KR20220027054A - Sealing agent for display elements, vertical conduction material, and display element - Google Patents

Abstract

An object of this invention is to provide the sealing compound for display elements from which the display element excellent in reliability in a high-temperature, high-humidity environment can be obtained. Moreover, this invention aims at providing the vertical conduction material and display element which use this sealing compound for display elements.
The present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, the polar component term in the formula for surface free energy by the Owens-Wendt method of the cured product is 6.0 or less, and the storage modulus of the cured product at 121°C It is this sealing compound for display elements 50 Mpa or more.

Description

Sealing agent for display elements, vertical conduction material, and display element

This invention relates to the sealing compound for display elements from which the display element excellent in the reliability in high-temperature, high-humidity environment can be obtained. Moreover, this invention relates to the vertical conduction material and display element which use this sealing compound for display elements.

In recent years, a liquid crystal display element, an organic electroluminescent display element, etc. are widely used as a display element which has characteristics, such as thin shape, light weight, and low power consumption. In these display elements, sealing, such as a liquid crystal and a light emitting layer, is normally performed with the sealing compound formed using curable resin composition.

For example, as a liquid crystal display element, the liquid crystal display element which used the sealing compound of light-heat combined use hardening type which is disclosed by patent document 1, patent document 2 from viewpoints such as tact time shortening and optimization of the amount of liquid crystal used is disclosed has been

Moreover, the performance corresponding to the pressure cooker test (PCT) in the conditions of 121 degreeC, 100% RH, and 2 atm is also calculated|required by a display element as high reliability in drive in a high temperature, high humidity environment, etc. In order to obtain the display element which has high reliability, it is necessary to make sealing compound into the thing excellent in heat-and-moisture resistance.

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

An object of this invention is to provide the sealing compound for display elements from which the display element excellent in the reliability in high-temperature, high-humidity environment can be obtained. Moreover, an object of this invention is to provide the vertical conduction material and display element which use this sealing compound for display elements.

The present invention contains a curable resin, a polymerization initiator and/or a thermosetting agent, the polar component term in the formula for surface free energy by the Owens-Wendt method of the cured product is 6.0 or less, and the storage modulus of the cured product at 121°C It is this sealing compound for display elements 50 Mpa or more.

Hereinafter, the present invention will be described in detail.

When this inventor confirmed about the display element which generate|occur|produced the display defect when it driven in PCT (121 degreeC, 100%RH, 2 atm) environment, it confirmed that bubble penetration existed in the display element. Then, this inventor makes the polar component term in the formula of the surface free energy by the Owens-Wendt method of the hardened|cured material of the sealing compound for display elements become below a specific value, and the storage elastic modulus in 121 degreeC of the hardened|cured material It was reviewed to make it more than a specific value. As a result, invasion of foam|bubble can be suppressed and it discovers that the sealing compound for display elements from which the display element excellent in the reliability in a high-temperature, high-humidity environment can be obtained, and came to complete this invention.

When the effect that the display element excellent in reliability in the high-temperature, high-humidity environment in the sealing compound for display elements of this invention can be obtained uses the sealing compound for display elements of this invention as sealing compound for liquid crystal display elements particularly prominently.

As for the sealing compound for display elements of this invention, the polar component term (henceforth simply a "polar component term") in the formula of the surface free energy by the Owens-Wendt method of hardened|cured material is 6.0 or less. When the said polar component term is 6.0 or less, and the storage elastic modulus in 121 degreeC of hardened|cured material is 50 Mpa or more, the sealing compound for display elements of this invention is excellent in the effect which suppresses the penetration|invasion of the bubble in a high-temperature, high-humidity environment becomes a thing A preferable upper limit of the polar component term is 5.7, and a more preferable upper limit is 5.3.

In addition, although there is no especially preferable lower limit of the said polar component term, a practical lower limit is 4.5.

Specifically, the polar component term is calculated by measuring the contact angles of the cured product with water and methylene iodide (3 μL of dripping, 30 seconds after dropping) of the cured product with a contact angle meter at 25° C., respectively, and calculated by the following formula can do.

γs = γsd + γsp

72.8 (1 + cosθH) = 2 (21.8 γsd) ^1/2 + 2 (51.0 γsp) ^1/2

50.8 (1 + cosθI) = 2 (48.5 γsd) ^1/2 + 2 (2.3 γsp) ^1/2

γs: surface free energy

γsd : Dispersion component term of surface free energy

γsp : polar component of surface free energy

θH : contact angle for water

θI: contact angle with respect to methylene iodide

In addition, the following are used as hardened|cured material for which the said polar component term is measured. That is, the sealing compound was apply|coated to one of the alkali-free glass of 2 sheets, the other alkali-free glass was piled up from the top of the applied sealing compound, and 100 mW/cm2 ultraviolet-ray (wavelength 365 nm) was applied to 30 using a metal halide lamp. After second irradiation, one alkali free glass is peeled, heated at 120 degreeC for 1 hour, and what thermosetted the sealing compound is used. As the alkali-free glass, OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm, surface roughness 0.2 nmRa) is used.

