JP7053471B2 - Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Description

The present invention relates to a sealant for a liquid crystal display element, which is excellent in coatability, curability, and low liquid crystal stain resistance. The present invention also relates to a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, a photothermal combination curing type as disclosed in Patent Document 1 and Patent Document 2 is used. A liquid crystal dripping method called a dripping method using a sealing agent is used.
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, in a state where the sealant is uncured, fine droplets of liquid crystal are dropped into the seal frame of the substrate, the other substrate is overlapped under vacuum, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing. Then, it is heated to perform the main curing, and a liquid crystal display element is manufactured. Currently, this dropping method is the mainstream method for manufacturing liquid crystal display elements.

By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and handheld game machines are widespread, miniaturization of devices is the most sought after issue. As a method of miniaturization, a narrowing of the frame of the liquid crystal display unit can be mentioned. For example, the position of the seal portion is arranged under the black matrix (hereinafter, also referred to as a narrow frame design).
With such a narrow frame design, there is a problem that the distance from the pixel area to the sealant is short in the liquid crystal display element, and display unevenness is likely to occur due to the liquid crystal being contaminated by the sealant. rice field.

Japanese Unexamined Patent Publication No. 2001-133794 International Publication No. 02/02718

An object of the present invention is to provide a sealant for a liquid crystal display element, which is excellent in coatability, curability, and low liquid crystal stain resistance. Another object of the present invention is to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

The present invention is a sealing agent for a liquid crystal display element containing a curable resin and a polymerization initiator, and the curable resin is a partially (meth) acrylic-modified novolak type epoxy resin (A) and a partial (meth). It contains an acrylic-modified non-novolak type epoxy resin (B) and a non-novolak type epoxy (meth) acrylate (C), and the content of the above-mentioned partial (meth) acrylic-modified novolak-type epoxy resin (A) is the above-mentioned curability. 3 parts by weight or more and 9 parts by weight or less in 100 parts by weight of the resin, and the content of the (meth) acrylic-modified non-novolac type epoxy resin (B) is 25 parts by weight or less in 100 parts by weight of the curable resin. The ratio of the partial (meth) acrylic-modified non-novolak type epoxy resin (B) to the above-mentioned partial (meth) acrylic-modified novolak type epoxy resin (A) is 1 or more, and the above-mentioned non-novolak type epoxy (meth). The content of the acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the curable resin, and the portion (meth) acrylic modified novolak type epoxy resin (A) has a weight average molecular weight. It is a sealant for a liquid crystal display element of 700 or more and 2000 or less.
The present invention will be described in detail below.

The present inventor has studied the use of a partially (meth) acrylic-modified epoxy resin having a relatively high molecular weight as the curable resin in order to improve the low liquid crystal contamination property of the sealant for a liquid crystal display element. However, when such a curable resin is used, the obtained sealant for a liquid crystal display element may be inferior in coatability and curability. Therefore, the present inventor sets a specific content ratio of the partially (meth) acrylic-modified novolak-type epoxy resin, the partially (meth) acrylic-modified non-novolak-type epoxy resin, and the non-novolak-type epoxy (meth) acrylate. We considered using it in combination with. As a result, they have found that a sealant for a liquid crystal display element having excellent coatability, curability, and low liquid crystal stain resistance can be obtained, and have completed the present invention.

The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin includes a partially (meth) acrylic-modified novolak-type epoxy resin (A) (hereinafter, also referred to as “(A) component”) and a partially (meth) acrylic-modified non-novolac-type epoxy resin (B) (hereinafter, also referred to as “component”). It also contains "(B) component") and a non-novolak type epoxy (meth) acrylate (C) (hereinafter, also referred to as "(C) component"). By containing the above-mentioned component (A), the above-mentioned (B) component, and the above-mentioned (C) component so that the content ratios are in the range described later, the sealant for a liquid crystal display element of the present invention has a coating property. It has excellent curability and low liquid crystal contamination.
In the present specification, in the above-mentioned "partially (meth) acrylic modified novolak type epoxy resin", a part of the epoxy group of the novolak type epoxy resin reacts with (meth) acrylic acid, and the (meth) acryloyl group is introduced. Means something.
In the above-mentioned "partially (meth) acrylic modified non-novolak type epoxy resin", a part of the epoxy group of the non-novolak type epoxy resin (hereinafter, also referred to as "non-novolak type epoxy resin") reacts with (meth) acrylic acid. (Meta) Means the one to which an acryloyl group is introduced.
The above-mentioned "non-novolak type epoxy (meth) acrylate" means that all the epoxy groups of the non-novolak type epoxy resin react with (meth) acrylic acid and the (meth) acryloyl group is introduced.
The above-mentioned "(meth) acrylic" means acrylic or methacrylic, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryloyl" means acryloyl or methacryloyl.

