclon HP4032, Epiclon EXA-4700 (all are made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said phenol novolak-type epoxy compounds, Epiclon N-770 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said o-cresol novolak-type epoxy compounds, Epiclon N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said dicyclopentadiene novolak-type epoxy compounds, Epiclon HP7200 (made by DIC Corporation) etc. are mentioned, for example.

As what is marketed among the said biphenyl novolak-type epoxy compounds, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.

As what is marketed among the said naphthol novolak-type epoxy compounds, ESN-165S (made by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) etc. is mentioned, for example.

As what is marketed among the said glycidylamine type epoxy compounds, jER 630 (made by Mitsubishi Chemical Corporation), Epiclon 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example.

Among the above-mentioned alkyl polyol type epoxy compounds, for example, ZX-1542 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Epiclon 726 (manufactured by DIC Corporation), and Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) are listed, for example. ), Denacol EX-611 (manufactured by Nagase Chemical Co., Ltd.), etc.

As a commercial thing among the said rubber-modified epoxy compounds, for example, YR-450, YR-207 (both are manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); Epolead PB (manufactured by Daicel Corporation), etc. are mentioned.

As what is marketed among the said glycidyl ester compounds, Denacol EX-147 (made by Nagase Chemical Co., Ltd.) etc. are mentioned, for example.

Examples of other commercially available epoxy compounds include: YDC-1312, YSLV-80XY, and YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.); XAC4151 (manufactured by Asahi Kasei Corporation); jER 1031, jER 1032 (all manufactured by Mitsubishi Chemical Corporation); EXA-7120 (manufactured by DIC Corporation); TEPIC (manufactured by Nissan Chemical Corporation), etc.

Among the above-mentioned epoxy (meth)acrylates, for example, epoxy (meth)acrylates manufactured by Daicel Allnex Corporation and epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Industry Co., Ltd. may be mentioned. Ester, epoxy (meth)acrylate manufactured by Kyōeisha Chemical Co., Ltd., epoxy (meth)acrylate manufactured by Nagase Chemical Co., Ltd., etc.

Examples of epoxy (meth)acrylates manufactured by Daicel allnex include EBECRYL 860, EBECRYL 3200, EBECRYL 3201, EBECRYL 3412, EBECRYL 3600, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, EBECRYL 3800, EBECRYL 6040, EBECRYL RDX63182, etc.

As epoxy (meth)acrylate manufactured by the said Shin-Nakamura Chemical Industry Co., Ltd., EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 etc. are mentioned, for example.

Examples of epoxy (meth)acrylates manufactured by Kyōeisha Chemical Co., Ltd. include Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester 400EA, etc.

As epoxy (meth)acrylate manufactured by the said Nagase Chemical Co., Ltd., Denacol Acrylate DA-141, Denacol Acrylate DA-314, Denacol Acrylate DA-911 etc. are mentioned, for example.

The above-mentioned (meth)acrylate urethane can be prepared, for example, by mixing 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound having 2 isocyanate groups in the presence of a catalytic amount of a tin-based compound. Equivalent to react to obtain.

As said isocyanate compound, isophorone diisocyanate, 2, 4- tolyl diisocyanate, 2, 6- tolyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene can be mentioned, for example diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, bitoluidine diisocyanate, stubble diisocyanate Isocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethyl ethylene diisocyanate, 1,6,11- Undecane triisocyanate, etc.

Moreover, the chain-extended isocyanate compound obtained by the reaction of a polyhydric alcohol and an excess isocyanate compound can also be used as the said isocyanate compound.

As said polyol, ethylene glycol, propylene glycol, glycerol, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, etc. are mentioned, for example.

As the (meth)acrylic acid derivative having the above-mentioned hydroxyl group, for example, hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of dihydric alcohol, and mono(meth)acrylic acid of trihydric alcohol can be mentioned. ester or di(meth)acrylate, epoxy (meth)acrylate, etc.

Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and the like.

As said dihydric alcohol, ethylene glycol, propylene glycol, 1, 3- propylene glycol, 1, 3- butanediol, 1, 4- butanediol, polyethylene glycol, etc. are mentioned, for example.