Moreover, as said contact angle meter, the fully automatic contact angle meter DMo-701 (made by Kyowa Interface Science, Inc.) etc. is mentioned, for example.

The following are considered as the reason which can suppress the invasion of a bubble by using the sealing compound for display elements of this invention.

That is, in addition to the storage elastic modulus at 121°C of the cured product described later of 50 MPa or more, since the polar component term is 6.0 or less, the cured product itself is not only excellent in moisture resistance, but also has high affinity with an alignment film and the like, so that the interface Adhesiveness becomes favorable, and as a result, it is estimated that the penetration|invasion of the water|moisture content which becomes a cause of a bubble is suppressed.

As for the sealing compound for display elements of this invention, the minimum of the storage elastic modulus in 121 degreeC of hardened|cured material is 50 Mpa. When the storage elastic modulus in 121 degreeC of the said hardened|cured material is 50 Mpa or more, and the said polar component term is 6.0 or less, the sealing compound for display elements of this invention is the effect which suppresses the penetration|invasion of the bubble in a high-temperature, high-humidity environment. becomes excellent. The minimum with a preferable storage elastic modulus in 121 degreeC of the said hardened|cured material is 60 Mpa, and a more preferable minimum is 80 Mpa.

Moreover, after irradiating a 100 mW/cm<2> ultraviolet-ray to a sealing compound for 30 second as hardened|cured material which measures a storage elastic modulus, what heated and hardened at 120 degreeC for 1 hour is used.

In addition, the said storage modulus can be measured using the dynamic viscoelasticity measuring apparatus under the conditions of test piece width 5mm, thickness 0.35mm, grip width 25mm, temperature increase rate 10 degreeC/min, and frequency 5Hz.

Examples of the dynamic viscoelasticity measuring device include DVA-200 (manufactured by IT Instrumentation and Control Company).

The sealing compound for display elements of this invention WHEREIN: As a method of making the storage elastic modulus in 121 degreeC of the said polar component term and the said hardened|cured material into the above-mentioned ranges, respectively, of each structural component contained in the sealing compound for display elements The method of adjusting the kind and its content rate is preferable.

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

It is preferable that the said curable resin contains the compound which has an epoxy group.

By including the compound which has the said epoxy group, the effect which the sealing compound for display elements obtained suppresses the penetration|invasion of the bubble in high-temperature, high-humidity environment becomes more excellent.

As a compound which has the said epoxy group, For example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a 2,2'- diallylbisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, Propylene oxide addition bisphenol A epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac Epoxy compound, orthocresol novolac type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthalenephenol novolak type epoxy compound, glycidylamine type epoxy compound, alkyl polyol type epoxy compound A compound, a rubber-modified epoxy compound, a glycidyl ester compound, etc. are mentioned.

As what is marketed among the said bisphenol A epoxy compounds, jER828EL, jER1004 (all are made by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (made by DIC Corporation), etc. are mentioned, for example.

As what is marketed among the said bisphenol F-type epoxy compounds, jER806, jER4004 (all are made by Mitsubishi Chemical Corporation), EPICLON EXA-830CRP (made by DIC Corporation), etc. are mentioned, for example.

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

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

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

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

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

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

As what is marketed among the said sulfide-type epoxy compounds, YSLV-50TE (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

As what is marketed among the said diphenyl ether type|mold epoxy compound, YSLV-80DE (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

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

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

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

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

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

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

As what is marketed among the said naphthalenephenol novolak-type epoxy compounds, ESN-165S (made by Nittetsu Chemical & Materials) etc. is mentioned, for example.

As what is marketed among the said glycidylamine type epoxy compound, jER630 (made by Mitsubishi Chemical Corporation), EPICLON 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemicals), etc. are mentioned, for example.

Among the above alkyl polyol-type epoxy compounds, commercially available ones include, for example, ZX-1542 (manufactured by Nittetsu Chemical & Materials Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Eporite 80 MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611 (manufactured by Nagase Chemtex Co., Ltd.) and the like.

As what is marketed among the said rubber-modified epoxy compounds, YR-450, YR-207 (all are made by Nittetsu Chemical & Materials), Epolide PB (made by Daicel), etc. are mentioned, for example.

As what is marketed among the said glycidyl ester compound, Denacol EX-147 (made by Nagase Chemtex) etc. is mentioned, for example.

Among the compounds having an epoxy group, other commercially available compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Chemical Co., Ltd.), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Corporation), and the like.

As a compound which has the said epoxy group, a partially (meth)acryl modified|denatured epoxy compound is also used preferably.

In addition, in this specification, the said partially (meth)acryl-modified epoxy compound is an epoxy group and (meth)acryloin in 1 molecule which can be obtained by reacting the epoxy group of a part of the compound which has two or more epoxy groups with (meth)acrylic acid. means a compound having at least one diary each.