Since the component (A) is a novolak type, the viscosity increases slowly even if the molecular weight is relatively high from the viewpoint of low liquid crystal contamination, and it is difficult to deteriorate the coatability.
The lower limit of the weight average molecular weight of the component (A) is 700, and the upper limit is 2000. When the weight average molecular weight of the component (A) is 700 or more, the obtained sealant for a liquid crystal display element becomes excellent in low liquid crystal contamination. When the weight average molecular weight of the component (A) is 2000 or less, the obtained sealant for a liquid crystal display element has excellent coatability. The preferable lower limit of the weight average molecular weight of the component (A) is 750, the preferable upper limit is 1500, the more preferable lower limit is 800, and the more preferable upper limit is 1200.
In the present specification, the weight average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.

Examples of the component (A) include a partially (meth) acrylic-modified phenol novolac type epoxy resin, a partially (meth) acrylic-modified orthocresol novolac-type epoxy resin, a partially (meth) acrylic-modified dicyclopentadiene novolac-type epoxy resin, and a portion. Examples thereof include (meth) acrylic-modified biphenyl novolac type epoxy resin and partially (meth) acrylic-modified naphthalene phenol novolac type epoxy resin. Of these, a partially (meth) acrylic-modified phenol novolac type epoxy resin is preferable.

The component (A) is a novolak type epoxy resin by reacting a part of the epoxy group of the novolak type epoxy resin with the (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. And can be obtained in a mixture of novolak type epoxy (meth) acrylate.
In the present specification, the above-mentioned "novolak type epoxy (meth) acrylate" means that all the epoxy groups of the novolak type epoxy resin react with (meth) acrylic acid and the (meth) acryloyl group is introduced. ..

Examples of the novolak type epoxy resin used as a raw material for the component (A) include phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, and naphthalenephenol novolak type epoxy. Examples include resin.

The content of the component (A) is such that the lower limit is 3 parts by weight and the upper limit is 9 parts by weight in 100 parts by weight of the curable resin. When the content of the component (A) is 3 parts by weight or more, the obtained sealing agent for a liquid crystal display element becomes excellent in low liquid crystal contamination. When the content of the component (A) is 9 parts by weight or less, the obtained sealant for a liquid crystal display element has excellent coatability. The preferable lower limit of the content of the component (A) is 4 parts by weight, the preferable upper limit is 8 parts by weight, and the more preferable upper limit is 7 parts by weight.

Examples of the component (B) include a partially (meth) acrylic-modified bisphenol A-type epoxy resin, a partially (meth) acrylic-modified bisphenol F-type epoxy resin, a partially (meth) acrylic-modified bisphenol E-type epoxy resin, and a partial (meth) component. Acrylic modified bisphenol S type epoxy resin, partially (meth) acrylic modified 2,2'-diallyl bisphenol A type epoxy resin, partially (meth) acrylic modified hydrogenated bisphenol type epoxy resin, partially (meth) acrylic modified propylene oxide added bisphenol A Type epoxy resin, partial (meth) acrylic modified resorcinol type epoxy resin, partial (meth) acrylic modified biphenyl type epoxy resin, partial (meth) acrylic modified sulfide type epoxy resin, partial (meth) acrylic modified diphenyl ether type epoxy resin, partial (meth) Meta) acrylic modified dicyclopentadiene type epoxy resin, partial (meth) acrylic modified naphthalene type epoxy resin, partial (meth) acrylic modified glycidylamine type epoxy resin, partial (meth) acrylic modified alkyl polyol type epoxy resin, partial (meth) Acrylic modified rubber modified epoxy resin and the like can be mentioned. Of these, a partially (meth) acrylic-modified bisphenol A type epoxy resin is preferable.

