WO2023032543A1

WO2023032543A1 - Liquid crystal display element sealant and liquid crystal display element

Info

Publication number: WO2023032543A1
Application number: PCT/JP2022/029229
Authority: WO
Inventors: 剛大浦; 啓太鈴木
Original assignee: 積水化学工業株式会社
Priority date: 2021-09-03
Filing date: 2022-07-29
Publication date: 2023-03-09
Also published as: JP7512404B2; JPWO2023032543A1; TW202323492A

Abstract

A purpose of the present invention is to provide a liquid crystal display element sealant having excellent curability with respect to long wavelength light. Another purpose of the present invention is to provide a liquid crystal display element formed by using said liquid crystal display element sealant. A liquid crystal display element sealant according to the present invention contains a curable resin, a photopolymerization initiator, and a filler. The photopolymerization initiator contains at least one selected from the group consisting of titanocene compounds and compounds having two or more carbazole backbones per molecule. The filler has a sphericity of 1.00-1.05 and a mean particle diameter of 1.0 μm or less.

Description

Sealant for liquid crystal display element and liquid crystal display element

The present invention relates to a sealant for liquid crystal display elements. The present invention also relates to a liquid crystal display element using the sealant for a liquid crystal display element.

In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, a photo-heat curing type seal disclosed in Patent Document 1 and Patent Document 2 A liquid crystal dropping method called a dropping method using an agent is used.
In the dripping method, first, a frame-shaped seal pattern is formed on one of two electrode-attached transparent substrates by dispensing. Next, while the sealant is not yet cured, liquid crystal microdroplets are dropped on the entire surface of the frame of the transparent substrate, the other transparent substrate is immediately attached, and the sealant is irradiated with light such as ultraviolet rays for temporary curing. . After that, the liquid crystal is annealed for final curing by heating, and a liquid crystal display element is produced. If the bonding of the substrates is performed under reduced pressure, the liquid crystal display element can be manufactured with extremely high efficiency.

JP-A-2001-133794 WO 02/092718

2. Description of the Related Art In today's world where mobile devices with liquid crystal panels such as mobile phones and portable game machines are widely used, miniaturization of devices is the most demanded issue. As a method for miniaturizing the device, narrowing the frame of the liquid crystal display portion is mentioned, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as narrow frame design).
However, in the narrow frame design, the sealant is placed directly under the black matrix, so if the dripping method is used, the light emitted during photocuring of the sealant will be blocked. In the future, if the frame becomes narrower and the liquid crystal material is changed, there is a risk that liquid crystal contamination will occur due to the uncured sealant component eluting into the liquid crystal, even if the sealant has no problems in the past. . Therefore, there has been a demand for a sealant that is more excellent in reducing liquid crystal contamination.

In addition, ultraviolet irradiation is usually used as a method for photocuring sealants, but in recent years, from the viewpoint of eliminating the photomask process and reducing energy consumption, manufacturing liquid crystal display elements using visible light. is in progress. The wavelength of the light irradiated to cure the sealant is becoming longer year by year, and there has been a demand for a sealant that can be cured with light of a longer wavelength.

An object of the present invention is to provide a sealant for a liquid crystal display device that exhibits excellent curability with respect to long-wavelength light. Another object of the present invention is to provide a liquid crystal display device using the sealant for a liquid crystal display device.

The present disclosure 1 is a sealant for a liquid crystal display element containing a curable resin, a photopolymerization initiator and a filler, wherein the photopolymerization initiator is a compound having two or more carbazole skeletons in one molecule, and , at least one selected from the group consisting of titanocene compounds, and the filler has a sphericity of 1.00 or more and 1.05 or less and an average particle size of 1.0 μm or less. It is a sealant for devices.
Present Disclosure 2 is a sealant for a liquid crystal display element according to Present Disclosure 1, which contains a compound represented by the following formula (1).
In the present disclosure 3, the photopolymerization initiator is a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), and a compound represented by the following formula (4-3). The sealant for a liquid crystal display element according to the present disclosure 1 or 2, containing at least one selected from the group consisting of the compounds.
The present disclosure 4 is the sealant for a liquid crystal display element of the present disclosure 1, 2 or 3 containing a thermal polymerization initiator.
5 of the present disclosure is a liquid crystal display device having a cured product of the sealant for a liquid crystal display device of 1, 2, 3 or 4 of the present disclosure.

