CN117043669A - Sealing agent for liquid crystal display element and liquid crystal display element - Google Patents

Sealing agent for liquid crystal display element and liquid crystal display element Download PDF

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Publication number
CN117043669A
CN117043669A CN202280023056.1A CN202280023056A CN117043669A CN 117043669 A CN117043669 A CN 117043669A CN 202280023056 A CN202280023056 A CN 202280023056A CN 117043669 A CN117043669 A CN 117043669A
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Prior art keywords
liquid crystal
crystal display
meth
display element
acrylate
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Chinese (zh)
Inventor
柴田大辅
大浦刚
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0647—Polyepoxides

Abstract

The purpose of the present invention is to provide a sealant for a liquid crystal display element, which has excellent visible light curability and adhesion to an alignment film, and which can provide a liquid crystal display element having excellent reliability. The present invention also provides a liquid crystal display element using the sealant for a liquid crystal display element. The present invention relates to a sealant for a liquid crystal display element, comprising a curable resin and a photopolymerization initiator, wherein the curable resin comprises a compound having an aromatic ring and a polymerizable functional group, the aromatic ring content of the compound being 50% or more, the photopolymerization initiator comprises a compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic groups in 1 molecule, and the difference between the solubility parameter of the entire curable resin and the solubility parameter of the compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic groups in 1 molecule is 2.0 or less.

Description

Sealing agent for liquid crystal display element and liquid crystal display element
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which has excellent curability by visible light and adhesion to an alignment film, and can provide a liquid crystal display element having excellent reliability. The present invention also relates to a liquid crystal display element using the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element such as a liquid crystal display cell, a liquid crystal dropping method called a dropping method using a sealant as disclosed in patent document 1 and patent document 2 has been used from the viewpoints of shortening a tact time and optimizing a use amount of liquid crystal.
In the dropping process, first, a frame-like seal pattern is formed on one of 2 substrates having charges by a dispensing method. Next, droplets of liquid crystal were dropped into the sealing frame of the substrate in a state where the sealant was not cured, and the other substrate was overlapped under vacuum, and the sealant was cured, to produce a liquid crystal display element. The dropping process is currently the mainstream of the method for manufacturing liquid crystal display elements.
However, in modern times, in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are used, miniaturization of the device is the most desirable task. As a method of downsizing, for example, a process of narrowing a frame of a liquid crystal display portion, in which a position of a seal portion is arranged under a black matrix (hereinafter, also referred to as "narrow frame design") is performed.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2001-133794
Patent document 2: international publication No. 02/092718
Disclosure of Invention
Problems to be solved by the invention
With the narrow frame design, the distance from the pixel region to the sealant in the liquid crystal display element is getting shorter, and the sealant is often disposed on the alignment film. Therefore, the sealant is required to have excellent adhesion to the alignment film.
In addition, although ultraviolet irradiation is generally performed as a method of photocuring the sealant, particularly in the liquid crystal dropping process, there is a problem in that the sealant is cured after dropping the liquid crystal, and thus the liquid crystal is deteriorated by the ultraviolet irradiation. Therefore, in order to prevent deterioration of the liquid crystal due to ultraviolet rays, an operation of curing the sealant by light irradiation through a cut filter or the like is performed. Therefore, a sealant excellent in visible light curability is demanded.
The purpose of the present invention is to provide a sealant for a liquid crystal display element, which has excellent visible light curability and adhesion to an alignment film, and which can provide a liquid crystal display element having excellent reliability. The present invention also provides a liquid crystal display element using the sealant for a liquid crystal display element.
Means for solving the problems
The present disclosure 1 relates to a sealant for a liquid crystal display element, comprising a curable resin and a photopolymerization initiator, wherein the curable resin comprises a compound having an aromatic ring and a polymerizable functional group, and the content of the aromatic ring is 50% or more, the photopolymerization initiator comprises a compound having 1 or more photopolymerization initiator groups and 3 or more heterocycle groups in 1 molecule, and the difference between the solubility parameter of the curable resin as a whole and the compound having 1 or more photopolymerization initiator groups and 3 or more heterocycle groups in 1 molecule is 2.0 or less.
The present disclosure 2 relates to a sealant for a liquid crystal display element of the present disclosure 1, wherein the content of the compound having an aromatic ring and a polymerizable functional group and having a content of 50% or more of the aromatic ring is 15 parts by weight or more based on 100 parts by weight of the entire curable resin.
The present disclosure 3 relates to a sealant for a liquid crystal display element of the present disclosure 1 or 2, wherein at least 1 of the heterocyclic rings included in the compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic rings in 1 molecule is a thiophene ring.
The present disclosure 4 relates to a sealant for a liquid crystal display element of the present disclosure 1, 2 or 3, wherein the glass transition temperature of the cured product is 85 ℃ or higher.
The present disclosure 5 is a liquid crystal display element comprising a cured product of the sealant for a liquid crystal display element of the present disclosure 1, 2, 3 or 4.
The present invention will be described in detail below.
The present inventors studied to use a compound having a soft skeleton as a curable resin for improving the adhesion to an alignment film of a sealant for a liquid crystal display element, and studied to use a photopolymerization initiator having excellent reactivity to light having a long wavelength for making the visible light curability excellent. However, when the blending amount of the compound having a soft skeleton is increased in order to further improve the adhesion to the alignment film, the visible light curability of the obtained sealant for a liquid crystal display element may be deteriorated. The inventors of the present invention considered that the reason why the visible light curability is poor is that the compatibility of the curable resin containing the compound having a soft skeleton with the photopolymerization initiator is low. Accordingly, the present inventors studied to use a compound having an aromatic ring and a polymerizable functional group, the aromatic ring content of which is 50% or more, as a curable resin, and a compound having 1 or more photopolymerization initiator groups and 3 or more heterocycles in 1 molecule, as a photopolymerization initiator. On the other hand, it was studied that the difference between the solubility parameter of the curable resin as a whole and the solubility parameter of a compound having 1 or more photopolymerization initiator groups and 3 or more heterocycles in 1 molecule was 2.0 or less. As a result, it has been found that a sealant for a liquid crystal display element having excellent curability by visible light and adhesion to an alignment film can be obtained, and the present invention has been completed. In addition, the sealant for a liquid crystal display element of the present invention contains a compound having an aromatic ring content of 50% or more as a curable resin, and thus can raise the glass transition temperature of a cured product, and thus can obtain a liquid crystal display element excellent in reliability even when exposed to a high-temperature and high-humidity environment.