The component (B) is a non-novolak type by reacting a part of the epoxy group of the non-novolak type epoxy resin with the (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. It can be obtained in a mixture of an epoxy resin and a non-novolak type epoxy (meth) acrylate.

Examples of the non-novolac type epoxy resin used as a raw material for the component (B) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and 2,2'-diallyl bisphenol. A-type epoxy resin, hydrogenated bisphenol-type epoxy resin, propylene oxide-added bisphenol A-type epoxy resin, resorcinol-type epoxy resin, biphenyl-type epoxy resin, sulfide-type epoxy resin, diphenyl ether-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthalene-type Examples thereof include an epoxy resin, a glycidylamine type epoxy resin, an alkylpolypoly type epoxy resin, and a rubber-modified epoxy resin.

The upper limit of the content of the component (B) is 25 parts by weight in 100 parts by weight of the curable resin. When the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight or less, the obtained sealant for a liquid crystal display element is excellent in low liquid crystal contamination. The preferable upper limit of the content of the component (B) in 100 parts by weight of the curable resin is 22 parts by weight, and the more preferable upper limit is 20 parts by weight.
Further, the ratio of the component (B) to the component (A) is 1 or more. By setting the ratio of the component (B) to the component (A) to 1 or more, the obtained sealant for a liquid crystal display element becomes excellent in coatability. The preferable lower limit of the ratio of the component (B) to the component (A) is 1.2, and the more preferable lower limit is 1.5.
The "ratio of the component (B) to the component (A)" means the content of the component (B) / the content of the component (A).

Examples of the component (C) include bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol E type epoxy (meth) acrylate, bisphenol S type epoxy (meth) acrylate, and 2,2'. -Diallyl bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol type epoxy (meth) acrylate, propylene oxide-added bisphenol A type epoxy (meth) acrylate, resorcinol type epoxy (meth) acrylate, biphenyl type epoxy (meth) acrylate, sulfide Type epoxy (meth) acrylate, diphenyl ether type epoxy (meth) acrylate, dicyclopentadiene type epoxy (meth) acrylate, naphthalene type epoxy (meth) acrylate, glycidylamine type epoxy (meth) acrylate, alkyl polyol type epoxy (meth) acrylate , Rubber-modified epoxy (meth) acrylate and the like. Of these, bisphenol A type epoxy (meth) acrylate is preferable.

The component (C) can be obtained by reacting all the epoxy groups of the non-novolak type epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the non-novolak type epoxy resin used as a raw material for the component (C) include the same as the non-novolak type epoxy resin used as a raw material for the component (B).

The content of the component (C) is such that the lower limit is 10 parts by weight and the upper limit is 45 parts by weight in 100 parts by weight of the curable resin. When the content of the component (C) in 100 parts by weight of the curable resin is 10 parts by weight or more, the obtained sealant for a liquid crystal display element has excellent photocurability. When the content of the component (C) is 45 parts by weight or less, the obtained sealant for a liquid crystal display element has excellent adhesiveness. The preferable lower limit of the content of the component (C) in 100 parts by weight of the curable resin is 14 parts by weight, and the more preferable lower limit is 18 parts by weight.

The sealant for a liquid crystal display element of the present invention may further contain other polymerizable compounds as the curable resin as long as the object of the present invention is not impaired.
Examples of the above-mentioned other polymerizable compounds include the above-mentioned novolak type epoxy resin, the above-mentioned non-novolac type epoxy resin, the above-mentioned novolak type epoxy (meth) acrylate, and other (meth) acrylic compounds. ..

Examples of the other (meth) acrylic compound include a (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, and a (meth) acrylic acid derivative having a hydroxyl group in an isocyanate compound. Examples thereof include urethane (meth) acrylate obtained by reacting with.
From the viewpoint of reactivity, the other (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule.

Among the above (meth) acrylic acid ester compounds, monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, iso Myristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl ( Meta) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 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, ethylcarbi Thor (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, Imid (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- ( Examples thereof include 2- (meth) acryloyloxyethyl phosphate, 2- (meth) acryloyloxyethyl phosphate, and glycidyl (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane. Didioldi (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meta) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate ) Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate. , Dimethylol dicyclopentadienyldi (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, Examples thereof include polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.

