KR102549659B1 - Sealing agent for liquid crystal display elements, top and bottom conduction materials, and liquid crystal display elements - Google Patents

Abstract

An object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, hardenability, and low liquid-crystal staining property. Moreover, this invention aims at providing the top-and-bottom conduction material and liquid crystal display element formed using this sealing compound for liquid crystal display elements.
The present invention is a sealing agent for a liquid crystal display element 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)acryl-modified non-novolak-type It contains an epoxy resin (B) and a non-novolak-type epoxy (meth)acrylate (C), and the content of the partially (meth)acrylic-modified novolak-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 partial (meth)acrylic modified non-novolac type epoxy resin (B) The ratio of the partially (meth)acrylic-modified non-novolak-type epoxy resin (B) to the acrylic-modified novolak-type epoxy resin (A) is 1 or more, and the content of the nonvolak-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 partially (meth)acrylic-modified novolak-type epoxy resin (A) has a weight average molecular weight of 700 or more and 2000 or less. am.

Description

Sealing agent for liquid crystal display elements, top and bottom conduction materials, and liquid crystal display elements

The present invention relates to a sealing compound for a liquid crystal display element having excellent applicability, curability and low liquid crystal staining properties. Moreover, this invention relates to the vertical conduction material and liquid crystal display element formed using the sealing compound for liquid crystal display elements.

In recent years, as a manufacturing method of liquid crystal display elements such as liquid crystal display cells, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, a light-heat combined use hardening type sealing agent disclosed in Patent Document 1 and Patent Document 2 A liquid crystal dropping method called a dropping method using a liquid crystal is used.

In the dropping method, first, a rectangular seal pattern is formed on one side of a substrate on which two electrodes are formed by dispensing. Next, in a state where the sealant is not cured, liquid crystal droplets 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 temporarily cure. Then, main hardening is performed by heating, and a liquid crystal display element is produced. Currently, this dripping method is the mainstream of the manufacturing method of a liquid crystal display element.

[0003] By the way, in modern times where mobile devices having various liquid crystal panels, such as mobile phones and portable game consoles, are widespread, miniaturization of devices is the most demanded subject. As a method of miniaturization, narrowing of the frame of the liquid crystal display unit can be cited. For example, arranging the position of the seal unit under the black matrix has been implemented (hereinafter, also referred to as narrow frame design).

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

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

An object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, hardenability, and low liquid-crystal staining property. Moreover, this invention aims at providing the top-and-bottom conduction material and liquid crystal display element formed using this sealing compound for liquid crystal display elements.

The present invention is a sealing agent for a liquid crystal display element 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)acryl-modified non-novolak-type It contains an epoxy resin (B) and a non-novolak-type epoxy (meth)acrylate (C), and the content of the partially (meth)acrylic-modified novolak-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 partial (meth)acrylic modified non-novolac type epoxy resin (B) The ratio of the partially (meth)acrylic-modified non-novolak-type epoxy resin (B) to the acrylic-modified novolac-type epoxy resin (A) is 1 or more, and the content of the nonvolac-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 partially (meth)acrylic-modified novolak-type epoxy resin (A) has a weight average molecular weight of 700 or more and 2000 or less. am.

The present invention is described in detail below.

This inventor examined using a partial (meth)acrylic-modified epoxy resin with a comparatively high molecular weight as a curable resin in order to improve the low liquid-crystal staining property of the sealing compound for liquid crystal display elements. However, when such a curable resin is used, the sealing agent for liquid crystal display elements obtained may be inferior in applicability and sclerosis|hardenability. Therefore, the present inventors have combined a partially (meth)acrylic-modified novolac-type epoxy resin, a partially (meth)acryl-modified nonvolac-type epoxy resin, and a nonvolak-type epoxy (meth)acrylate so as to have a specific content ratio, respectively. use was reviewed. As a result, it was found that a sealing compound for liquid crystal display elements excellent in applicability, curability and low liquid crystal staining properties could be obtained, and the present invention was completed.