The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin contains a compound having an aromatic ring and a polymerizable functional group, and the aromatic ring content is 50% or more (hereinafter, also referred to as "curable resin of the present invention"). The curable resin of the present invention is contained in combination with a photopolymerization initiator described later, so that the sealant for a liquid crystal display element of the present invention is excellent in the visible light curability and the adhesion to an alignment film, and a liquid crystal display element excellent in reliability can be obtained.
The lower limit of the content ratio of the aromatic ring in the curable resin of the present invention is 50%. Since the curable resin of the present invention having a content of the aromatic ring of 50% or more easily has a skeleton close to that of the alignment film, the curable resin of the present invention is contained, and thus the sealant for a liquid crystal display element of the present invention is excellent in adhesion to the alignment film. Further, since the curable resin of the present invention having a content of the aromatic ring of 50% or more tends to have a rigid skeleton, the glass transition temperature of the cured product of the sealant for a liquid crystal display element of the present invention tends to be high by containing the curable resin of the present invention, and a liquid crystal display element excellent in reliability can be obtained. The content of the aromatic ring in the curable resin of the present invention is more preferably 55% or more.
The content of the aromatic ring in the curable resin of the present invention is not limited to a preferable upper limit, but is limited to a substantially upper limit of 75%.
In the present specification, the term "content of aromatic rings" refers to a ratio of the total of molecular weights of aromatic rings contained in 1 molecule of the compound to the molecular weight of 1 molecule of the compound. The term "molecular weight of an aromatic ring" refers to the sum of the atomic weights of only carbon atoms constituting the ring of the aromatic ring. For example, in the case of a compound (molecular weight 492) represented by the formula (2-1) described later, the total of the molecular weights of 1 of the 4 aromatic rings and the atomic weights of 6 carbon atoms, that is, 72, and the content ratio of the aromatic rings is ((4×72)/(492) ×100=59%.
The curable resin of the present invention preferably has 3 or more aromatic rings in 1 molecule. By providing the curable resin of the present invention with 3 or more aromatic rings in 1 molecule, the sealing agent for a liquid crystal display element of the present invention has more excellent adhesion to an alignment film, and can provide a liquid crystal display element with more excellent reliability. In addition, from the viewpoint of coatability and the like, the curable resin of the present invention preferably has 6 or less aromatic rings in 1 molecule.
The aromatic ring of the curable resin of the present invention may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
Specific examples of the aromatic ring included in the curable resin of the present invention include benzene ring, naphthalene ring, anthracene ring, and furan ring. Among them, benzene rings are preferable.
The curable resin of the present invention preferably has a structure represented by the following formulas (1-1) to (1-4) as a structure containing the aromatic ring.
[ chemical formula 1]
In the formulae (1-1) to (1-4), the bond position is represented.
Examples of the polymerizable functional group included in the curable resin of the present invention include an epoxy group and a (meth) acryl group. Among them, an epoxy group is preferable.
In the present specification, the "(meth) acryl" means acryl or methacryl.
The lower limit of the molecular weight of the curable resin of the present invention is preferably 200, and the upper limit is preferably 2000. By setting the molecular weight of the curable resin of the present invention to 200 or more, the sealant for a liquid crystal display element of the present invention is more excellent in low liquid crystal contamination. The curable resin of the present invention has a molecular weight of 2000 or less, and thus the sealing agent for a liquid crystal display element of the present invention is more excellent in coatability. The lower limit of the molecular weight of the curable resin of the present invention is more preferably 400, and the upper limit is preferably 800.
In the present specification, the "molecular weight" is a molecular weight obtained from a structural formula of a compound having a specific molecular structure, but a compound having a wide distribution of polymerization degrees and a compound having no specific modified site may be represented by a weight average molecular weight.
In the present specification, the term "weight average molecular weight" is a value obtained by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converted into polystyrene. Examples of the column used for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa electric company).
Specifically, the curable resin of the present invention is preferably a compound represented by the following formula (2-1) (the aromatic ring content is 59%), a compound represented by the following formula (2-2) (the aromatic ring content is 58%), a compound represented by the following formula (2-3) (the aromatic ring content is 65%), or a compound represented by the following formula (2-4) (the aromatic ring content is 62%).
[ chemical formula 2]
The curable resin may contain other curable resins than the curable resin of the present invention.
In the case of containing the other curable resin, the preferable lower limit of the content of the curable resin of the present invention in 100 parts by weight of the curable resin is 15 parts by weight. When the content of the curable resin of the present invention is 15 parts by weight or more, the obtained sealant for a liquid crystal display element has more excellent adhesion to an alignment film, and a liquid crystal display element having more excellent reliability can be obtained. In addition, the upper limit of the content of the curable resin of the present invention is preferably 50 parts by weight, more preferably 30 parts by weight, from the viewpoint of low liquid crystal contamination property and the like.
Examples of the other curable resin include (meth) acrylic compounds other than those included in the curable resin of the present invention, and epoxy compounds other than those included in the curable resin of the present invention.
In the present specification, the "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the "(meth) acrylic compound" means a compound having a (meth) acryloyl group.
Examples of the (meth) acrylic compound that can be used as the other curable resin include a (meth) acrylate compound, an epoxy (meth) acrylate, and a urethane (meth) acrylate. Among them, epoxy (meth) acrylate is preferable. From the viewpoint of reactivity, the (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in 1 molecule.
In the present specification, the term "(meth) acrylate" refers to an acrylate or a methacrylate. The "epoxy (meth) acrylate" refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the monofunctional compound among the (meth) acrylate compounds include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (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, dicyclopentenyl (meth) acrylate, and process for the preparation of the same, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the 2-functional compound in the (meth) acrylate compound include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene oxide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (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.
