CN108351561B - Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element - Google Patents

Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element Download PDF

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CN108351561B
CN108351561B CN201780003640.XA CN201780003640A CN108351561B CN 108351561 B CN108351561 B CN 108351561B CN 201780003640 A CN201780003640 A CN 201780003640A CN 108351561 B CN108351561 B CN 108351561B
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liquid crystal
crystal display
display element
compound
type epoxy
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CN108351561A (en
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松井庆枝
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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
    • 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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • 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
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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

Abstract

The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which can provide a liquid crystal display element having excellent adhesion, low liquid crystal contamination, and excellent display performance. Further, an object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element. The present invention is a sealant for a liquid crystal display element, comprising a curable resin, and further comprising a polymerization initiator and/or a thermal curing agent, wherein the curable resin comprises: a compound represented by the following formula (1) and a compound having 2 or more epoxy groups in 1 molecule, wherein the content of the compound having 2 or more epoxy groups in 1 molecule is 5 to 25 parts by weight in 100 parts by weight of the curable resin, and the adhesive strength of the cured product to a glass substrate is 290N/cm2The above. In the formula (1), R1Represents a hydrogen atom or a methyl group, R2Represents a group represented by the following formula (2-1) or (2-2), R3Represents a structure derived from an acid anhydride, R4Represents a structure derived from an epoxy compound, X represents a lactone ring-opening structure, n represents an integer of 1 to 6, and a represents an integer of 1 to 4. In the formula (2-1), the symbol denotes a bonding site. In the formula (2-2), b represents an integer of 0 to 8, c represents an integer of 0 to 3, d represents an integer of 0 to 8, e represents an integer of 0 to 8, any one of b, c and d is 1 or more, and represents a bonding position.
Figure DDA0001634135740000011

Description

Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element
Technical Field
The present invention relates to a sealant for a liquid crystal display element, which can provide a liquid crystal display element having excellent adhesiveness, low liquid crystal contamination, and excellent display performance. The present invention also relates to a vertical conduction material and a liquid crystal display element produced using the sealant for a liquid crystal display element.
Background
In recent years, as a method for manufacturing a liquid crystal display element, a liquid crystal dropping method called a dropping method using a photo-thermal curing type sealing agent containing a curable resin, a photopolymerization initiator, and a thermal curing agent as disclosed in patent documents 1 and 2 has been used from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used.
In the one drop fill process, first, a frame-shaped seal pattern is formed by dispensing on one of two transparent substrates with electrodes. Next, in a state where the sealant is not cured, droplets of liquid crystal are dropped onto the entire surface of the sealant on the transparent substrate within the frame, another transparent substrate is immediately stacked, and the seal portion is irradiated with light such as ultraviolet light to perform precuring. Thereafter, the liquid crystal display element is manufactured by heating and main curing. The liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under reduced pressure, and this one drop fill process is now the mainstream of the method for manufacturing a liquid crystal display element.
In addition, in recent years in which various mobile devices with liquid crystal panels such as mobile phones and portable game machines are widespread, miniaturization of the devices is the most demanded issue. As a method for downsizing the device, a narrow frame of a liquid crystal display portion is given, and for example, a position of a sealing portion is disposed below a black matrix (hereinafter, also referred to as a narrow frame design). However, in the narrow frame design, since the sealant is disposed directly below the black matrix, if the one drop process is performed, light irradiated when the sealant is photocured is blocked, and the light cannot reach the inside of the sealant, which causes a problem that the curing becomes insufficient. Therefore, if the curing of the sealant is insufficient, uncured sealant components are eluted into the liquid crystal, and the liquid crystal is easily contaminated.
