KR20200030493A - Sealing agent for liquid crystal display elements, upper and lower conductive materials and liquid crystal display elements - Google Patents

Abstract

An object of the present invention is to provide a sealant for a liquid crystal display device having excellent coatability, curability and low liquid crystal contamination. In addition, an object of the present invention is to provide a top and bottom conducting material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.
The present invention is a sealant for a liquid crystal display device containing a curable resin and a polymerization initiator, wherein the curable resin is a partially (meth) acrylic modified novolac-type epoxy resin (A) and a partially (meth) acrylic modified non-novolac type The epoxy resin (B) and the non-novolac-type epoxy (meth) acrylate (C) are contained, and the content of the partial (meth) acryl-modified novolac-type epoxy resin (A) is in 100 parts by weight of the curable resin. 3 parts by weight or more and 9 parts by weight or less, and the content of the partial (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, and the part (meth) The ratio of the partial (meth) acrylic-modified non-novolac-type epoxy resin (B) to the acrylic-modified novolac-type epoxy resin (A) is 1 or more, and the content of the non-novolac-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, and the partial (meth) acrylic modified novolac-type epoxy resin (A) has a weight average molecular weight of 700 or more and 2000 or less. to be.

Description

Sealing agent for liquid crystal display elements, upper and lower conductive materials and liquid crystal display elements

The present invention relates to a sealant for a liquid crystal display device having excellent coatability, curability and low liquid crystal contamination. Moreover, this invention relates to the up-and-down conduction material and liquid crystal display element formed using the sealing agent for liquid crystal display elements.

In recent years, as a manufacturing method of a liquid crystal display element such as a liquid crystal display cell, from the viewpoints of shortening the tact time and optimizing the amount of liquid crystal used, a curing agent for a photothermal combined curing type as disclosed in Patent Documents 1 and 2 A liquid crystal dropping method called a dropping method using is used.

In the dropping method, first, a rectangular seal pattern is formed on one of the substrates on which two electrodes are formed by dispensing. Subsequently, in the state where the sealing agent is uncured, a small droplet of liquid crystal is dropped into the sealing frame of the substrate, the other substrate is superimposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Then, this curing is performed by heating to produce a liquid crystal display element. Currently, this dripping method is mainstream of a method for manufacturing a liquid crystal display element.

By the way, in the modern days in which mobile devices having various liquid crystal panels, such as mobile phones and portable game machines, are being spread, miniaturization of devices is the most demanded task. As a method of miniaturization, narrowing of the frame of the liquid crystal display may be mentioned, and for example, it is practiced to arrange the position of the seal under the black matrix (hereinafter also referred to as narrow frame design).

With such a narrow frame design, there is a problem in the liquid crystal display element that the distance from the pixel region to the sealing agent is getting closer, and display unevenness due to contamination of the liquid crystal by the sealing agent is likely to occur.

Japanese Patent Application Publication No. 2001-133794 International Publication No. 02/092718

An object of the present invention is to provide a sealant for a liquid crystal display device having excellent coatability, curability and low liquid crystal contamination. In addition, an object of the present invention is to provide a top and bottom conducting material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.

The present invention is a sealing agent for a liquid crystal display device containing a curable resin and a polymerization initiator, wherein the curable resin is a partially (meth) acrylic modified novolac-type epoxy resin (A) and a partially (meth) acrylic modified non-novolac type The epoxy resin (B) and the non-novolac-type epoxy (meth) acrylate (C) are contained, and the content of the partial (meth) acryl-modified novolac-type epoxy resin (A) is in 100 parts by weight of the curable resin. 3 parts by weight or more and 9 parts by weight or less, and the content of the partial (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, and the part (meth) The ratio of the partially (meth) acryl-modified non-novolac-type epoxy resin (B) to the acrylic-modified novolac-type epoxy resin (A) is 1 or more, and the content of the non-novolac-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, and the partial (meth) acrylic modified novolac-type epoxy resin (A) has a weight average molecular weight of 700 or more and 2000 or less. to be.

The present invention will be described in detail below.

The present inventor has considered using a partially (meth) acrylic modified epoxy resin having a relatively high molecular weight as a curable resin in order to improve the low-liquid crystal contamination of the sealing agent for liquid crystal display elements. However, when such a curable resin is used, the sealing agent for liquid crystal display elements obtained may become inferior in coatability and curability. Therefore, the present inventors combined partial (meth) acrylic-modified novolac-type epoxy resins, partial (meth) acryl-modified non-novolac-type epoxy resins, and non-novolac-type epoxy (meth) acrylates, respectively, to a specific content ratio. It was considered to be used. As a result, it was found that a sealing agent for a liquid crystal display element excellent in coatability, curability and low-liquid crystal contamination was obtained, leading to completion of the present invention.