In addition, in this specification, the said "(meth)acryloyl" means acryloyl or methacryloyl.

As what is marketed among the said partially (meth)acrylic-modified epoxy compounds, UVACURE1561, KRM8287 (all are made by Daicel Allnex), MEM-5000H (made by Neo Chemical) etc. are mentioned, for example.

The minimum with preferable content of the compound which has the said epoxy group in 100 weight part of said curable resins is 10 weight part, and a preferable upper limit is 60 weight part. When content of the compound which has the said epoxy group is 10 weight part or more, the effect which the sealing compound for display elements obtained suppresses the penetration|invasion of the bubble in high-temperature, high-humidity environment becomes more excellent. When content of the compound which has the said epoxy group is 60 weight part or less and using the sealing compound for display elements obtained as a sealing compound for liquid crystal display elements, it becomes the thing excellent in low-liquid-crystal contamination property. The minimum with more preferable content of the compound which has the said epoxy group is 20 weight part, and a more preferable upper limit is 40 weight part.

It is preferable that the said curable resin contains a (meth)acrylic compound.

As said (meth)acrylic compound, a (meth)acrylic acid ester compound, epoxy (meth)acrylate, urethane (meth)acrylate, etc. are mentioned, for example. Especially, epoxy (meth)acrylate is preferable. Moreover, it is preferable that the said (meth)acryl compound has two or more (meth)acryloyl groups in 1 molecule from a reactive viewpoint.

In addition, in this specification, the said "(meth)acryl" means acryl or methacryl, and the said "(meth)acryl compound" means a compound having a (meth)acryloyl group. In addition, the said "(meth)acrylate" means an acrylate or a methacrylate, and the said "epoxy (meth)acrylate" represents the compound which made all the epoxy groups in an epoxy compound react with (meth)acrylic acid.

Since it becomes easy to make the glass transition temperature of the hardened|cured material of the sealing compound for display elements obtained into the range mentioned later, it is preferable that the said curable resin contains the compound which has a methacryloyl group as said (meth)acryl compound.

When the said curable resin contains the compound which has the said methacryloyl group, it is preferable that the methacryl ratio represented by following formula (I) is 0.3 or more. When the said methacryl ratio is 0.3 or more, it becomes easier to make the glass transition temperature of the hardened|cured material of the sealing compound for display elements obtained into the range mentioned later. As for the said methacryl ratio, it is more preferable that it is 0.5 or more, and it is still more preferable that it is 0.6 or more.

Methacryl Ratio = (W _M /E _M )/(W _A /E _A + W _M /E _M ) (I)

In the formula (I), E _A is the acryloyl group equivalent (g/mol) of the compound having an acryloyl group, E _M is the methacryloyl group equivalent (g/mol) of the compound having a methacryloyl group, W _A is content (weight part) of the compound which has an acryloyl group, W _M is content (weight part) of the compound which has a methacryloyl group.

In addition, the said "acryloyl group equivalent" is a value obtained by dividing the weight (g) of the compound having an acryloyl group by the number of moles (mol) of the acryloyl group contained in the compound having an acryloyl group. When the said curable resin contains the compound (A1, A2, ...) which has a plurality of said acryloyl groups, "W _A /E _A " in said formula (I) is each compound having an acryloyl group. On the other hand, it means the sum total (W _A1 /E _A1 + W _A2 /E _A2 +...) of the value calculated|required by dividing content of the compound which has an acryloyl group by the acryloyl group equivalent. When the said curable resin does not contain the compound which has the said acryloyl group, let "W _A /E _A " in the said Formula (I) be 0.

In addition, the "methacryloyl group equivalent" is a value obtained by dividing the weight (g) of the compound having a methacryloyl group by the number of moles (mol) of the methacryloyl group contained in the compound having a methacryloyl group am. When the said curable resin contains the compound ( _M1 , M2, ...) which has a plurality of said methacryloyl groups, "W _M /EM" in said Formula (I) has each methacryloyl group About a compound, it means the sum total (W _M1 /E _M1 + W _M2 /E _M2 +...) of the value calculated|required by dividing content of the compound which has a methacryloyl group by the methacryloyl group equivalent.

As a monofunctional thing among the said (meth)acrylic acid ester compound, For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, 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, 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, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxy Ethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl ( Meth) acrylate etc. are mentioned.

Moreover, as a bifunctional thing among the said (meth)acrylic acid ester compound, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, and 1, 6- hexanediol are, for example. Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylic rate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, propylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethyloldicyclopentadienyldi(meth)acrylate, ethylene oxide-modified isocyanuric acid di(meth)acrylate, 2-hydroxy- 3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth)acrylate, polybutadienediol di(meth)acrylate, etc. are mentioned.

Moreover, as trifunctional or more than trifunctional thing among the said (meth)acrylic acid ester compound, trimethylol propane tri(meth)acrylate, ethylene oxide addition trimethylol propane tri(meth)acrylate, 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)acrylic Rate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are mentioned.