Among the above (meth) acrylic acid ester compounds, those having trifunctionality or higher include, for example, trimethylol propanetri (meth) acrylate, ethylene oxide-added trimethylol propanetri (meth) acrylate, and propylene oxide-added trimethylol propanetri (meth) acrylate. Meta) acrylate, caprolactone-modified trimethylol propantri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerintri (meth) acrylate, propylene oxide-added glycerintri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include tris (meth) acryloyloxyethyl phosphate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with respect to an isocyanate compound in the presence of a catalytic amount of a tin-based compound.

Examples of the isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and hydrogenated products. MDI, Polymeric MDI, 1,5-naphthalenediocyanate, Norbornan diisocyanate, Trizine diisocyanate, Xylylene diisocyanate (XDI), Hydrogenated XDI, Lysine diisocyanate, Triphenylmethane triisocyanate, Tris (isocyanatephenyl) thiophosphate, Tetramethylxylylene diisocyanate Examples thereof include isocyanates and 1,6,11-undecantry isocyanates.

Further, as the isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyol with an excess isocyanate compound can also be used.
Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.

Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of dihydric alcohol, mono (meth) acrylate of trihydric alcohol or di (meth) acrylate. And so on.
Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Can be mentioned.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, and glycerin.

The other (meth) acrylic compound preferably has a hydrogen-bonding unit such as an -OH group, an -NH- group, and an -NH ₂ group from the viewpoint of suppressing liquid crystal contamination.

The sealant for a liquid crystal display element of the present invention contains a polymerization initiator.
Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators and the like.

As the radical polymerization initiator, a photoradical polymerization initiator that generates radicals by light irradiation or a thermal radical polymerization initiator that generates radicals by heating can be used.

Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.

Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, and 1,2- (dimethylamino). -2-((4-Methylphenyl) Methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2) , 4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl)- 2-Hydroxy-2-methyl-1-propane-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime), 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
The photoradical polymerization initiator may be used alone or in combination of two or more.

Examples of the thermal radical polymerization initiator include those made of an azo compound, an organic peroxide and the like. Of these, an initiator composed of a polymer azo compound (hereinafter, also referred to as “polymer azo initiator”) is preferable.
The thermal radical polymerization initiator may be used alone or in combination of two or more.
In the present specification, the polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing the (meth) acryloyl group by heat.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is in this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.
In the present specification, the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.

Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable.
Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group and the like.
Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like. Be done.
Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.

As the cationic polymerization initiator, a photocationic polymerization initiator is preferably used.
The photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. May be.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salt, aromatic halonium salt and aromatic sulfonium salt, and organic metal complexes such as iron-allene complex, titanosen complex and arylsilanol-aluminum complex. Can be mentioned.

Examples of commercially available photocationic polymerization initiators include ADEKA PTOMER SP-150 and ADEKA PTOMER SP-170 (both manufactured by ADEKA).

The content of the polymerization initiator has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization initiator is in this range, the obtained sealant for a liquid crystal display element is excellent in storage stability and curability while suppressing liquid crystal contamination. The more preferable lower limit of the content of the polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The sealant for a liquid crystal display element of the present invention preferably contains a thermosetting agent.
Examples of the heat-curing agent include organic acid hydrazide, imidazole derivative, amine compound, polyvalent phenolic compound, acid anhydride and the like. Of these, solid organic acid hydrazide is preferably used.
The thermosetting agent may be used alone or in combination of two or more.

Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrandine, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Japan Finechem Co., Ltd., and organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Japan Finechem Co., Ltd. include MDH and the like.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, and Amicure UDH.

The content of the thermosetting agent is preferably 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the thermosetting agent is in this range, the obtained sealant for a liquid crystal display element becomes more excellent in curability while maintaining excellent coatability and storage stability. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a filler for the purpose of improving the viscosity, further improving the adhesiveness by the stress dispersion effect, improving the coefficient of linear expansion, improving the moisture resistance of the cured product, and the like. preferable.

As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous soil, smectite, bentonite, montmorillonite, sericite, active white clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.
The filler may be used alone or in combination of two or more.

The preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight. When the content of the filler is in this range, it is possible to further exert the effect of improving the adhesiveness while suppressing the deterioration of the coatability and the like. The more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealant for a liquid crystal display element of the present invention is from the viewpoint of improving the flexibility and adhesiveness of the cured product, suppressing the insertion of the liquid crystal into the sealant, and suppressing the elution of the sealant into the liquid crystal display. It preferably contains soft particles.