As flat panel terminals and mobile terminals have become popular, liquid crystal display devices are increasingly required to have durability against impact tests, drop tests, and the like. In addition, with the narrow-frame design, moisture resistance reliability such as driving under a high-temperature and high-humidity environment is required, and the sealant is further required to have a performance of preventing water from entering from the outside. That is, from the viewpoint of improving the impact resistance and moisture resistance reliability of the liquid crystal display element, it is necessary to improve the adhesion between the sealant and the substrate or the like. However, it is difficult to produce a sealant having excellent adhesiveness and low liquid crystal contamination (excellent low liquid crystal contamination).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-133794
Patent document 2: japanese laid-open patent publication No. 5-295087
Disclosure of Invention
Problems to be solved by the invention
The present invention relates to a sealant for a liquid crystal display element, which can provide a liquid crystal display element having excellent adhesiveness, low liquid crystal contamination, and excellent display performance. Further, an object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealant for a liquid crystal display element.
Means for solving the problems
The present invention is a sealant for a liquid crystal display element, comprising a curable resin, and further comprising a polymerization initiator and/or a thermal curing agent, wherein the curable resin comprises: a compound represented by the following formula (1) and a compound having 2 or more epoxy groups in 1 molecule, wherein the content of the compound having 2 or more epoxy groups in 1 molecule is 5 to 25 parts by weight in 100 parts by weight of the curable resin, and the adhesive strength of the cured product to a glass substrate is 290N/cm2The above.
Figure BDA0001634135730000021
In the formula (1), R1Represents a hydrogen atom or aRadical, R2Represents a group represented by the following formula (2-1) or (2-2), R3Represents a structure derived from an acid anhydride, R4Represents a structure derived from an epoxy compound, X represents a lactone ring-opening structure, n represents an integer of 1 to 6, and a represents an integer of 1 to 4.
Figure BDA0001634135730000031
In the formula (2-1), the symbol denotes a bonding site.
In the formula (2-2), b represents an integer of 0 to 8, c represents an integer of 0 to 3, d represents an integer of 0 to 8, e represents an integer of 0 to 8, any one of b, c and d is 1 or more, and represents a bonding position.
The present invention will be described in detail below.
The present inventors have studied that by using a compound represented by the above formula (1) as a curable resin, a sealant having excellent adhesion to a sealant for a liquid crystal display element and low liquid crystal staining property can be obtained. However, when the obtained sealing agent is used, there is a problem that an image sticking, a decrease in contrast, or a decrease in response speed may occur particularly in a high-definition liquid crystal display element.
The inventor considers that: the reason why the residual image or the like is generated in the display element is that the compound represented by the above formula (1) remaining in the cured product of the sealant precipitates and adheres to the alignment film, which causes a reduction in the alignment controlling force. Namely, it is considered that: in a high-definition liquid crystal display element in which the number of wirings is large due to a high pixel density, a portion of a sealant disposed below the wirings becomes large, light cannot sufficiently reach the sealant due to the wirings, and an unreacted compound represented by the above formula (1) is likely to precipitate.
As a result of further intensive studies, the present inventors have found that a sealant for a liquid crystal display element, which can provide a liquid crystal display element having excellent adhesion, low liquid crystal contamination, and excellent display performance, can be obtained by using a compound represented by the above formula (1) in combination with a compound having 2 or more epoxy groups in 1 molecule and setting the content of the compound having 2 or more epoxy groups in 1 molecule to a specific range, and have completed the present invention.
The sealant for a liquid crystal display element of the present invention contains a curable resin.
The curable resin contains a compound represented by the formula (1). By containing the compound represented by the formula (1), the sealant for a liquid crystal display element of the present invention has excellent adhesiveness and low liquid crystal contamination.
In the above formula (1), R2Represents a group represented by the above formula (2-1) or (2-2). Wherein R is a group represented by formula (I) and R is a group represented by formula (II) in the above formula (II)2Preferably a group represented by the formula (2-2) wherein b is 1 to 4, c is 0, and d is 0 (a linear oxyalkylene group having 1 to 4 carbon atoms).
In the above formula (1), R3Represents a structure derived from an acid anhydride.
Examples of the acid anhydride include phthalic anhydride, maleic anhydride, succinic anhydride, and citraconic anhydride. Among them, phthalic anhydride is preferable.
In the above formula (1), R4Represents a structure derived from an epoxy compound.