In formula (1), each R ¹ is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), each R ² is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), each R ³ is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), R ⁴ is a bond, a structure having an arylene group, or a structure having a heteroarylene group.

The present invention will be described in detail below.
The inventors of the present invention have investigated the production of a liquid crystal display device by curing a sealant by irradiating light with a longer wavelength than in the past. However, even when a known photopolymerization initiator that is said to be more reactive to visible light is used, the sealant cannot be sufficiently cured when irradiated with light of such a long wavelength, resulting in liquid crystal contamination. could cause In recent years, the wiring of the liquid crystal display element has become complicated and the wiring density has increased, so the light incidence efficiency of the incident light to the sealant has decreased. The inventors of the present invention have found that the causes of liquid crystal contamination when irradiated with long-wavelength light are that the incident light cannot be uniformly scattered and the uncured portion of the sealant increases, and that the long-wavelength light When irradiated with light, although the surface curability is excellent, the surface curability is reduced. Therefore, the liquid crystal is inserted during heating, and the contact area with the liquid crystal increases. Therefore, the present inventors have found that by using a combination of a specific photopolymerization initiator and a filler having a specific range of sphericity and average particle size, the curability to long-wavelength light (light-shielding part curing The inventors have found that it is possible to obtain a sealant for a liquid crystal display element which is excellent in (hardness, deep-part curability, and surface curability), and have completed the present invention.
The case where the sealant is cured by irradiation with light having a long wavelength means the case where the sealant is cured by irradiation with visible light, specifically light with a wavelength of 450 nm.

The sealant for liquid crystal display elements of the present invention contains a photopolymerization initiator.
The photopolymerization initiator contains at least one selected from the group consisting of compounds having two or more carbazole skeletons in one molecule and titanocene compounds. By using at least one selected from the group consisting of a compound having two or more carbazole skeletons in one molecule and a titanocene compound as the photopolymerization initiator in combination with a filler described later, the liquid crystal display of the present invention can be obtained. The element sealant has excellent curability with respect to long-wavelength light. Among them, the photopolymerization initiator has excellent reactivity to light in a wide range of wavelengths from ultraviolet rays (specifically, a wavelength of 340 nm) to visible light (specifically, a wavelength of 450 nm), and can store the sealant. Since it has almost no reactivity to light with a wavelength of a yellow lamp (specifically, a wavelength of 580 nm) that is irradiated when doing so, it is preferable that the compound represented by the above formula (1) is included. .

In the above formula (1), each R ¹ is independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group optionally having an ether bond or an amide bond, wherein 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 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 R ¹ is a cycloalkyl group, examples of the cycloalkyl group include a cyclohexyl group and a cyclobutyl group.
When R ¹ is an aralkyl group, examples of the aralkyl group include a phenylmethyl group and a 2-naphthylmethyl group.
When R ¹ is a heterocyclic group, the heterocyclic group includes, for example, a 2-benzofuranyl group.
When R ¹ is an aryl group, examples of the aryl group include a phenyl group and a 1-naphthyl group. Among them, a phenyl group is preferred.
Examples of the polar group include a hydroxy group, a carboxyl group, and an amino group. Among them, when the sealing agent for a liquid crystal display element of the present invention is used for adhesion of electronic parts, etc., a carboxyl group is preferable from the viewpoint that the cationic component can be supplemented because the surrounding environment contains a large amount of cationic component.

In the above formula (1), each R ² is independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group optionally having an ether bond or an amide bond, wherein 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 R ² is an alkyl group, the alkyl group includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a 2-ethylhexyl group and the like. Among them, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are preferable.
When 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 R ² is an aralkyl group, examples of the aralkyl group include a phenylmethyl group.
When R ² is a heterocyclic group, the heterocyclic group includes, for example, a 2-benzothiophenyl group.
When R ² is an aryl group, examples of the aryl group include a phenyl group.
Examples of the polar group include a hydroxy group, a carboxyl group, and an amino group. Among them, when the sealing agent for a liquid crystal display element of the present invention is used for adhesion of electronic parts, etc., a carboxyl group is preferable from the viewpoint that the cationic component can be supplemented because the surrounding environment contains a large amount of cationic component.
When R ² is an alkyl group having a polar group, examples of the alkyl group having a polar group include a carboxymethyl group and a 2-carboxyethyl group.
When R ² is a cycloalkyl group having a polar group, examples of the cycloalkyl group having a polar group include a 2-carboxycyclohexyl group and a 2-carboxy-4-methylcyclohexyl group.

