TWI785071B - Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element - Google Patents

Abstract

The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property. Moreover, the object of this invention is to provide the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a polymerization initiator. Modified non-novolac type epoxy resin (B) and non-novolac type epoxy (meth) acrylate (C), the content of the above-mentioned part (meth) acrylic modified novolac type epoxy resin (A) is In 100 parts by weight of the above-mentioned curable resin, it is more than 3 parts by weight and not more than 9 parts by weight. The content of the above-mentioned partially (meth)acrylic modified non-novolac epoxy resin (B) is 25 parts by weight or less, and the ratio of the above-mentioned partially (meth)acrylic-modified non-novolac epoxy resin (B) to the above-mentioned partially (meth)acrylic-modified novolak-type epoxy resin (A) is 1 or more , the content of the above-mentioned 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 above-mentioned curable resin, and the above-mentioned part of the (meth)acrylic acid modified novolac The weight average molecular weight of type epoxy resin (A) is more than 700 and less than 2000.

Description

Sealant for liquid crystal display element, upper and lower conduction material, and liquid crystal display element

The present invention relates to a sealant for liquid crystal display elements which is excellent in applicability, curability and low liquid crystal contamination. Moreover, this invention relates to the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

In recent years, as a method of manufacturing liquid crystal display elements such as liquid crystal display units, from the perspectives of shortening the production time (tact time) and optimizing the amount of liquid crystals used, the methods disclosed in Patent Document 1 and Patent Document 2 have been used. The liquid crystal dropping method is called the dropping method, which combines light and heat with a hardening sealant.

In the dropping method, first, a rectangular seal pattern is formed by dispensing on one of the two substrates with electrodes. Next, liquid crystal droplets are dropped into the sealing frame of the substrate while the sealant is not hardened, another substrate is superimposed under vacuum, and the sealed portion is irradiated with light such as ultraviolet rays to pre-cure. Then, it heats and hardens mainly, and manufactures a liquid crystal display element. At present, the dropping method is the mainstream of the method for manufacturing liquid crystal display elements.

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

Along with this kind of narrow frame design, there is the following problem: In the liquid crystal display element, the distance between the pixel area and the sealant becomes shorter, and the display unevenness caused by the contamination of the liquid crystal by the sealant tends to occur.

[Prior Art Literature]

[Patent Document]

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

Patent Document 2: International Publication No. 02/092718

The object of this invention is to provide the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property. Moreover, the object of this invention is to provide the up-down conduction material and liquid crystal display element which used this sealing compound for liquid crystal display elements.

The present invention is a sealant for liquid crystal display elements, which contains a curable resin and a polymerization initiator. Modified non-novolac type epoxy resin (B) and non-novolac type epoxy (meth) acrylate (C), the content of the above-mentioned part (meth) acrylic modified novolac type epoxy resin (A) is In 100 parts by weight of the above-mentioned curable resin, it is more than 3 parts by weight and not more than 9 parts by weight. The content of the above-mentioned partially (meth)acrylic modified non-novolac epoxy resin (B) is 25 parts by weight or less, and the ratio of the above-mentioned partially (meth)acrylic-modified non-novolac epoxy resin (B) to the above-mentioned partially (meth)acrylic-modified novolak-type epoxy resin (A) is 1 or more , the content of the above-mentioned 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 above-mentioned curable resin, and the above-mentioned part of the (meth)acrylic acid modified novolac The weight average molecular weight of type epoxy resin (A) is more than 700 and less than 2000.

Hereinafter, the present invention will be described in detail.

In order to improve the low liquid crystal contamination of the sealant for liquid crystal display elements, the present inventors researched the use of a relatively high molecular weight partially (meth)acrylic modified epoxy resin as a curable resin. However, when such a curable resin is used, the obtained sealant for liquid crystal display elements may be poor in applicability or curability. Therefore, the inventors of the present invention have studied to mix a part of (meth)acrylic acid modified novolac type epoxy resin, a part of (meth)acrylic acid modified non-novolac type epoxy resin and a non-novolac Type epoxy (meth)acrylates are used in combination. As a result, the sealant for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property was obtained, and completed this invention.

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

The above curable resin contains a part of (meth)acrylic modified novolac epoxy resin (A) (hereinafter also referred to as "(A) component"), a part of (meth)acrylic modified non-novolac epoxy Resin (B) (hereinafter also referred to as "component (B)") and non-novolac epoxy (meth)acrylate (C) (hereinafter also referred to as "component (C)"). By containing the above-mentioned (A) component, the above-mentioned (B) component, and the above-mentioned (C) component so that the content ratio becomes the following range respectively, the sealant for liquid crystal display elements of this invention becomes coating property, curability, and low liquid crystal Those with excellent pollution.