As the epoxy compound, the same compound as a compound having 2 or more epoxy groups in 1 molecule described later can be preferably used.
In the formula (1), X represents a lactone ring-opening structure.
Examples of the lactone include β -propiolactone, β -butyrolactone, γ -valerolactone, δ -valerolactone, ε -caprolactone, γ -heptalactone, γ -nonalactone, γ -decalactone, δ -decalactone, γ -dodecalactone, δ -dodecalactone, γ -undecalactone, δ -undecalactone, and 7-butyl-2-oxacycloheptanone. Among them, lactones having 3 to 7 carbon atoms in the linear chain part of the main skeleton at the time of ring opening are preferable.
In the formula (1), n represents an integer of 1 to 6. Among them, n is preferably an integer of 1 to 5 from the viewpoint of adhesiveness of the obtained sealant for a liquid crystal display element and flexibility of a cured product.
In the formula (1), a represents an integer of 1 to 4. Among them, the above a is preferably an integer of 2 to 4 from the viewpoint of improving the heat resistance of the cured product of the obtained sealant for a liquid crystal display element, and more preferably 2 from the viewpoint of storage stability.
The lower limit of the molecular weight of the compound represented by the above formula (1) is preferably 700, and the upper limit is preferably 2100. By setting the molecular weight of the compound represented by the formula (1) to be in this range, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness and low liquid crystal contamination.
The lower limit of the content of the compound represented by the formula (1) in 100 parts by weight of the curable resin is preferably 5 parts by weight, and the upper limit is preferably 50 parts by weight. When the content of the compound represented by the formula (1) is in this range, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness and low liquid crystal contamination. The content of the compound represented by the above formula (1) is more preferably as high as 30 parts by weight.
The curable resin contains a compound having 2 or more epoxy groups in 1 molecule (hereinafter, also referred to as "polyfunctional epoxy compound"). Since the polyfunctional epoxy compound is likely to cause contamination of liquid crystals, it is generally preferable to reduce the amount of the compound to be blended within a range not affecting the adhesiveness. On the other hand, in the sealant for a liquid crystal display element of the present invention, the content of the polyfunctional epoxy compound is not set to a range for the purpose of satisfying both adhesiveness and liquid crystal staining properties, but is set to a range described later. As a result, even when the compound represented by the formula (1) is used, the compound represented by the formula (1) can be prevented from precipitating from the cured product, and the resulting liquid crystal display device can be prevented from generating an afterimage or the like, thereby achieving excellent display performance.
Examples of the polyfunctional epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, 2' -diallylbisphenol A type epoxy compounds, hydrogenated bisphenol type epoxy compounds, propylene oxide-added bisphenol A type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, thioether type epoxy compounds, diphenyl ether type epoxy compounds, dicyclopentadiene type epoxy compounds, naphthalene type epoxy compounds, phenol novolac type epoxy compounds, o-cresol novolac type epoxy compounds, dicyclopentadiene novolac type epoxy compounds, biphenyl novolac type epoxy compounds, naphthol novolac type epoxy compounds, glycidyl amine type epoxy compounds, alkyl polyhydric alcohol type epoxy compounds, rubber-modified epoxy compounds, epoxy resins, and epoxy resins, Glycidyl ester compounds, and the like.
The lower limit of the content of the polyfunctional epoxy compound is 5 parts by weight and the upper limit is 25 parts by weight in 100 parts by weight of the curable resin. When the content of the polyfunctional epoxy compound is 5 parts by weight or more, the effect of suppressing precipitation of the compound represented by the formula (1) is excellent, and the occurrence of an afterimage or the like in the obtained liquid crystal display element can be suppressed. By setting the content of the polyfunctional epoxy compound to 25 parts by weight or less, the obtained sealant for a liquid crystal display element is excellent in low liquid crystal contamination. The content of the polyfunctional epoxy compound preferably has a lower limit of 7 parts by weight, a higher limit of 23 parts by weight, a higher limit of 10 parts by weight, and a higher limit of 20 parts by weight.