Examples of the compound having 3 or more functions among the (meth) acrylate compounds include: 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, glycerol tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) acryloxyethyl 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: epoxy (meth) acrylate obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method, and the like.
Examples of the epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2' -diallyl bisphenol A type epoxy compound, hydrogenated bisphenol type epoxy compound, propylene oxide addition bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, thioether type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound, o-cresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy compound, naphthol novolac type epoxy compound, glycidol amine type epoxy compound, alkyl polyol type epoxy compound, rubber modified type epoxy compound, glycidyl ester compound, and the like.
Examples of commercial products of the bisphenol A type epoxy compound include jER828EL and jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-850CRP (manufactured by DIC corporation), and the like.
Examples of commercial products of the bisphenol F type epoxy compound include jER806 and jER4004 (both manufactured by Mitsubishi chemical corporation).
Examples of commercial products of the bisphenol S type epoxy compound include EPICLON EXA1514 (manufactured by DIC Co.).
Examples of the commercial products of the 2,2' -diallylbisphenol A type epoxy compound include RE-810NM (manufactured by Japanese chemical Co., ltd.).
Examples of commercial products of the hydrogenated bisphenol type epoxy compound include EPICLON EXA7015 (manufactured by DIC Co.).
Examples of commercial products obtained by adding propylene oxide to bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Examples of commercial products of the resorcinol-type epoxy compound include EX-201 (manufactured by Nagase ChemteX Co., ltd.).
Examples of commercial products of the biphenyl epoxy compounds include jER YX-4000H (manufactured by mitsubishi chemical company).
Examples of commercial products of the above-mentioned thioether-type epoxy compounds include YSLV-50TE (NIPPON STEEL Chemical & Material Co.) and the like.
Examples of commercial products of the diphenyl ether type epoxy compounds include YSLV-80DE (NIPPON STEEL Chemical & Material Co.) and the like.
Examples of commercial products of the dicyclopentadiene type epoxy compound include EP-4088S (manufactured by ADEKA Co., ltd.).
Examples of the commercial products of the naphthalene type epoxy compound include EPICLON HP4032 and EPICLON EXA-4700 (both manufactured by DIC Co.).
Examples of the commercial products of the phenol novolac type epoxy compounds include EPICLON N-770 (manufactured by DIC Co., ltd.).
Examples of the commercial products of the o-cresol novolac type epoxy compounds include EPICLON N-670-EXP-S (manufactured by DIC Co., ltd.).
Examples of commercial products of the dicyclopentadiene phenol type epoxy compound include EPICLON HP7200 (manufactured by DIC Co.).
Examples of commercial products of the biphenyl novolac type epoxy compounds include NC-3000P (manufactured by Japanese chemical Co., ltd.).
Examples of the commercial products of the naphthol novolac type epoxy compounds include ESN-165S (NIPPON STEEL Chemical & Material Co.).
Examples of commercial products of the glycidylamine-type epoxy compounds include jor 630 (manufactured by mitsubishi chemical Co., ltd.), epicalon 430 (manufactured by DIC corporation), tetra-X (manufactured by mitsubishi gas chemical Co., ltd.), and the like.
Examples of commercial products of the alkyl polyol type epoxy compound include ZX-1542 (NIPPON STEEL Chemical & Material Co., ltd.), EPICLON 726 (DIC Co., ltd.), EPOLIGHT 80MFA (Co., ltd.), denacol EX-611 (Nagase ChemteX Co., ltd.), and the like.
Examples of the commercial products of the rubber-modified epoxy compound include YR-450, YR-207 (both NIPPON STEEL Chemical and Material Co., ltd.), epolead PB (Daicel Co., ltd.), and the like.
Examples of the commercial products of the above glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Co., ltd.).
Examples of other commercially available products of the epoxy compounds include YDC-1312, YSLV-80XY, YSLV-90CR (both manufactured by NIPPON STEEL Chemical & Material Co., ltd.), XAC4151 (manufactured by Asahi chemical Co., ltd.), jER1031, jER1032 (both manufactured by Mitsubishi chemical Co., ltd.), EXA-7120 (manufactured by DIC Co., ltd.), TEPIC (manufactured by Nissan chemical Co., ltd.), and the like.
Examples of the commercial products of the epoxy (meth) acrylate include: epoxy (meth) acrylate manufactured by DAICEL-ALLNEX, epoxy (meth) acrylate manufactured by Xinzhongcun chemical industry Co., ltd., epoxy (meth) acrylate manufactured by Kagaku chemical Co., ltd., epoxy (meth) acrylate manufactured by Nagase ChemteX, epoxy (meth) acrylate manufactured by KSM, and the like.
Examples of the epoxy (meth) acrylate manufactured by DAICEL-all ex company include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL8342, EBECRYL RDX63182, KRM8416, and the like.
Examples of the epoxy (meth) acrylate include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, and EMA-1020.
Examples of the epoxy (meth) acrylate manufactured by the co-company chemical company include: 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 Ester3000A, epoxy Ester 200EA, epoxy Ester 400EA, etc.
Examples of the epoxy (meth) acrylate include Denacol Acrylate DA-141, denacol Acrylate DA-314, denacol Acrylate DA-911, and the like, which are manufactured by Nagase ChemteX corporation.
Examples of the epoxy (meth) acrylate produced by KSM include BAEM-100.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with a polyfunctional isocyanate compound in the presence of a catalytic amount of a tin compound.
Examples of the polyfunctional isocyanate compound include: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, 1,6, 11-undecane triisocyanate, etc.
In addition, as the above polyfunctional isocyanate compound, it is also possible to use: a chain-extended polyfunctional isocyanate compound obtained by reacting a polyol with an excess of the polyfunctional isocyanate compound.
Examples of the polyhydric alcohol 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 a diol, mono (meth) acrylate or di (meth) acrylate of a triol, and epoxy (meth) acrylate.
Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
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 triol include trimethylolethane, trimethylolpropane, and glycerin.
Examples of the epoxy (meth) acrylate include bisphenol a epoxy (meth) acrylate.