Furthermore, in this specification, the above-mentioned "partial (meth)acrylic acid modified novolak type epoxy resin" means that a part of the epoxy group of the novolak type epoxy resin reacts with (meth)acrylic acid, and the ( Meth)acryl.

The above-mentioned "partial (meth)acrylic modified non-novolac epoxy resin" refers to a part of the epoxy resin that is not a novolak type epoxy resin (hereinafter, also referred to as "non-novolac epoxy resin") React with (meth)acrylic acid to introduce (meth)acryl group.

The above-mentioned "non-novolak epoxy (meth)acrylate" means that all the epoxy groups of the non-novolac epoxy resin react with (meth)acrylic acid to introduce (meth)acryl groups.

The above-mentioned "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryl" means acryl or methacrylate. Acrylyl.

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

The lower limit of the weight average molecular weight of the said (A) component is 700, and the upper limit is 2000. By making the weight average molecular weight of the said (A) component 700 or more, the sealing compound for liquid crystal display elements obtained becomes what is excellent in low liquid-crystal contamination property. By making the weight average molecular weight of the said (A) component into 2000 or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferable lower limit of the weight average molecular weight of the said (A) component is 750, the preferable upper limit is 1500, the more preferable lower limit is 800, and the more preferable upper limit is 1200.

In addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). 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 Co., Ltd.) etc. are mentioned, for example.

Examples of the above-mentioned (A) component include partially (meth)acrylic modified phenol novolac epoxy resins, partially (meth)acrylic modified o-cresol novolak epoxy resins, partially (meth)acrylic acid modified Acrylic modified dicyclopentadiene novolak type epoxy resin, partly (meth)acrylic acid modified biphenyl novolak type epoxy resin, partly (meth)acrylic acid modified naphthol novolak type epoxy resin, etc. Among them, a partially (meth)acrylic modified phenol novolak type epoxy resin is preferable.

The above-mentioned (A) component can be reacted with (meth)acrylic acid in part of the epoxy group of the novolac-type epoxy resin in the presence of an alkaline catalyst according to a conventional method, and the above-mentioned (A) component, novolac-type Obtained from a mixture of epoxy resin and novolac epoxy (meth)acrylate.

In addition, in this specification, the above-mentioned "novolak-type epoxy (meth)acrylate" means that all the epoxy groups of the novolac-type epoxy resin react with (meth)acrylic acid to introduce (meth) Acryl-based ones.

Examples of the novolak-type epoxy resin used as the raw material of the above-mentioned component (A) include: phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, dicyclopentadiene novolac-type epoxy resin , biphenyl novolac epoxy resin, naphthol novolac epoxy resin, etc.

The content of the said (A) component is 3 weight part with a minimum and 9 weight part with an upper limit in 100 weight part of said curable resins. By making content of the said (A) component 3 weight part or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in low liquid-crystal contamination property. By making content of the said (A) component 9 weight part or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferred lower limit of the content of the above-mentioned (A) component is 4 parts by weight, the preferred upper limit is 8 parts by weight, and the more preferred upper limit is 7 parts by weight.

As the above-mentioned (B) component, for example, partially (meth)acrylic modified bisphenol A epoxy resin, partially (meth)acrylic modified bisphenol F epoxy resin, partially (meth)acrylic modified High-quality bisphenol E epoxy resin, partially (meth)acrylic modified bisphenol S epoxy resin, partially (meth)acrylic modified 2,2'-diallyl bisphenol A epoxy resin, Partially (meth)acrylic modified hydrogenated bisphenol type epoxy resin, partially (meth)acrylic modified propylene oxide added bisphenol A type epoxy resin, partially (meth)acrylic modified resorcinol type Epoxy resin, partially (meth)acrylic modified biphenyl type epoxy resin, partially (meth)acrylic modified sulfide type epoxy resin, partially (meth)acrylic modified diphenyl ether type epoxy resin Oxygen resin, partly (meth)acrylic acid modified dicyclopentadiene type epoxy resin, partly (meth)acrylic acid modified naphthalene type epoxy resin, partly (meth)acrylic acid modified epoxypropylamine type epoxy resin , Partial (meth)acrylic modified alkyl polyol type epoxy resin, partial (meth)acrylic modified rubber modified epoxy resin, etc. Among them, partial (meth)acrylic acid modified bisphenol A epoxy resin is preferred.

The above-mentioned (B) component can be reacted in the above-mentioned (B) component, non-phenolic epoxy resin by making a part of the epoxy group of the non-novolac type epoxy resin react with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method. Obtained from a mixture of varnish-type epoxy resin and non-novolak-type epoxy (meth)acrylate.