Examples of the flexible particles include silicone-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, nitrile-based particles, and the like. Of these, silicone-based particles and vinyl-based particles are preferable.
The flexible particles may be used alone or in combination of two or more.

As the silicone-based particles, silicone rubber particles are preferable from the viewpoint of dispersibility in the resin.

As the vinyl-based particles, (meth) acrylic particles are preferably used.
The (meth) acrylic particles can be obtained by polymerizing a monomer as a raw material by a known method. Specifically, for example, a method of suspend-polymerizing a monomer in the presence of a radical polymerization initiator, or swelling a seed particle by allowing a non-crosslinked seed particle to absorb the monomer in the presence of a radical polymerization initiator. Examples thereof include a method of subjecting the seeds to polymerization.

Examples of the monomer as a raw material for forming the (meth) acrylic particles include alkyl (meth) acrylates, oxygen atom-containing (meth) acrylates, nitrile-containing monomers, and fluorine-containing (meth) acrylates. Examples thereof include monofunctional monomers.
Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and 2-. Examples thereof include ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Examples of the oxygen atom-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth) acrylate.
Examples of the nitrile-containing monomer include (meth) acrylonitrile.
Examples of the fluorine-containing (meth) acrylates include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.
Among them, alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the amount of deformation when a 1 g load is applied can be increased.

Further, in order to have a crosslinked structure, a polyfunctional monomer may be used as a monomer as a raw material for forming the (meth) acrylic particles.
Examples of the polyfunctional monomer include tetramethylolmethanetetra (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanedi (meth) acrylate, trimethylolpropanetri (meth) acrylate, and dipentaerythritol. Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate , (Poly) tetramethylenedi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isocyanuric acid skeleton tri (meth) acrylate and the like. Among them, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, because the molecular weight between cross-linking points is large and the amount of deformation when a 1 g load is applied can be increased. Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are preferred.

Regarding the amount of the crosslinkable monomer used, the preferable lower limit is 1% by weight and the preferable upper limit is 90% by weight in the whole monomer used as a raw material for forming the (meth) acrylic particles. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when kneaded with other sealant components, problems such as swelling do not occur and it becomes easy to disperse uniformly. .. When the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered. The more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and the more preferable upper limit is 80% by weight.

Furthermore, in addition to these acrylic monomers, styrene-based monomers, vinyl ethers, carboxylic acid vinyl esters, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurates, triallyl isocyanurates, Monomers such as triallyl trimeritate, divinylbenzene, diallylphthalate, diallylacrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, and vinyltrimethoxysilane may be used.
Examples of the styrene-based monomer include styrene, α-methylstyrene, trimethoxysilylstyrene and the like.
Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and the like.
Examples of the carboxylic acid vinyl esters include vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate and the like.
Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, and butadiene.
Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, chlorostyrene and the like.

As the (meth) acrylic particles, core-shell (meth) acrylate copolymer fine particles are also preferably used.
Examples of commercially available core-shell (meth) acrylate copolymer fine particles include F351 (manufactured by Aica Kogyo Co., Ltd.) and the like.

Further, as the vinyl-based particles, for example, polyvinylbenzene benzene particles, polychloroprene particles, butadiene rubber particles and the like may be used.

The preferable lower limit of the average particle size of the soft particles is 0.01 μm, and the preferable upper limit is 10 μm. When the average particle size of the flexible particles is in this range, the effect of improving the flexibility and adhesiveness of the obtained cured product of the sealant for a liquid crystal display element becomes more excellent. The more preferable lower limit of the average particle diameter of the soft particles is 0.1 μm, and the more preferable upper limit is 8 μm.
In the present specification, the average particle size of the flexible particles means a value obtained by measuring using a laser diffraction type particle size distribution measuring device. As the laser diffraction type particle size distribution measuring device, Master Sizar 2000 (manufactured by Malvern) or the like can be used.