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

As an epoxy compound used as a raw material for synthesizing the said epoxy (meth)acrylate, For example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, and 2,2'- diallylbisphenol A Epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type Epoxy compound, naphthalene type epoxy compound, phenol novolak type epoxy compound, orthocresol novolak type epoxy compound, dicyclopentadiene novolak type epoxy compound, biphenyl novolak type epoxy compound, naphthalenephenol novolak type epoxy compound, gly A cydylamine type epoxy compound, an alkyl polyol type epoxy compound, a rubber-modified type epoxy compound, a glycidyl ester compound, etc. are mentioned.

As what is marketed among the said epoxy (meth)acrylates, For example, the epoxy (meth)acrylate by the Daicel Allnex company, the epoxy (meth)acrylate by the Shin-Nakamura Chemical Industry Co., Ltd., Kyoeisha Chemical Co., Ltd. Manufactured epoxy (meth)acrylate, the epoxy (meth)acrylate by the Nagase Chemtex company, the epoxy (meth)acrylate by the KSM company, etc. are mentioned.

As the epoxy (meth)acrylate manufactured by Daicel Allnex, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, DX can be heard

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

As the epoxy (meth)acrylate manufactured by Kyoeisha Chemical, for example, epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, Epoxy ester 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, etc. are mentioned.

As said Nagase Chemtex company make epoxy (meth)acrylate, denacol acrylate DA-141, denacol acrylate DA-314, denacol acrylate DA-911 etc. are mentioned, for example.

As said KSM company epoxy (meth)acrylate, BAEM-100 etc. are mentioned, for example.

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

Examples of the polyfunctional isocyanate compound include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, Triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, tetramethylxylylene diisocyanate, 1,6,11- undecane triisocyanate, etc. are mentioned.

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

Examples of the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyetherdiol, polyesterdiol, and polycaprolactonediol.

As the (meth)acrylic acid derivative having a hydroxyl group, for example, hydroxyalkyl mono(meth)acrylate, dihydric alcohol mono(meth)acrylate, trihydric alcohol mono(meth)acrylate or di( Meth)acrylate, epoxy (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.

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 trihydric alcohol, trimethylolethane, a trimethylol propane, glycerol etc. are mentioned, for example.

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

As what is marketed among the said urethane (meth)acrylates, For example, the urethane (meth)acrylate by the Toa Synthesis company, the urethane (meth)acrylate by the Daicel Allnex company, the urethane by the Negami Kogyo company (meth)acrylate, the urethane (meth)acrylate by the Shin-Nakamura Chemical Industry company, the urethane (meth)acrylate by the Kyoeisha Chemical company, etc. are mentioned.

Examples of the urethane (meth)acrylate manufactured by Toa Synthesis Co., Ltd. include M-1100, M-1200, M-1210, M-1600, and the like.

As said Daicel Allnex urethane (meth)acrylate, For example, EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL88, EBECRYL4842, EBECRYL4858, EBECRYL880, EBECRYL880. EBECRYL8807, EBECRYL9260, etc. are mentioned.

Examples of the urethane (meth)acrylate manufactured by Negami Kogyo Co., Ltd. include Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320 HB, Art resin UN-7100, Art resin UN-9000A, Art resin UN-9000H, etc. are mentioned.

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

As said Kyoeisha Chemical company urethane (meth)acrylate, For example, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA- 306T etc. are mentioned.

It is preferable that the compound which has a flexible frame|skeleton is included, and, as for the said curable resin, it is more preferable that the epoxy compound which has a flexible frame|skeleton, and/or the (meth)acrylic compound which has a flexible frame|skeleton is included. By using the compound which has such a flexible skeleton, it becomes easier to make the storage elastic modulus in 121 degreeC of the said hardened|cured material into the above-mentioned range.

It is preferable that it is at least 1 sort(s) chosen from the group which consists of a ring-opening structure of a lactone, an alkylene oxide structure, and a rubber structure, and, as for the said flexible skeleton, the ring-opening structure of a lactone is more preferable.

In addition, in the present specification, the "rubber structure" refers to a vulcanized rubber structure formed by adding sulfur to raw rubber, a synthetic rubber structure by double bonds formed in the molecular main chain by addition polymerization, and polymethylsiloxane using a peroxide. It means a structure exhibiting rubber elasticity, such as a silicone rubber structure formed by crosslinking or the like.

Examples of the lactone include γ-undecalactone, ε-caprolactone, γ-decalactone, σ-dodecalactone, γ-nonalactone, γ-nonanolactone, γ-valerolactone, σ -valerolactone, β-butyrolactone, γ-butyrolactone, β-propiolactone, σ-hexanolactone, 7-butyl-2-oxepanone, and the like. Especially, when ring-opening, it is preferable that carbon number of the linear part of a main skeleton becomes 5-7.

As said alkylene oxide structure, an ethylene oxide structure, a propylene oxide structure, a butylene oxide structure, etc. are mentioned, for example.