As said trihydric alcohol, trimethylolethane, trimethylolpropane, glycerol etc. are mentioned, for example.

As said epoxy (meth)acrylate, bisphenol A type epoxy acrylate etc. are mentioned, for example.

Among the above-mentioned (meth)acrylate urethanes, for example, (meth)acrylate urethanes manufactured by Toagosei Co., Ltd., and (meth)acrylic acid manufactured by Daicel Allnex Corporation may be mentioned. Urethane, (meth)acrylate urethane manufactured by Negami Kogyo Co., Ltd., (meth)acrylate urethane manufactured by Shin-Nakamura Chemical Industry Co., Ltd., (meth)acrylate manufactured by Kyeisha Chemical Co., Ltd. ) acrylic urethane, etc.

As the (meth)acrylate urethane manufactured by the said Toagosei Corporation, M-1100, M-1200, M-1210, M-1600 etc. are mentioned, for example.

Examples of (meth)acrylic urethanes manufactured by Daicel allnex include EBECRYL 210, EBECRYL 220, EBECRYL 230, EBECRYL 270, EBECRYL 1290, EBECRYL 2220, EBECRYL 4827, EBECRYL 4842, EBECRYL 4858 , EBECRYL 5129, EBECRYL 6700, EBECRYL 8402, EBECRYL 8803, EBECRYL 8804, EBECRYL 8807, EBECRYL 9260, etc.

Examples of (meth)acrylic urethanes manufactured by Negami Kogyo include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN- 7100, Artresin UN-9000A, Artresin UN-9000H, etc.

Examples of (meth)acrylate urethanes manufactured by the above-mentioned Shin-Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U- 6LPA, U-10H, U-15HA, U-108, U-108A, U-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, etc.

Examples of (meth)acrylate urethanes manufactured by Kyōeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA- 306I, UA-306T, etc.

It is preferable that the said curable resin further contains an epoxy compound for the purpose of improving the adhesiveness of the sealing compound for liquid crystal display elements obtained. As said epoxy compound, the epoxy compound which becomes a raw material for synthesizing the said epoxy (meth)acrylate, a partial (meth)acrylic-acid modified epoxy compound, etc. are mentioned, for example.

In addition, in this specification, the above-mentioned partial (meth)acrylic acid-modified epoxy compound means a compound having at least one epoxy group and one (meth)acryloyl group in one molecule, for example, by using It is obtained by reacting a part of epoxy groups of an epoxy compound having two or more epoxy groups in one molecule with (meth)acrylic acid.

When the sealing compound for liquid crystal display elements of this invention contains the said epoxy compound, it is preferable to use the (meth)acryloyl group in the sum total of the (meth)acryloyl group and the epoxy group in the said curable resin. The ratio of 30 mol % or more and 95 mol % or less. By making the ratio of the said (meth)acryloyl group into 30 mol% or more, the sealing compound for liquid crystal display elements obtained becomes the thing more excellent in low liquid-crystal contamination property. By making the ratio of the said (meth)acryloyl group into 95 mol% or less, the sealing compound for liquid crystal display elements obtained becomes the thing which is more excellent in adhesiveness.

From the viewpoint of further suppressing the contamination of liquid crystals, the curable resin is preferably one having hydrogen-bonding units such as -OH group, -NH- group, and -NH ₂ group.

The sealing compound for liquid crystal display elements of this invention contains a maleimide compound.

By using the said maleimide compound, even if the sealing compound for liquid crystal display elements of this invention uses the photopolymerization initiator of this invention, generation|occurence|production of a foreign material can be suppressed.

In addition, in this invention, the said maleimide compound is not contained in curable resin.

The preferred lower limit of the molecular weight of the maleimide compound is 400. By making the molecular weight of the above-mentioned maleimide compound 400 or more, the obtained sealing compound for liquid crystal display elements is more excellent in the effect of simultaneously realizing the improvement of the curability of long-wavelength light and the suppression of foreign matter generation. By. A more preferable lower limit of the molecular weight of the above-mentioned maleimide compound is 500.