The preferred lower limit of the hardness of the soft particles is 10, and the preferred upper limit is 50. When the hardness of the flexible particles is in this range, the effect of improving the flexibility and adhesiveness of the obtained cured product of the sealant for a liquid crystal display element becomes more excellent. The more preferable lower limit of the hardness of the soft particles is 20, and the more preferable upper limit is 40.
In the present specification, the hardness of the flexible particles means the hardness of Durometer A measured by a method according to JIS K 6253.

The preferable lower limit of the content of the soft particles in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 50 parts by weight. When the content of the flexible particles is in this range, the effect of improving the flexibility and adhesiveness of the obtained cured product of the sealant for a liquid crystal display element becomes more excellent. The more preferable lower limit of the content of the soft particles is 10 parts by weight, and the more preferable upper limit is 30 parts by weight.

The sealant for a liquid crystal display element of the present invention preferably contains a silane coupling agent for the purpose of further improving the adhesiveness. The silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the sealing agent to the substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are preferably used.
The silane coupling agent may be used alone or in combination of two or more.

The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving the adhesiveness can be further exhibited while suppressing the occurrence of liquid crystal contamination. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.

The sealant for a liquid crystal display element of the present invention may contain a light-shielding agent. By containing the above-mentioned light-shielding agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.

Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
The light-shielding agent may be used alone or in combination of two or more.

The titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting a light-shielding property to the sealant for a liquid crystal display element of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. It is a light-shielding agent. As the light-shielding agent contained in the sealant for a liquid crystal display element of the present invention, a substance having high insulating properties is preferable, and titanium black is also preferable as the light-shielding agent having high insulating properties.

The above titanium black exerts a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, and oxidation. Surface-treated titanium black, such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
Further, the liquid crystal display element manufactured by using the sealant for a liquid crystal display element of the present invention containing the titanium black as a light shielding agent has sufficient light shielding properties, so that there is no light leakage and a high contrast is obtained. It is possible to realize a liquid crystal display element having excellent image display quality.

Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd.
Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13RN, 14M-C and the like.
Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tilak D and the like.

The preferable lower limit of the specific surface area of the titanium black is 13 m ² / g, the preferable upper limit is 30 m ² / g, the more preferable lower limit is 15 m ² / g, and the more preferable upper limit is 25 m ² / g.
Further, the preferable lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferable upper limit is 3 Ω · cm, the more preferable lower limit is 1 Ω · cm, and the more preferable upper limit is 2.5 Ω · cm.

The primary particle diameter of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, but the preferable lower limit is 1 nm and the preferable upper limit is 5 μm. When the primary particle size of the light-shielding agent is in this range, the viscosity and thixotropy of the obtained sealant for a liquid crystal display element do not increase significantly, and the coatability is improved. The more preferable lower limit of the primary particle diameter of the light-shielding agent is 5 nm, the more preferable upper limit is 200 nm, the further preferable lower limit is 10 nm, and the further preferable upper limit is 100 nm.
The primary particle size of the light-shielding agent is measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS). be able to.

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the effect of improving the light-shielding property is further improved without significantly reducing the adhesiveness, the strength after curing, and the drawability of the obtained sealant for the liquid crystal display element. It can be demonstrated. A more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.

The sealant for a liquid crystal display element of the present invention further contains, if necessary, a stress relaxation agent, a reactive diluent, a rocking agent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor and the like. It may contain an agent.

As a method for producing the sealant for a liquid crystal display element of the present invention, for example, a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer is used to polymerize with a curable resin. Examples thereof include a method of mixing the initiator with an additive such as a thermosetting agent or a silane coupling agent added as needed.

The sealant for a liquid crystal display element of the present invention has a preferable lower limit of 100 Pa · s and a preferable upper limit of 800 Pa · s measured under the conditions of 25 ° C. and 1 rpm using an E-type viscometer. When the viscosity is in this range, the obtained sealant for a liquid crystal display element has excellent coatability. The more preferable lower limit of the viscosity is 200 Pa · s, and the more preferable upper limit is 700 Pa · s.

By blending conductive fine particles with the sealant for a liquid crystal display element of the present invention, a vertically conductive material can be manufactured. A vertically conductive material containing a sealing agent for a liquid crystal display element of the present invention and conductive fine particles is also one of the present inventions.

As the conductive fine particles, a metal ball, a resin fine particle having a conductive metal layer formed on the surface thereof, or 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 excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

A liquid crystal display element using the sealant for a liquid crystal display element of the present invention or the vertically conductive material of the present invention is also one of the present inventions.

