JP7084550B2 - Sealant for liquid crystal display element, vertical conduction material, display element - Google Patents

Description

The present invention relates to a curable resin composition, a sealant for a display element using the curable resin composition, a sealant for a liquid crystal display element, a vertical conductive material, a display element, an adhesive for an electronic component, and the like. Regarding electronic components.

In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption. In such display elements and other electronic devices, a curable resin composition is usually used for sealing a liquid crystal display or a light emitting layer, adhering various electronic components, and the like.
For example, in the manufacture of a liquid crystal display element, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, dripping using a curable resin composition as disclosed in Patent Document 1 and Patent Document 2 as a sealing agent. A liquid crystal dropping method called a construction method is used.
In the dropping method, first, a frame-shaped seal pattern is formed on one of the two transparent substrates with electrodes by dispensing. Next, in a state where the sealant is uncured, fine droplets of liquid crystal are dropped on the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately bonded, and the sealed portion is irradiated with light such as ultraviolet rays to perform temporary curing. .. After that, it is heated at the time of liquid crystal annealing to perform main curing to produce a liquid crystal display element. If the substrates are bonded together under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency, and this dropping method is currently the mainstream method for manufacturing the liquid crystal display element.

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

In the present age when mobile devices with various liquid crystal panels such as mobile phones and handheld game machines are widespread, miniaturization of devices is the most sought after issue. As a method for reducing the size of the device, a narrowing of the frame of the liquid crystal display unit is mentioned. For example, the position of the seal portion is arranged under the black matrix (hereinafter, also referred to as a narrow frame design).
However, in the narrow frame design, the sealant is placed directly under the black matrix, so if the dropping method is used, the light emitted when the sealant is photocured is blocked and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. When the curing of the sealant is insufficient as described above, there is a problem that the uncured sealant component is eluted in the liquid crystal display and the liquid crystal display is contaminated.
In addition, ultraviolet irradiation is usually performed as a method of photocuring the sealant, but in the liquid crystal dropping method in particular, since the sealant is cured after the liquid crystal is dropped, the liquid crystal is deteriorated by irradiating with ultraviolet rays. There was a problem of doing. Therefore, in order to prevent deterioration of the liquid crystal due to ultraviolet rays, a photopolymerization initiator having excellent reactivity with long-wavelength light is blended, and the sealant is cured by light irradiation through a cut filter or the like. Further, when the sealant is irradiated with light, the element is usually exposed by covering the element with a mask so as not to damage the display element, but in recent years, the exposure can be performed without a mask. In addition, there is a demand for a sealing agent that can be cured by irradiating visible light with low energy.

On the other hand, even in the case of adhesives for electronic parts used in other electronic devices, when they are cured by irradiating them with ultraviolet rays, other peripheral members may be deteriorated by light. Curing with light of wavelength is being considered.

An object of the present invention is to provide a curable resin composition having excellent visible light curability and adhesiveness, and also having excellent low liquid crystal contamination property when used as a sealant for a liquid crystal display element. Further, in the present invention, a sealant for a display element containing the curable resin composition, a sealant for a liquid crystal display element, a vertical conduction material, and a cured product of the sealant for the display element, the liquid crystal display element. It is an object of the present invention to provide a display element having a cured product of a sealant for use or a cured product of the vertically conductive material. Further, it is an object of the present invention to provide an adhesive for electronic parts containing the curable resin composition and an electronic component bonded with a cured product of the adhesive for electronic parts.

The present invention is a sealant for a liquid crystal display element containing a curable resin and a photopolymerization initiator, wherein the photopolymerization initiator is a seal for a liquid crystal display element containing a compound represented by the following formula (1). It is an agent .

In formula (1), R ¹ has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), R ² has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), R ³ has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), ^R4 is a structure having a bond, an arylene group, or a heteroarylene group.
The present invention will be described in detail below.

When a photopolymerization initiator having excellent reactivity with long wavelength light is blended in a curable resin composition used as a sealing agent for a liquid crystal display element and photocured by light in the visible light region having a wavelength exceeding 420 nm, the sealing agent is used. There was a problem that the liquid crystal could be contaminated. Further, when a photopolymerization initiator having excellent reactivity to long wavelength light is blended in an adhesive for electronic parts and photocured by light in the visible light region having a wavelength exceeding 420 nm, sufficient adhesiveness cannot be obtained. There was a problem that there was.
Therefore, the present inventor has studied the use of a compound having a specific structure as a photopolymerization initiator to be blended in a curable resin composition. As a result, they have found that it is possible to obtain a curable resin composition which is excellent in visible light curability and adhesiveness and also excellent in low liquid crystal contamination when used as a sealant for a liquid crystal display element. It came to be completed.