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

The said curable resin is partially (meth) acrylic-modified novolac-type epoxy resin (A) (hereinafter also referred to as "(A) component"), and partially (meth) acryl-modified non-novolac-type epoxy resin (B) (hereinafter, It also contains "(B) component") and non-novolac-type epoxy (meth) acrylate (C) (hereinafter also referred to as "(C) component"). By containing the said (A) component, the said (B) component, and the said (C) component so that content ratio may respectively be the range mentioned later, the sealing agent for liquid crystal display elements of this invention is coatability, curability, and low liquid crystal contamination. This becomes excellent.

In addition, in the present specification, in the "partial (meth) acrylic modified novolac-type epoxy resin", a part of the novolac-type epoxy resin reacts with (meth) acrylic acid to introduce a (meth) acryloyl group. Means

The `` partial (meth) acrylic-modified non-novolac-type epoxy resin '' is a part of an epoxy group that is not a novolac-type epoxy resin (hereinafter also referred to as a `` non-novolac-type epoxy resin '') and reacts with (meth) acrylic acid, ( It means that the (meth) acryloyl group was introduced.

The above-mentioned "non-novolac-type epoxy (meth) acrylate" means that the epoxy group of all non-novolac-type epoxy resins reacts with (meth) acrylic acid to introduce (meth) acryloyl groups.

The "(meth) acrylic" means acrylic or methacryl, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acryloyl" means acryloyl or Methacryloyl.

Since the component (A) is a novolac type, even if the molecular weight is relatively high from the viewpoint of low-liquid crystal contamination, the viscosity rise is gentle and it is difficult to deteriorate the coatability.

The said (A) component has a lower limit of a weight average molecular weight of 700 and an upper limit of 2000. When the weight average molecular weight of the said (A) component is 700 or more, the sealing agent for liquid crystal display elements obtained becomes what has excellent low liquid crystal contamination. When the weight average molecular weight of the said (A) component is 2000 or less, the sealing agent for liquid crystal display elements obtained becomes what is excellent in coatability. The preferable lower limit of the weight average molecular weight of the component (A) is 750, the preferred upper limit is 1500, the more preferred lower limit is 800, and the more preferred upper limit is 1200.

In addition, in this specification, the said weight average molecular weight is the value calculated | required by polystyrene conversion by performing measurement using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column when measuring the weight average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Electric Works) etc. is mentioned, for example.

As said (A) component, for example, partial (meth) acryl-modified phenol novolac-type epoxy resin, partial (meth) acryl-modified orthocresol novolac-type epoxy resin, partial (meth) acryl-modified dicyclopentadiene furnace And a convex-type epoxy resin, a partially (meth) acrylic-modified biphenyl novolac-type epoxy resin, and a partially (meth) acrylic-modified naphthalenephenol novolac-type epoxy resin. Especially, partial (meth) acryl-modified phenol novolak-type epoxy resin is preferable.

The component (A) is reacted with (meth) acrylic acid in the presence of a basic catalyst, according to a conventional method, with some epoxy groups of the novolac-type epoxy resin, so that the component (A), the novolac-type epoxy resin and the novolac It can be obtained in a mixture of a type epoxy (meth) acrylate.

In addition, in this specification, the said "novolak-type epoxy (meth) acrylate" means that the epoxy group of all novolak-type epoxy resins reacts with (meth) acrylic acid, and a (meth) acryloyl group is introduced.

Examples of the novolac-type epoxy resin as a raw material for the component (A) include, for example, phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, dicyclopentadiene novolac-type epoxy resins, and biphenyl novolacs. Type epoxy resins, naphthalene phenol novolac type epoxy resins, and the like.

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

As said component (B), for example, partial (meth) acrylic-modified bisphenol A-type epoxy resin, partial (meth) acryl-modified bisphenol F-type epoxy resin, partial (meth) acryl-modified bisphenol E-type epoxy resin, part ( Meth) acrylic modified bisphenol S-type epoxy resin, partially (meth) acrylic modified 2,2'-diallylbisphenol A type epoxy resin, partially (meth) acrylic modified hydrogenated bisphenol type epoxy resin, partially (meth) acrylic modified propylene oxide Addition 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 di Phenyl ether type epoxy resin, partial (meth) acrylic modified dicyclopentadiene type epoxy resin, partial (meth) acrylic modified naphthalene type epoxy resin, part And a (meth) acryl-modified glycidylamine-type epoxy resin, a partial (meth) acryl-modified alkylpolyol-type epoxy resin, and a partial (meth) acryl-modified rubber-modified epoxy resin. Especially, partial (meth) acrylic-modified bisphenol A type epoxy resin is preferable.