As a method for manufacturing a liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps.
First, the sealant for a liquid crystal display element of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film and a polyethylene terephthalate substrate by screen printing, dispenser coating, or the like to form a frame-shaped seal. Perform the step of forming a pattern. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, fine droplets of liquid crystal are dropped and applied in the frame of the seal pattern of the substrate, and another substrate is superposed under vacuum. After that, a step of irradiating the seal pattern portion of the sealant for a liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and a step of heating the temporarily cured sealant to perform main curing are performed. A liquid crystal display element can be obtained by the method.

According to the present invention, it is possible to provide a sealant for a liquid crystal display element having excellent coatability, curability, and low liquid crystal stain resistance. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

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

(Preparation of novolak type curable resin mixture (A1))
557 parts by weight of a phenol novolac type epoxy resin (“EPICLON N-740” manufactured by DIC Corporation) was dissolved in 900 mL of toluene, and then 0.3 g of triphenylphosphine was added to prepare a uniform solution. 122 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, and then reflux stirring was further performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a novolak type curable resin mixture (A1).
By ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolak type curable resin mixture (A1) was 11.8% by weight of a partially acrylic modified phenol novolac type epoxy resin and 68% of a phenol novolac type epoxy resin. It was confirmed that the mixture contained 6.6% by weight and 19.6% by weight of phenol novolac type epoxy acrylate.
The weight average molecular weight of the obtained partially acrylic modified phenol novolac type epoxy resin was 1200.

(Preparation of novolak type curable resin mixture (A2))
395 parts by weight of a phenol novolac type epoxy resin (“EPICLON N-730S” manufactured by DIC Corporation) was dissolved in 900 mL of toluene, and then 0.3 g of triphenylphosphine was added to prepare a uniform solution. 94 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, and then reflux stirring was further performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a novolak type curable resin mixture (A2).
By ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolak type curable resin mixture (A2) was 11.8% by weight of a partially acrylic modified phenol novolac type epoxy resin and 68% of a phenol novolac type epoxy resin. It was confirmed that the mixture contained 6.6% by weight and 19.6% by weight of phenol novolac type epoxy acrylate.
The weight average molecular weight of the obtained partially acrylic modified phenol novolac type epoxy resin was 800.

(Preparation of novolak type curable resin mixture (A3))
965 parts by weight of a phenol novolac type epoxy resin (“EPICLON N-770” manufactured by DIC Corporation) was dissolved in 1800 mL of toluene, and then 0.3 g of triphenylphosphine was added to prepare a uniform solution. 216 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, and then reflux stirring was further performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a novolak type curable resin mixture (A3).
By ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolak type curable resin mixture (A3) was 11.8% by weight of a partially acrylic modified phenol novolac type epoxy resin and 68% of a phenol novolac type epoxy resin. It was confirmed that the mixture contained 6.6% by weight and 19.6% by weight of phenol novolac type epoxy acrylate.
The weight average molecular weight of the obtained partially acrylic modified phenol novolac type epoxy resin was 2500.

(Preparation of non-novolak type curable resin mixture (B1))
After dissolving 326 parts by weight of bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER 828EL") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. 72 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, and then reflux stirring was further performed for 6 hours. Then, toluene was removed under reduced pressure to obtain a non-novolak type curable resin mixture (B1).
By ¹ H-NMR, ¹³ C-NMR, and FT-IR, the non-novolak type curable resin mixture (B1) contains 50% by weight of a partially acrylic modified bisphenol A type epoxy resin and 25% by weight of a bisphenol A type epoxy resin. %, It was confirmed that the mixture contained 25% by weight of bisphenol A type epoxy acrylate.

(Examples 1 to 10, Comparative Examples 1 to 8)
According to the compounding ratios shown in Tables 1 and 2, each material is stirred with a planetary stirrer (Sinky, "Awatori Rentaro"), and then uniformly mixed with three ceramic rolls. Sealing agents for liquid crystal display elements of Examples 1 to 10 and Comparative Examples 1 to 8 were obtained.

<Evaluation>
The following evaluations were performed on the sealants for each liquid crystal display element obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(viscosity)
The viscosities of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples were measured at 25 ° C. and 1 rpm using an E-type viscometer (“DV-III” manufactured by Brookfield).