The curable resin composition of the present invention contains a photopolymerization initiator.
The photopolymerization initiator contains a compound represented by the above formula (1). By using the compound represented by the above formula (1) as the photopolymerization initiator, the curable resin composition of the present invention has excellent visible light curability and adhesiveness, and can be used as a sealing agent for a liquid crystal display element. When used, it is also excellent in low liquid crystal contamination.

In the above formula (1), R ¹ is an alkyl group, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an alkyl group having 1 to 20 carbon atoms, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have an ether bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group are polar groups. May have.
When the R ¹ is an alkyl group having 1 to 20 carbon atoms, the alkyl group is preferably a methyl group or an ethyl group.
When the above R ¹ is a cycloalkyl group, examples of the cycloalkyl group include a cyclohexyl group and a cyclobutyl group.
When the above R ¹ is an aralkyl group, examples of the aralkyl group include a phenylmethyl group and a 2-naphthylmethyl group.
When the above R ¹ is a heterocyclic group, examples of the heterocyclic group include a 2-benzofuranyl group and the like.
When the above R ¹ is an aryl group, examples of the aryl group include a phenyl group and a 1-naphthyl group. Of these, a phenyl group is preferable.
Examples of the polar group include a hydroxy group, a carboxyl group, an amino group and the like. Among them, when the curable resin composition of the present invention is used for adhesion of electronic parts or the like, a carboxyl group is preferable from the viewpoint that the cation component can be supplemented because the cation component increases in the surrounding environment.

In the above formula (1), R ² is an alkyl group, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an alkyl group having 1 to 20 carbon atoms, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have an ether bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group are polar groups. May have.
When the above R ² is an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-ethylhexyl group and the like. Of these, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are preferable.
When the above R ² is a cycloalkyl group, examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. The cycloalkyl group may have an alkyl group.
When the above R ² is an aralkyl group, examples of the aralkyl group include a phenylmethyl group and the like.
When the above R ² is a heterocyclic group, examples of the heterocyclic group include a 2-benzothiophenyl group and the like.
When the above R ² is an aryl group, examples of the aryl group include a phenyl group and the like.
Examples of the polar group include a hydroxy group, a carboxyl group, an amino group and the like. Among them, when the curable resin composition of the present invention is used for adhesion of electronic parts or the like, a carboxyl group is preferable from the viewpoint that the cation component can be supplemented because the cation component increases in the surrounding environment.
When the above R ² is an alkyl group having a polar group, examples of the alkyl group having the polar group include a carboxymethyl group and a 2-carboxyethyl group.
When the above R ² is a cycloalkyl group having a polar group, examples of the cycloalkyl group having the polar group include a 2-carboxycyclohexyl group and a 2-carboxy-4-methylcyclohexyl group.

In the above formula (1), R ³ independently has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an amide bond, which may have an ether bond or an amide bond, respectively. It is an aryl group which may have an ether bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group are polar groups. May have.
When the above R ³ is an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-ethylhexyl group and the like. Of these, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are preferable. The alkyl group may have an aryl group.
When the above R ³ is a cycloalkyl group, examples of the cycloalkyl group include a cyclohexyl group.
When the above R ³ is an aralkyl group, examples of the aralkyl group include a 2-naphthylmethyl group and the like.
When the above R ³ is a heterocyclic group, examples of the heterocyclic group include a 2-thienyl group and the like.
When the above R ³ is an aryl group, examples of the aryl group include a phenyl group and the like. Examples of the polar group include a hydroxy group, a carboxyl group, an amino group and the like. Among them, when the curable resin composition of the present invention is used for adhesion of electronic parts or the like, a carboxyl group is preferable from the viewpoint that the cation component can be supplemented because the cation component increases in the surrounding environment.
When the above R ³ is an alkyl group having a polar group, examples of the alkyl group having the polar group include 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group and 3-carboxypropyl group. Examples thereof include 1-carboxypentyl group and carboxy (phenyl) methyl group.

In the above formula (1), ^R4 is a structure having a bond, an arylene group, or a heteroarylene group.
When the above R ⁴ has a structure having an arylene group, examples of the arylene group include a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-naphthylene group and the like. Specific examples of the structure having an arylene group include structures represented by the following formulas (2-1) to (2-5).
When the above R ⁴ has a structure having a heteroarylene group, examples of the heteroarylene group include a thienylene group, a furanylene group, a pyridylene group and the like. Of these, the thienylene group is preferable. Specific examples of the structure having a heteroarylene group include structures represented by the following formulas (3-1) to (3-6).