In the above formula (1), each R ³ is independently an alkyl group having 1 to 20 carbon atoms which may have an ether bond or an amide bond, a cycloalkyl group, an aralkyl group, a heterocyclic group, or an aryl group optionally having an ether bond or an amide bond, wherein 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 R ³ is an alkyl group, examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, 2-ethylhexyl group and the like. Among them, 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 R ³ is a cycloalkyl group, examples of the cycloalkyl group include a cyclohexyl group.
When R ³ is an aralkyl group, the aralkyl group includes, for example, a 2-naphthylmethyl group.
When R ³ is a heterocyclic group, the heterocyclic group includes, for example, a 2-thienyl group.
When R ³ is an aryl group, examples of the aryl group include a phenyl group. Examples of the polar group include a hydroxy group, a carboxyl group, and an amino group. Among them, when the sealing agent for a liquid crystal display element of the present invention is used for adhesion of electronic parts, etc., a carboxyl group is preferable from the viewpoint that the cationic component can be supplemented because the surrounding environment contains a large amount of cationic component.
When R ³ is an alkyl group having a polar group, examples of the alkyl group having a polar group include 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group, 3-carboxypropyl group, 1-carboxypentyl group, carboxy(phenyl)methyl group and the like.

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

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

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

Among them, the photopolymerization initiator has excellent reactivity to light with a long wavelength (e.g., a wavelength of 450 nm) and excellent stability under a yellow lamp, so the photopolymerization initiator is a compound represented by the above formula (1). , the compound represented by the formula (4-1), the compound represented by the formula (4-2), and at least one selected from the group consisting of the compound represented by the formula (4-3) It preferably contains seeds.

The content of the compound represented by the above formula (1) has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 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 sealing agent for liquid crystal display elements has excellent curability to long-wave light. When the content of the compound represented by the above formula (1) is 5 parts by weight or less, the obtained sealing compound for liquid crystal display elements is excellent in low liquid crystal contamination. A more preferred lower limit to the content of the compound represented by formula (1) is 0.1 parts by weight, and a more preferred upper limit is 2 parts by weight.

The sealing compound for liquid crystal display elements of the present invention contains a filler.
The filler has a sphericity of 1.00 or more and 1.05 or less and an average particle diameter of 1.0 μm or less. By using a filler having a sphericity of 1.00 or more and 1.05 or less and an average particle diameter of 1.0 μm or less in combination with the above photopolymerization initiator, the liquid crystal display of the present invention can be obtained. The element sealant has excellent curability with respect to long-wavelength light.

The filler has a sphericity of 1.00 or more and 1.05 or less. Since the sphericity of the filler is within this range, the sealant for a liquid crystal display element of the present invention can uniformly scatter incident light even with long-wavelength light, and the light-shielding portion curability is improved. become excellent. A preferable upper limit of the sphericity is 1.04, and a more preferable upper limit is 1.02. The sphericity is most preferably 1.00.
In this specification, the above-mentioned "sphericity" means the average value of the ratio of the major axis to the minor axis (major axis/minor axis) of particles. Specifically, it means the average value of (major axis/minor axis) measured for the cross section having the maximum cross-sectional area in 10 particles observed at a magnification of 10,000 using a scanning electron microscope. At this time, particles for which the cross-section with the maximum cross-sectional area cannot be observed are not taken as targets for deriving the sphericity. As the scanning electron microscope, a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) or the like can be used.

The filler has an average particle size of 1.0 μm or less. When the average particle size of the filler is 1.0 μm or less, the sealant for liquid crystal display elements of the present invention is excellent in deep-part curability. A preferable upper limit of the average particle size of the filler is 0.9 μm, and a more preferable upper limit is 0.8 μm.
In this specification, the average particle size of the filler means a value obtained by measuring the particles before being mixed with the sealant using a laser diffraction particle size distribution analyzer. In addition, the particles contained in the sealant were obtained by dispersing the uncured sealant in a mixed solvent of water and acetonitrile, and dispersing the above-mentioned filler, using a laser diffraction particle size distribution analyzer. can be measured by Mastersizer 2000 (manufactured by Malvern) or the like can be used as the laser diffraction particle size distribution analyzer.