The curable resin may contain other curable resins in addition to the compound represented by formula (1) and the polyfunctional epoxy compound, within a range not to impair the object of the present invention.
Examples of the other curable resin include other (meth) acrylic compounds other than the compound represented by formula (1), and compounds having 1 epoxy group in 1 molecule (hereinafter, also referred to as "monofunctional epoxy compounds").
In the present specification, the "(meth) acrylic" refers to an acrylic or methacrylic, the "(meth) acrylic compound" refers to a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group.
Examples of the other (meth) acrylic compounds include (meth) acrylate compounds obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, (meth) acrylic acid esters obtained by reacting (meth) acrylic acid with an epoxy compound, urethane (meth) acrylates obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like. Among them, epoxy (meth) acrylates are preferred. In addition, the (meth) acrylic compound preferably has 2 or more (meth) acryloyl groups in 1 molecule from the viewpoint of reactivity.
In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate, and 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 in the above-mentioned (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, and mixtures thereof, 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, tetrahydrofurfuryl (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2, 3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, and mixtures thereof, Imino (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 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, and mixtures thereof, Neopentyl glycol di (meth) acrylate, ethylene oxide-added bisphenol a di (meth) acrylate, propylene oxide-added bisphenol a di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadiene 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, as the compound having 3 or more functions in the (meth) acrylate compound, examples thereof 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) 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 products obtained by reacting an epoxy compound with (meth) acrylic acid by a conventional method in the presence of a basic catalyst.
As the epoxy compound to be used as a raw material for synthesizing the epoxy (meth) acrylate, the same polyfunctional epoxy compounds as described above can be used.
Examples of commercially available Epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 (both manufactured by Daicel-Allnex Corporation), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (both manufactured by Mitsukamura chemical industries), Epoxy Ester M-600A, Epoxy Ester EM 40, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester A1600, Epoxy Ester EA-3000, Epoxy Ester DA (manufactured by Decolon Corporation), Epoxy Ester DA-3000, and the like.
The urethane (meth) acrylate obtained by reacting the (meth) acrylic acid derivative having a hydroxyl group with the isocyanate compound can be obtained, for example, by reacting 2 equivalents of the (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of the isocyanate compound having 2 isocyanate groups in the presence of a catalytic amount of a tin compound.
Examples of the isocyanate compound which becomes a raw material of the urethane (meth) acrylate 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, tolidine diisocyanate, Xylylene Diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diisocyanate, 1, 6, 11-undecane triisocyanate, and the like.
As the isocyanate compound which is a raw material of the urethane (meth) acrylate, for example, an isocyanate compound in which a chain is extended by a reaction of a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, or the like with an excessive amount of an isocyanate compound can be used.
Examples of the (meth) acrylic acid derivative having a hydroxyl group which is a raw material of the urethane (meth) acrylate include monoalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate, mono-and di- (meth) acrylates of dihydric alcohols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol, mono-and di- (meth) acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin, and epoxy (meth) acrylates such as bisphenol a type epoxy acrylate.
Examples of commercially available products of the above urethane (meth) acrylate include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toyo Synthesis Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL 7, EBECRYL9260 (all manufactured by Daicel-Allnex Co., Ltd.), Art Resin UN-330, Art Resin SH-500B, Art Resin UN-1200TPK, Art Resin UN-1255, Art Resin UN-3320, Art Resin 7100, Art Resin SH-9000, Art Resin HA-9000, Art-9006, and HA-9006U (all manufactured by Daicel-Allen-Alex Co., Ltd.), and HA-2U-9006, HA-9004, commercially available from ArtHA-2U, HA-9006, HA-K, 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, UA-W2A (all manufactured by Ninghamun chemical industries Co., Ltd.), AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all manufactured by Kyoho chemical Co., Ltd.), and the like.
Examples of the monofunctional epoxy compound include a partially (meth) acrylic-modified epoxy resin.