It is preferable that the said rubber structure is a structure which has an unsaturated bond in a principal chain, or a structure which has a polysiloxane skeleton in a principal chain.

As a structure which has an unsaturated bond in the said main chain, the structure etc. which have skeleton by superposition|polymerization of conjugated diene are mentioned, for example in a main chain.

Examples of the skeleton by polymerization of the conjugated diene include an acrylonitrile-butadiene skeleton, a polybutadiene skeleton, a polyisoprene skeleton, a styrene-butadiene skeleton, a polyisobutylene skeleton, and a polychloroprene skeleton.

The minimum with preferable content of the compound which has the said flexible skeleton in 100 weight part of said curable resins is 5 weight part, and a preferable upper limit is 30 weight part. When content of the compound which has the said flexible skeleton is this range, it becomes easier to make the storage elastic modulus in 121 degreeC of the hardened|cured material of the sealing compound for display elements obtained into the range mentioned above. The minimum with more preferable content of the compound which has the said flexible skeleton is 10 weight part, and a more preferable upper limit is 20 weight part.

The sealing compound for display elements of this invention contains a polymerization initiator and/or a thermosetting agent.

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

As said radical polymerization initiator, the radical photopolymerization initiator which generate|occur|produces a radical by light irradiation, the thermal radical polymerization initiator which generate|occur|produces a radical by heating, etc. are mentioned.

Examples of the radical photopolymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, etc. can be heard

Specific examples of the radical photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2 -(Dimethylamino)-2-((4-methylphenyl)methyl)-1-(4-(4-morpholinyl)phenyl)-1-butanone, 2,2-dimethoxy-1,2-diphenyl Ethan-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-benzoyloxime), 2,4,6- trimethylbenzoyl diphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. are mentioned.

As said thermal radical polymerization initiator, what is comprised from an azo compound, an organic peroxide, etc. is mentioned, for example. Especially, the polymeric azo initiator comprised from a polymeric azo compound is preferable.

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

The preferable lower limit of the number average molecular weight of the said high molecular weight azo compound is 1000, and a preferable upper limit is 300,000. When the number average molecular weight of the said polymeric azo compound is this range, it can mix easily with curable resin, and when using the sealing compound for display elements obtained for a liquid crystal display element, the adverse influence to a liquid crystal can be prevented. A more preferable lower limit of the number average molecular weight of the high molecular weight azo compound is 5000, a more preferable upper limit is 100,000, a more preferable lower limit is 10,000, and a more preferable upper limit is 90,000.

In addition, in this specification, the said number average molecular weight is a 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 Corporation) etc. are mentioned, for example.

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

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

Specific examples of the high molecular weight azo compound include a polycondensate of 4,4'-azobis(4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis(4-cyanophene). carbonic acid) and a polycondensate of 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 from Fujifilm Wako Pure Pharmaceutical Co., Ltd.) etc. are mentioned, for example.

Moreover, as what is marketed as an azo compound which is not a polymer|macromolecule, V-65, V-501 (all are made by FUJIFILM Wako Pure Pharmaceutical Co., Ltd.) etc. are mentioned, for example.

Examples of the organic peroxide include ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, peroxyester, diacylperoxide, and peroxydicarbonate.

As said cationic polymerization initiator, a photocationic polymerization initiator can be used preferably. The said photocationic polymerization initiator will not be specifically limited if it generate|occur|produces a protonic acid or a Lewis acid by light irradiation, The thing of an ionic photo-acid generating type may be sufficient, and a nonionic photo-acid generating type may be sufficient as it.

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

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

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

As for content of the said polymerization initiator, with respect to 100 weight part of said curable resin, a preferable minimum is 0.1 weight part, and a preferable upper limit is 30 weight part. When content of the said polymerization initiator is 0.1 weight part or more, the sealing compound for display elements obtained becomes a thing more excellent in sclerosis|hardenability. When content of the said polymerization initiator is 30 weight part or less, the sealing compound for display elements obtained becomes a thing more excellent in storage stability. A more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.

As said thermosetting agent, organic acid hydrazide, an imidazole derivative, an amine compound, polyhydric phenol type compound, an acid anhydride etc. are mentioned, for example. Among them, solid organic acid hydrazide is preferably used.

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

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.

As what is marketed among the said organic acid hydrazide, the organic acid hydrazide by the Otsuka Chemical company, organic acid hydrazide by the Nippon Finechem company, organic acid hydrazide by Ajinomoto Fine Techno, etc. are mentioned, for example. .

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

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

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

As for content of the said thermosetting agent, with respect to 100 weight part of said curable resin, a preferable minimum is 1 weight part, and a preferable upper limit is 50 weight part. When content of the said thermosetting agent is 1 weight part or more, the sealing compound for display elements obtained becomes a thing more excellent in thermosetting. When content of the said thermosetting agent is 50 weight part or less, the sealing compound for display elements obtained becomes more excellent in applicability|paintability and storage stability. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

It is preferable that the sealing compound for display elements of this invention contains a filler for the purpose of viscosity adjustment, the adhesive improvement by a stress dispersion effect, the improvement of a coefficient of linear expansion, the moisture resistance improvement of hardened|cured material, etc.