In addition, from the viewpoint of reactivity, a preferable upper limit of the molecular weight of the maleimide compound is 1,500, and a more preferable upper limit is 1,000.

From the viewpoint of reactivity, the above-mentioned maleimide compound is preferably a polyfunctional maleimide compound having two or more maleimide groups in one molecule.

As the above-mentioned polyfunctional maleimide compound, a compound represented by the following formula (3) or a compound represented by the following formula (4) can be preferably used.

In formula (3), R ¹ represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 2 to 40.

In formula (4), R ² represents a divalent aliphatic group having 1 to 40 carbon atoms.

In the above formula (4), the carbon number of R ² is preferably 12-36. Moreover, R ² preferably has an aliphatic ring.

Specific examples of the compound represented by the above formula (4) include 1,4-bis(maleimide)butane, 1,20-bismaleimide-10, 11-dioctyleicosane (a compound represented by the following formula (5-1)), 1-heptyl-maleimide-2-n-octylmaleimide-4-octyl -5-heptylcyclohexane (a compound represented by the following formula (5-2)), 1,2-diendenoctylmaleimide-3-octyl-4-hexylcyclohexane (the following compound represented by formula (5-3)) and the like.

The compound represented by the above formula (4) can be synthesized, for example, by the method described in the specification of US Pat. No. 5,973,166.

Among the above-mentioned maleimide compounds, examples of monofunctional maleimide compounds having one maleimide group in one molecule include N-biotinyl- N'-(3-maleimidopropionyl)-3,6-dioxooctane-1,8-diamine and the like.

The preferred lower limit of the content of the above-mentioned maleimide compound in 100 parts by weight of the total of the above-mentioned curable resin and the above-mentioned maleimide compound is 2 parts by weight, and a preferred upper limit is 50 parts by weight. By making content of the said maleimide compound into 2 weight part or more, the sealing compound for liquid crystal display elements obtained becomes the thing which is more excellent in the effect of suppressing generation|occurrence|production of a foreign material. By making content of the said maleimide compound 50 weight part or less, the sealing compound for liquid crystal display elements obtained becomes the thing which is more excellent in photocurability. A more preferable lower limit of the content of the maleimide compound is 3 parts by weight, a further preferable lower limit is 5 parts by weight, and an especially preferable lower limit is 10 parts by weight. The more preferable upper limit of the content of the above-mentioned maleimide compound is 45 parts by weight, and the more preferable upper limit is 40 parts by weight, and the more preferable upper limit is 35 parts by weight, the most preferable upper limit is 30 parts by weight, and the best upper limit is 25 parts by weight.

The sealing compound for liquid crystal display elements of this invention may contain a thermosetting agent.

As said thermosetting agent, an organic acid hydrazine, an imidazole derivative, an amine compound, a polyphenol type compound, an acid anhydride etc. are mentioned, for example. Among them, organic acid hydrazine can be preferably used.

As said organic acid hydrazine, sebacic acid hydrazine, isophthalic acid dihydrazine, adipic acid hydrazine, malonic acid hydrazine, etc. are mentioned, for example.

As what is marketed among the said organic acid hydrazine, the organic acid hydrazine by Otsuka Chemical Co., Ltd., the organic acid hydrazine by Ajinomoto Fine-Techno company, etc. are mentioned, for example.

As the organic acid hydrazine manufactured by the above-mentioned Otsuka Chemical Co., Ltd., SDH, ADH, etc. are mentioned, for example.

As the organic acid hydrazine produced by the above-mentioned Ajinomoto Fine-Techno Co., Ltd., Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J, etc. are mentioned, for example.

The content of the above-mentioned thermosetting agent is preferably 1 part by weight and the upper limit is preferably 50 parts by weight relative to 100 parts by weight of the total of the curable resin and the maleimide compound. By making content of the said thermosetting agent into this range, thermosetting property can be made more excellent, without deteriorating coatability etc. of the sealing compound for liquid crystal display elements obtained. A more preferable upper limit of the content of the above thermosetting agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of the present invention preferably contains a filler for the purpose of increasing the viscosity, improving the adhesiveness due to the stress dispersion effect, and improving the coefficient of linear expansion.