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

The curable resin is a partially (meth)acrylic-modified novolac-type epoxy resin (A) (hereinafter also referred to as "component (A)") and a partially (meth)acryl-modified non-novolak-type epoxy resin (B) (hereinafter, Also referred to as "component (B)") and a non-novolak type epoxy (meth)acrylate (C) (hereinafter also referred to as "component (C)") are contained. By containing the component (A), the component (B), and the component (C) so that the content ratio is within the ranges described below, respectively, the sealant for liquid crystal display elements of the present invention has applicability, curability, and low liquid crystal staining properties. this will be excellent

In the present specification, the "partially (meth)acrylic-modified novolak-type epoxy resin" refers to a reaction in which a part of the epoxy group of the novolac-type epoxy resin reacts with (meth)acrylic acid to introduce a (meth)acryloyl group. means that

The "partially (meth)acrylic-modified non-novolak-type epoxy resin" refers to a non-novolak-type epoxy resin (hereinafter, also referred to as "nonvolac-type epoxy resin") reacting with (meth)acrylic acid, ( It means that a meth)acryloyl group is introduced.

The above "nonvolak-type epoxy (meth)acrylate" means that the epoxy groups of all nonvolak-type epoxy resins react with (meth)acrylic acid to introduce (meth)acryloyl groups.

The above "(meth)acryl" means acryl or methacryl, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or means methacryloyl.

Since the component (A) is a novolak type, from the viewpoint of low liquid crystal staining property, even if the molecular weight is relatively high, the viscosity increase is moderate, and the coating property is not easily deteriorated.

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 resulting sealing compound for liquid crystal display elements has excellent low liquid crystal staining properties. When the weight average molecular weight of the component (A) is 2000 or less, the obtained sealing compound for liquid crystal display elements has excellent coating properties. A preferable lower limit of the weight average molecular weight of the component (A) is 750, a preferable upper limit is 1500, a more preferable lower limit is 800, and a more preferable upper limit is 1200.

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

Examples of the component (A) include partially (meth)acrylic-modified phenol novolak-type epoxy resins, partially (meth)acrylic-modified orthocresol novolac-type epoxy resins, and partially (meth)acrylic-modified dicyclopentadiene phenols. A rockfish-type epoxy resin, a partially (meth)acrylic-modified biphenyl novolak-type epoxy resin, and a partially (meth)acryl-modified naphthalenephenol novolac-type epoxy resin. Among them, partially (meth)acrylic-modified phenol novolak-type epoxy resins are preferred.

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

In the present specification, the term "novolak-type epoxy (meth)acrylate" means that the epoxy groups of all novolac-type epoxy resins react with (meth)acrylic acid to introduce (meth)acryloyl groups.

Examples of the novolac-type epoxy resins used as the raw material of the component (A) include phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, dicyclopentadiene novolac-type epoxy resins, and biphenyl novolaks. type epoxy resins, naphthalene phenol novolak type epoxy resins, and the like.

The content of the component (A) has a lower limit of 3 parts by weight and an upper limit of 9 parts by weight in 100 parts by weight of the curable resin. When content of the said (A) component is 3 weight part or more, the sealing compound for liquid crystal display elements obtained becomes the thing excellent in low liquid-crystal staining property. When content of the said (A) component is 9 weight part or less, the sealing compound for liquid crystal display elements obtained becomes a thing excellent in applicability. A preferable lower limit of the content of the component (A) is 4 parts by weight, a preferable upper limit is 8 parts by weight, and a more preferable upper limit is 7 parts by weight.

As the component (B), for example, partially (meth)acrylic modified bisphenol A type epoxy resin, partially (meth)acrylic modified bisphenol F type epoxy resin, partially (meth)acrylic modified bisphenol E type epoxy resin, partial ( 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, partially (meth)acryl modified resorcinol type epoxy resin, partially (meth)acryl modified biphenyl type epoxy resin, partially (meth)acryl modified sulfide type epoxy resin, partially (meth)acryl modified di Phenylether type epoxy resin, partially (meth)acrylic modified dicyclopentadiene type epoxy resin, partially (meth)acrylic modified naphthalene type epoxy resin, partially (meth)acrylic modified glycidylamine type epoxy resin, partial (meth)acrylic Modified alkyl polyol-type epoxy resins, partially (meth)acrylic-modified rubber-modified epoxy resins, and the like are exemplified. Among them, partially (meth)acrylic-modified bisphenol A type epoxy resins are preferred.