An inorganic filler or an organic filler can be used as the filler.
Examples of inorganic fillers include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide. , calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and core-shell particles thereof.
The above fillers may be used alone, or two or more of them may be used in combination.

As for the content of the filler, a preferable lower limit is 1 part by weight and a preferable upper limit is 40 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the filler is within this range, the effect of improving the curability with respect to long-wavelength light is excellent without deteriorating the applicability and the like. A more preferable lower limit of the content of the filler is 3 parts by weight.

The sealant for liquid crystal display elements 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, and urethane (meth)acrylates. Among them, epoxy (meth)acrylate is preferred. 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 "(meth)acryl" means acrylic or methacryl, the above "(meth)acrylic compound" means a compound having a (meth)acryloyl group, and the above "( meth)acryloyl" means acryloyl or methacryloyl. Moreover, the above-mentioned "(meth)acrylate" means acrylate or methacrylate. Furthermore, the above-mentioned "epoxy (meth)acrylate" represents a compound obtained by reacting all epoxy groups in an epoxy compound 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 ( 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, methoxypolyethyleneglycol (meth)acrylate, phenoxydiethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethyl carbi tall (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imido (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalate, 2-( meth)acryloyloxyethyl 2-hydroxypropyl phthalate, 2-(meth)acryloyloxyethyl phosphate, glycidyl (meth)acrylate and the like.

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, 1,6-hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) ) acrylate, polypropylene glycol di(meth)acrylate, neopentyl 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 , dimethyloldicyclopentadienyl di(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, polybutadiene diol di(meth)acrylate and the like.

Further, among the above (meth)acrylic acid ester compounds, trifunctional or higher ones include, for example, trimethylolpropane tri(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added trimethylolpropane tri( meth)acrylate, caprolactone-modified trimethylolpropane tri(meth)acrylate, ethylene oxide-added isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, propylene oxide-added glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

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 epoxy compounds that are raw materials for synthesizing the epoxy (meth)acrylate include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, and 2,2′-diallylbisphenol A type epoxy compounds. , 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 Novolac-type epoxy compounds, ortho-cresol novolac-type epoxy compounds, dicyclopentadiene novolak-type epoxy compounds, biphenyl novolak-type epoxy compounds, naphthalenephenol novolak-type epoxy compounds, glycidylamine-type epoxy compounds, alkylpolyol-type epoxy compounds, rubber-modified epoxy compounds , glycidyl ester compounds, and the like.

Commercially available bisphenol A type epoxy compounds include, for example, 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).
Examples of commercially available 2,2'-diallylbisphenol 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).
Examples of commercially available propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Commercially available resorcinol-type epoxy compounds include, for example, EX-201 (manufactured by Nagase ChemteX Corporation).
Commercially available biphenyl-type epoxy compounds include, for example, jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide-type epoxy compounds include YSLV-50TE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by Nippon Steel Chemical & Materials Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene-type epoxy compounds include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Corporation).
Examples of commercially available phenolic novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Corporation).
Examples of commercially available ortho-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Corporation).
Examples of commercially available dicyclopentadiene novolac type epoxy compounds include EPICLON HP7200 (manufactured by DIC Corporation).
Commercially available biphenyl novolac type epoxy compounds include, for example, NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalenephenol novolac type epoxy compounds include ESN-165S (manufactured by Nippon Steel 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 Co., Ltd.), and the like.
Examples of commercially available alkyl polyol type epoxy compounds include ZX-1542 (manufactured by Nippon Steel Chemical & Materials), EPICLON 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), and Denacol EX. -611 (manufactured by Nagase ChemteX Corporation) and the like.
Examples of commercially available rubber-modified epoxy compounds include YR-450 and YR-207 (both manufactured by Nippon Steel Chemical & Materials) and Epolead PB (manufactured by Daicel).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Other commercially available epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical & Materials), XAC4151 (manufactured by Asahi Kasei), jER1031, and jER1032. (all manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.