As the above-mentioned filler, an inorganic filler or an organic filler can be used.

Examples of the inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide , magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

As said organic filler, polyester microparticles|fine-particles, polyurethane microparticles|fine-particles, vinyl polymer microparticles|fine-particles, acrylic polymer microparticles|fine-particles etc. are mentioned, for example.

The above-mentioned fillers may be used alone or in combination of two or more.

The preferable lower limit of the content of the above-mentioned filler in 100 parts by weight of the sealing agent for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. By making content of the said filler into this range, when coating property etc. are not deteriorated, effects, such as improvement of adhesiveness, are more excellent. A more preferable lower limit of the content of the above filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

It is preferable that the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent. The above-mentioned silane coupling agent mainly functions as an adhering aid for favorably adhering a sealant to a substrate and the like.

As the above-mentioned silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isopropyltrimethoxysilane, and 3-isopropyltrimethoxysilane can be preferably used. Cyanopropyl trimethoxysilane, etc. These systems are excellent in the effect of improving adhesion to substrates and the like, and by chemically bonding with the curable resin, the curable resin can be inhibited from flowing out into the liquid crystal.

The preferable lower limit of the content of the above-mentioned silane coupling agent in 100 parts by weight of the sealing agent for liquid crystal display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. By making content of the said silane coupling agent into this range, generation|occurrence|production of liquid crystal contamination is suppressed, and the effect of improving adhesiveness is more excellent. A more preferable lower limit of the content of the above-mentioned silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

The sealing compound for liquid crystal display elements of this invention may further contain additives, such as a reactive diluent, a thixotropic agent, a spacer, a hardening accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor, as needed.

As a method of manufacturing the sealing compound for liquid crystal display elements of this invention, the following method etc. are mentioned, for example: Using mixers, such as a homodisperser, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll mill, etc. , Mix the curable resin, the photopolymerization initiator of the present invention, the maleimide compound, and the silane coupling agent added as needed.

A vertical conduction material can be produced by mixing electroconductive fine particles with the sealing compound for liquid crystal display elements of this invention. Moreover, it is also one of this invention to contain the sealing compound for liquid crystal display elements of this invention, and the up-down conduction material of electroconductive microparticles|fine-particles.

As said electroconductive fine particle, the thing which formed the electroconductive metal layer on the surface of a resin fine particle, a metal ball, etc. can be used. Among them, those having a conductive metal layer formed on the surface of the resin fine particles are preferred because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

Moreover, the liquid crystal display element which used the sealing compound for liquid crystal display elements of this invention or the up-down conduction material of this invention is also one of this invention.

As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method can be preferably used, and specifically, for example, a method having each of the following steps can be mentioned.

First, the following steps are performed: on one of two substrates, such as a glass substrate with electrodes such as ITO films or a polyethylene terephthalate substrate, by screen printing, dispensing machine coating, etc. The sealing compound for liquid crystal display elements is formed into a frame-shaped sealing pattern. Then, the following steps are performed: in the state where the sealant for liquid crystal display elements of the present invention is not hardened, droplets of liquid crystal are applied dropwise in the frame of the sealing pattern of the substrate, and another substrate is overlapped under vacuum. Then, a liquid crystal display element can be obtained by performing a method of irradiating the sealing pattern part of the sealing compound for liquid crystal display elements of the present invention with light through a 420 nm cut-off filter or the like, and making the sealing compound light with long-wavelength light. hardening. Moreover, in addition to the step of photohardening the sealant described above, a step of heating the sealant to thermally harden the sealant may be performed.

According to the present invention, it is possible to provide a sealing compound for liquid crystal display elements which is excellent in curability to long-wavelength light and suppresses the generation of foreign matter. Moreover, according to this invention, the up-down conduction material and liquid crystal display element can be provided using this sealing compound for liquid crystal display elements.

Hereinafter, the present invention will be described in more detail by showing examples, but the present invention is not limited to these examples.