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

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

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

The minimum with preferable content of the said filler in 100 weight part of sealing compounds for display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part. When content of the said filler is this range, effects, such as an adhesive improvement, can be exhibited more, suppressing deterioration of applicability|paintability etc. A more preferable lower limit of the content of the filler is 20 parts by weight, and a more preferable upper limit thereof is 60 parts by weight.

It is preferable that the sealing compound for display elements of this invention contains a silane coupling agent. The said silane coupling agent mainly has a role as an adhesion|attachment adjuvant for bonding a sealing compound, a board|substrate, etc. favorably.

As the silane coupling agent, for example, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane or the like is preferably used. When these silane coupling agents are excellent in the effect of improving the adhesiveness with a board|substrate etc., and using the sealing compound for display elements obtained for a liquid crystal display element, the outflow of curable resin to a liquid crystal can be suppressed.

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

The minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part. When the sealing compound for display elements obtained by content of the said silane coupling agent being this range is more excellent in adhesiveness, and using the sealing compound for display elements obtained for a liquid crystal display element, generation|occurrence|production of a liquid-crystal contamination can be suppressed becomes a thing A more preferable lower limit of content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.

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

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 type.

The titanium black is a substance having a higher transmittance in the vicinity of an ultraviolet region, particularly, light with a wavelength of 370 nm or more and 450 nm or less, compared to the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the said titanium black is a light-shielding agent which has a property which provides light-shielding property to the sealing compound for display elements of this invention by sufficiently shielding the light of the wavelength of a visible region, and transmits the light of the wavelength of the vicinity of an ultraviolet region. As a light-shielding agent contained in the sealing compound for 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 said titanium black exhibits sufficient effect even if it is not surface-treated, the thing whose surface is treated with organic components, such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, etc. Surface-treated titanium black, such as those coated with an inorganic component of Especially, the thing processed with the organic component is preferable at the point which can improve insulation more.

Moreover, since the display element manufactured using the sealing compound for display elements of this invention containing the said titanium black as a light-shielding agent has sufficient light-shielding property, it has high contrast without light leakage, and has excellent image display quality. A display element can be realized.

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

12S, 13M, 13M-C, 13R-N, 14M-C etc. are mentioned as said Mitsubishi Materials titanium black, for example.

As said titanium black manufactured by Ako Chemical Co., Ltd., Tirac D etc. are mentioned, for example.

A preferable lower limit of the specific surface area of the titanium black is 13 m2/g, a preferable upper limit is 30 m2/g, a more preferable lower limit is 15 m2/g, and a more preferable upper limit is 25 m2/g.

In addition, a preferable lower limit of the volume resistance 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.

Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between board|substrates of a display element, A preferable lower limit is 1 nm, and a preferable upper limit is 5000 nm. When the primary particle diameter of the said light-shielding agent is this range, light-shielding property can be made into a more excellent thing, without worsening the drawing property of the sealing compound for display elements obtained, etc. 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 more preferable lower limit is 10 nm, and a more preferable upper limit is 100 nm.

The primary particle diameter of the light-shielding agent can be measured by dispersing the light-shielding agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).

The minimum with preferable content of the said light-shielding agent in 100 weight part of sealing compounds for display elements of this invention is 5 weight part, and a preferable upper limit is 80 weight part. When content of the said light-shielding agent is this range, the effect of improving light-shielding property becomes more excellent, suppressing the adhesiveness of the sealing compound for display elements obtained, the intensity|strength after hardening, and the deterioration of drawing property. 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 more preferable lower limit is 30 parts by weight, and a more preferable upper limit is 60 parts by weight.

The sealing compound for display elements of this invention may contain additives, such as a reactive diluent, a spacer, a hardening accelerator, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent, further as needed.

As a method of manufacturing the sealing compound for display elements of this invention, for example, using a mixer, curable resin, a polymerization initiator and/or a thermosetting agent, and the method of mixing the silane coupling agent added as needed, etc. and the like.

As said mixer, a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, three rolls etc. are mentioned, for example.

As for the sealing compound for display elements of this invention, the preferable minimum of the glass transition temperature of hardened|cured material is 125 degreeC. When the glass transition temperature of the said hardened|cured material is 125 degreeC or more, the effect which the sealing compound for display elements obtained suppresses the penetration|invasion of the bubble in high-temperature, high-humidity environment becomes more excellent. A more preferable lower limit of the glass transition temperature of the cured product is 130°C.

Moreover, from an adhesive viewpoint, the preferable upper limit of the glass transition temperature of the said hardened|cured material is 170 degreeC.

In addition, in this specification, the said "glass transition temperature" means the temperature at which the maximum resulting from micro-Brownian motion appears among the maximums of loss tangent (tanδ) obtained by dynamic viscoelasticity measurement. The said glass transition temperature can be measured by the conventionally well-known method using a dynamic viscoelasticity measuring apparatus etc.