Commercially available epoxy (meth)acrylates include, for example, epoxy (meth)acrylate manufactured by Daicel Allnex, epoxy (meth)acrylate manufactured by Shin-Nakamura Chemical Industry, epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. ( meth) acrylate, epoxy (meth) acrylate manufactured by Nagase ChemteX Corporation, and the like.
上記ダイセル・オルネクス社製のエポキシ（メタ）アクリレートとしては、例えば、ＥＢＥＣＲＹＬ８６０、ＥＢＥＣＲＹＬ３２００、ＥＢＥＣＲＹＬ３２０１、ＥＢＥＣＲＹＬ３４１２、ＥＢＥＣＲＹＬ３６００、ＥＢＥＣＲＹＬ３７００、ＥＢＥＣＲＹＬ３７０１、ＥＢＥＣＲＹＬ３７０２、ＥＢＥＣＲＹＬ３７０３、ＥＢＥＣＲＹＬ３７０８、ＥＢＥＣＲＹＬ３８００、ＥＢＥＣＲＹＬ６０４０、ＥＢＥＣＲＹＬＲＤＸ６３１８２等が挙げられる。
Examples of epoxy (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
Examples of the epoxy (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd. include, 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 and the like.
Examples of epoxy (meth)acrylates manufactured by Nagase ChemteX Co., Ltd. include Denacol acrylate DA-141, Denacol acrylate DA-314, Denacol acrylate DA-911, and the like.

The urethane (meth)acrylate can be obtained, for example, by reacting a polyfunctional isocyanate compound with a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin 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), Hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) thiophosphate, tetramethyl xylylene diisocyanate, 1,6,11-undecane triisocyanate, and the like.

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, polycaprolactone diol and the like.

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

Examples of commercially available urethane (meth) acrylates include urethane (meth) acrylate manufactured by Toagosei Co., Ltd., urethane (meth) acrylate manufactured by Daicel Allnex, and urethane (meth) acrylate manufactured by Negami Kogyo Co., Ltd. acrylate, urethane (meth)acrylate manufactured by Shin-Nakamura Chemical Co., Ltd., urethane (meth)acrylate manufactured by Kyoeisha Chemical Co., Ltd., and the like.
Examples of the urethane (meth)acrylates manufactured by Toagosei Co., Ltd. include M-1100, M-1200, M-1210 and M-1600.
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mentioned.
Examples of the urethane (meth)acrylate manufactured by Neagari Kogyo Co., Ltd. include, for example, Artresin UN-330, Artresin SH-500B, Artresin UN-1200TPK, Artresin UN-1255, Artresin UN-3320HB, Artresin UN- 7100, Artresin UN-9000A, Artresin UN-9000H and the like.
The urethane (meth)acrylates manufactured by Shin-Nakamura Chemical Co., Ltd. include, 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 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, and UA-306T. be done.

The curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the obtained sealing agent for liquid crystal display elements. Examples of the epoxy compound include an epoxy compound that serves as a raw material for synthesizing the epoxy (meth)acrylate described above, a partially (meth)acryl-modified epoxy compound, and the like.
In the present specification, the 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, which can be obtained by

When the curable resin contains the (meth)acrylic compound and the epoxy compound, or when the partially (meth)acryl-modified epoxy compound is contained, the (meth)acryloyl group in the curable resin and the epoxy It is preferable that the ratio of the (meth)acryloyl group in the total of the groups is 30 mol % or more and 95 mol % or less. When the ratio of the (meth)acryloyl group is within this range, the resulting sealant for liquid crystal display elements has excellent adhesion while suppressing the occurrence of liquid crystal contamination.

The curable resin has a hydrogen-bonding unit such as —OH group, —NH— group, or —NH ₂ group, from the viewpoint of making the obtained sealing agent for liquid crystal display element more excellent in low liquid crystal contamination resistance. is preferred.

The curable resins may be used alone, or two or more of them may be used in combination.

The sealing compound for liquid crystal display elements of the present invention preferably contains a thermal polymerization initiator.
By containing the above thermal polymerization initiator, the obtained sealing compound for a liquid crystal display element cures quickly when heated, and has excellent surface curability, and is more excellent in the effect of suppressing penetration of the liquid crystal.

Examples of the thermal polymerization initiator include those composed of azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator composed of a polymeric azo compound is preferable.
The above thermal polymerization initiators may be used alone, or two or more of them may be used in combination.
As used herein, the term "polymeric azo compound" refers to a compound having an azo group and a number average molecular weight of 300 or more, which generates a radical capable of curing a (meth)acryloyloxy group by heat. means.