(Production of compound represented by formula (2-1))

-9-酮87重量份、及作為單官能環氧化合物之對三級丁基苯基環氧丙醚(ADEKA公司製造，「ED-509S」)62重量份攪拌48小時一面進行反應，藉此獲得上述式(2-1)表示之化合物(m=1)。作為鹼性觸媒，使用PS-PPh₃(Biotage Japan公司製造，於聚苯乙烯(PS)載持三苯基膦而成之鹼性觸媒)5.2重量份。 In the presence of an alkaline catalyst, 2-(carboxymethoxy)-9H-sulfur was prepared at 110°C

87 parts by weight of -9-ketone and 62 parts by weight of p-tertiary butylphenyl glycidyl ether (manufactured by ADEKA, "ED-509S") as a monofunctional epoxy compound were reacted while stirring for 48 hours. The compound (m=1) represented by the above formula (2-1) is obtained. As an alkaline catalyst, 5.2 parts by weight of PS-PPh ₃ (manufactured by Biotage Japan, an alkaline catalyst obtained by supporting triphenylphosphine on polystyrene (PS)) was used.

In addition, the structure of the obtained compound represented by the said formula (2-1) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

-9-酮與對三級丁基苯基環氧丙醚之摻合比率係以莫耳比計，為2-(羧基甲氧基)-9H-硫

-9-酮：對三級丁 基苯基環氧丙醚=1：1。 Also, 2-(carboxymethoxy)-9H-thio

The blending ratio of -9-keto and p-tertiary butylphenyl glycidyl ether is in molar ratio, 2-(carboxymethoxy)-9H-sulfur

-9-keto: p-tertiary butyl phenyl glycidyl ether = 1:1.

(Preparation of compound represented by formula (2-2))

-9-酮69重量份、及作為單官能環氧化合物之對三級丁基苯基環氧丙醚(ADEKA公司製造，「ED-509S」)62重量份攪拌48小時一面進行反應，藉此獲得上述式(2-2)表示之化合物。作為鹼性觸媒，使用PS-PPh₃(Biotage Japan公司製造，於聚苯乙烯(PS)載持三苯基膦而成之鹼性觸媒)5.2重量份。 In the presence of an alkaline catalyst, 2-hydroxy-9H-sulfur was dissolved at 110°C.

69 parts by weight of -9-ketone and 62 parts by weight of p-tertiary butylphenyl glycidyl ether (manufactured by ADEKA, "ED-509S") as a monofunctional epoxy compound were reacted while stirring for 48 hours. The compound represented by the above formula (2-2) is obtained. As an alkaline catalyst, 5.2 parts by weight of PS-PPh ₃ (manufactured by Biotage Japan, an alkaline catalyst obtained by supporting triphenylphosphine on polystyrene (PS)) was used.

In addition, the structure of the obtained compound represented by the said formula (2-2) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

-9-酮與對三級丁基苯基環氧丙醚之摻合比率係以莫耳比計，為2-羥基-9H-硫

-9-酮：對三級丁基苯基環氧丙醚=1：1。 Also, 2-hydroxy-9H-thio

The blending ratio of -9-ketone and p-tertiary butylphenyl glycidyl ether is in molar ratio, which is 2-hydroxy-9H-sulfur

-9-keto: p-tertiary butyl phenyl glycidyl ether = 1:1.

(Examples 1 to 9 and Comparative Examples 1 to 3)

According to the mixing ratios described in Tables 1 and 2, each material was mixed using a planetary mixer (manufactured by Thinky, "Defoaming and Stirring Taro"), and then mixed using a three-roll mill to prepare Examples 1- 9 and the sealing compound for liquid crystal display elements of Comparative Examples 1-3.

Furthermore, the photopolymerization initiators used in the examples and comparative examples were dissolved in acrylonitrile so as to have a concentration of 0.1 mg/mL, and then a spectrophotometer (manufactured by Hitachi High-Tech Scientific Corporation, "U- 3900") to measure the extinction coefficient at a wavelength of 430 nm. The results are shown in Tables 1 and 2.