Examples of commercial products of the urethane (meth) acrylate include: urethane (meth) acrylate manufactured by east asia synthesis company, urethane (meth) acrylate manufactured by DAICEL-ALLNEX company, urethane (meth) acrylate manufactured by the company of the industry on the root, urethane (meth) acrylate manufactured by the company of the new yo chemical industry, urethane (meth) acrylate manufactured by the company of the co-Rong chemical industry, and the like.
Examples of the urethane (meth) acrylate produced by the east Asia synthetic company include M-1100, M-1200, M-1210, and M-1600.
Examples of urethane (meth) acrylates manufactured by Daicel-ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260, and the like.
Examples of urethane (meth) acrylates produced by the above-mentioned on-the-root industries include Artesin UN-330, artesin SH-500B, artesin UN-1200TPK, artesin UN-1255, artesin UN-3320HB, artesin UN-7100, artesin UN-9000A, and Artesin UN-9000H.
Examples of the urethane (meth) acrylate include U-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, 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, and UA-W2A.
As urethane (meth) acrylate produced by the company of Cooperation, AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T and the like are mentioned, for example.
Examples of the epoxy compound that can be used as the other curable resin include: an epoxy compound which is a raw material for synthesizing the epoxy (meth) acrylate, a partially (meth) acrylic acid-modified epoxy compound, and the like.
In the present specification, the above-mentioned partial (meth) acrylic-modified epoxy compound means: for example, a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in the molecule, which is obtained by reacting a part of epoxy groups of an epoxy compound having 2 or more epoxy groups in the molecule with (meth) acrylic acid, can be used.
The other curable resin preferably has an-OH group, -NH-group, from the viewpoint of making the low liquid crystal contamination of the obtained sealant for a liquid crystal display element more excellent 2 Hydrogen-bonding units such as radicals.
The ratio of the (meth) acryloyl group in the total of the (meth) acryloyl groups and the epoxy groups in the curable resin is preferably 30 mol% or more and 95 mol% or less. When the ratio of the (meth) acryloyl groups is in this range, the resulting sealant for a liquid crystal display element suppresses the occurrence of liquid crystal contamination and is more excellent in adhesion.
The sealant for a liquid crystal display element of the present invention contains a photopolymerization initiator.
The photopolymerization initiator includes a compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic rings in 1 molecule (hereinafter, also referred to as "photopolymerization initiator of the present invention"). By incorporating the photopolymerization initiator of the present invention in combination with the curable resin of the present invention, the sealant for a liquid crystal display element of the present invention is excellent in the visible light curability and the adhesion to an alignment film, and a liquid crystal display element excellent in reliability can be obtained.
The photopolymerization initiator of the present invention has 1 or more photopolymerization initiator groups in 1 molecule.
In the present specification, the term "photopolymerization initiator" refers to a group that promotes polymerization of the curable resin by generating radicals or the like by hydrogen abstraction, cleavage, or the like by light irradiation.
Examples of the photopolymerization initiator group include an oxime ester group and a thioxanthone group. Among them, oxime ester groups are preferable.
The photopolymerization initiator of the present invention has 3 or more heterocyclic rings in 1 molecule.
The photopolymerization initiator of the present invention preferably has 3 or more heterocyclic rings in 1 molecule. The number of heterocyclic rings in 1 molecule of the photopolymerization initiator of the present invention is not limited to a preferable upper limit, but is limited to substantially 5 or less.
The heterocycle of the photopolymerization initiator of the present invention is preferably an aromatic heterocycle.
Examples of the aromatic heterocycle include a thiophene ring, a furan ring, a pyridine ring, and a carbazole ring.
In addition, it is preferable that at least 1 of the heterocyclic rings of the photopolymerization initiator of the present invention is a thiophene ring.
The photopolymerization initiator of the present invention is preferably a compound represented by the following formula (3) in view of further excellent adhesion to an alignment film, visible light curability and low liquid crystal contamination property of the obtained sealant for a liquid crystal display element.
[ chemical formula 3]
In the formula (3), R 1 Each independently is 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 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 may have a polar group. In the formula (3), R 2 Each independently is 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 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 may have a polar group. In the formula (3), R 3 Each independently is 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 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 may have a polar group. In the formula (3), R 4 Is a structure with heteroarylene.
In the above formula (3), R 1 Each independently is 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 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 may have a polar group.
The above R 1 In the case of an alkyl group having 1 to 20 carbon atoms, methyl and ethyl groups are preferable as the alkyl group.
The above R 1 In the case of cycloalkyl, examples of the cycloalkyl include cyclohexyl and cyclobutyl.
The above R 1 In the case of an aralkyl group, examples of the aralkyl group include a phenylmethyl group and a 2-naphthylmethyl group.
The above R 1 In the case of a heterocyclic group, examples of the heterocyclic group include a 2-benzofuranyl group and the like.
The above R 1 In the case of an aryl group, examples of the aryl group include a phenyl group and a 1-naphthyl group. Among them, phenyl is preferable.
Examples of the polar group include a hydroxyl group, a carboxyl group, and an amino group. Among them, carboxyl groups are preferable.
In the above formula (3), R 2 Each independently is 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 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 may have a polar group.
The above R 2 In the case of an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a 2-ethylhexyl group. Among them, methyl, ethyl, propyl, butyl, pentyl are preferable.
The above R 2 In the case of cycloalkyl, examples of the cycloalkyl include cyclopentyl and cyclohexyl. The cycloalkyl group may have an alkyl group.
The above R 2 In the case of an aralkyl group, examples of the aralkyl group include a phenylmethyl group and the like.
The above R 2 In the case of a heterocyclic group, examples of the heterocyclic group include a 2-benzothienyl group and the like.
The above R 2 In the case of an aryl group, the aryl group includes a phenyl group and the like.
Examples of the polar group include a hydroxyl group, a carboxyl group, and an amino group. Among them, carboxyl groups are preferable.
The above R 2 In the case of an alkyl group having a polar group, examples of the alkyl group having a polar group include carboxymethyl group and 2-carboxyethyl group.
The above R 2 In the case of cycloalkyl having a polar group, the cycloalkyl having a polar group is used as the cycloalkyl having a polar groupExamples of cycloalkyl include 2-carboxycyclohexyl and 2-carboxy-4-methylcyclohexyl.