Moreover, after irradiating a 100 mW/cm<2> ultraviolet-ray to a sealing compound for 30 second as hardened|cured material which measures the said glass transition temperature, what heated and hardened at 120 degreeC for 1 hour is used.

The preferable upper limit of the water absorption after performing the high-temperature, high-humidity test which exposes hardened|cured material in the environment of 121 degreeC, 100%RH, and 2 atm for 24 hours with the sealing compound for display elements of this invention is 4.0 weight%. When the said water absorption is 4.0 weight% or less, the effect which the sealing compound for display elements of this invention suppresses the penetration|invasion of the bubble in high-temperature, high-humidity environment becomes more excellent. A more preferable upper limit of the water absorption is 3.0% by weight, and a more preferable upper limit is 2.5% by weight.

Moreover, although there is no especially preferable lower limit of the said water absorption, a practical lower limit is 1.0 weight%.

In addition, the said "water absorption rate" is calculated by the following formula when the weight before the high temperature, high humidity test is W ₁ , and the weight after the high temperature, high humidity test is W ₂ .

Water absorption (wt%) = ((W ₂ - W ₁ )/W ₁ ) × 100

Moreover, after irradiating a 100 mW/cm<2> ultraviolet-ray to a sealing compound for 30 second as hardened|cured material which measures the said water absorption, what heated and hardened at 120 degreeC for 1 hour is used.

A vertical conduction material can be manufactured by mix|blending electroconductive microparticles|fine-particles with the sealing compound for display elements of this invention. The vertical conduction material containing the sealing compound for display elements of this invention and electroconductive fine particles is also one of this invention.

The conductive fine particles are not particularly limited, and metal balls or those in which a conductive metal layer is formed on the surface of the resin fine particles can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because of the excellent elasticity of the resin fine particles, the conductive connection is possible without damaging the transparent substrate or the like.

The display element which has the hardened|cured material of the sealing compound for display elements of this invention or the hardened|cured material of the vertical conduction material of this invention is also one of this invention. As a display element of this invention, a liquid crystal display element is preferable.

As a method of manufacturing a liquid crystal display element using the sealing compound for display elements of this invention, the liquid crystal dropping method is used preferably, and the method etc. which have the following each process specifically are mentioned.

First, the sealing compound for display elements of this invention is apply|coated by screen printing, dispenser application|coating, etc. to one of two transparent substrates which have electrodes, such as an ITO thin film, and the process of forming a frame-shaped sealing pattern is implemented. Next, the liquid crystal microdroplets are drip apply|coated to the whole surface inside the frame of a seal pattern, and the process of superimposing the other transparent substrate under vacuum is implemented. Then, a liquid crystal display element can be obtained by the method of performing the process of irradiating light, such as an ultraviolet-ray, to a sealing pattern part, the process of temporarily hardening a sealing compound, and the process of heating and main hardening the sealing compound made temporarily hardening. .

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for display elements from which the display element excellent in the reliability in high-temperature, high-humidity environment can be obtained can be provided. Moreover, according to this invention, the vertical conduction material and display element which use this sealing compound for display elements can be provided.

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

(Examples 1 to 7, Comparative Examples 1 to 5)

According to the compounding ratio of Tables 1, 2, after mixing each material using the planetary stirrer, the sealing compound for display elements was prepared by mixing further using 3 rolls. As the planetary stirrer, Awatori Rentaro (manufactured by Thinkki) was used.

In Tables 1 and 2, "NEM-5000H" is about 50% by weight of partially methacrylic-modified bisphenol A epoxy compound, about 25% by weight of bisphenol A epoxy methacrylate, and about 25% by weight of bisphenol A epoxy compound. A mixture containing 25% by weight (about 75% by weight of the compound having an epoxy group). In addition, in Tables 1 and 2, "KRM8287" contains about 50% by weight of partially acrylic modified bisphenol E epoxy compound, about 25% by weight of bisphenol E epoxy acrylate, and about 25% by weight of bisphenol E epoxy compound. a mixture (the content of the compound having an epoxy group is about 75% by weight).

Each obtained sealing compound for display elements was apply|coated to one of the alkali free glass of 2 sheets, another alkali free glass was piled up from the top of the apply|coated sealing compound, and 100 mW/cm<2> ultraviolet-ray (wavelength 365nm) using a metal halide lamp After irradiating ) for 30 seconds, the other alkali free glass was peeled, it heated at 120 degreeC for 1 hour, the sealing compound was thermosetted, and the hardened|cured material was obtained. As alkali-free glass, OA-10G (manufactured by Nippon Electric Glass Co., Ltd., thickness 0.7 mm, surface roughness 0.2 nmRa) was used. About the obtained hardened|cured material, in 25 degreeC, the contact angle with water and methylene iodide was measured using the contact angle meter (3 microliters of dripping amount, 30 seconds after dripping), and the polar component term was computed by the above-mentioned formula. . As the contact angle meter, a fully automatic contact angle meter DMo-701 (manufactured by Kyowa Interface Science Co., Ltd.) was used. The results are shown in Tables 1 and 2.