In the formulas (2-1) to (2-5), * represents a bonding position.

In equations (3-1) to (3-6), * represents a bonding position.

Since the compound represented by the above formula (1) is excellent in reactivity to visible light and low liquid crystal contamination, the compounds represented by the following formulas (4) to (9) are used in the above formula (1). A compound in which at least one of R ² and R ³ is a group represented by the following formula (10) is preferable, a compound represented by the following formula (4), and at least R ² and R ³ in the above formula (1). A compound whose one is a group represented by the following formula (10) is more preferable.

In formula (10), R ⁵ has an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group, an aralkylene group, a heterocyclic group, or an ether bond or an amide bond, which may have an ether bond or an amide bond. It is an arylene group that may have, and * represents a bond position.

As the compound in which at least one of R ² and R ³ in the above formula (1) is a group represented by the above formula (10), a compound represented by the following formula (11) is preferable.

Regarding the content of the compound represented by the above formula (1), the preferable lower limit is 0.01 part by weight and the preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the compound represented by the above formula (1) is 0.01 parts by weight or more, the obtained curable resin composition becomes more excellent in visible light curability. When the content of the compound represented by the above formula (1) is 5 parts by weight or less, the obtained curable resin composition is excellent in low liquid crystal contamination property when used as a sealant for a liquid crystal display element. Become. The more preferable lower limit of the content of the compound represented by the above formula (1) is 0.1 parts by weight, and the more preferable upper limit is 2 parts by weight.

The curable resin composition of the present invention contains a curable resin.
The curable resin preferably contains a (meth) acrylic compound.
Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. Further, the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
In the present specification, the above-mentioned "(meth) acrylic" means acrylic or methacrylic, and the above-mentioned "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the above-mentioned "((meth) acryloyl group". "Meta) Acryloyl" means acryloyl or methacryloyl. Further, the above-mentioned "(meth) acrylate" means acrylate or methacrylate. Further, the above-mentioned "epoxy (meth) acrylate" refers to a compound in which all the epoxy groups in the epoxy compound are reacted with (meth) acrylic acid.

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

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

Among the above (meth) acrylic acid ester compounds, examples thereof include trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, and propylene oxide-added trimethylolpropane tri (meth) acrylate. Meta) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include tris (meth) acryloyloxyethyl phosphate, trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.

Examples of the epoxy compound used as a raw material for synthesizing the above epoxy (meth) acrylate include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, and 2,2'-diallyl bisphenol A type 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, biphenylnovolak type epoxy compound, naphthalenephenol novolak type epoxy compound, glycidylamine type epoxy compound, alkylpolypoly type epoxy compound, rubber-modified epoxy compound , Glycidyl ester compound and the like.

Examples of commercially available bisphenol A type epoxy compounds include jER828EL, jER1004 (all manufactured by Mitsubishi Chemical Corporation), EPICLON EXA-850CRP (manufactured by DIC Corporation), and the like.
Examples of commercially available bisphenol F type epoxy compounds include jER806 and jER4004 (both manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available bisphenol S-type epoxy compounds include EPICLON EXA1514 (manufactured by DIC Corporation) and the like.
Examples of commercially available 2,2'-diallyl bisphenol A type epoxy compounds include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available hydrogenated bisphenol type epoxy compounds include EPICLON EXA7015 (manufactured by DIC Corporation) and the like.
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available biphenyl type epoxy compounds include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like.
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA Corporation) and the like.
Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation) and the like.
Examples of commercially available orthocresol novolak type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation) and the like.
Examples of commercially available dicyclopentadiene novolak type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation) and the like.
Examples of commercially available biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.) and the like.
Examples of commercially available naphthalene phenol novolac type epoxy compounds include ESN-165S (manufactured by Nittetsu Chemical & Materials Co., Ltd.).
Examples of commercially available glycidylamine type epoxy compounds include jER630 (manufactured by Mitsubishi Chemical Corporation), EPICLON 430 (manufactured by DIC Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Company, Inc.) and the like.
Among the above alkyl polyol type epoxy compounds, for example, ZX-1542 (manufactured by Nittetsu Chemical & Materials Co., Ltd.), EPICLON 726 (manufactured by DIC Corporation), Epolite 80MFA (manufactured by Kyoei Co., Ltd.), Denacol EX -611 (manufactured by Nagase ChemteX Corporation) and the like can be mentioned.
Examples of commercially available rubber-modified epoxy compounds include YR-450, YR-207 (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), Epolide PB (manufactured by Daicel Co., Ltd.), and the like.
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation) and the like.
Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nittetsu Chemical & Materials Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031 and jER1032. (All manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.