In the above formula (3), R 3 Each independently is 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 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 may have a polar group.
The above R 3 In the case of an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a 2-ethylhexyl group. Among them, methyl, ethyl, propyl, butyl, pentyl are preferable. The above alkyl group may have an aryl group.
The above R 3 In the case of cycloalkyl, the cycloalkyl includes cyclohexyl and the like.
The above R 3 In the case of an aralkyl group, examples of the aralkyl group include a 2-naphthylmethyl group and the like.
The above R 3 In the case of a heterocyclic group, examples of the heterocyclic group include a 2-thienyl group and the like.
The above R 3 In the case of an aryl group, the aryl group includes a phenyl group and the like. Examples of the polar group include a hydroxyl group, a carboxyl group, and an amino group. Among them, carboxyl groups are preferable.
The above R 3 In the case of 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, and carboxyl (phenyl) methyl group.
In the above formula (3), R 4 Is a structure with heteroarylene.
As R as above 4 Examples of the heteroarylene group include a thienyl group, a furanylene group (Japanese) and a pyridyl group (Japanese) group. Among them, thienyl is preferable.
Specific examples of the structure having a heteroarylene group include structures represented by the following formulas (4-1) to (4-6).
[ chemical formula 4]
In the formulae (4-1) to (4-6), the bond position is represented.
As the photopolymerization initiator of the present invention, compounds represented by the following formulas (5-1) to (5-3) are more preferable.
[ chemical formula 5]
The content of the photopolymerization initiator of the present invention is preferably limited to 0.01 parts by weight and the upper limit is preferably 5 parts by weight based on 100 parts by weight of the curable resin. When the content of the photopolymerization initiator of the present invention is 0.01 parts by weight or more, the obtained sealant for a liquid crystal display element is further excellent in the visible light curability. When the content of the photopolymerization initiator of the present invention is 5 parts by weight or less, the resulting sealant for a liquid crystal display element is more excellent in low liquid crystal contamination. The more preferable lower limit of the content of the photopolymerization initiator of the present invention is 0.1 part by weight, and the more preferable upper limit is 2 parts by weight.
The difference between the solubility parameter (SP value) of the entire curable resin and the photopolymerization initiator of the present invention is 2.0 or less. By setting the difference between the SP value of the entire curable resin and the SP value of the photopolymerization initiator of the present invention to 2.0 or less, the compatibility between the curable resin and the photopolymerization initiator of the present invention becomes excellent, and the content of the photopolymerization initiator can be reduced to a small level, and as a result, the visible light curing of the sealant for a liquid crystal display element of the present invention becomes excellent. The difference between the SP value of the entire curable resin and the photopolymerization initiator of the present invention is preferably 1.5 or less, more preferably 1.0 or less, and most preferably 0.
In the present specification, the SP value is a hansen solubility parameter, and can be derived from a structural formula by calculation using HSP software. As the HSP software, hansen Solubility Parameter in Practice (hsppi) can be used. The SP value of the entire curable resin is an average value of SP values based on the weight fractions of the respective curable resin components.
The sealing agent for a liquid crystal display element of the present invention may contain a sensitizer, but from the viewpoint of low liquid crystal contamination, it is preferable that the sealing agent does not contain the sensitizer. The sealant for a liquid crystal display element of the present invention is excellent in visible light curability even if it does not contain a sensitizer, by containing the photopolymerization initiator of the present invention.
Examples of the sensitizer include ethyl 4- (dimethylamino) benzoate, 9, 10-dibutoxyanthracene, 2, 4-diethylthioxanthone, 2-dimethoxy-1, 2-diphenylethane-1-one, benzophenone, 2, 4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4 '-bis (dimethylamino) benzophenone, and 4-benzoyl-4' -methyldiphenyl sulfide.
The lower limit of the content of the sensitizer is preferably 0.01 parts by weight, and the upper limit is preferably 3 parts by weight, based on 100 parts by weight of the curable resin. The sensitizer is contained in an amount of 0.01 parts by weight or more, whereby the sensitization effect is further exhibited. By setting the content of the sensitizer to 3 parts by weight or less, light can be transmitted to a deep portion without the absorption becoming excessive. The lower limit of the content of the sensitizer is more preferably 0.1 parts by weight, and the upper limit is more preferably 1 part by weight.
The sealant for a liquid crystal display element of the present invention may contain a thermal polymerization initiator within a range that does not hinder the object of the present invention.
Examples of the thermal polymerization initiator include thermal polymerization initiators including azo compounds and organic peroxides. Among them, a polymeric azo initiator containing a polymeric azo compound is preferable.
The thermal polymerization initiator may be used alone or in combination of 2 or more.
In the present specification, the "polymer azo compound" refers to a compound having an azo group and having a number average molecular weight of 300 or more, which generates radicals capable of curing (meth) acryloyloxy groups by heat.
In the present specification, the "number average molecular weight" is a value obtained by Gel Permeation Chromatography (GPC), measurement using tetrahydrofuran as a solvent, and conversion to polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa electric company).
The number average molecular weight of the polymer azo compound is preferably 1000 at the lower limit and 30 tens of thousands at the upper limit. When the number average molecular weight of the polymer azo compound is in this range, contamination of the liquid crystal can be suppressed and the polymer azo compound can be easily mixed with the curable resin. The number average molecular weight of the polymer azo compound is more preferably limited to 5000, more preferably to 10 ten thousand, still more preferably to 1 ten thousand, and still more preferably to 9 ten thousand.
Examples of the polymer azo compound include: a polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via azo groups.
The polymer azo compound having a structure in which a plurality of units such as polyalkylene oxide are bonded via an azo group is preferably a polymer azo compound having a polyethylene oxide structure.
Specific examples of the polymer azo compound include: polycondensates of 4,4 '-azobis (4-cyanovaleric acid) and polyalkylene glycol, polycondensates of 4,4' -azobis (4-cyanovaleric acid) and polydimethylsiloxane having terminal amino groups, and the like.
Examples of commercial products of the polymer azo compound include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (both manufactured by Fuji photo-pure chemical Co., ltd.).