(Applicability)
Using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER300"), the sealants for each liquid crystal display element obtained in Examples and Comparative Examples were applied onto a glass substrate. When the dispense nozzle is fixed at 400 μm, the nozzle gap is 30 μm, and the application pressure is fixed at 300 kPa, "○" indicates that the application can be performed without blurring or sagging, and "○" indicates that there is no fading or sagging, but there is fading or sagging. The coatability was evaluated as "Δ", when the coating was cut off or when the coating could not be performed at all, as "x".

(Curability)
About 5 μm of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples was applied onto a glass substrate, and then glass substrates of the same size were superposed. Then, using a metal halide lamp, ultraviolet rays having a wavelength of 365 nm were irradiated at 3000 mJ / cm ² . Using an infrared spectroscope (“FTS3000” manufactured by BIORAD), the amount of change (decrease rate) of the (meth) acryloyl group-derived peak before and after light irradiation was measured.
When the reduction rate of the peak derived from the (meth) acryloyl group after light irradiation was 95% or more, it was "◎", when it was 85% or more and less than 95%, it was "○", and when it was 75% or more and less than 85%. The curability was evaluated as "Δ" when it was present and as "x" when it was less than 75%.

(Low LCD pollution)
A silica spacer (manufactured by Sekisui Chemical Co., Ltd., "SI-H055") was blended in an amount of 1% by weight with the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and defoamed to contain the sealant. After removing the foam, the syringe was filled with a syringe for dispensing (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.), and the foam was removed again. Next, using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER300"), a sealant was applied to one of the two glass substrates with an ITO thin film so as to draw a frame. Subsequently, minute droplets of TN liquid crystal display (manufactured by Chisso, "JC-5001LA") are dropped and applied into the frame of the sealant by a liquid crystal dropping device, and the other glass substrate with an ITO thin film is laminated and used as a vacuum bonding device. The two substrates were bonded together under a reduced pressure of 5 Pa. After irradiating the bonded cells with ultraviolet rays of 3000 mJ / cm ² with a metal halide lamp, the sealant was thermally cured by heating at 120 ° C. for 60 minutes to prepare a liquid crystal display element. The obtained liquid crystal display element was stored for 100 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC3.5V, and the presence or absence of display unevenness (color unevenness) was visually observed. "○" when no display unevenness is seen, "△" when there is display unevenness in the peripheral part of the liquid crystal display element, and the display unevenness extends not only to the peripheral part of the liquid crystal display element but also to the central part. The low liquid crystal contamination property was evaluated with the case of "x".

According to the present invention, it is possible to provide a sealant for a liquid crystal display element having excellent coatability, curability, and low liquid crystal stain resistance. Further, according to the present invention, it is possible to provide a vertically conductive material and a liquid crystal display element using the sealant for a liquid crystal display element.

Claims (3)

A sealant for a liquid crystal display element containing a curable resin and a polymerization initiator.
The curable resin includes a partially (meth) acrylic-modified novolak-type epoxy resin (A), a partially (meth) acrylic-modified non-novolak-type epoxy resin (B), and a non-novolak-type epoxy (meth) acrylate (C). Contains,
The content of the partial (meth) acrylic modified novolak type epoxy resin (A) is 3 parts by weight or more and 9 parts by weight or less in 100 parts by weight of the curable resin.
The content of the partial (meth) acrylic-modified non-novolak type epoxy resin (B) is 25 parts by weight or less in 100 parts by weight of the curable resin, and the partial (meth) acrylic-modified novolak type epoxy resin ( The ratio of the partial (meth) acrylic-modified non-novolac type epoxy resin (B) to A) is 1 or more.
The content of the non-novolak type epoxy (meth) acrylate (C) is 10 parts by weight or more and 45 parts by weight or less in 100 parts by weight of the curable resin.
The partial (meth) acrylic-modified novolak type epoxy resin (A) is a sealant for a liquid crystal display element having a weight average molecular weight of 700 or more and 2000 or less. A vertically conductive material containing the sealing agent for a liquid crystal display element according to claim 1 and conductive fine particles. A liquid crystal display element using the sealant for a liquid crystal display element according to claim 1 or the vertically conductive material according to claim 2.