Among the above-mentioned epoxy (meth) acrylates, commercially available ones include, for example, epoxy (meth) acrylate manufactured by Dycel Ornex, epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and epoxy manufactured by Kyoei Co., Ltd. Examples thereof include meta) acrylate and epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation.
Examples of the epoxy (meth) acrylate manufactured by Dycel Ornex include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3702, EBECRYL3701
Examples of the epoxy (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 and the like.
Examples of the epoxy (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy ester 200PA, epoxy ester 80MFA, epoxy ester 3002M, epoxy ester 3002A, and epoxy ester 1600A. Examples thereof include epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, and epoxy ester 400EA.
Examples of the epoxy (meth) acrylate manufactured by Nagase ChemteX include denacole acrylate DA-141, denacole acrylate DA-314, and denacole acrylate DA-911.

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

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), and the like. Hydrogenated MDI, Polymeric MDI, 1,5-naphthalenediocyanate, Norbornan diisocyanate, Trizine diisocyanate, Xylylene diisocyanate (XDI), Hydrogenated XDI, Lysine diisocyanate, Triphenylmethane triisocyanate, Tris (isocyanatephenyl) thiophosphate, Tetramethyl Examples thereof include xylylene diisocyanate and 1,6,11-undecantry isocyanate.

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

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

Among the above urethane (meth) acrylates, commercially available ones include, for example, urethane (meth) acrylate manufactured by Toa Synthetic Co., Ltd., urethane (meth) acrylate manufactured by Dycel Ornex, and urethane (meth) manufactured by Negami Kogyo Co., Ltd. Examples thereof include acrylate, urethane (meth) acrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth) acrylate manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210, M-1600 and the like.
上記ダイセル・オルネクス社製のウレタン（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ２１０、ＥＢＥＣＲＹＬ２２０、ＥＢＥＣＲＹＬ２３０、ＥＢＥＣＲＹＬ２７０、ＥＢＥＣＲＹＬ１２９０、ＥＢＥＣＲＹＬ２２２０、ＥＢＥＣＲＹＬ４８２７、ＥＢＥＣＲＹＬ４８４２、ＥＢＥＣＲＹＬ４８５８、ＥＢＥＣＲＹＬ５１２９、ＥＢＥＣＲＹＬ６７００、ＥＢＥＣＲＹＬ８４０２、ＥＢＥＣＲＹＬ８８０３、ＥＢＥＣＲＹＬ８８０４、ＥＢＥＣＲＹＬ８８０７、ＥＢＥＣＲＹＬ９２６０等がCan be mentioned.
Examples of the urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. include Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320HB, and Art Resin UN-. 7100, Art Resin UN-9000A, Art Resin UN-9000H and the like can be mentioned.
Examples of the urethane (meth) acrylate manufactured by Shin Nakamura Chemical Industry Co., Ltd. include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, and the like. 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- Examples thereof include 4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A and the like.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha Chemical Co., Ltd. include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T and the like. Be done.

The curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the obtained curable resin composition. Examples of the epoxy compound include an epoxy compound used as a raw material for synthesizing the above-mentioned epoxy (meth) acrylate, a partially (meth) acrylic-modified epoxy compound, and the like.
In the present specification, the above-mentioned partially (meth) acrylic-modified epoxy compound means, for example, reacting a part of the epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid. Means a compound having one or more epoxy groups and one or more (meth) acryloyl groups in one molecule.

When the curable resin contains the (meth) acrylic compound and the epoxy compound, or when the partially (meth) acrylic-modified epoxy compound is contained, the (meth) acryloyl group and the epoxy in the curable resin It is preferable that the ratio of the (meth) acryloyl group in the total with the group is 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl group is in this range, the obtained curable resin composition is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination when used as a sealant for a liquid crystal display element. Will be.

The curable resin has -OH group, -NH- group, and -NH ₂ groups from the viewpoint of being superior in low liquid crystal contamination property when the obtained curable resin composition is used as a sealant for a liquid crystal display element. Those having a hydrogen-bonding unit such as are preferable.

The curable resin may be used alone or in combination of two or more.

The curable resin composition of the present invention may contain a sensitizer, but does not contain the sensitizer from the viewpoint of low liquid crystal contamination when used as a sealant for a liquid crystal display element. Is preferable. By containing the compound represented by the above formula (1) as the photopolymerization initiator, the curable resin composition of the present invention has excellent visible light curability even if it does not contain a sensitizer. ..