Moreover, after irradiating a 100 mW/cm<2> ultraviolet-ray (wavelength 365 nm) for 30 second about each obtained sealing compound for display elements using a metal halide lamp, the hardened|cured material was obtained by heating at 120 degreeC for 1 hour. About the obtained hardened|cured material, using the dynamic viscoelasticity measuring apparatus, the storage modulus in 121 degreeC was measured under the conditions of test piece width 5mm, thickness 0.35mm, grip width 25mm, temperature increase rate 10 degreeC/min, and frequency 5Hz. did. Moreover, the temperature of the local maximum of loss tangent (tan δ) was calculated|required as a glass transition temperature. As the dynamic viscoelasticity measuring device, DVA-200 (manufactured by IT Instrumentation & Control Co., Ltd.) was used. The results are shown in Tables 1 and 2.

Moreover, after irradiating a 100 mW/cm<2> ultraviolet-ray (wavelength 365 nm) for 30 second about each obtained sealing compound for display elements using a metal halide lamp, the hardened|cured material was obtained by heating at 120 degreeC for 1 hour. About the obtained hardened|cured material, the high temperature, high humidity test exposed in the environment of 121 degreeC, 100%RH, and 2 atm for 24 hours was implemented, and the water absorption was computed by the formula mentioned above. The results are shown in Tables 1 and 2.

<Evaluation>

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

(Reliability under high temperature, high humidity environment)

1 weight part of spacer particle|grains were uniformly disperse|distributed to 100 weight part of sealing compounds for display elements obtained by the Example and the comparative example. As the spacer particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Industry Co., Ltd.) was used. The sealing compound in which the spacer particle|grains were disperse|distributed was filled in the syringe for dispensing, and after performing a defoaming process, it was apply|coated as if drawing a rectangular frame on the transparent substrate with an orientation film and an ITO thin film with a dispenser. As a syringe, PSY-10E (manufactured by Musashi Engineering) was used, and as a dispenser, SHOTMASTER300 (manufactured by Musashi Engineering) was used. Then, the microdroplet of the liquid crystal was drip-coated on the entire surface in the flame|frame of a sealing compound, and the other transparent board|substrate was bonded together immediately. As the liquid crystal, JC-5004 LA (manufactured by Chisso Corporation) was used. Immediately after bonding a transparent substrate together, after irradiating a 100 mW/cm<2> ultraviolet-ray (wavelength 365 nm) for 30 second using a metal halide lamp to a sealing compound part, the liquid crystal display element was obtained by heating at 120 degreeC for 1 hour. About the sealing compound for each display element obtained by the Example and the comparative example, 20 liquid crystal display elements were respectively produced.

The obtained liquid crystal display element was exposed on PCT conditions (121 degreeC, 100%RH, 2 atm) for 24 hours. The presence or absence of a bubble was confirmed by visual observation about the liquid crystal display element after exposure to PCT conditions.

A case in which bubbles were not confirmed in all 20 liquid crystal display elements was “◎”, a case in which bubbles were confirmed in 1 or more and 3 or less liquid crystal display elements was “○”, and 4 or more and 8 or less liquid crystal display elements were When a bubble was confirmed "(triangle|delta)", the case where a bubble was confirmed in 9 or more liquid crystal display elements was made into "x", and the reliability in a high-temperature, high-humidity environment was evaluated.

Industrial Applicability

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for display elements from which the display element excellent in the reliability in high-temperature, high-humidity environment can be obtained can be provided. Moreover, according to this invention, the vertical conduction material and display element which use this sealing compound for display elements can be provided.

Claims (6)

It contains a curable resin, a polymerization initiator and/or a thermosetting agent,
The polar component term in the expression of surface free energy by the Owens-Wendt method of the cured product is 6.0 or less,
The storage elastic modulus in 121 degreeC of hardened|cured material is 50 Mpa or more, The sealing compound for display elements characterized by the above-mentioned. The method of claim 1,
The curable resin contains a compound having an epoxy group,
The sealing compound for display elements whose content of the compound which has the said epoxy group in 100 weight part of said curable resins is 10 weight part or more and 60 weight part or less. 3. The method of claim 1 or 2,
The said curable resin contains the compound which has the ring-opening structure of a lactone, The sealing compound for display elements. 4. The method of claim 1, 2 or 3,
The sealing compound for display elements whose water absorption after performing the high-temperature, high-humidity test which exposes hardened|cured material in 121 degreeC, 100%RH, and the environment of 2 atm for 24 hours is 4.0 weight% or less. The vertical conduction material containing the sealing compound for display elements of Claim 1, 2, 3, or 4, and electroconductive fine particles. The display element which has the hardened|cured material of the sealing compound for display elements of Claim 1, 2, 3, or 4, or the hardened|cured material of the vertical conduction material of Claim 5.