The component (B) is reacted with (meth) acrylic acid in the presence of a basic catalyst in the presence of a basic catalyst according to a conventional method, in which some epoxy groups of the non-novolac-type epoxy resin are reacted with the component (B), the non-novolac-type epoxy resin and the non-novolac It can be obtained in a mixture of a type epoxy (meth) acrylate.

As a non-novolac-type epoxy resin used as a raw material for the component (B), for example, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, 2,2'- Diallyl bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide-added bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide epoxy resin, diphenyl ether epoxy resin, dish And clopentadiene-type epoxy resins, naphthalene-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, and rubber-modified epoxy resins.

The content of the component (B) is, in 100 parts by weight of the curable resin, the upper limit is 25 parts by weight. When the content of the component (B) in 100 parts by weight of the curable resin is 25 parts by weight or less, the resulting sealant for a liquid crystal display device 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.

In addition, the ratio of the component (B) to the component (A) is 1 or more. When the ratio of the component (B) to the component (A) is 1 or more, the resulting sealant for a liquid crystal display device is excellent in coating properties. The preferable lower limit of the ratio of the component (B) to the component (A) is 1.2, and the lower limit is more preferably 1.5.

In addition, "the ratio of the said (B) component with respect to the said (A) component" means content of the said (B) component / content of the said (A) component.

As the component (C), for example, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol E type epoxy (meth) acrylate, bisphenol S type epoxy (meth) acrylic Rate, 2,2'-diallylbisphenol type A epoxy (meth) acrylate, hydrogenated bisphenol type epoxy (meth) acrylate, propylene oxide addition bisphenol type A 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, etc. The can. Especially, bisphenol A type epoxy (meth) acrylate is preferable.

The said (C) component can be obtained by making the epoxy group of all non-novolak-type epoxy resins react with (meth) acrylic acid in presence of a basic catalyst according to a conventional method.

As a non-novolac-type epoxy resin which becomes a raw material of the said (C) component, the thing similar to the non-novolak-type epoxy resin which becomes a raw material of the said (B) component is mentioned.

The content of the component (C) is, in 100 parts by weight of the curable resin, the lower limit is 10 parts by weight and the upper limit is 45 parts by weight. When the content of the component (C) in 100 parts by weight of the curable resin is 10 parts by weight or more, the resulting sealant for a liquid crystal display element becomes excellent in photocurability. When the content of the component (C) is 45 parts by weight or less, the sealing agent for a liquid crystal display element obtained is excellent in 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 sealing agent for liquid crystal display elements of the present invention may further contain other polymerizable compounds as the curable resin in a range that does not impair the object of the present invention.

Examples of the other polymerizable compound include, for example, the novolac-type epoxy resin described above, the non-novolac-type epoxy resin described above, the novolac-type epoxy (meth) acrylate described above, and other ( And meth) acrylic compounds.

As said other (meth) acrylic compound, it is obtained, for example, by (meth) acrylic acid ester compound obtained by reacting the compound which has a hydroxyl group with (meth) acrylic acid, and (meth) acrylic acid derivative which has a hydroxyl group with an isocyanate compound. Urethane (meth) acrylate and the like.

It is preferable that the said other (meth) acrylic compound has 2 or more (meth) acryloyl groups in 1 molecule from a reactive viewpoint.

Among the (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, isomiristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentenyl (meth) ) Acrylate, benzyl (meth) acrylic Ytte, 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, ethyl carbitol ( Meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl ( Meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acrylic Loyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyl oxide Cyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, etc. are mentioned.

Moreover, among the (meth) acrylic acid ester compounds, bifunctional ones include, for example, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, and 1,6-hexanediol Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic Rate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate ) Acrylate, tripropylene glycol di (meth) 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, e Renoxide addition bisphenol F di (meth) acrylate, dimethyloldicyclopentadienyldi (meth) acrylate, ethylene oxide-modified isocyanurate di (meth) acrylate, 2-hydroxy-3- (meth) acryloyl Oxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyetherdiol di (meth) acrylate, polyesterdiol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene And diol di (meth) acrylate.

In addition, among the (meth) acrylic acid ester compound, trifunctional or higher functional groups include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, and propylene oxide-added trimethylolpropane tree. (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide addition isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tree (meth) acrylic Rate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The.