The component (B) is obtained by reacting a part of the epoxy groups of the nonvolac-type epoxy resin with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method, so that the component (B) and the nonvolak-type epoxy resin and the nonvolac It can be obtained in a mixture of type epoxy (meth)acrylates.

Examples of the nonvolak-type epoxy resins used as the raw material of the component (B) include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol S epoxy resins, and 2,2'- Diallylbisphenol 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, dish A clopentadiene type epoxy resin, a naphthalene type epoxy resin, a glycidylamine type epoxy resin, an alkyl polyol type epoxy resin, a rubber modification type epoxy resin, etc. are mentioned.

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 content of the said (B) component in 100 weight part of said curable resin is 25 weight part or less, the sealing compound for liquid crystal display elements obtained becomes a thing excellent in low liquid-crystal staining property. A 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 a more preferable upper limit is 20 parts by weight.

Moreover, the ratio of the said (B) component to the said (A) component is 1 or more. By making the ratio of the said (B) component with respect to the said (A) component into 1 or more, the sealing compound for liquid crystal display elements obtained becomes a thing excellent in applicability. A preferable lower limit of the ratio of the component (B) to the component (A) is 1.2, and a more preferable lower limit is 1.5.

In addition, "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 epoxy (meth)acrylate, bisphenol F epoxy (meth)acrylate, bisphenol E epoxy (meth)acrylate, and bisphenol S epoxy (meth)acrylate. rate, 2,2'-diallylbisphenol A type epoxy (meth)acrylate, hydrogenated bisphenol type epoxy (meth)acrylate, propylene oxide added bisphenol A type epoxy (meth)acrylate, resorcinol type epoxy (meth) Acrylates, 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)acrylates, glycidylamine-type epoxy (meth)acrylates, alkyl polyol-type epoxy (meth)acrylates, rubber-modified epoxy (meth)acrylates, and the like. Especially, bisphenol A epoxy (meth)acrylate is preferable.

Component (C) can be obtained by reacting the epoxy groups of all nonvolak type epoxy resins with (meth)acrylic acid in the presence of a basic catalyst according to a conventional method.

Examples of the nonvolak-type epoxy resin used as a raw material of the component (C) include those similar to the non-novolak-type epoxy resin used as a raw material of the component (B).

The content of the component (C) has a lower limit of 10 parts by weight and an upper limit of 45 parts by weight in 100 parts by weight of the curable resin. When content of the said (C)component in 100 weight part of said curable resin is 10 weight part or more, the sealing compound for liquid crystal display elements obtained becomes a thing excellent in photocurability. When the content of the component (C) is 45 parts by weight or less, the resulting sealing compound for liquid crystal display elements has excellent adhesive properties. A 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 a more preferable lower limit is 18 parts by weight.

The sealing compound for liquid crystal display elements of this invention may further contain other polymeric compounds as said curable resin within the range which does not impair the objective of this invention.

Examples of the other polymerizable compounds include the novolac-type epoxy resins described above, the non-novolak-type epoxy resins described above, the novolak-type epoxy (meth)acrylates described above, and other ( A meth)acrylic compound etc. are mentioned.

Examples of the other (meth)acrylic compounds include (meth)acrylic acid ester compounds obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and (meth)acrylic acid derivatives obtained by reacting an isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group. Urethane (meth)acrylate etc. are mentioned.

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

Examples of monofunctional among the above (meth)acrylic acid ester compounds include 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, isomyristyl (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 ) Acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl ( Meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl ( meth)acrylate, ethylcarbitol (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)acryloyloxy Ethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl 2-hydroxypropylphthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl ( Meth) acrylate etc. are mentioned.

In addition, as a bifunctional thing among the said (meth)acrylic acid ester compounds, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol, for example Di(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,10-decanedioldi(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate 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, ethylene oxide added bisphenol F di(meth)acrylate, dimethylol dicyclopentadienyl di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, 2-hydroxy- 3-(meth)acryloyloxypropyl (meth)acrylate, carbonatedioldi(meth)acrylate, polyetherdioldi(meth)acrylate, polyesterdioldi(meth)acrylate, polycaprolactonedioldi (meth)acrylate, polybutadiene diol di(meth)acrylate, etc. are mentioned.