Examples of the non-novolac epoxy resin used as the raw material for the above-mentioned component (B) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, and bisphenol S epoxy resin. Epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin , biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, epoxypropylamine type epoxy resin, alkyl poly Alcohol epoxy resin, rubber modified epoxy resin, etc.

Content of the said (B) component is 25 weight part of upper limits in 100 weight part of said curable resins. By making content of the said (B) component in 100 weight part of said curable resins 25 weight part or less, the sealing compound for liquid crystal display elements obtained becomes what is excellent in low liquid crystal contamination property. The preferable upper limit of content of the said (B) component in 100 weight part of said curable resins is 22 weight part, and a more preferable upper limit is 20 weight part.

Moreover, the ratio of the said (B) component with respect 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 1 or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. The preferable lower limit of the ratio of the said (B) component with respect to the said (A) component is 1.2, and a more preferable lower limit is 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 said (C)component, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, bisphenol E type epoxy (meth)acrylate, Bisphenol S type epoxy (meth)acrylate, 2,2'-diallyl bisphenol A type epoxy (meth)acrylate, hydrogenated bisphenol type epoxy (meth)acrylate, epoxy Propane addition bisphenol A type epoxy (meth)acrylate, resorcinol type epoxy (meth)acrylate, biphenyl type epoxy (meth)acrylate, thioether type epoxy (meth)acrylate ) acrylate, diphenyl ether type epoxy (meth) acrylate, dicyclopentadiene type epoxy (meth) acrylate, naphthalene type epoxy (meth) acrylate, epoxypropylamine type epoxy ( Meth)acrylate, alkyl polyol type epoxy (meth)acrylate, rubber modified epoxy (meth)acrylate, etc. Among these, bisphenol A type epoxy (meth)acrylate is preferable.

The above-mentioned (C) component can be obtained by reacting all the epoxy groups of the non-novolac type epoxy resin with (meth)acrylic acid in the presence of an alkaline catalyst according to a conventional method.

Examples of the non-novolak epoxy resin used as the raw material of the above-mentioned component (C) include the same ones as the non-novolac epoxy resin used as the raw material of the above-mentioned component (B).

The content of the above-mentioned (C) component is 10 weight part with a minimum in 100 weight part of said curable resins, and an upper limit is 45 weight part. By making content of the said (C)component in 100 weight part of said curable resins 10 weight part or more, the obtained sealing compound for liquid crystal display elements becomes what is excellent in photocurability. By making content of the said (C)component 45 weight part or less, the obtained sealing compound for liquid crystal display elements becomes what is excellent in adhesiveness. The preferable lower limit of content of the said (C)component in 100 weight part of said curable resins is 14 weight part, and a more preferable lower limit is 18 weight part.

The sealing compound for liquid crystal display elements of this invention may further contain another polymeric compound as said curable resin in the range which does not inhibit the object of this invention.

As said other polymeric compound, the said novolak type epoxy resin, the said non-novolac type epoxy resin, the said novolak type epoxy (meth)acrylate, other (meth)acryl compounds etc. are mentioned, for example.

Examples of other (meth)acrylic compounds include: (meth)acrylate compounds obtained by reacting a compound having a hydroxyl group with (meth)acrylic acid; Urethane (meth)acrylate obtained by reacting acrylic acid derivatives with isocyanate compounds, etc.

From the viewpoint of reactivity, it is preferable that the above-mentioned other (meth)acrylic compound has two or more (meth)acryl groups in one molecule.

Examples of the monofunctional ones among the above-mentioned (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate , Isononyl (meth)acrylate, Isodecyl (meth)acrylate, Lauryl (meth)acrylate, Isomyristyl (meth)acrylate, Stearyl (meth)acrylate, (Meth) 2-Hydroxyethyl acrylate, 2-Hydroxypropyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, Cyclohexyl (meth)acrylate, ( Isocamphoryl methacrylate, Dicyclopentenyl (meth)acrylate, Benzyl (meth)acrylate, 2-Methoxyethyl (meth)acrylate, 2-Ethoxy (meth)acrylate Ethyl ester, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, methoxypolyethylene glycol ( Meth)acrylate, Phenoxy Diethylene Glycol (Meth) Acrylate, Phenoxy Polyethylene Glycol (Meth) Acrylate, Tetrahydrofurfuryl (Meth) Acrylate, Ethyl Carbitol ( Meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H (meth)acrylate - Octafluoropentyl ester, imide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(methyl)succinate ) acryloxyethyl ester, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxyethyl phthalate, 2-hydroxypropyl phthalate, phosphoric acid 2-(meth)acryloxyethyl ester, glycidyl (meth)acrylate, etc.

In addition, examples of bifunctional ones among the above-mentioned (meth)acrylate compounds include: 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 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)acrylate, 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, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl diacrylate Alcohol 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, dimethyloldicyclopentadiene di(meth)acrylate, ethylene oxide modified isocyanuric acid di(meth)acrylate, (meth)acrylic acid 2-Hydroxy-3-(meth)acryloxypropyl ester, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate Acrylate, polycaprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.