Examples of the sensitizer include ethyl 4- (dimethylamino) benzoate, 9,10-dibutoxyanthracene, 2,4-diethylthioxanthone, and 2,2-dimethoxy-1,2-diphenylethan-1-one. , Benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like.

When the sensitizer is contained, the content of the sensitizer is preferably 0.01 part by weight and a preferable upper limit of 3 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the sensitizer is 0.01 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The more preferable lower limit of the content of the sensitizer is 0.1 parts by weight, and the more preferable upper limit is 1 part by weight.

The curable resin composition of the present invention may contain a thermal polymerization initiator as long as the object of the present invention is not impaired.
Examples of the thermal polymerization initiator include those made of an azo compound, an organic peroxide and the like. Of these, a polymer azo initiator composed of a polymer azo compound is preferable.
The thermal polymerization initiator may be used alone or in combination of two or more.
In the present specification, the above-mentioned "polymer azo compound" is a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth) acryloyloxy group by heat. means.

The preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo compound is in this range, it can be easily mixed with the curable resin. In particular, when the obtained curable resin composition is used as a sealant for a liquid crystal display element, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The more preferable lower limit of the number average molecular weight of the polymer azo compound is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.

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

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

The content of the thermal polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting initiator is 0.05 parts by weight or more, the curable resin composition of the present invention becomes more excellent in thermosetting property. When the content of the thermal polymerization initiator is 10 parts by weight or less, the curable resin composition of the present invention becomes more excellent in storage stability, and when used as a sealing agent for a liquid crystal display element, low liquid crystal contamination It will also be superior in sex. The more preferable lower limit of the content of the thermal polymerization initiator is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention may contain a thermosetting agent.
Examples of the heat-curing agent include organic acid hydrazide, imidazole derivative, amine compound, polyhydric phenolic compound, acid anhydride and the like. Of these, organic acid hydrazide is preferably used.
The thermosetting agent may be used alone or in combination of two or more.

Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd., and the like.
Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J and the like.

Regarding the content of the thermosetting agent, the preferable lower limit is 1 part by weight and the preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the thermosetting resin composition can be made more excellent in thermosetting property without deteriorating the coatability and the like. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The curable resin composition of the present invention preferably contains a filler for the purpose of improving the viscosity, improving the adhesiveness by the stress dispersion effect, improving the linear expansion coefficient, and the like.

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

Regarding the content of the filler, the preferable lower limit is 30 parts by weight and the preferable upper limit is 80 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the filler is in this range, the effect of improving the adhesiveness and the like is excellent without deteriorating the coatability and the like. The more preferable lower limit of the content of the filler is 45 parts by weight, and the more preferable upper limit is 65 parts by weight.

The curable resin composition of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the curable resin composition to a substrate or the like.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane and the like are preferably used. These have an excellent effect of improving the adhesiveness with a substrate or the like, and when the obtained curable resin composition is used as a sealing agent for a liquid crystal display element, they are chemically bonded to the curable resin into the liquid crystal. The outflow of the curable resin can be suppressed.
The silane coupling agent may be used alone or in combination of two or more.

The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the curable resin composition of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is in this range, the obtained curable resin composition becomes more excellent in adhesiveness. In particular, when the obtained curable resin composition is used as a sealant for a liquid crystal display element, the adhesiveness is improved while suppressing the occurrence of liquid crystal contamination. The more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention further contains additives such as a reactive diluent, a rocking agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary. May be good.

As a method for producing the curable resin composition of the present invention, for example, a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer is used to photopolymerize the curable resin with the curable resin. Examples thereof include a method of mixing the initiator and a silane coupling agent or the like to be added as needed.

The curable resin composition of the present invention is suitably used as a sealing agent for a display element, and more preferably used as a sealing agent for a liquid crystal display element. A sealant for a display element containing the curable resin composition of the present invention and a sealant for a liquid crystal display element containing the curable resin composition of the present invention are also one of the present inventions, respectively.

By blending conductive fine particles with the curable resin composition of the present invention, a vertically conductive material can be produced. A vertically conductive material containing the curable resin composition of the present invention and conductive fine particles is also one of the present inventions.

As the conductive fine particles, a metal ball, a resin fine particle having a conductive metal layer formed on the surface thereof, or the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.