The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with 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, and diphenylmethane-4,4 '. -Diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalenediisocyanate, norbornanediisocyanate, tolidine diisocyanate, xylylenediisocyanate (XDI), hydrogenated XDI, lysinediisocyanate, triphenyl And methanetriisocyanate, tris (isocyanatephenyl) thiophosphate, tetramethylxylylenediisocyanate, 1,6,11-undecantriisocyanate, and the like.

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

Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyetherdiol, polyester diol, polycaprolactone diol, and the like.

As the (meth) acrylic acid derivative having the hydroxyl group, for example, hydroxyalkyl mono (meth) acrylate, mono (meth) acrylate of divalent alcohol, mono (meth) acrylate or di () of trivalent alcohol And meth) acrylates.

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

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol.

As said trivalent alcohol, trimethylol ethane, trimethylolpropane, glycerin etc. are mentioned, for example.

It is preferable that the said other (meth) acrylic compound has a hydrogen bondable unit, such as -OH group, -NH- group, -NH ₂ group from a viewpoint of suppressing liquid crystal contamination.

The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator.

As said polymerization initiator, a radical polymerization initiator, a cationic polymerization initiator, etc. are mentioned, for example.

As the radical polymerization initiator, a photo-radical 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 photo-radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.

As the photo-radical polymerization initiator, specifically, for example, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 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) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (4 -(2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1,2-octanedione2- (O-benzoyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

The photo-radical polymerization initiators may be used alone or in combination of two or more.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, an initiator (hereinafter also referred to as "polymeric azo initiator") made of a polymer azo compound is preferable.

The said thermal radical polymerization initiator may be used individually and may be used in combination of 2 or more type.

In addition, in the present specification, the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat, having a number average molecular weight of 300 or more.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferred upper limit is 300,000. When the number average molecular weight of the polymer azo compound is within this range, it is possible to easily mix 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 more preferable lower limit is 10,000, and the more 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, measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). As a column when measuring the number average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Electric Works) etc. is mentioned, for example.

As said polymer azo compound, what has a structure in which the units, such as polyalkylene oxide and polydimethylsiloxane, is couple | bonded via an azo group, for example is mentioned.

As the polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded through the azo group, it is preferable to have a polyethylene oxide structure.

The polymer azo compound is specifically, for example, a polycondensation product of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, or 4,4'-azobis (4-cyanophene). Carbonate) and polydimethylsiloxane having terminal amino groups.

As what is marketed among the said polymeric azo compounds, VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all are the Fuji Film Wako Pure Chemical Industries Ltd.) etc. are mentioned, for example.

Moreover, as what is marketed as an azo compound rather than a polymer, V-65, V-501 (all are manufactured by Fuji Film Wako Pure Chemical Industries), etc. are mentioned, for example.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.

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 of an ionic photoacid generation type or a nonionic photoacid generation type.

Examples of the photocationic polymerization initiator include organic metal complexes such as onium salts such as aromatic diazonium salts, aromatic halonium salts, aromatic sulfonium salts, iron-allen complexes, titanocene complexes, and arylsilaneol-aluminum complexes. Logistics and the like.

As what is marketed among the said photocationic polymerization initiators, adeka optomer SP-150, adeka optomer SP-170 (all are manufactured by ADEKA) etc. are mentioned, for example.

As for content of the said polymerization initiator, with respect to 100 weight part of said curable resins, a preferable lower limit is 0.01 weight part, and a preferable upper limit is 10 weight part. When the content of the polymerization initiator is within this range, the sealing agent for a liquid crystal display element obtained becomes more 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.

It is preferable that the sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.

Examples of the heat curing agent include organic acid hydrazide, imidazole derivatives, amine compounds, polyhydric phenolic compounds, and acid anhydrides. Among them, a solid organic acid hydrazide is preferably used.

The said heat curing agent may be used individually and may be used in combination of 2 or more type.

Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropyl hydantoin, sebacic acid dihydrazide, isophthalic acid dihydrazide, and adipic acid di Hydrazide, dihydrazide malonate, etc. are mentioned.

Examples of the solid organic acid hydrazide that is commercially available include, for example, organic acid hydrazide from Otsuka Chemical, organic acid hydrazide from Nippon Finechem, organic acid hydrazide from Ajinomoto Fine Techno, and the like. You can.

Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.

Examples of the organic acid hydrazide manufactured by Nippon Finechem Co., Ltd. include MDH and the like.

Examples of the organic acid hydrazide manufactured by Ajinomoto Fine Techno Corporation include Amicure VDH, Amicure VDH-J, Amicure UDH and the like.