Examples of azo compounds other than the polymer include V-65 and V-501 (both manufactured by Fuji photo-pure chemical Co., ltd.).
Examples of the organic peroxide include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
The preferable lower limit of the content of the thermal polymerization initiator is 0.05 parts by weight and the preferable upper limit is 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 sealant for a liquid crystal display element of the present invention is more excellent in thermosetting property. When the content of the thermal polymerization initiator is 10 parts by weight or less, the sealant for a liquid crystal display element of the present invention is further excellent in storage stability and low liquid crystal contamination. The lower limit of the content of the thermal polymerization initiator is more preferably 0.1 part by weight, and the upper limit is more preferably 5 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a thermosetting agent.
Examples of the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, and acid anhydrides. Among them, organic acid hydrazides are suitably used.
The above-mentioned thermosetting agents may be used alone or in combination of 2 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 the commercial products of the organic acid hydrazide include organic acid hydrazides manufactured by Otsuka chemical company, and organic acid hydrazides manufactured by Ajinomoto Fine-Techno company.
Examples of the organic acid hydrazide manufactured by Otsuka chemical Co., ltd include SDH, ADH, MDH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno include Ajicure VDH, ajicure VDH-J, ajicure UDH, and Ajicure UDH-J.
The content of the thermosetting agent is preferably 1 part by weight at a lower limit and 50 parts by weight at an upper limit, based on 100 parts by weight of the curable resin. By setting the content of the thermosetting agent to this range, thermosetting properties can be further improved without deteriorating the coatability and the like of the obtained sealing agent for a liquid crystal display element. The more preferable upper limit of the content of the above-mentioned thermosetting agent is 30 parts by weight.
The sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of increasing viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, and the like.
As the filler, an inorganic filler and an organic filler can be used.
Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, calcium carbonate, magnesium hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate.
Examples of the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The above fillers may be used alone or in combination of 2 or more.
The preferable lower limit of the content of the filler is 30 parts by weight and the preferable upper limit is 80 parts by weight relative to 100 parts by weight of the curable resin. When the content of the filler is within this range, the effect of improving the adhesion and the like is further improved without deteriorating the coating property and the like. The lower limit of the content of the filler is more preferably 45 parts by weight, and the upper limit is more preferably 65 parts by weight.
The sealing agent for a liquid crystal display element of the present invention preferably contains a silane coupling agent. The silane coupling agent mainly has a role as an adhesion promoter for favorably adhering a sealing agent for a liquid crystal display element to a substrate or the like.
Examples of suitable silane coupling agents include 3-aminopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, and 3-isocyanatopropyl trimethoxysilane. These are excellent in the effect of improving the adhesion to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemical bonding with the curable resin.
The silane coupling agent may be used alone or in combination of 2 or more.
The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the resulting sealant for a liquid crystal display element suppresses the occurrence of liquid crystal contamination, and is further excellent in adhesion. The more preferable lower limit of the content of the above silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may further contain additives such as a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, as necessary.
Examples of the method for producing the sealant for a liquid crystal display element of the present invention include: a method of mixing the curable resin, the photopolymerization initiator, and the silane coupling agent, if necessary, using a mixer such as a homodisperser, homomixer, universal mixer, planetary mixer, kneader, or three-roll mixer.
The sealant for a liquid crystal display element of the present invention preferably has a glass transition temperature of 85 ℃ or higher. By setting the glass transition temperature of the cured product to 85 ℃ or higher, the sealant for a liquid crystal display element of the present invention can provide a liquid crystal display element having more excellent reliability even when exposed to a high-temperature and high-humidity environment. The lower limit of the glass transition temperature of the cured product is more preferably 100 ℃.
In addition, from the viewpoint of adhesion to a substrate or the like, the upper limit of the glass transition temperature of the cured product is preferably 150 ℃, and more preferably 130 ℃.
The glass transition temperature of the cured product can be obtained as a temperature at which the maximum value of loss tangent (tan delta) is measured at-80 to 200 ℃ and 10Hz using a dynamic viscoelasticity measuring apparatus. The cured product obtained by measuring the glass transition temperature was used as follows: the sealant for a liquid crystal display element was irradiated with 3000mJ/cm 2 After the light of (2), the cured product was cured by heating at 120℃for 60 minutes.
By incorporating conductive fine particles into the sealing agent for a liquid crystal display element of the present invention, a vertically conductive material can be produced.
As the conductive fine particles, metal balls, conductive fine particles having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, conductive fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because conductive connection can be performed without damaging the transparent substrate or the like due to excellent elasticity of the resin fine particles.
The liquid crystal display element comprising the cured product of the sealant for a liquid crystal display element of the present invention is also one of the present invention.
In addition, as the liquid crystal display element of the present invention, a liquid crystal display element of a narrow frame design is preferable. Specifically, the width of the frame portion around the liquid crystal display portion is preferably 2mm or less.
The width of the sealant for a liquid crystal display element of the present invention applied in the production of the liquid crystal display element of the present invention is preferably 1mm or less.
The sealant for a liquid crystal display element of the present invention can be suitably used for manufacturing a liquid crystal display element by a liquid crystal dropping process. Examples of the method for manufacturing the liquid crystal display element of the present invention by the liquid crystal dropping method include the following methods.
First, a step of forming a frame-like seal pattern by applying the sealant for a liquid crystal display element of the present invention to one of 2 transparent substrates having an electrode such as an ITO thin film and an alignment film by screen printing, dispenser coating, or the like is performed. Next, the following steps are performed: in the state where the sealing agent for a liquid crystal display element of the present invention is not cured, minute droplets of liquid crystal are applied dropwise to the inside of the frame of the sealing pattern of the substrate, and another transparent substrate is superimposed under vacuum. Then, a liquid crystal display element can be obtained by performing the steps of: and a step of irradiating the sealing pattern portion of the sealing agent for a liquid crystal display element of the present invention with light having a long wavelength through a cut-off filter or the like to thereby photo-cure the sealing agent. In addition to the step of photocuring the sealant, a step of heating the sealant to thermally cure the sealant may be performed.