Moreover, as a thing more than trifunctional among the said (meth)acrylic acid ester compounds, for example, trimethylol-propane tri(meth)acrylate, ethylene oxide addition trimethylol-propane tri(meth)acrylate, and propylene oxide addition trimethylol-propane tri (meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide added glycerin tri(meth)acrylate rate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta( meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

As said urethane (meth)acrylate, it can obtain, for example by making a (meth)acrylic acid derivative which has a hydroxyl group react with an isocyanate compound in the presence of a catalytic amount of a tin-type 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-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenyl Methane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecane triisocyanate, etc. are mentioned.

Moreover, as said isocyanate compound, the chain extension isocyanate compound obtained by reaction of a polyol and 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)acrylates, mono(meth)acrylates of dihydric alcohols, mono(meth)acrylates of trihydric alcohols, or di( Meth) acrylate etc. are mentioned.

Examples of the hydroxyalkyl mono(meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 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 trihydric alcohol, trimethylolethane, a trimethylol propane, glycerol etc. are mentioned, for example.

From the viewpoint of suppressing liquid crystal contamination, the other (meth)acrylic compound preferably has a hydrogen bondable unit such as -OH group, -NH- group, or -NH ₂ group.

The sealing compound 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, an optical radical polymerization initiator that generates radicals by light irradiation and a thermal radical polymerization initiator that generates radicals by heating can be used.

As said radical photopolymerization initiator, a benzophenone compound, an acetophenone compound, an acylphosphine oxide compound, a titanocene compound, an oxime ester compound, a benzoin ether compound, a thioxanthone compound etc. are mentioned, for example.

As said radical photopolymerization initiator, specifically, for example, 1-hydroxycyclohexylphenyl ketone, 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-octanedione 2- (O-benzoyl oxime), 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned.

The said radical photopolymerization initiator may be used independently and may be used in combination of 2 or more types.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, the initiator which consists of a polymeric azo compound (henceforth a "polymeric azo initiator") is preferable.

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

In addition, in this specification, a polymeric azo compound means a compound with a number average molecular weight of 300 or more which has an azo group and produces|generates the radical which can harden a (meth)acryloyl group by heat.

A preferable lower limit of the number average molecular weight of the polymeric azo compound is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the polymeric azo compound is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. A more preferable lower limit of the number average molecular weight of the polymeric azo compound is 5000, a more preferable upper limit is 100,000, a still more preferable lower limit is 10,000, and a still more preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and calculated|required by polystyrene conversion. As a column at the time of measuring the number average molecular weight by polystyrene conversion by GPC, Shodex LF-804 (made by Showa Denko) etc. is mentioned, for example.

Examples of the polymeric azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded through an azo group.

As the polymeric azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded through the azo group, those having a polyethylene oxide structure are preferable.

Specifically, as the polymeric azo compound, for example, a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol or 4,4'-azobis(4-cyanophene) carbonic acid) and a polydimethylsiloxane having a terminal amino group; and the like.

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

Moreover, as what is marketed as an azo compound other than a polymer, V-65 and V-501 (all manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), 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 a protonic acid or a Lewis acid upon light irradiation, and may be of an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, organometallic complexes such as iron-alene complexes, titanocene complexes, and arylsilanol-aluminum complexes. logistics, etc.

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

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 content of the said polymerization initiator is this range, the sealing compound for liquid crystal display elements obtained becomes a thing more excellent in storage stability and sclerosis|hardenability, suppressing liquid-crystal contamination. A more preferable lower limit of the content of the polymerization initiator is 0.1 part by weight, and a more preferable upper limit is 5 parts by weight.

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

Examples of the thermal curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenolic compounds, and acid anhydrides. Especially, solid organic acid hydrazide is used preferably.

The said thermosetting agent may be used independently and may be used in combination of 2 or more types.

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

Examples of commercially available solid organic acid hydrazides include organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazide manufactured by Nippon FineChem, and organic acid hydrazide manufactured by Ajinomoto Fine Techno Co., Ltd. can

As said organic acid hydrazide by Otsuka Chemical Co., Ltd., SDH, ADH, etc. are mentioned, for example.