In addition, dimaleimide acetate (manufactured by DIC Corporation, "LUMICURE MIA200") of polytetramethylene ether glycol described as a maleimide compound in the table is the above formula ( 3) The compound represented.

<Evaluation>

The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(photocurable)

1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of the sealing compounds for liquid crystal display elements obtained in Examples and Comparative Examples. Next, the sealant was filled into a dispensing syringe (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"), and after defoaming treatment, it was applied with a dispenser (manufactured by Musashi High-Technology, Inc., "SHOTMASTER 300"). on a glass substrate. A glass substrate of the same size was bonded to the substrate by a vacuum bonding device under a reduced pressure of 5 Pa. The sealant portion of the bonded glass substrate was irradiated with light of 100 mW/cm ² for 10 seconds using a metal halide lamp. The illumination was performed in two modes, a case without a 420nm cutoff filter, and a case with a 420nm cutoff filter.

The FT-IR measurement of the sealant was performed using an infrared spectrometer (manufactured by BIORAD, Inc., "FTS3000"), and the amount of change in the peak derived from the (meth)acryloyl group before and after irradiation was measured to evaluate the curability. The case where the peak from the (meth)acryloyl group was reduced by more than 80% after illumination was set as "◎", the case where the reduction by more than 70% and less than 80% was set as "○", and the reduction by more than 50% and The case of less than 70% was made into "△", and the case of less than 50% of the reduction of the peak derived from the (meth)acryloyl group after irradiation was made into "X", and the photocurability was evaluated.

(foreign object prevention)

1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Industry Co., Ltd., "Micropearl SI-H050") was dispersed in 100 parts by weight of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples, directly under the fluorescent lamp Set aside for 3 hours. Next, the sealant was filled into a dispensing syringe (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"), and after defoaming treatment, it was applied with a dispenser (manufactured by Musashi High-Technology, Inc., "SHOTMASTER 300"). on a glass substrate. A glass substrate of the same size was bonded to the substrate by a vacuum bonding device under a reduced pressure of 5 Pa. At this time, if a foreign matter is generated in the sealant when it is placed directly under the fluorescent lamp, the foreign matter is bitten between the substrates, resulting in a gap defect.

The substrates to be bonded were confirmed, and the case where no gap defect occurred at all was set as "○", the case where gap defect occurred slightly was set as "△", and the case where gap defect occurred significantly was set as "x", and the foreign matter prevention was evaluated. sex.

[Industrial Availability]

According to the present invention, it is possible to provide a sealing compound for liquid crystal display elements which is excellent in curability to long-wavelength light and suppresses the generation of foreign matter. Moreover, according to this invention, the up-down conduction material and liquid crystal display element can be provided using this sealing compound for liquid crystal display elements.

Claims (7)

A sealing agent for liquid crystal display elements, comprising a curable resin, a photopolymerization initiator and a maleimide compound, the extinction coefficient of the photopolymerization initiator at a wavelength of 430 nm is 0.8×10 ² mL/g·cm The above, and the photopolymerization initiator is a compound having a structure represented by the following formula (1):

In formula (1), * is a bonding position. The sealing compound for liquid crystal display elements according to claim 1, wherein the compound having the structure represented by the formula (1) is a compound having one structure represented by the formula (1) in one molecule. The sealing compound for liquid crystal display elements according to claim 2, wherein the compound having the structure represented by the formula (1) is represented by the compound represented by the following formula (2-1) and/or the following formula (2-2). The compound:

In formulas (2-1) and (2-2), R is a structure derived from a monofunctional epoxy compound; in formula (2-1), m is an integer of 1 to 5. The sealing compound for liquid crystal display elements according to claim 1, 2 or 3, wherein the maleimide compound is a polyfunctional maleene having two or more maleimide groups in one molecule Diimide compound. The sealing compound for liquid crystal display elements as described in Claim 1 or 2 whose molecular weight of the maleimide compound is 400 or more. A vertical conduction material comprising the liquid crystal display element sealant and conductive fine particles according to claim 1, 2, 3, 4, or 5. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1, 2, 3, 4 or 5, or the upper and lower conduction material according to claim 6.