In addition, examples of trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(methyl ) acrylate, propylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition isocyanuric Acid tri(meth)acrylate, Glycerin tri(meth)acrylate, Propylene oxide added glycerol tri(meth)acrylate, Neopentylthritol tri(meth)acrylate, Phosphate tri[(meth)acrylate ) acryloxyethyl] ester, bis(trimethylolpropane) tetra(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteopentylthritol penta(meth)acrylate , diperythritol hexa(meth)acrylate, etc.

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-methylene diisocyanate, 2,6-methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene Diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, benzylidine diisocyanate, stubble diisocyanate Isocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethyl stubble diisocyanate, 1,6,11- Undecane triisocyanate, etc.

In addition, as the above-mentioned isocyanate compound, a chain-extended isocyanate compound obtained by reacting a polyhydric alcohol with an excess of isocyanate compound can also be used.

Examples of the above-mentioned polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.

Examples of (meth)acrylic acid derivatives having a hydroxyl group include hydroxyalkyl mono(meth)acrylate, mono(meth)acrylate of diol, and mono(meth)acrylic acid of triol. ester or di(meth)acrylate, etc.

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

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

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

From the viewpoint of suppressing liquid crystal contamination, the above-mentioned other (meth)acrylic compounds are preferably those having hydrogen-bonding units such as -OH group, -NH- group, and -NH ₂ group.

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

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

As said radical polymerization initiator, the photo radical polymerization initiator which generate|occur|produces a radical by irradiation of light, or the thermal radical polymerization initiator which generates a radical by heating can be used.

化合物等。 Examples of the photoradical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, 9-oxysulfur compounds, and

compound etc.

啉基苯基)丁酮、1,2-(二甲基胺基)-2-((4-甲基苯基)甲基)-1-(4-(4--

啉基)苯基)-1-丁酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-(4-甲硫基苯基)-2-N-

啉基丙烷-1-酮、1-(4-(2-羥基乙氧基)-苯基)-2-羥基-2-甲基-1-丙烷-1-酮、1-(4-(苯硫基)苯基)-1,2-辛二酮-2-(O-苯甲醯基肟)、2,4,6-三甲基苯甲醯基二苯基氧化膦、安息香甲醚、安息香乙醚、安息香異丙醚等。 As the above-mentioned photoradical polymerization initiator, specifically, for example, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-N-

Linylphenyl) butanone, 1,2-(dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4--

Linyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(2,4,6-trimethylbenzoyl ) phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-N-

Linylpropan-1-one, 1-(4-(2-hydroxyethoxy)-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-(benzene Thio)phenyl)-1,2-octanedione-2-(O-benzoyl oxime), 2,4,6-trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ether, Benzoin ether, benzoin isopropyl ether, etc.

The said photoradical polymerization initiator may be used individually, and may use it in combination of 2 or more types.

As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. are mentioned, for example. Among them, an initiator composed of a high-molecular azo compound (hereinafter, also referred to as a "high-molecular azo initiator") is preferable.

The said thermal radical polymerization initiator may be used individually, and may use it in combination of 2 or more types.

In addition, in this specification, a high molecular weight azo compound means the compound which has an azo group and generates the radical which hardens (meth)acryl group by heat, and has a number average molecular weight of 300 or more.

The preferable lower limit of the number average molecular weight of the above-mentioned polymeric azo compound is 1000, and the preferable upper limit is 300,000. By making the number average molecular weight of the said high molecular weight azo compound into this range, liquid crystal contamination can be suppressed, and it can mix easily with curable resin. The more preferable lower limit of the number average molecular weight of the above-mentioned 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 by measuring using tetrahydrofuran as a solvent by gel permeation chromatography (GPC). 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 Co., Ltd.) etc. are mentioned, for example.

As said high molecular azo compound, the thing which has the structure which unit, such as polyalkylene oxide and polydimethylsiloxane, couple|bonds via an azo group, is mentioned, for example.

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

Specific examples of the polymeric azo compound include: a polycondensate of 4,4'-azobis(4-cyanovaleric acid) and polyalkylene glycol, or 4,4'- Condensation product of nitrogen bis(4-cyanovaleric acid) and polydimethylsiloxane with terminal amino group, etc.

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, what is marketed as an azo compound which is not a polymer includes, for example, V-65, V-501 (both are manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, Peroxydicarbonate, etc.

As the above cationic polymerization initiator, a photocationic polymerization initiator can be preferably used.

The above-mentioned photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by irradiation of light, and may be an ionic photoacid generating type or a nonionic photoacid generating type.