A display element having a cured product of the sealant for a display element of the present invention, a cured product of the sealant for a liquid crystal display element of the present invention, or a cured product of a vertically conductive material of the present invention is also one of the present inventions. ..
As the display element of the present invention, a liquid crystal display element using the sealant for the liquid crystal display element of the present invention is preferable, and a liquid crystal display element having a narrow frame design is more preferable. Specifically, the width of the frame portion around the liquid crystal display unit is preferably 2 mm or less.
Further, when the liquid crystal display element of the present invention is manufactured, the coating width of the sealant for the liquid crystal display element of the present invention is preferably 1 mm or less.

As a method for manufacturing a liquid crystal display element as the display element of the present invention, a liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps.
First, a step of applying the sealant for a liquid crystal display element of the present invention to one of two transparent substrates having an electrode such as an ITO thin film and an alignment film by screen printing, dispenser application, or the like to form a frame-shaped seal pattern. I do. Next, in a state where the liquid crystal display element sealant of the present invention is uncured, fine droplets of liquid crystal are dropped and applied in the frame of the seal pattern of the substrate, and the other transparent substrate is superposed under vacuum. After that, the liquid crystal display element can be obtained by a method of performing a step of photocuring the sealant by irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light through a cut filter or the like. Further, in addition to the step of photo-curing the sealant, a step of heating the sealant to thermally cure it may be performed.

The curable resin composition of the present invention is also suitably used for adhering electronic components. If the curable resin composition of the present invention is used as an adhesive for electronic parts, low-energy light can be used for light irradiation during curing, so that deterioration of other members can be suppressed.
An adhesive for electronic components containing the curable resin composition of the present invention and an electronic component bonded with a cured product of the adhesive for electronic components of the present invention are also one of the present inventions, respectively.

According to the present invention, it is possible to provide a curable resin composition having excellent visible light curability and adhesiveness, and also having excellent low liquid crystal contamination property when used as a sealant for a liquid crystal display element. Further, according to the present invention, a sealant for a display element containing the curable resin composition, a sealant for a liquid crystal display element, a vertical conduction material, and a cured product of the sealant for the display element, the liquid crystal. It is possible to provide a display element having a cured product of a sealant for a display element or a cured product of the vertically conductive material. Further, according to the present invention, it is possible to provide an adhesive for electronic components containing the curable resin composition and an electronic component bonded with a cured product of the adhesive for electronic components.

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

(Synthesis of compound represented by formula (4))
5 parts by weight of N-ethylcarbazole, 2.81 parts by weight of 2,5-thiophenedicarboxylic acid dichloride, and 3.76 parts by weight of aluminum chloride were added to 40 mL of dichloromethane, and the mixture was stirred overnight at room temperature. To the obtained reaction solution, 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added, and the mixture was further stirred at room temperature for 4 hours. The obtained reaction solution was poured into ice water, and then the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous magnesium sulfate and concentrated to obtain the product (A1).
3 parts by weight of the obtained product (A1), 0.76 parts by weight of hydroxylammonium chloride, and 0.86 parts by weight of pyridine were added to 30 mL of ethanol and stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate and concentrated to give the product (B1).
After dissolving 1.5 parts by weight of the obtained product (B1) in 25 parts by weight of N, N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10 ° C. or lower, 0.78 parts by weight of triethylamine was added dropwise, and the mixture was stirred at room temperature for 4 hours. The obtained reaction solution was poured into water and then filtered. The filtrate was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane: hexane = 2: 1) to obtain a compound represented by the above formula (4).
The structure of the obtained compound represented by the above formula (4) was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of compound represented by formula (9))
5 parts by weight of N- (2-ethylhexyl) carbazole, 2.81 parts by weight of 2,5-thiophenedicarboxylic acid dichloride and 3.76 parts by weight of aluminum chloride were added to 40 mL of dichloromethane and stirred overnight at room temperature. To the obtained reaction solution, 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added, and the mixture was further stirred at room temperature for 4 hours. The obtained reaction solution was poured into ice water, and then the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous magnesium sulfate and concentrated to obtain the product (A2).
3 parts by weight of the obtained product (A2), 0.76 parts by weight of hydroxylammonium chloride, and 0.86 parts by weight of pyridine were added to 30 mL of ethanol and stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate and concentrated to give the product (B2).
After dissolving 1.5 parts by weight of the obtained product (B2) in 25 parts by weight of N, N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10 ° C. or lower, 0.78 parts by weight of triethylamine was added dropwise, and the mixture was stirred at room temperature for 4 hours. The obtained reaction solution was poured into water and then filtered. The filtrate was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (dichloromethane: hexane = 2: 1) to obtain a compound represented by the above formula (9).
The structure of the obtained compound represented by the above formula (9) was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR.