The content of the heat curing agent is preferably a lower limit of 1 part by weight and a preferred upper limit of 50 parts by weight relative to 100 parts by weight of the curable resin. When the content of the heat curing agent is within this range, the resulting sealant for a liquid crystal display device is one having superior curability while maintaining excellent coatability and storage stability. The upper limit with more preferable content of the said thermosetting agent is 30 weight part.

It is preferable that the sealing agent for liquid crystal display elements of this invention contains a filler for the purpose of improving viscosity, further adhesiveness by a stress dispersion effect, improvement of linear expansion rate, improvement of moisture resistance of hardened | cured material, etc.

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 earth, smectite, bentonite, montmorillonite, sericite, activated 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 fillers 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 sealing agent for a liquid crystal display element of the present invention is 10 parts by weight, and the preferred upper limit is 70 parts by weight. When the content of the filler is within this range, effects such as improvement in adhesiveness can be exhibited more while suppressing deterioration of coatability and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.

The sealing agent for a liquid crystal display element of the present invention contains flexible particles from the viewpoint of improving the flexibility and adhesiveness of a cured product, or inhibiting the liquid crystal from entering the sealing agent or preventing the sealing agent from eluting from the liquid crystal. It is preferred.

Examples of the flexible particles include silicon-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Especially, silicone type particle | grains and vinyl type particle | grains are preferable.

The said flexible particle may be used individually and may be used in combination of 2 or more type.

As the silicone-based particles, silicone rubber particles are preferable from the viewpoint of dispersibility in 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 suspension polymerization of a monomer in the presence of a radical polymerization initiator, a method of seed polymerization by swelling the seed particles by absorbing the monomer in a non-crosslinked species particle in the presence of a radical polymerization initiator, etc. You can.

Examples of the monomer used 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. And monofunctional monomers such as compounds.

Examples of the alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate, Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobor Neil (meth) acrylate etc. are mentioned.

Examples of the oxygen atom-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, and glycidyl (meth). And acrylates.

As said nitrile containing monomer, (meth) acrylonitrile etc. are mentioned, for example.

As said fluorine-containing (meth) acrylates, trifluoromethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, etc. are mentioned, for example.

Among these, alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the amount of strain when a 1 g load is added can be increased.

Moreover, in order to have a crosslinked structure, you may use a polyfunctional monomer as a monomer used 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, and trimethylolpropanetri (meth) ) Acrylate, 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) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) And acrylate, isocyanuric skeleton tri (meth) acrylate, and the like. Among them, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, () because the molecular weight between the crosslinking points is large and the amount of deformation when a 1 g load is added can be increased. Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are preferred.

The amount of the crosslinkable monomer used is, in the whole monomer as a raw material for forming the (meth) acrylic particles, the preferred lower limit is 1% by weight and the preferred upper limit is 90% by weight. When the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when kneaded with other sealing agent components, problems such as swelling and the like are not caused, 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.

Further, in addition to these acrylic monomers, styrene-based monomers, vinyl ethers, carboxylic acid vinyl esters, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate , Divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ- (meth) acryloxypropyltrimethoxysilane, and monomers such as vinyltrimethoxysilane may be used.

Examples of the styrene-based monomers include styrene, α-methylstyrene, and trimethoxysilylstyrene.

As said vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, etc. are mentioned, for example.

As said carboxylic acid vinyl ester, vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, etc. are mentioned, for example.

As said unsaturated hydrocarbon, ethylene, propylene, isoprene, butadiene etc. are mentioned, for example.

Examples of the halogen-containing monomers include vinyl chloride, vinyl fluoride, and chlorstyrene.

As the (meth) acrylic particles, core shell (meth) acrylate copolymer fine particles are also preferably used.

As what is marketed among the said core shell (meth) acrylate copolymer microparticles | fine-particles, F351 (made by Aika Corporation) etc. is mentioned, for example.

Moreover, as said vinyl type particle | grains, you may use polydivinylbenzene particle, polychloroprene particle, butadiene rubber particle, etc., for example.

The preferable lower limit of the average particle diameter of the flexible particles is 0.01 μm, and the preferred upper limit is 10 μm. When the average particle diameter of the flexible particles is within this range, the effect of improving the flexibility and adhesiveness of the cured product of the sealing agent for a liquid crystal display element obtained becomes more excellent. The lower limit of the average particle diameter of the flexible particles is more preferably 0.1 µm, and the upper limit is more preferably 8 µm.

In addition, in this specification, the average particle diameter of the said flexible particle means the value obtained by measuring using a laser diffraction type particle size distribution measuring device. As the laser diffraction type particle size distribution measuring device, a master sizer 2000 (manufactured by Malvern) can be used.