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

As said organic acid hydrazide by Ajinomoto Fine Techno, Inc., Amicure VDH, Amicure VDH-J, Amicure UDH etc. are mentioned, for example.

The content of the thermal curing agent has a preferable lower limit of 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 content of the said thermosetting agent is this range, sclerosis|hardenability becomes a thing more excellent, with the sealing compound for liquid crystal display elements obtained maintaining the excellent coatability and storage stability. A more preferable upper limit of the content of the thermal curing agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of the present invention preferably contains a filler for the purpose of improving the viscosity, further improving the adhesiveness due to the stress dispersing effect, improving the coefficient of linear expansion, and improving the moisture resistance of the cured product.

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 microparticles, polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.

The said filler may be used independently and may be used in combination of 2 or more types.

A preferable lower limit of the content of the filler in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 10 parts by weight, and a preferable upper limit is 70 parts by weight. By the content of the said filler being this range, effects, such as an improvement of adhesiveness, can be exhibited more, suppressing deterioration, such as applicability|paintability. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealing agent for liquid crystal display elements of the present invention contains flexible particles from the viewpoint of improving the flexibility, adhesiveness, etc. of a cured product, or suppressing liquid crystal from entering the sealing agent or eluting the sealing agent into the liquid crystal. it is desirable

Examples of the flexible particles include silicone-based particles, vinyl-based particles, urethane-based particles, fluorine-based particles, and nitrile-based particles. Among them, silicone-based particles and vinyl-based particles are preferable.

The said flexible particle|grains may be used independently and may be used in combination of 2 or more types.

As said silicone type particle|grains, silicone rubber particle|grains are preferable from a viewpoint of dispersibility with respect to 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 monomers in the presence of a radical polymerization initiator, a method of seed polymerization by causing monomers to be absorbed into non-crosslinked species particles in the presence of a radical polymerization initiator to swell the species particles, and the like can

Examples of monomers used as raw materials 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 .

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, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, isobor Nyl (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)acrylate. Acrylates etc. are mentioned.

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

Examples of the fluorine-containing (meth)acrylates include trifluoromethyl (meth)acrylate and pentafluoroethyl (meth)acrylate.

Among them, alkyl (meth)acrylates are preferable from the viewpoint that the Tg of the homopolymer is low and the amount of deformation when a load of 1 g 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 said (meth)acrylic particle.

Examples of the polyfunctional monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. )Acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, glycerol tri(meth)acrylate, glycerol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate )Acrylate, (poly)propylene glycoldi(meth)acrylate, (poly)tetramethylenedi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth) Acrylates, isocyanuric acid skeleton tri(meth)acrylate, and the like are exemplified. Among them, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, ( Poly)tetramethylenedi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, and 1,6-hexanedioldi(meth)acrylate are preferred.

The usage amount of the crosslinkable monomer is preferably 1% by weight as a lower limit and 90% by weight as a preferable upper limit based on the total amount of monomers used as raw materials for forming the (meth)acrylic particles. When the usage amount of the crosslinkable monomer is 1% by weight or more, the solvent resistance is improved, and when kneaded with other sealing agent components, problems such as swelling do not occur, and it becomes easy to disperse uniformly. When the amount of the crosslinkable monomer is 90% by weight or less, the recovery rate can be reduced. A more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.

In addition to these acrylic monomers, styrenic 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)acryloxypropyl trimethoxysilane, and vinyl trimethoxysilane may be used.

As said styrene type monomer, styrene, (alpha)-methylstyrene, trimethoxysilyl styrene etc. are mentioned, for example.

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

Examples of the carboxylic acid vinyl esters include vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate.

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

Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, and chlorostyrene.

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

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

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

The lower limit of the average particle size of the flexible particles is preferably 0.01 μm, and the upper limit is preferably 10 μm. When the average particle diameter of the said flexible particle is this range, the effect of improving the softness|flexibility and adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained becomes more excellent. A more preferable lower limit of the average particle diameter of the flexible particles is 0.1 μm, and a more preferable upper limit is 8 μm.

In addition, in this specification, the average particle diameter of the said soft particle means the value obtained by measuring using a laser diffraction type particle size distribution analyzer. As the laser diffraction type particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Corporation) or the like can be used.