Examples of the above-mentioned photocationic polymerization initiator include: onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic halonium salts; iron-arene complexes and titanocene complexes; , aryl silanol-aluminum complexes and other organometallic complexes, etc.

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

With respect to 100 parts by weight of the above-mentioned curable resin, the lower limit of the content of the polymerization initiator is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight. By making content of the said polymerization initiator into this range, the obtained sealing compound for liquid crystal display elements suppresses contamination of a liquid crystal, and is more excellent in storage stability or curability. A more preferable lower limit of the content of the above-mentioned polymerization initiator is 0.1 parts 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.

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

The above thermosetting agents may be used alone or in combination of two or more.

Examples of the solid organic acid hydrazide include: 1,3-bis(hydrazinocarbonylethyl)-5-isopropylhydantoin, dihydrazide sebacate, dihydrazide isophthalate, Adipic acid hydrazine, malonate hydrazine, etc.

Examples of commercially available solid organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Japan Finechem, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno.

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

Examples of the organic acid hydrazide produced by Japan Finechem include MDH and the like.

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

With respect to 100 parts by weight of the curable resin as a whole, the content of the above-mentioned thermosetting agent has a preferable lower limit of 1 part by weight, and a preferable upper limit of 50 parts by weight. By making content of the said thermosetting agent into this range, the obtained sealing compound for liquid crystal display elements becomes what is more excellent in curability in the state which maintained the excellent applicability or storage stability. The more preferable upper limit of the content of the said thermosetting agent is 30 weight part.

The sealant for liquid crystal display elements of the present invention is preferably for the purpose of increasing the viscosity, further improving the adhesiveness brought about by the stress dispersion effect, improving the linear expansion rate, and improving the moisture resistance of the cured product. filler.

As said 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, bentonite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, and iron oxide. , magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, etc.

As said organic filler, a polyester microparticle, a polyurethane microparticle, a vinyl polymer microparticle, an acrylic polymer microparticle etc. are mentioned, for example.

These fillers may be used alone or in combination of two or more.

The preferable lower limit of content of the said filler in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part. By making content of the said filler into this range, deterioration of applicability etc. can be suppressed, and effects, such as improvement of adhesiveness, can be exhibited further. A more preferable lower limit of the content of the above filler is 20 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealant for liquid crystal display elements of the present invention preferably contains soft particles from the viewpoint of improving the flexibility and adhesiveness of the cured product, or suppressing the insertion of liquid crystal into the sealant or the dissolution of the sealant into the liquid crystal.

Examples of the soft 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 above soft particles may be used alone or in combination of two or more.

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

(meth)acrylic particles can be preferably used as the above-mentioned vinyl particles.

The said (meth)acrylic particle can be obtained by polymerizing the monomer used as a raw material by a well-known method. Specifically, for example, the following methods can be mentioned: Suspension polymerization of the monomer in the presence of a radical polymerization initiator; Absorption of the monomer by non-crosslinked seed particles in the presence of a radical polymerization initiator, by This swells the seed particles to carry out seed polymerization.

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, fluorine-containing Monofunctional monomers such as (meth)acrylates.

Examples of the alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate, Base) hexyl acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate Esters, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.

Examples of the above-mentioned oxygen atom-containing (meth)acrylates include: 2-hydroxyethyl (meth)acrylate, glycerin (meth)acrylate, polyoxyethylene (meth)acrylate, (meth) Glycidyl acrylate, etc.

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

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

Among them, alkyl (meth)acrylates are preferred because the Tg of the homopolymer is low and the amount of deformation when a load of 1 g is applied can be increased.

Moreover, in order to make it have a crosslinked structure, you may use a polyfunctional monomer as a monomer used as a raw material for forming the said (meth)acryl particle.

Examples of the polyfunctional monomer include tetramethylolmethane tetra(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, diperythritol hexa(meth)acrylate, diperythritol 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 glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, isocyanuric acid skeleton tri(meth)acrylate, etc. Among them, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di( Meth)acrylate, (poly)tetramethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate Acrylate.

The usage-amount of the said crosslinkable monomer is based on the whole monomer used as a raw material for forming the said (meth)acrylic particle, Preferably the lower limit is 1 weight%, and a more preferable upper limit is 90 weight%. By making the amount of the above-mentioned cross-linking monomer to be more than 1% by weight, the solvent resistance is improved, and it is easy to uniformly disperse without causing problems such as swelling when kneading with other sealant components. The recovery rate can be reduced by making the usage-amount of the said crosslinkable monomer into 90 weight% or less. The more preferable lower limit of the usage-amount of the said crosslinkable monomer is 3 weight%, and the more preferable upper limit is 80 weight%.