A preferable lower limit of the number average molecular weight of the above high-molecular azo compound is 1,000, and a preferable upper limit thereof is 300,000. When the number average molecular weight of the high-molecular-weight azo compound is within this range, it can be easily mixed with the curable resin while suppressing liquid crystal contamination. The lower limit of the number average molecular weight of the high-molecular azo compound is more preferably 5,000, the upper limit is 100,000, the lower limit is still more preferably 10,000, and the upper limit is still more preferably 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, one having a polyethylene oxide structure is preferable.
Specific examples of the high-molecular azo compound include polycondensates 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.
Examples of commercially available polymeric azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). be done.
Examples of non-polymeric azo compounds include V-65 and V-501 (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

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

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 thermal polymerization initiator is 0.05 parts by weight or more, the sealing agent for liquid crystal display elements of the present invention becomes excellent in thermosetting property. When the content of the thermal polymerization initiator is 10 parts by weight or less, the sealant for liquid crystal display elements of the present invention is excellent in low liquid crystal contamination and storage stability. A more preferred lower limit to the content of the thermal polymerization initiator is 0.1 parts by weight, and a more preferred upper limit is 5 parts by weight.

The sealing compound for liquid crystal display elements of the present invention may contain a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among them, organic acid hydrazides are preferably used.
The thermosetting agents may be used alone, or two or more of them may be used in combination.

Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide.
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 hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.

The content of the thermosetting agent has a preferable lower limit of 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is within this range, the obtained sealing compound for liquid crystal display elements can be made more excellent in thermosetting properties without deteriorating the applicability and the like. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.

The sealing compound for liquid crystal display elements of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly serves as an adhesion assistant for good adhesion between the sealing agent and the substrate.

As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesiveness to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
The silane coupling agents may be used alone, or two or more of them may be used in combination.

A preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the liquid crystal display element sealing compound of the present invention is 0.1 parts by weight, and a preferable upper limit thereof is 10 parts by weight. When the content of the silane coupling agent is within this range, the effect of improving adhesion while suppressing the occurrence of liquid crystal contamination is more excellent. A more preferable lower limit to the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.

The sealing agent for liquid crystal display elements of the present invention further contains additives such as reactive diluents, thixotropic agents, spacers, curing accelerators, antifoaming agents, leveling agents and polymerization inhibitors, if necessary. may

As a method for producing the sealing agent for a liquid crystal display element 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 mix a curable resin with light. For example, a method of mixing a polymerization initiator with a sensitizer or a silane coupling agent to be added as necessary.

By blending the conductive fine particles into the liquid crystal display element sealant of the present invention, a vertically conductive material can be produced.

As the conductive fine particles, a metal ball, a resin fine particle having a conductive metal layer formed on its surface, or the like can be used. Among them, the one in which a 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 liquid crystal display element having a cured product of the sealant for a liquid crystal display element of the present invention is also one aspect of the present invention.
As the liquid crystal display element of the present invention, a liquid crystal display element having a narrow frame design is preferable. Specifically, it is preferable that the width of the frame portion around the liquid crystal display section is 2 mm or less.
Moreover, it is preferable that the coating width of the sealant for a liquid crystal display element of the present invention when manufacturing the liquid crystal display element of the present invention is 1 mm or less.

As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used, and specific examples thereof include a method including the following steps.
First, a step of applying the sealant for a liquid crystal display element of the present invention by screen printing, dispenser coating, or the like to one of two transparent substrates having an electrode such as an ITO thin film and an alignment film to form a frame-shaped seal pattern. I do. Next, a step is performed in which the liquid crystal liquid crystal sealing agent of the present invention is in an uncured state, and liquid crystal microdroplets are applied dropwise within the frame of the seal pattern of the substrate, and the other transparent substrate is superimposed under vacuum. Thereafter, a liquid crystal display element can be obtained by a method of performing a step of photocuring the sealing agent by irradiating the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention with light through a cut filter or the like. In addition to the step of photocuring the sealant, a step of heating the sealant to thermally cure it may be performed.

ADVANTAGE OF THE INVENTION According to this invention, the sealing compound for liquid crystal display elements which is excellent in curability with respect to the light of a long wavelength can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display element using the sealant for a liquid crystal display element.