A preferable lower limit of the hardness of the flexible particle is 10, and a preferable upper limit is 50. The effect of improving the flexibility and adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained becomes more excellent because the hardness of the said flexible particle|grain is this range. A more preferable lower limit of the hardness of the flexible particle is 20, and a more preferable upper limit is 40.

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

A preferable lower limit of the content of the flexible particles in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 5 parts by weight, and a preferable upper limit is 50 parts by weight. When content of the said flexible particle|grain is this range, the effect of improving the softness|flexibility and adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements 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 compound 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 auxiliary agent for good adhesion between the sealant 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 types.

A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealing compound for a liquid crystal display device of the present invention is 0.1 part by weight, and a preferable upper limit is 10 parts by weight. When content of the said silane coupling agent is within this range, the effect of improving adhesiveness can be exhibited more, suppressing generation|occurrence|production 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 compound 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 suitably as a light-shielding sealing agent.

Examples of the light-shielding 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 types.

The titanium black is a material that has higher transmittance to light in the vicinity of the ultraviolet region, particularly with a wavelength of 370 nm to 450 nm, compared to the average transmittance to light with a wavelength of 300 nm to 800 nm. That is, the titanium black imparts light-shielding properties to the sealant for liquid crystal display elements of the present invention by sufficiently shielding light of wavelengths in the visible region, while transmitting light of wavelengths in the vicinity of the ultraviolet region. . As a light-shielding agent contained in the sealing compound for liquid crystal display elements of this invention, a substance with high insulation is preferable, and titanium black is preferable also as a light-shielding agent with high insulation.

Although the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, those whose surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. It is also possible to use titanium black that has been surface-treated, such as coated with an inorganic component of . Especially, what is processed with the organic component is preferable at the point which can improve insulation more.

Moreover, since the liquid crystal display element manufactured using the sealing compound for liquid crystal display elements of this invention containing the said titanium black as a light-shielding agent has sufficient light-shielding property, there is no light leakage, it has high contrast, and it has excellent image display quality. A liquid crystal display element having a can be realized.

As what is marketed among the said titanium blacks, titanium black by the Mitsubishi Material company, titanium black by the Ako Kasei company, etc. are mentioned, for example.

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

As titanium black by the said Ako Kasei Co., Ltd., Tyrac D etc. are mentioned, for example.

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

In addition, a preferable lower limit of the volume resistivity of the titanium black is 0.5 Ω cm, a preferable upper limit is 3 Ω cm, a more preferable lower limit is 1 Ω cm, and a more preferable upper limit is 2.5 Ω cm.

The primary particle size 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 a preferable lower limit is 1 nm and a preferable upper limit is 5 μm. When the primary particle size of the light-shielding agent is within this range, the viscosity and thixotropy of the sealing compound for liquid crystal display elements obtained do not increase significantly, and the applicability becomes more excellent. A more preferable lower limit of the primary particle diameter of the light-shielding agent is 5 nm, a more preferable upper limit is 200 nm, a still more preferable lower limit is 10 nm, and a still more preferable upper limit is 100 nm.

In addition, the primary particle size of the light-shielding agent is measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) can do.

A preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealing compound for liquid crystal display elements of the present invention is 5 parts by weight, and a preferable upper limit is 80 parts by weight. When content of the said light-shielding agent is this range, the adhesiveness of the sealing compound for liquid crystal display elements obtained, and the intensity|strength and drawing property after hardening do not fall large, but the effect of improving light-shielding property can be exhibited more. 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 still more preferable lower limit is 30 parts by weight, and a still more preferable upper limit is 60 parts by weight.

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

As a method for producing the sealing compound for a liquid crystal display element of the present invention, for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin and , the method of mixing additives, such as a polymerization initiator and a thermal curing agent and a silane coupling agent added as needed, etc. are mentioned.

The preferable lower limit of the viscosity measured on 25 degreeC and 1 rpm conditions of the sealing compound for liquid crystal display elements of this invention using E-type viscosity meter is 100 Pa.s, and a preferable upper limit is 800 Pa.s. When the said viscosity is this range, the sealing compound for liquid crystal display elements obtained becomes a thing excellent in applicability. A more preferable lower limit of the said viscosity is 200 Pa·s, and a more preferable upper limit is 700 Pa·s.