Furthermore, in addition to these acrylic monomers, styrene monomers, vinyl ethers, vinyl carboxylates, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, isocyanuric acid tris Allyl ester, triallyl trimellitate, divinylbenzene, diallyl phthalate, diallyl acrylamide, diallyl ether, γ-(meth)acryloxy Propyltrimethoxysilane, vinyltrimethoxysilane and other monomers.

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

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

As said vinyl carboxylate, 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.

As said halogen-containing monomer, vinyl chloride, vinyl fluoride, chlorostyrene, etc. are mentioned, for example.

As the above-mentioned (meth)acrylic particles, core-shell (meth)acrylate copolymer fine particles can also be preferably used.

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

In addition, as the above-mentioned vinyl-based particles, for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles, etc. can also be used.

The preferred lower limit of the average particle size of the soft particles is 0.01 μm, and the preferred upper limit is 10 μm. By making the average particle diameter of the said flexible particle into this range, the effect of improving the flexibility or adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the average particle diameter of the soft 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 the laser diffraction particle size distribution measuring apparatus. As the above-mentioned laser diffraction particle size distribution measuring device, Mastersizer 2000 (manufactured by Malvern Co., Ltd.) or the like can be used.

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

In addition, in this specification, the hardness of the said soft particle|grain means the A-type durometer hardness measured by the method based on JISK 6253.

The preferred lower limit of the content of the soft particles in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the upper limit is preferably 50 parts by weight. By making content of the said flexible particle into this range, the effect of improving the flexibility or adhesiveness of the hardened|cured material of the sealing compound for liquid crystal display elements obtained is more excellent. A more preferable lower limit of the content of the soft 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 above-mentioned silane coupling agent mainly functions as an adhesive auxiliary agent for bonding the sealant and the substrate etc. well.

As said silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc. can be preferably used.

The above-mentioned silane coupling agents may be used alone or in combination of two or more.

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

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

As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black etc. are mentioned, for example. Among them, titanium black is preferred.

The said sunscreen agent may be used individually, and may use it in combination of 2 or more types.

The above-mentioned titanium black is a material having a higher transmittance for light in the vicinity of the ultraviolet region, especially for light with a wavelength of 370 nm to 450 nm, than the average transmittance for light with a wavelength of 300 nm to 800 nm. That is, the above-mentioned titanium black is a light-shielding agent having the property of imparting 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, and, on the other hand, shielding light of wavelengths near the ultraviolet region. through. As the light-shielding agent contained in the sealing compound for liquid crystal display elements of this invention, it is preferable that it is a substance with high insulating property, and as a light-shielding agent with high insulating property, titanium black is also preferable.

Even if the above-mentioned titanium black is not surface-treated, it can also exert sufficient effects. It is also possible to use those whose surface has been treated with organic components such as coupling agents, or those treated with inorganic components such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide. Titanium black with surface treatment such as component coating. Among them, those treated with an organic component are preferable in terms of further improving insulation properties.

Also, the liquid crystal display element manufactured by using the sealant for liquid crystal display element of the present invention containing the above-mentioned titanium black as a light-shielding agent has sufficient light-shielding property, so it can realize that there is no leakage of light, has a higher contrast ratio, and has Liquid crystal display element with excellent image display quality.

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

Examples of titanium black manufactured by Mitsubishi Materials Corp. include 12S, 13M, 13M-C, 13R-N, and 14M-C.

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

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

Also, the lower limit of the volume resistance of the titanium black is preferably 0.5Ω‧cm, the upper limit is 3Ω‧cm, the lower limit is 1Ω‧cm, and the upper limit is 2.5Ω‧cm.

The primary particle size of the light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the lower limit is preferably 1 nm, and the upper limit is preferably 5 μm. By making the primary particle diameter of the said light-shielding agent into this range, the viscosity and thixotropy of the sealing compound for liquid crystal display elements obtained will not increase significantly, and it will become more excellent in applicability. The more preferable lower limit of the primary particle diameter of the above-mentioned 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 said light-shielding agent can be measured by dispersing the said light-shielding agent in a solvent (water, an organic solvent, etc.) using a particle size distribution meter (for example, "NICOMP 380ZLS" manufactured by PARTICLE SIZING SYSTEMS).

The preferable lower limit of the content of the said light-shielding agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 5 weight part, and a preferable upper limit is 80 weight part. By making content of the said light-shielding agent into this range, the effect of improving light-shielding property can be exhibited further, when the adhesiveness of the sealing compound for liquid crystal display elements obtained, the intensity|strength after hardening, and drawing property do not fall significantly. A more preferable lower limit of the content of the above-mentioned sunscreen agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealant for liquid crystal display elements of the present invention may further contain additives such as stress relieving agents, reactive diluents, thixotropic agents, spacers, hardening accelerators, defoamers, leveling agents, and polymerization inhibitors as necessary.