In the present specification, the partially (meth) acrylic-modified epoxy resin refers to a compound having 1 epoxy group and 1 or more (meth) acryloyl groups in 1 molecule, and can be obtained, for example, by reacting a part of the epoxy groups of the polyfunctional epoxy compound with (meth) acrylic acid.
The other curable resin preferably has-OH group, -NH-group, or-NH-group from the viewpoint of suppressing liquid crystal contamination2Hydrogen bonding units such as hydrogen bonding units.
The sealant for a liquid crystal display element of the present invention contains a polymerization initiator and/or a thermal curing agent.
As the polymerization initiator, a radical polymerization initiator can be preferably used.
Examples of the radical polymerization initiator include a thermal radical polymerization initiator which generates radicals by heating, and a photo radical polymerization initiator which generates radicals by light irradiation.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone compounds.
Examples of commercially available products of the photo radical polymerization initiator include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, Lucirin TPO (all manufactured by BASF corporation), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical industry Co., Ltd.), KR-02 (manufactured by Light Chemical Company).
Examples of the thermal radical polymerization initiator include initiators containing azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator containing a polymeric azo compound is preferable.
In the present specification, the macromolecular azo initiator refers to a compound having an azo group, capable of generating a radical that cures a (meth) acryloyloxy group by heat, and having a number average molecular weight of 300 or more.
The number average molecular weight of the polymeric azo initiator preferably has a lower limit of 1000 and an upper limit of 30 ten thousand. When the number average molecular weight of the polymeric azo initiator is in this range, the azo initiator can be easily mixed with the curable resin while preventing adverse effects on the liquid crystal. The number average molecular weight of the polymeric azo initiator is preferably 5000 as the lower limit, more preferably 10 ten thousand as the upper limit, still more preferably 1 ten thousand as the lower limit, and yet more preferably 9 ten thousand as the upper limit.
In the present specification, the number average molecular weight is a value measured by Gel Permeation Chromatography (GPC) and determined based on polystyrene conversion. Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
Examples of the polymeric azo initiator include compounds having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
The polymer azo initiator having a structure in which a plurality of polyalkylene oxide units and the like are bonded to each other via the azo group is preferably a compound having a polyethylene oxide structure. Examples of such a polymeric azo initiator include a polycondensate of 4, 4 '-azobis (4-cyanovaleric acid) and a polyalkylene glycol, and a polycondensate of 4, 4' -azobis (4-cyanovaleric acid) and a polydimethylsiloxane having a terminal amino group, and specifically include VPE-0201, VPE-0401, VPE-0601, VPS-0501 and VPS-1001 (both manufactured by Wako pure chemical industries, Ltd.).
Further, examples of azo compounds which are not polymers include V-65 and V-501 (both manufactured by Wako pure chemical industries, Ltd.).
Examples of the organic peroxide include ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, and the like.
The lower limit of the content of the polymerization initiator is preferably 0.1 part by weight and the upper limit is preferably 30 parts by weight with respect to 100 parts by weight of the entire curable resin. When the content of the polymerization initiator is in this range, the obtained sealant for a liquid crystal display element can maintain excellent storage stability and is more excellent in curability. The lower limit of the content of the polymerization initiator is more preferably 1 part by weight, the upper limit is more preferably 10 parts by weight, and the upper limit is more preferably 5 parts by weight.
Examples of the heat-curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, acid anhydrides, and the like. Among them, solid organic acid hydrazides are suitably used.
Examples of the solid organic acid hydrazide include 1, 3-bis (hydrazinocarbonylethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and commercially available products thereof include SDH, ADH (available from Otsuka chemical Co., Ltd.), MDH (available from Finechem Co., Ltd., Japan), Amicure VDH-J, and Amicure UDH (available from Aomoto Fine technologies Co., Ltd.).
The lower limit of the content of the heat-curing agent is preferably 1 part by weight, and the upper limit is preferably 50 parts by weight, based on 100 parts by weight of the entire curable resin. When the content of the thermosetting agent is in this range, the obtained sealant for a liquid crystal display element can maintain excellent coatability and storage stability, and is more excellent in curability. The more preferable upper limit of the content of the thermal curing agent is 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a polymerization inhibitor from the viewpoint of improving storage stability and the like.