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

(Synthesis of compound represented by formula (4-1))
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 stirred overnight at room temperature. 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added to the obtained reaction solution, and the mixture was further stirred at room temperature for 4 hours. After the resulting reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous magnesium sulfate and concentrated to give 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 resulting reaction solution was poured into ice water and then filtered. After the filtrate was washed with water, it was dissolved in ethyl acetate, dried with anhydrous magnesium sulfate and concentrated to obtain the product (B1).
After 1.5 parts by weight of the obtained product (B1) was dissolved in 25 parts by weight of N,N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. 0.78 parts by weight of triethylamine was added dropwise to the resulting solution while cooling to 10° C. or lower, and the mixture was stirred at room temperature for 4 hours. The resulting 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 the compound represented by the above formula (4-1).
The structure of the obtained compound represented by formula (4-1) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

(Synthesis of compound represented by formula (4-2))
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. 2.21 parts by weight of acetyl chloride and 3.76 parts by weight of aluminum chloride were added to the obtained reaction solution, and the mixture was further stirred at room temperature for 4 hours. After the resulting reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate and concentrated to obtain 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 resulting reaction solution was poured into ice water and then filtered. After the filtrate was washed with water, it was dissolved in ethyl acetate, dried with anhydrous magnesium sulfate and concentrated to obtain the product (B2).
After 1.5 parts by weight of the obtained product (B2) was dissolved in 25 parts by weight of N,N-dimethylformamide, 0.59 parts by weight of acetyl chloride was added. 0.78 parts by weight of triethylamine was added dropwise to the resulting solution while cooling to 10° C. or lower, and the mixture was stirred at room temperature for 4 hours. The resulting 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 the compound represented by the above formula (4-2).
The structure of the obtained compound represented by formula (4-2) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

(Synthesis of compound represented by formula (4-3))
5 parts by weight of ethyl 3-(9H-carbazol-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. . 1.84 parts by weight of 2,5-thiophenedicarboxylic acid dichloride and 5.24 parts by weight of aluminum chloride were added to the resulting reaction solution, and the mixture was further stirred at room temperature for 4 hours. After the resulting reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate and concentrated to give product (A3).
To 4.0 parts by weight of product (A3) in 20 mL of ethanol was added 2.77 parts by weight of an aqueous sodium hydroxide solution having a concentration of 20% by weight, 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 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 parts by weight of hydroxylammonium chloride, and 0.65 parts by weight of pyridine were added to 30 mL of ethanol and stirred under reflux for 10 hours. The resulting reaction solution was poured into ice water and then filtered. After the filtrate was washed with water, it was dissolved in ethyl acetate, dried with anhydrous sodium sulfate and concentrated to obtain the product (C3).
After 1.5 parts by weight of the obtained product (C3) was dissolved in 20 parts by weight of N,N-dimethylformamide, 0.45 parts by weight of acetyl chloride was added. 0.59 parts by weight of triethylamine was added dropwise to the obtained solution while cooling to 10° C. or lower, and the mixture was stirred at room temperature for 4 hours. The resulting 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 (4-3) was obtained.
The structure of the obtained compound represented by the above formula (4-3) was confirmed by ¹ H-NMR, ¹³ C-NMR and FT-IR.

(Examples 1 to 27 and Comparative Examples 1 to 7)
According to the compounding ratio described in Tables 1 to 3, after mixing each material using a planetary stirrer, the liquid crystals of Examples 1 to 27 and Comparative Examples 1 to 7 were further mixed using three rolls. A sealant for display elements was prepared. Awatori Mixer (manufactured by Thinky Corporation) was used as the planetary stirrer.

<Evaluation>
Each sealant for liquid crystal display elements obtained in Examples and Comparative Examples was evaluated as follows. The results are shown in Tables 1-3.

(Light shielding part curability for light with a wavelength of 340 nm)
Each liquid crystal display element sealant obtained in Examples and Comparative Examples was filled in a syringe for dispensing, subjected to defoaming treatment, and then spread on a glass substrate with a dispenser so that the thickness of the sealant was 4 μm. was applied to PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as a syringe for dispensing, and SHOTMASTER 300 (manufactured by Musashi Engineering Co., Ltd.) was used as a dispenser. A slit glass having a thickness of 500 μm having an opening with a slit width of 100 μm was placed on the sealing agent of the substrate coated with the sealing agent, and light of 100 mW/cm ² was applied from above the slit glass using a metal halide lamp for 30 seconds. After irradiation, a test piece for measuring the curability of the light shielding portion was obtained. Light irradiation was performed through a cut filter (340 nm cut filter) that cuts light with a wavelength of 340 nm or less. The slit glass was removed from the obtained test piece, and the distance (curing distance) where the sealant was cured from directly below the slit glass opening toward the slit glass light shielding portion was measured when the slit glass opening was set to 0 μm. The curing distance is measured by FT-IR measurement of the sealant using an infrared spectrometer, measuring the amount of change in the peak derived from the (meth)acryloyl group, and measuring the peak derived from the (meth)acryloyl group after light irradiation. % or more was judged to be cured. As an infrared spectrometer, FTS3000 (manufactured by BIORAD) was used.