As a method of producing the sealing agent for liquid crystal display elements of the present invention, for example, the following methods are mentioned: using a mixer such as a homogeneous disperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mill. , Mix curable resin, polymerization initiator, thermosetting agent or additives such as silane coupling agent if necessary.

The preferred lower limit of the viscosity of the sealant for liquid crystal display elements of the present invention is 100 Pa‧s, and the preferred upper limit is 800 Pa‧s measured using an E-type viscometer at 25°C and 1 rpm. By making the said viscosity into this range, the obtained sealing compound for liquid crystal display elements becomes what is excellent in applicability. A more preferable lower limit of the above viscosity is 200Pa‧s, and a more preferable upper limit is 700Pa‧s.

By mixing conductive fine particles in the sealing compound for liquid crystal display elements of the present invention, vertical conduction materials can be produced. Moreover, the upper-bottom conduction material containing the sealing compound for liquid crystal display elements of this invention, and electroconductive fine particle is also one of this invention.

As said electroconductive microparticles|fine-particles, what formed the electroconductive metal layer on the surface of a metal ball, the resin microparticles, etc. can be used. Among them, the one having the conductive metal layer formed on the surface of the resin fine particles is preferable because conductive connection can be realized without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.

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

As a method of manufacturing the liquid crystal display element of this invention, the liquid crystal dropping method can be used preferably, Specifically, the method etc. which have the following each process are mentioned, for example.

First, the following steps are carried out: on one of the two substrates, such as a glass substrate with an electrode such as an ITO film or a polyethylene terephthalate substrate, apply the film of the present invention by screen printing, dispenser coating, etc. Sealant for liquid crystal display elements and form a frame-shaped seal pattern. Then, the following steps are carried out: in the uncured state of the sealant for liquid crystal display elements of the present invention, droplets of liquid crystal are drop-coated in the frame of the seal pattern of the substrate, and another substrate is superimposed under vacuum. Then, a liquid crystal display element can be obtained by performing the following steps: irradiating light such as ultraviolet rays to the sealing pattern portion of the sealant for liquid crystal display elements of the present invention to precure the sealant; and heating the precured sealant For formal hardening.

According to this invention, the sealing compound for liquid crystal display elements excellent in applicability, curability, and low liquid crystal contamination property can be provided. Moreover, according to this invention, the upper-bottom conduction material and the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

Hereinafter, examples are disclosed and the present invention will be described in more detail, but the present invention is not limited to these examples.

(Production of Novolac Type Curable Resin Mixture (A1))

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

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

In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 1,200.

(Production of Novolac Type Curable Resin Mixture (A2))

After dissolving 395 parts by weight of a phenol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLONN-730S") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After dripping 94 parts by weight of acrylic acid in the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Then, a novolak type curable resin mixture (A2) was obtained by depressurizingly removing toluene.

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

In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 800.

(Production of Novolac Type Curable Resin Mixture (A3))

After dissolving 965 parts by weight of a phenol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLON N-770") in 1800 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. In the obtained solution, 216 weight part of acrylic acid was dripped under reflux stirring for 2 hours, and then reflux stirring was performed for 6 hours. Then, 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, it was confirmed that the novolac type curable resin mixture (A3) contained 11.8% by weight of a part of acrylic modified phenol novolak type epoxy resin, 68.6% by weight of A mixture of phenol novolac epoxy resin and 19.6% by weight of phenol novolak epoxy acrylate.

In addition, the weight average molecular weight of the partially acrylic-modified phenol novolak type epoxy resin obtained was 2,500.

(Preparation of Non-Novolac Type Curable Resin Mixture (B1))

After dissolving 326 parts by weight of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical, "jER 828EL") in 900 mL of toluene, 0.3 g of triphenylphosphine was added to prepare a uniform solution. After 72 parts by weight of acrylic acid was dropped into the obtained solution under reflux stirring for 2 hours, reflux stirring was further performed for 6 hours. Next, by removing toluene under reduced pressure, a non-novolac type curable resin mixture (B1) was obtained.

By ¹ H-NMR, ¹³ C-NMR and FT-IR, it was confirmed that the non-novolac type curable resin mixture (B1) contained 50% by weight of a part of acrylic modified bisphenol A type epoxy resin, 25% by weight A mixture of bisphenol A type epoxy resin and 25% by weight of bisphenol A type epoxy acrylate.

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

According to the blending ratios recorded in Tables 1 and 2, after stirring each material with a planetary stirring device (manufactured by Thinky Corporation, "Foaming Stirring Taro"), the examples were obtained by uniformly mixing with a ceramic three-roll mill 1~10. Sealants for liquid crystal display elements of comparative examples 1~8.