By blending conductive fine particles with the sealing compound for liquid crystal display elements of the present invention, an upper and lower conduction material can be produced. An upper and lower conduction material containing the sealant for liquid crystal display elements of the present invention and conductive fine particles is also one of the present invention.

As the conductive fine particles, metal balls, resin fine particles having a conductive metal layer formed on the surface thereof, and the like can be used. Among them, those in which a conductive metal layer is formed on the surface of the resin fine particles are preferable in that conductive connection can be made without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

A liquid crystal display element formed using the sealant for liquid crystal display elements of the present invention or the upper and lower conduction material of the present invention is also one of the present 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, a method having each of the following steps is exemplified.

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 or a polyethylene terephthalate substrate on which electrodes such as ITO thin films are formed, by screen printing, dispenser application, etc. to form a frame-shaped seal pattern. Carry out the forming process. Next, in a state where the sealant for a liquid crystal display device of the present invention is not cured, a step of applying droplets of liquid crystal into a frame of a seal pattern of a substrate is carried out, and another substrate is superimposed under vacuum. After that, by a method of performing a step of temporarily curing the sealant by irradiating light such as ultraviolet rays to the seal pattern portion of the sealant for liquid crystal display device of the present invention and a step of heating the temporarily cured sealant to harden the main part , a liquid crystal display element can be obtained.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements excellent in applicability, hardenability, and low liquid-crystal staining property can be provided. Moreover, according to this invention, the top-down conduction material and liquid crystal display element formed using this sealing compound for liquid crystal display elements can be provided.

The present invention will be described in more detail by way of examples below, but the present invention is not limited only to these examples.

(Preparation of novolak-type curable resin mixture (A1))

After dissolving 557 parts by weight of a phenol novolak-type epoxy resin (“EPICLON N-740” manufactured by DIC Corporation) 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 for 2 hours under reflux stirring, and then reflux stirring was further performed for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a novolak-type curable resin mixture (A1).

According to ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolak-type curable resin mixture (A1) contained 11.8% by weight of a partially acrylic-modified phenol novolak-type epoxy resin and 68.6 weight percent of a phenol novolak-type epoxy resin. %, and it was confirmed that it was a mixture containing 19.6% by weight of phenol novolak-type epoxy acrylate.

Moreover, 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))

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

According to ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolac-type curable resin mixture (A2) contained 11.8% by weight of partially acrylic-modified phenol novolac-type epoxy resin and 68.6 weight percent of phenol novolak-type epoxy resin. %, and it was confirmed that it was a mixture containing 19.6% by weight of phenol novolak-type epoxy acrylate.

Moreover, 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))

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

According to ¹ H-NMR, ¹³ C-NMR, and FT-IR, the novolac-type curable resin mixture (A3) contained 11.8% by weight of partially acrylic-modified phenol novolac-type epoxy resin and 68.6 weight percent of phenol novolak-type epoxy resin. %, and it was confirmed that it was a mixture containing 19.6% by weight of phenol novolak-type epoxy acrylate.

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

(Preparation of non-novolac-type curable resin mixture (B1))

After dissolving 326 parts by weight of bisphenol A type epoxy resin ("jER 828EL" manufactured by Mitsubishi Chemical Corporation) 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 for 2 hours under reflux stirring, reflux stirring was further performed for 6 hours. Subsequently, toluene was removed under reduced pressure to obtain a nonvolak-type curable resin mixture (B1).

According to ¹ H-NMR, ¹³ C-NMR and FT-IR, the nonvolak-type curable resin mixture (B1) contains 50% by weight of partially acrylic-modified bisphenol A type epoxy resin, 25% by weight of bisphenol A type epoxy resin, It was confirmed that it was a mixture containing 25% by weight of bisphenol A epoxy acrylate.

(Examples 1 to 10, Comparative Examples 1 to 8)

According to the mixing ratios shown in Tables 1 and 2, each material was stirred with a planetary stirring device (manufactured by Thinky Co., Ltd., "Awatori Rentaro"), and then mixed uniformly with three ceramic rolls to compare Examples 1 to 10 The sealing compound for liquid crystal display elements of Examples 1-8 was obtained.