The preferable lower limit of the hardness of the flexible particles is 10, and the preferred upper limit is 50. When the hardness of the flexible particles is within this range, the effect of improving the flexibility and adhesiveness of the cured product of the sealing agent for a liquid crystal display element obtained becomes more excellent. The lower limit of the hardness of the flexible particles is more preferably 20, and the upper limit is more preferably 40.

In addition, in this specification, the hardness of the said flexible particle means the durometer A hardness measured by the method based on JISK6253.

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

It is preferable that the sealing agent for liquid crystal display elements of this invention contains a silane coupling agent for the purpose of further improving adhesiveness. The silane coupling agent mainly has a role as an adhesion aid for good adhesion between the sealing agent and the substrate.

As said silane coupling agent, 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, etc. are used preferably, for example.

The said silane coupling agent may be used independently and may be used in combination of 2 or more type.

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

The sealing agent for liquid crystal display elements of this invention may contain a light-shielding agent. By containing the said light-shielding agent, the sealing agent for liquid crystal display elements of this invention can be used conveniently as a light-shielding sealing agent.

Examples of the light blocking agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Especially, titanium black is preferable.

The said light-shielding agent may be used independently and may be used in combination of 2 or more type.

The titanium black is a material having a high transmittance for light near the ultraviolet region, particularly at wavelengths of 370 nm or more and 450 nm or less, compared to the average transmittance of light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black is a light-shielding agent having a property of imparting light-shielding property to the sealing agent for liquid crystal display elements of the present invention by sufficiently shielding light of a wavelength in the visible light region, while transmitting light having a wavelength near the ultraviolet region. . As a light-shielding agent contained in the sealing agent for liquid crystal display elements of this invention, a material with high insulation is preferable, and titanium black is also preferable as a light-shielding agent with high insulation.

The titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, or silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. It is also possible to use titanium black with a surface treatment, such as one coated with an inorganic component. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.

Moreover, the liquid crystal display element manufactured using the sealing agent for liquid crystal display elements of the present invention containing the titanium black as a light blocking agent has sufficient light shielding property, and thus does not leak light, has high contrast, and has excellent image display quality. It is possible to realize a liquid crystal display element having.

As what is marketed among the said titanium black, the titanium black by Mitsubishi Materialrial Co., Ltd., the titanium black by Ako Chemical Co., etc. is mentioned, for example.

Examples of the titanium black manufactured by Mitsubishi Materialrial Co., Ltd. include 12S, 13M, 13M-C, 13R-N, and 14M-C.

As the titanium black manufactured by Ako Chemical Industries, for example, Tirak D and the like can be mentioned.

The preferred lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferred upper limit is 30 m 2 / g, the more preferred lower limit is 15 m 2 / g, and the more preferred upper limit is 25 m 2 / g.

Moreover, the preferable lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred 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 preferred lower limit is 1 nm and the preferred upper limit is 5 μm. When the primary particle diameter of the light-shielding agent is within this range, the viscosity and thixotropy of the sealant for the liquid crystal display element obtained are not significantly increased, and the coating property is more excellent. The lower limit of the primary particle diameter of the light-shielding agent is 5 nm, the more preferable upper limit is 200 nm, the more preferable lower limit is 10 nm, and the more preferable upper limit is 100 nm.

In addition, the primary particle diameter 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 system (for example, manufactured by PARTICLE SIZING SYSTEMS, "NICOMP 380ZLS"). can do.

The preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing agent for a liquid crystal display element of the present invention is 5 parts by weight, and the preferred upper limit is 80 parts by weight. When the content of the light-shielding agent is within this range, the adhesiveness of the sealing agent for a liquid crystal display element obtained, the strength after curing, and the drawability are not significantly reduced, and the effect of improving the light-shielding property can be exhibited more. The more preferable lower limit of the content of the light blocking agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the more preferable lower limit is 30 parts by weight, and the more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention may further contain additives such as a stress reliever, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary.

As a method for manufacturing the sealing agent for a liquid crystal display element of the present invention, for example, a homodisper, a homo mixer, a universal mixer, a planetary mixer, a kneader, a mixer such as three rolls, and a curable resin and And a method of mixing additives such as a polymerization initiator and a thermal curing agent or a silane coupling agent added as necessary.

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

By mixing the conductive fine particles with the sealing agent for a liquid crystal display element of the present invention, an upper and lower conduction material can be produced. The top and bottom conducting material containing the sealing agent for liquid crystal display elements of this invention and electroconductive fine particles is also one of this invention.