Effects of the invention
According to the present invention, a sealant for a liquid crystal display element, which has excellent curability by visible light and adhesion to an alignment film, and which can provide a liquid crystal display element having excellent reliability, can be provided. Further, according to the present invention, a liquid crystal display element using the sealant for a liquid crystal display element can be provided.
Detailed Description
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(production of Compound of formula (2-1))
A200 mL three-necked round bottom flask equipped with a thermometer, condenser, dean-Stark trap, dropping funnel and stirrer was prepared. To the three-necked round bottom flask, 38g of 2, 2-bis (2-hydroxy-5-biphenyl) propane (manufactured by Tokyo chemical industry Co., ltd.), 174g of epichlorohydrin (manufactured by Tokyo chemical industry Co., ltd.) and 3.8g of benzyl trimethyl ammonium chloride (manufactured by Tokyo chemical industry Co., ltd.) were charged. Next, the resultant mixture was heated to about 50℃under reduced pressure of 50 Torr (Torr) with stirring, and 28.2g of a 48% aqueous sodium hydroxide solution (manufactured by Kanto chemical Co., ltd.) was added dropwise over 3 hours. In the water/epichlorohydrin mixture distilled off by azeotropy, stirring was continued while returning epichlorohydrin to the reaction system. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 90g of toluene and 30g of methyl isobutyl ketone were added, and washed 4 times with 150mL of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to give yellow color 38g of the compound represented by the above formula (2-1) as a transparent viscous material. The structure of the obtained compound represented by the formula (2-1) is obtained by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(production of Compound represented by the formula (2-2))
The procedure was similar to the "(production of a compound represented by the formula (2-1)", except that 38g of 2, 2-bis (2-hydroxy-5-biphenyl) propane was replaced with 26g of 4,4' -dihydroxy-p-terphenyl, to obtain 26g of the compound represented by the formula (2-2). The structure of the obtained compound represented by the formula (2-2) is obtained by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(production of the Compound represented by the formula (2-3))
The procedure of the above "(preparation of Compound represented by formula (2-1)" was repeated except that 38g of 2, 2-bis (2-hydroxy-5-biphenylyl) propane was replaced with 44g of 5,5'- (1-phenylenediol) bis [ (1, 1' -biphenyl) -2-ol ], to obtain 44g of Compound represented by formula (2-3).
The structure of the obtained compound represented by the formula (2-3) is obtained by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(production of the Compound represented by the formula (2-4))
The same procedure as described above (preparation of Compound represented by formula (2-1)) was repeated except that 35g of 4,4' -dihydroxytetraphenyl methane was used instead of 38g of 2, 2-bis (2-hydroxy-5-biphenyl) propane, to obtain 35g of Compound represented by formula (2-4).
The structure of the obtained compound represented by the formula (2-4) is obtained by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(Synthesis of Compound represented by the formula (5-1))
5 parts by weight of N-ethylcarbazole, 2.81 parts by weight of 2, 5-thiophenedicarboxychloride and 3.76 parts by weight of aluminum chloride were added to 40mL of methylene chloride, and the mixture was stirred at room temperature overnight. 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. After the obtained reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, and concentrated to give a product (A1).
3 parts by weight of the obtained product (A1), 0.76 part by weight of ammonium hydroxychloride and 0.86 part by weight of pyridine were added to 30mL of ethanol, and the mixture was stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water, followed by filtration. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate and concentrated to give a 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 part by weight of acetyl chloride was added. While cooling the obtained solution to 10℃or lower, 0.78 parts by weight of triethylamine was added dropwise thereto, 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), whereby the compound represented by the above formula (5-1) was obtained.
The structure of the obtained compound represented by the above formula (5-1) is represented by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(Synthesis of Compound represented by the formula (5-2))
5 parts by weight of N- (2-ethylhexyl) carbazole, 2.81 parts by weight of 2, 5-thiophenedicarboxychloride and 3.76 parts by weight of aluminum chloride were added to 40mL of methylene chloride, and the mixture was stirred at room temperature overnight. 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. After the obtained reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, dried over anhydrous magnesium sulfate, and concentrated to give a product (A2).
3 parts by weight of the obtained product (A2), 0.76 part by weight of ammonium hydroxychloride and 0.86 part by weight of pyridine were added to 30mL of ethanol, and stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water, followed by filtration. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous magnesium sulfate and concentrated to give 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 part by weight of acetyl chloride was added. While cooling the obtained solution to 10℃or lower, 0.78 parts by weight of triethylamine was added dropwise thereto, 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), whereby the compound represented by the above formula (5-2) was obtained.
The structure of the obtained compound represented by the above formula (5-2) is represented by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
(Synthesis of Compound represented by the formula (5-3))
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 80mL of methylene chloride, and stirred at room temperature overnight. To the obtained reaction solution, 1.84 parts by weight of 2, 5-thiophenedicarboxychloride and 5.24 parts by weight of aluminum chloride were added, and the mixture was further stirred at room temperature for 4 hours. After the obtained reaction solution was poured into ice water, the organic layer was extracted with ethyl acetate. The extracted solution was washed with a saturated aqueous sodium hydrogencarbonate solution and brine, dried over anhydrous sodium sulfate, and concentrated to give a product (A3).
To 4.0 parts by weight of the product (A3) in 20mL of ethanol was added 2.77 parts by weight of a 20% aqueous sodium hydroxide solution, and the mixture was refluxed for 3 hours. After the completion of the reaction, 50mL of water was added, the mixture was acidified with concentrated hydrochloric acid, and extracted with ethyl acetate. The ethyl acetate layer was then washed with water and brine, was 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 ammonium hydroxychloride and 0.65 part by weight of pyridine were added to 30mL of ethanol, and the mixture was stirred under reflux for 10 hours. The obtained reaction solution was poured into ice water, followed by filtration. The filtrate was washed with water, dissolved in ethyl acetate, dried over anhydrous sodium sulfate and concentrated to give a 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. While cooling the obtained solution to 10℃or lower, 0.59 parts by weight of triethylamine was added dropwise thereto, and the mixture was stirred at room temperature for 4 hours. The obtained reaction solution was poured into water and then filtered. The compound was separated by silica gel column chromatography, whereby the compound represented by the above formula (5-3) was obtained.