(Synthesis of compound represented by formula (11))
5 parts by weight of ethyl 3- (9H-carbazole-9-yl) propionate, 2.64 parts by weight of hexanoyl chloride and 2.62 parts by weight of aluminum chloride were added to 80 mL of dichloromethane and stirred overnight at room temperature. .. To the obtained reaction solution, 1.84 parts by weight of 2,5-thiophenedicarboxylic acid dichloride and 5.24 parts by weight of aluminum chloride were added, and the mixture was further stirred at room temperature for 4 hours. The obtained reaction solution was poured into ice water, and then the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium hydrogen carbonate solution and brine, dried over anhydrous sodium sulfate and concentrated to obtain the product (A3).
To 4.0 parts by weight of the product (A3) in 20 mL of ethanol, 2.77 parts by weight of a 20% aqueous sodium hydroxide solution was added, and the mixture was refluxed for 3 hours. After completion of the reaction, 50 mL of water was added, acidified with concentrated hydrochloric acid, and then extracted with ethyl acetate. The ethyl acetate layer was washed with water and brine, then dried over anhydrous sodium sulfate and concentrated to give the product (B3).
3 parts by weight of the obtained product (B3), 0.58 part by weight of hydroxylammonium chloride, and 0.65 part by weight of pyridine were added to 30 mL of ethanol and stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water and then filtered. The filter was washed with water, dissolved in ethyl acetate, dried over anhydrous sodium sulfate and concentrated to give the product (C3).
After dissolving 1.5 parts by weight of the obtained product (C3) in 20 parts by weight of N, N-dimethylformamide, 0.45 parts by weight of acetyl chloride was added. While cooling the obtained solution to 10 ° C. or lower, 0.59 parts by weight of triethylamine was added dropwise, and the mixture was stirred at room temperature for 4 hours. The obtained reaction solution was poured into water and then filtered. By isolating the compound by silica gel column chromatography, the compound represented by the above formula (11) was obtained.
The structure of the obtained compound represented by the above formula (11) was confirmed by ¹ H-NMR, ¹³ C-NMR, and FT-IR.

(Examples 1 to 11 and Comparative Examples 1 to 3)
The curable resins of Examples 1 to 11 and Comparative Examples 1 to 3 were mixed by using a planetary stirrer and then further mixing using three rolls according to the compounding ratios shown in Table 1. The composition was prepared. As the planetary stirrer, Awatori Rentaro (manufactured by Shinky Co., Ltd.) was used.

<Evaluation>
The following evaluations were performed on each of the curable resin compositions obtained in Examples and Comparative Examples. The results are shown in Table 1.

(UV curability)
1 part by weight of the spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. Next, the sealant was filled in a syringe for dispensing, defoamed, and then applied onto a glass substrate with a dispenser. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used, and as a dispenser, SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used. A glass substrate of the same size was bonded to the substrate coated with the sealant under a reduced pressure of 5 Pa using a vacuum bonding device. A metal halide lamp was used to irradiate the sealing agent portion of the bonded glass substrate with light of 100 mW / cm ² for 10 seconds. The light irradiation was performed through a cut filter (340 nm cut filter) that cuts light having a wavelength of 340 m or less.
The FT-IR measurement of the sealant was performed using an infrared spectroscope, and the amount of change in the (meth) acryloyl group-derived peak before and after light irradiation was measured. As an infrared spectroscope, FTS3000 (manufactured by Bio-Rad) was used. "◎" when the peak derived from the (meth) acryloyl group decreased by 95% or more after light irradiation, "○" when it decreased by 90% or more and less than 95%, and "△" when it decreased by 70% or more and less than 90%. The UV curability was evaluated as "x" when the decrease in the peak derived from the (meth) acryloyl group after light irradiation was less than 70%.

(Visible light curability)
1 part by weight of the spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples. As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. Next, the sealant was filled in a syringe for dispensing, defoamed, and then applied onto a glass substrate with a dispenser. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used, and as a dispenser, SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used. A glass substrate of the same size was bonded to the substrate coated with the sealant under a reduced pressure of 5 Pa using a vacuum bonding device. A metal halide lamp was used to irradiate the sealing agent portion of the bonded glass substrate with light of 100 mW / cm ² for 10 seconds. The light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 m or less.
The FT-IR measurement of the sealant was performed using an infrared spectroscope, and the amount of change in the (meth) acryloyl group-derived peak before and after light irradiation was measured. As an infrared spectroscope, FTS3000 (manufactured by Bio-Rad) was used. "◎" when the peak derived from the (meth) acryloyl group decreased by 95% or more after light irradiation, "○" when it decreased by 90% or more and less than 95%, and "△" when it decreased by 70% or more and less than 90%. The UV curability was evaluated as "x" when the decrease in the peak derived from the (meth) acryloyl group after light irradiation was less than 70%.