<Evaluation>

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

(viscosity)

About each sealing compound for liquid crystal display elements obtained by the Example and the comparative example, the viscosity in 25 degreeC and 1 rpm conditions was measured using the E-type viscometer ("DV-III" by a Brookfield company).

(applicability)

Each sealing compound for liquid crystal display elements obtained in the Example and the comparative example was apply|coated on the glass substrate using the dispenser ("SHOTMASTER300" by the Musashi engineering company). When coating was applied with the dispense nozzle fixed at 400 μm, the nozzle gap at 30 μm, and the lead-out pressure at 300 kPa, the case where the coating was able to be applied without scratches or flow was “○”, and there was no break in coating, but there were no scratches or scratches. The case where flow occurred was evaluated as "Δ", and the case where coating breakage occurred or could not be applied at all was evaluated as "×".

(curable)

After apply|coating about 5 micrometers of each sealing compound for liquid crystal display elements 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 of ultraviolet rays having a wavelength of 365 nm were irradiated using a metal halide lamp. The amount of change (decrease rate) of the (meth)acryloyl group-derived peak before and after light irradiation was measured using an infrared spectrometer (“FTS3000” manufactured by BIORAD).

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

(Low liquid crystal contamination)

After blending 1% by weight of a silica spacer ("SI-H055", manufactured by Sekisui Chemical Industry Co., Ltd.) into each sealing compound for liquid crystal display elements obtained in Examples and Comparative Examples, and performing a defoaming treatment to remove air bubbles in the sealing compound, It was filled into a syringe for dispensing (manufactured by Musashi Engineering, "PSY-10E"), and defoaming treatment was performed again. Next, using a dispenser ("SHOTMASTER300" manufactured by Musashi Engineering Co., Ltd.), the sealing compound was applied to one of the glass substrates on which the ITO thin films were formed on two sheets in a manner of drawing a frame. Then, drop-coating of micro droplets of TN liquid crystal ("JC-5001LA" manufactured by Chisso Co., Ltd.) is carried out by a liquid crystal dropping device into a frame of a sealing agent, and the other glass substrate having an ITO thin film is overlapped and vacuum bonding device is applied. The two substrates were bonded together under a reduced pressure of 5 Pa. After irradiating a 3000 mJ/cm<2> ultraviolet-ray to the cell after bonding with a metal halide lamp, the sealing compound was thermosetted by heating at 120 degreeC for 60 minutes, and the liquid crystal display element was produced. After storing the obtained liquid crystal display element in an environment of a temperature of 80°C and a humidity of 90%RH for 100 hours, a voltage drive of AC 3.5 V was performed, and the presence or absence of display unevenness (color unevenness) was visually observed. The case where display unevenness was not observed at all was marked as "○", the case where display unevenness was present at the periphery of the liquid crystal display element was marked as "△", and the case where display unevenness spread not only to the periphery of the liquid crystal display element but also to the center was marked as "x". Low-liquid crystal contamination was evaluated.

industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements excellent in applicability, hardenability, and low liquid-crystal staining property can be provided. Moreover, according to this invention, the top-down conduction material and liquid crystal display element formed using this sealing compound for liquid crystal display elements can be provided.

Claims (3)

As a sealing agent for liquid crystal display elements containing a curable resin and a polymerization initiator,
The curable resin is a partially (meth)acrylic-modified novolak-type epoxy resin (A), a partially (meth)acryl-modified nonvolac-type epoxy resin (B), and a non-novolak-type epoxy (meth)acrylate (C). contains,
The content of the partially (meth)acrylic-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 partially (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 partially (meth)acryl-modified novolak-type epoxy resin (A) The ratio of the partial (meth)acrylic-modified non-novolak-type epoxy resin (B) to 1 or more,
The content of the nonvolak-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) has a weight average molecular weight of 700 or more and 2000 or less. An upper and lower conduction material containing the sealing compound for liquid crystal display elements according to claim 1 and conductive fine particles. A liquid crystal display element formed using the sealing compound for liquid crystal display elements according to claim 1 or the upper and lower conduction material according to claim 2.