As the conductive fine particles, a metal ball, a material having a conductive metal layer formed on the surface of the resin fine particles, etc. can be used. Among them, it is preferable to form a conductive metal layer on the surface of the resin fine particles, because of the excellent elasticity of the resin fine particles, a conductive connection is possible without damaging the transparent substrate or the like.

The liquid crystal display element which uses the sealing agent for liquid crystal display elements of this invention, or the top and bottom conduction material of this invention is also one of this invention.

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

First, the sealing agent for the liquid crystal display element of the present invention is applied to one of two substrates, such as a glass substrate or an electrode formed of an ITO thin film or a polyethylene terephthalate substrate, by screen printing, dispenser coating, or the like to form a seal pattern on the frame. The forming process is performed. Subsequently, in the state in which the sealing agent for a liquid crystal display element of the present invention is uncured, a small liquid droplet of liquid crystal is applied dropwise into a frame of a seal pattern of a substrate, and a process of superposing another substrate under vacuum is performed. Thereafter, a method of temporarily curing the sealing agent by irradiating light, such as ultraviolet rays, to the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention, and heating the temporary curing agent to thereby perform the main curing process. , A liquid crystal display element can be obtained.

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements excellent in coatability, curability, and low liquid crystal contamination can be provided. Further, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

(Preparation of a novolac-type curable resin mixture (A1))

After dissolving 557 parts by weight of phenol novolac-type epoxy resin (manufactured by DIC, "EPICLON N-740") in 900 ml of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. To the obtained solution, 122 parts by weight of acrylic acid was added dropwise under reflux stirring for 2 hours, and further reflux stirring was performed for 6 hours. Next, by removing the toluene under reduced pressure, a novolac-type curable resin mixture (A1) was obtained.

^{By 1} H-NMR, ¹³ C-NMR and FT-IR, the novolac-type curable resin mixture (A1) contains 11.8% by weight of a partially acrylic modified phenol novolac-type epoxy resin and 68.6% by weight of a phenol novolac-type epoxy resin. %, And it was confirmed that it was a mixture containing 19.6% by weight of phenol novolac-type epoxy acrylate.

Moreover, the weight average molecular weight of the obtained partial acrylic-modified phenol novolak-type epoxy resin was 1200.

(Preparation of novolac-type curable resin mixture (A2))

After dissolving 395 parts by weight of phenol novolac-type epoxy resin (DIC Corporation, "EPICLON N-730S") in 900 ml of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. After 94 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Next, by removing the toluene under reduced pressure, a novolac-type curable resin mixture (A2) was obtained.

^{By 1} H-NMR, ¹³ C-NMR and FT-IR, the novolac-type curable resin mixture (A2) contains 11.8% by weight of partially acrylic modified phenol novolac-type epoxy resin and 68.6 weight of phenol novolac-type epoxy resin. %, And it was confirmed that it was a mixture containing 19.6% by weight of phenol novolac-type epoxy acrylate.

Moreover, the weight average molecular weight of the obtained partial acrylic-modified phenol novolak-type epoxy resin was 800.

(Preparation of novolac-type curable resin mixture (A3))

After dissolving 965 parts by weight of phenol novolac-type epoxy resin (DIC Corporation, "EPICLON N-770") in 1800 ml of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. After 216 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a novolac-type curable resin mixture (A3).

^{By 1} H-NMR, ¹³ C-NMR and FT-IR, the novolac-type curable resin mixture (A3) contains 11.8% by weight of a partially acrylic modified phenol novolac-type epoxy resin and 68.6 weight of a phenol novolac-type epoxy resin. %, And it was confirmed that it was a mixture containing 19.6% by weight of phenol novolac-type epoxy acrylate.

Moreover, the weight average molecular weight of the obtained partial acrylic-modified phenol novolak-type epoxy resin was 2500.

(Production of non-volak-type curable resin mixture (B1))

After dissolving 326 parts by weight of bisphenol-A epoxy resin (Mitsubishi Chemical Corporation, "jER 828EL") in 900 ml of toluene, 0.3 g of triphenylphosphine was added to obtain a uniform solution. After 72 parts by weight of acrylic acid was added dropwise to the obtained solution under reflux stirring, reflux stirring was further performed for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a non-novolac-type curable resin mixture (B1).

^{By 1} H-NMR, ¹³ C-NMR, and FT-IR, the non-novolac-type curable resin mixture (B1) contains 50% by weight of partially acrylic modified bisphenol A-type epoxy resin and 25% by weight of bisphenol A-type epoxy resin, It was confirmed that it was a mixture containing 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 was stirred with a planetary stirring device (manufactured by Shinki Corporation, "Awatori Renta"), and then uniformly mixed with three rolls of ceramics to compare Examples 1 to 10. The sealing agent for liquid crystal display elements of Examples 1-8 was obtained.