(Low LCD pollution)
0.5 g of liquid crystal display (manufactured by Chisso, "JC-5001LA") is placed in a sample bottle, 0.1 g of each curable resin composition obtained in Examples and Comparative Examples is added, shaken, and then shaken at 120 ° C. The mixture was heated for 1 hour and returned to room temperature (25 ° C.). Dispensers of the curable resin compositions obtained in Examples and Comparative Examples on an alignment film of a glass substrate having a transparent electrode and an alignment film (manufactured by Nissan Chemical Industries, Ltd., "SE7942") so as to draw a square frame. Was applied with. Subsequently, fine droplets of the liquid crystal display taken out from the sample bottle were dropped and applied to the entire surface of the frame on the substrate, and another glass substrate was superposed in vacuum. The vacuum was released and a metal halide lamp was used to irradiate 100 mW / cm ² light for 10 seconds. The light irradiation was performed through a cut filter (420 nm cut filter) that cuts light having a wavelength of 420 m or less. Then, the sealant was thermally cured by heating at 120 ° C. for 1 hour to obtain a liquid crystal display element. With respect to the obtained liquid crystal display element, it was visually confirmed how an afterimage was generated when a DC voltage of 1 V was applied while an AC voltage of 1.5 V was applied. As a result, the display performance of the liquid crystal display element was evaluated as "○" when no afterimage was confirmed, "△" when a slight afterimage was confirmed, and "×" when a severe afterimage was confirmed. ..

(Adhesiveness)
1 part by weight of spacer fine particles was dispersed in 100 parts by weight of each curable resin composition obtained in Examples and Comparative Examples, and finely dropped onto one of two glass substrates with ITO thin film (30 × 40 mm). As the spacer fine particles, Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used. The other glass substrate with an ITO thin film was attached to this in a cross shape, irradiated with light of 100 mW / cm ² for 30 seconds with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to obtain an adhesive test piece. ..
The obtained adhesiveness test piece was subjected to a tensile test (5 mm / sec) with chucks arranged one above the other. When the value obtained by dividing the obtained measured value (kgf) by the seal coating cross-sectional area (cm ² ) is 1.5 kgf / cm ² or more, it is “◯”, and when it is less than 1.5 kgf / cm ² . Was evaluated as “x” to evaluate the adhesiveness.

According to the present invention, it is possible to provide a curable resin composition having excellent visible light curability and adhesiveness, and also having excellent low liquid crystal contamination property when used as a sealant for a liquid crystal display element. Further, according to the present invention, a sealant for a display element containing the curable resin composition, a sealant for a liquid crystal display element, a vertical conduction material, and a cured product of the sealant for the display element, the liquid crystal. It is possible to provide a display element having a cured product of a sealant for a display element or a cured product of the vertically conductive material. Further, according to the present invention, it is possible to provide an adhesive for electronic components containing the curable resin composition and an electronic component bonded with a cured product of the adhesive for electronic components.

Claims (6)

A sealant for a liquid crystal display element containing a curable resin and a photopolymerization initiator.
The photopolymerization initiator is a sealant for a liquid crystal display element, which comprises a compound represented by the following formula (1).

In formula (1), R ¹ has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), R ² has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), R ³ has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an ether, which may independently have an ether bond or an amide bond, respectively. It is an aryl group which may have a bond or an amide bond, and the alkyl group having 1 to 20 carbon atoms, the cycloalkyl group, the aralkyl group, the heterocyclic group, and the aryl group have a polar group. You may have. In formula (1), ^R4 is a structure having a bond, an arylene group, or a heteroarylene group. The sealant for a liquid crystal display element according to claim 1, wherein the photopolymerization initiator contains a compound represented by the following formula (4).

The sealant for a liquid crystal display element according to claim 1, wherein the photopolymerization initiator contains a compound represented by the following formula (11).

The liquid crystal display element according to claim 1, 2 or 3, wherein the content of the compound represented by the formula (1) is 0.01 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the curable resin. Sealant . A vertically conductive material containing the sealing agent for a liquid crystal display element according to claim 1, 2, 3 or 4, and conductive fine particles. A display element having a cured product of the sealant for a liquid crystal display element according to claim 1, 2, 3 or 4 , or a cured product of a vertically conductive material according to claim 5 .