<Evaluation>

The following evaluation was performed about each sealing compound for liquid crystal display elements obtained in 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 in the Example and the comparative example, the viscosity on the conditions of 25 degreeC and 1 rpm was measured using the E-type viscometer (made by Brookfield company, "DV-III").

(coatability)

The sealing compound for each liquid crystal display element obtained in the Example and the comparative example was apply|coated on the glass substrate using the dispenser ("SHOTMASTER 300" manufactured by Musashi High-tech Co., Ltd.). When the dispensing nozzle is fixed at 400 μm, the nozzle gap is fixed at 30 μm, and the discharge pressure is fixed at 300 kPa to apply, the case of successful coating without blurring or sagging is set as "○", although there is no coating The case where the fabric was cracked but blurred or sagging occurred was rated as "△", and the case where coating cracked or coating was not possible at all was rated as "×" to evaluate the coatability.

(hardening)

After applying the sealants for liquid crystal display elements obtained in Examples and Comparative Examples to about 5 μm on a glass substrate, glass substrates of the same size were stacked. Next, using a metal halide lamp, 3000 mJ/cm ² of ultraviolet light with a wavelength of 365 nm was irradiated. Using an infrared spectrometer (manufactured by BIORAD, "FTS3000"), the amount of change (decrease rate) of the peak derived from the (meth)acryl group before and after irradiation was measured.

When the reduction rate of the peak derived from the (meth)acryl group after irradiation was 95% or more, it was rated as "◎", when it was 85% or more and less than 95%, it was rated as "○", and when it was 75% or more Moreover, the case of less than 85% was set as "△", and the case of less than 75% was set as "×" to evaluate the curability.

(low liquid crystal contamination)

1% by weight of a silica spacer (manufactured by Sekisui Chemical Industry Co., Ltd., "SI-H055") was blended with each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples, and the sealant was removed by defoaming treatment. After removing air bubbles in the agent, fill it into a dispensing syringe (manufactured by Musashi High-Tech Co., Ltd., "PSY-10E"), and perform defoaming treatment again. Then, using a dispenser ("SHOTMASTER 300" manufactured by Musashi High-tech Co., Ltd.), the sealant was applied to form a picture frame on one of the two glass substrates with ITO films. Then, droplet coating of TN liquid crystal (manufactured by Chisso, "JC-5001LA") in the frame of sealant by liquid crystal dropping device, overlap another glass substrate with ITO film, and use vacuum bonding device Two substrates were bonded under a reduced pressure of 5 Pa. The bonded unit was irradiated with 3000mJ/cm ² of ultraviolet rays by a metal halide lamp, and then heated at 120°C for 60 minutes to thermally harden the sealant and produce a liquid crystal display element. After storing the obtained liquid crystal display element in an environment with a temperature of 80°C and a humidity of 90%RH for 100 hours, it was driven with a voltage of AC 3.5V, and the presence or absence of display unevenness (color unevenness) was visually observed. The case where display unevenness is not seen at all is set as "○", and the case where display unevenness is present in the peripheral part of the liquid crystal display element is set as "△". Display unevenness is not only present in the peripheral part of the liquid crystal display element but The case where it diffused to the central part was made into "x" and low liquid crystal contamination property was evaluated.

[Industrial availability]

According to the present invention, there can be provided a sealant for liquid crystal display elements excellent in applicability, curability and low liquid crystal contamination. Moreover, according to this invention, the upper-bottom conduction material and the liquid crystal display element which used this sealing compound for liquid crystal display elements can be provided.

Claims (3)

A sealant for liquid crystal display elements, containing curable resin and polymerization initiator, characterized in that: the curable resin contains part of (meth)acrylic acid modified novolak type epoxy resin (A), part of (meth) Acrylic modified non-novolac epoxy resin (B) and non-novolac epoxy (meth)acrylate (C), the content of this part of (meth)acrylic modified novolac epoxy resin (A) In 100 parts by weight of the hardening resin, it is more than 3 parts by weight and less than 9 parts by weight. The content of the part of (meth)acrylic modified non-novolac epoxy resin (B) is in 100 parts by weight of the hardening resin wherein, is 25 parts by weight or less, and the ratio of the part of the (meth)acrylic modified non-novolac epoxy resin (B) to the part of the (meth)acrylic modified novolac epoxy resin (A) 1 or more, the content of the non-novolak 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 part of the (meth)acrylic modified The weight average molecular weight of the novolac type epoxy resin (A) is 700 or more and 2,000 or less. A vertical conduction material, which contains the sealant for liquid crystal display elements described in Claim 1 and conductive fine particles. A liquid crystal display element, which is formed by using the sealant for liquid crystal display elements described in claim 1 or the upper and lower conductive materials described in claim 2.