<Evaluation>

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

(Viscosity)

About the sealing agent for each liquid crystal display element obtained by the Example and the comparative example, the viscosity at 25 degreeC and 1 rpm was measured using the E-type viscosity meter (Brookfield Corporation make, "DV-III").

(Coating)

Using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER300"), the sealing agent for each liquid crystal display element obtained in Examples and Comparative Examples was applied on a glass substrate. When the dispense nozzle was applied with 400 µm, nozzle gap 30 µm, and outlet pressure fixed at 300 고정, it was `` ○ '' that the coating could be applied without scratches or flow. When the flow occurred, "△", coating breakage occurred, or when no coating was applied at all, "x" was used to evaluate the coating properties.

(Curable)

After applying about 5 micrometers of the sealing agent for each liquid crystal display element obtained by the Example and the comparative example on a glass substrate, the glass substrate of the same size was superimposed. Subsequently, 3000 mJ / cm 2 was irradiated with ultraviolet rays having a wavelength of 365 nm using a metal halide lamp. The amount of change (reduction rate) before and after light irradiation of the peak derived from the (meth) acryloyl group was measured using an infrared spectroscopy device (manufactured by BIORAD, "FTS3000").

When the reduction rate of the peak derived from the (meth) acryloyl group after light irradiation was 95% or more, "◎", when it was 85% or more and less than 95%, "○", when it was 75% or more and less than 85%, "△" , When it was less than 75%, the curability was evaluated as "x".

(Low liquid crystal contamination)

After mixing the silica spacer (Sekisui Chemical Industries, Inc., "SI-H055") with 1% by weight of the sealing agent for each liquid crystal display element obtained in Examples and Comparative Examples, defoaming treatment to remove air bubbles in the sealing agent, The syringe for dispensing (manufactured by Musashi Engineering Co., Ltd., "PSY-10E") was charged and subjected to defoaming treatment again. Next, using a dispenser (manufactured by Musashi Engineering Co., Ltd., "SHOTMASTER300"), a sealing agent was applied as if drawing a frame on one of the glass substrates on which two ITO thin films were formed. Subsequently, micro droplets of TN liquid crystal (manufactured by Chisso Corporation, "JC-5001LA") were applied dropwise onto the frame made of a sealing agent with a liquid crystal dropping device, and the glass substrate on which the other ITO thin film was formed was overlaid and vacuum bonded. Two substrates were pasted together under a reduced pressure of 5 Pa. The cell after bonding was irradiated with ultraviolet rays of 3000 mJ / cm 2 with a metal halide lamp, followed by heating at 120 ° C. for 60 minutes to heat-cure the sealing agent to produce a liquid crystal display device. After the obtained liquid crystal display element was stored for 100 hours in an environment at a temperature of 80 ° C. and a humidity of 90% RH, a voltage driving of AC 3.5 V was performed, and the presence or absence of display unevenness (color unevenness) was visually observed. When the display unevenness was not seen at all, "○", the display non-uniformity in the peripheral portion of the liquid crystal display element was "△", and the display non-uniformity spread not only in the peripheral portion of the liquid crystal display element but also in the center portion as "x". Low liquid crystal contamination was evaluated.

Industrial availability

ADVANTAGE OF THE INVENTION According to this invention, the sealing agent for liquid crystal display elements excellent in coatability, curability, and low liquid crystal contamination can be provided. Further, according to the present invention, it is possible to provide a vertical conduction material and a liquid crystal display element formed by using the sealing agent for a liquid crystal display element.

Claims (3)

As a sealant for a liquid crystal display element containing a curable resin and a polymerization initiator,
The said curable resin is a partial (meth) acrylic-modified novolac-type epoxy resin (A), a partial (meth) acryl-modified non-novolac-type epoxy resin (B), and a non-novolac-type epoxy (meth) acrylate (C). Containing,
The content of the partial (meth) acryl-modified novolac-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-novolac-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 novolac-type epoxy resin (A) The ratio of the partial (meth) acrylic-modified non-novolac-type epoxy resin (B) to is 1 or more,
The content of the non-novolac-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 novolac-type epoxy resin (A) has a weight average molecular weight of 700 or more and 2000 or less, and is a sealing agent for a liquid crystal display device. A vertical conduction material containing the sealing agent for a liquid crystal display element according to claim 1 and conductive fine particles. A liquid crystal display element comprising the sealing agent for a liquid crystal display element according to claim 1 or the top and bottom conducting material according to claim 2.