(Light shielding part curability for light with a wavelength of 450 nm)
Except that the metal halide lamp and the 340 nm cut filter were not used and the light of 100 mW / cm was irradiated for ¹⁰ seconds using a 450 nm LED lamp, the light shielding part was performed in the same manner as in the above "(Light shielding part curability for light with a wavelength of 340 nm)". A test piece for measuring curability was obtained. As the 450 nm LED lamp, UELCL-P-450-X (manufactured by iGraphics) was used. The slit glass was removed from the obtained test piece, and the distance (curing distance) where the sealant was cured from directly below the slit glass opening toward the slit glass light shielding portion was measured when the slit glass opening was set to 0 μm. The curing distance is measured by FT-IR measurement of the sealant using an infrared spectrometer, measuring the amount of change in the peak derived from the (meth)acryloyl group, and measuring the peak derived from the (meth)acryloyl group after light irradiation. % or more was judged to be cured. As an infrared spectrometer, FTS3000 (manufactured by BIORAD) was used.

(Stability under yellow lamp (580 nm anti-cure property))
Each of the sealants for liquid crystal display elements obtained in Examples and Comparative Examples was applied to a release film in a thickness of 300 μm and allowed to stand in a yellow room for 8 hours. The stability under a yellow lamp (580 nm anti-curing property) was evaluated as "○" when the shape of the sealant after standing for 8 hours could not be maintained, and "Δ" when the shape of the sealant could be maintained.

(Surface Curability)
Each liquid crystal display element sealant obtained in Examples and Comparative Examples was applied onto a glass substrate in a thickness of 100 μm using a coating machine. A 450 nm LED lamp was used to irradiate the sealant portion of the substrate coated with the sealant with light of 100 mW/cm ² for 3 seconds. As the 450 nm LED lamp, UELCL-P-450-X (manufactured by iGraphics) was used. Then, by heating at 80° C. for 10 minutes, a test piece for measuring surface curability was obtained. Using a tack tester (manufactured by Lesca Co., Ltd., "tacking tester TAC-II"), the adhesive force of the sealant portion of the obtained test piece was measured.
The surface curability was evaluated as “⊚” when the measured value was 5 gf or less, “◯” when the measured value was more than 5 gf and less than 10 gf, and “X” when the measured value was 10 gf or more.

Claims

A sealant for a liquid crystal display element containing a curable resin, a photopolymerization initiator and a filler,
The photopolymerization initiator contains at least one selected from the group consisting of a compound having two or more carbazole skeletons in one molecule and a titanocene compound,
A sealant for a liquid crystal display element, wherein the filler has a sphericity of 1.00 or more and 1.05 or less and an average particle diameter of 1.0 µm or less.
The sealant for liquid crystal display elements according to claim 1, wherein the photopolymerization initiator contains a compound represented by the following formula (1).

In formula (1), each R 1 is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), each R 2 is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), each R 3 is independently an alkyl group, cycloalkyl group, aralkyl group, heterocyclic group, or ether having 1 to 20 carbon atoms which may have an ether bond or an amide bond. an aryl group optionally having a bond or an amide bond, wherein 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. In formula (1), R 4 is a bond, a structure having an arylene group, or a structure having a heteroarylene group.
The photopolymerization initiator is a compound represented by the following formula (4-1), a compound represented by the following formula (4-2), and a group consisting of a compound represented by the following formula (4-3). 3. The sealant for a liquid crystal display element according to claim 1 or 2, comprising at least one selected from.
4. The sealant for liquid crystal display elements according to claim 1, 2 or 3, which contains a thermal polymerization initiator.
A liquid crystal display device comprising a cured product of the liquid crystal display device sealant according to claim 1, 2, 3 or 4.