The structure of the obtained compound represented by the above formula (5-3) is represented by 1 H-NMR、 13 C-NMR and FT-IR were confirmed.
Examples 1 to 11 and comparative examples 1 to 4
The materials were stirred by a planetary stirring device (product of THINKY, "deaeration training Talang") in accordance with the mixing ratios shown in tables 1 and 2, and then uniformly mixed by a ceramic three-roll machine, to obtain the sealants for liquid crystal display elements of examples 1 to 11 and comparative examples 1 to 4.
< evaluation >
The sealants for liquid crystal display elements obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 and 2.
(visible light curability)
1 part by weight of spacer particles was dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples. As spacer particles, micropearl SI-H050 (manufactured by water chemical industry Co., ltd.) was used. Next, the sealing agent was filled in a dispensing syringe, and the glass substrate was coated with the sealing agent by a dispenser after the defoaming treatment. As a syringe for dispensing, PSY-10E (manufactured by Musashi Engineering Co.) was used, and SHOTMASTER300 (manufactured by Musashi Engineering Co.) was used as a dispenser. On the substrate coated with the sealant, glass substrates of the same size were bonded under reduced pressure of 5Pa by a vacuum bonding apparatus. Irradiating the sealant portion of the bonded glass substrate with 100mW/cm using a metal halide lamp 2 For 10 seconds. The light irradiates through a cut-off filter (420 nm cut-off filter) which cuts off the light with the wavelength below 420mLight sheet).
The sealant was subjected to FT-IR measurement using an infrared spectroscopic device, and the amount of change in the peak derived from the (meth) acryloyl group before and after light irradiation was measured. As the infrared spectroscopic device, FTS3000 (manufactured by BIORAD corporation) was used. The case where the peak from the (meth) acryloyl group after light irradiation was reduced by 80% or more was designated as "o", the case where the peak from the (meth) acryloyl group after light irradiation was reduced by 50% or more and less than 80% was designated as "Δ", the case where the peak from the (meth) acryloyl group after light irradiation was reduced by less than 50% was designated as "x", and the visible light curability was evaluated.
(adhesion to alignment film)
1 part by weight of spacer particles was dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples. An extremely small amount of a sealant for a liquid crystal display element in which spacer particles were dispersed was taken out to the center of a glass substrate having a polyimide alignment film for TN (manufactured by japanese chemical Co., ltd., "SE 6414"), and a glass substrate having the same type of polyimide alignment film for TN was stacked thereon. Developing the sealant for liquid crystal display element, and irradiating with 100mW/cm using metal halide lamp 2 After 30 seconds, the mixture was heated at 120℃for 1 hour to cure the sealant for a liquid crystal display element, thereby obtaining an adhesion test piece.
The bonding strength (bonding force) of each of the obtained bonding test pieces was measured using a tensiometer.
The bonding strength is 12kg/cm 2 The above cases were designated as "omicron", and 7.0kg/cm was used 2 Above and below 12kg/cm 2 The case of (C) is denoted as "delta", and the bonding strength is less than 7.0kg/cm 2 The case of (2) was marked "X", and the adhesiveness to the alignment film was evaluated.
(solubility)
The curable resin was mixed with the photopolymerization initiator in the same materials and the same compounding ratio as those of each example and each comparative example, and heated at 80℃for 20 minutes. The heated mixture was sandwiched between 2 glass plates with a gap of 20. Mu.m, and the transmitted light intensity was measured by an ultraviolet-visible spectrophotometer (manufactured by Varian Co., ltd., "Carry-5 spectrophotometer").
By the above measurement, the case where the reduction rate of the transmitted light intensity at the wavelength of 500nm was less than 20% was designated as "o", the case where 20% or more and less than 40% was designated as "Δ", the case where 40% or more was designated as "x", and the solubility was evaluated.
(glass transition temperature of cured product)
The sealant for each liquid crystal display element obtained in examples and comparative examples was irradiated with 100mW/cm using a metal halide lamp 2 After 30 seconds of heating at 120℃for 1 hour, a film having a thickness of 300 μm was produced as a test piece. The obtained test piece was subjected to dynamic viscoelasticity measurement at-50 to 200℃and 5Hz using a dynamic viscoelasticity measurement device ("DVA-200" manufactured by IT meter control Co.), and the temperature at which the maximum value of loss tangent (tan. Delta.) was obtained as the glass transition temperature.
TABLE 1
TABLE 2
Industrial applicability
According to the present invention, a sealant for a liquid crystal display element, which has excellent curability by visible light and adhesion to an alignment film, and which can provide a liquid crystal display element having excellent reliability, can be provided. Further, according to the present invention, a liquid crystal display element using the sealant for a liquid crystal display element can be provided.

Claims (5)

1. A sealant for a liquid crystal display element, characterized by comprising a curable resin and a photopolymerization initiator,
the curable resin contains a compound having an aromatic ring and a polymerizable functional group, the aromatic ring content being 50% or more,
the photopolymerization initiator comprises a compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic rings in 1 molecule,
the difference between the solubility parameter of the curable resin as a whole and the solubility parameter of the compound having 1 or more photopolymerization initiator groups and 3 or more heterocycles in 1 molecule is 2.0 or less.
2. The sealant for a liquid crystal display element according to claim 1, wherein the content of the compound having an aromatic ring and a polymerizable functional group in which the content of the aromatic ring is 50% or more is 15 parts by weight or more based on 100 parts by weight of the entire curable resin.
3. The sealant for a liquid crystal display element according to claim 1 or 2, wherein at least 1 of the heterocyclic rings of the compound having 1 or more photopolymerization initiator groups and 3 or more heterocyclic rings in 1 molecule is a thiophene ring.
4. The sealant for a liquid crystal display element according to claim 1, 2 or 3, wherein the cured product has a glass transition temperature of 85 ℃ or higher.
5. A liquid crystal display element comprising the cured product of the sealant for a liquid crystal display element according to claim 1, 2, 3 or 4.
CN202280023056.1A 2021-06-21 2022-06-20 Sealing agent for liquid crystal display element and liquid crystal display element Pending CN117043669A (en)

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