Examples of the polymerization inhibitor include 2, 6-di-tert-butylcresol, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 ' -methylenebis (4-methyl-6-tert-butylphenol), 2 ' -methylenebis (4-ethyl-6-tert-butylphenol), 4 ' -thiobis (3-methyl-6-tert-butylphenol), 4-butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis (1, 1-dimethyl-2- (. beta. - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) Ethyl) -2, 4, 8, 10-tetraoxaspiro (5, 5) undecane, tetrakis- (methylene-3- (3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl) propionate) methane, 1, 3, 5-tris (3', 5 '-di-tert-butyl-4' -hydroxybenzyl) -sec-triazine-2, 4, 6- (1H, 3H, 5H) trione, hydroquinone, p-methoxyphenol, and the like.
The lower limit of the content of the polymerization inhibitor is preferably 0.005 parts by weight and the upper limit thereof is preferably 0.2 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the polymerization inhibitor is in this range, the excellent curability of the obtained sealant for a liquid crystal display element can be maintained, and the effect of improving the storage stability and the like can be further exhibited. The lower limit of the content of the polymerization inhibitor is more preferably 0.007 parts by weight, and the upper limit is more preferably 0.18 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a filler for the purpose of increasing viscosity, further improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, improving moisture resistance of a cured product, and the like.
Examples of the filler include inorganic fillers such as 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, polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, and acrylic polymer microparticles.
The lower limit of the content of the filler in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is preferably 10 parts by weight, and the upper limit is preferably 70 parts by weight. When the content of the filler is in this range, the effect of improving the adhesiveness and the like can be further exhibited while suppressing the deterioration of the coatability and the like. The lower limit of the content of the filler is more preferably 20 parts by weight, and the upper limit is more preferably 60 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a silane coupling agent for the purpose of further improving adhesiveness. The silane coupling agent mainly functions as an adhesion aid for satisfactorily adhering the sealant to a substrate or the like.
As the silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like can be preferably used.
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 preferably has a lower limit of 0.1 part by weight and an upper limit of 10 parts by weight. When the content of the silane coupling agent is in this range, the effect of further improving the adhesiveness can be exerted while suppressing the occurrence of liquid crystal contamination. The lower limit of the content of the silane coupling agent is more preferably 0.3 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 may contain a light-shading agent. By containing the light-shading agent, the sealant for a liquid crystal display element of the present invention can be suitably used as a light-shielding sealant.
Examples of the light-shading agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Among them, titanium black is preferable.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly at a wavelength of 370 to 450nm, than the average transmittance for light having a wavelength of 300 to 800 nm. That is, the titanium black is a light-shading agent having the following properties: the sealant for a liquid crystal display element of the present invention is provided with light-shielding properties by sufficiently shielding light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. The light-shading agent contained in the sealant for a liquid crystal display element of the present invention is preferably a high-insulating material, and titanium black is also suitable as a high-insulating light-shading agent.
The above titanium black can exhibit sufficient effects without being surface-treated, but titanium black having a surface treated with an organic component such as a coupling agent, or surface-treated titanium black such as titanium black coated with an inorganic component such as silicon oxide, titanium oxide, germanium oxide, aluminum oxide, zirconium oxide, or magnesium oxide may be used. Among them, titanium black treated with an organic component is preferable because the insulation property can be further improved.
Further, since the liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, a liquid crystal display element having no light leakage, high contrast, and excellent image display quality can be realized.
Examples of commercially available products of the titanium black include 12S, 13M-C, 13R-N, and 14M-C (all manufactured by Mitsubishi corporation), Tilack D (manufactured by Gibberella kogaku Co., Ltd.), and the like.
The lower limit of the specific surface area of the titanium black is preferably 13m2A preferred upper limit of 30m2A more preferred lower limit is 15m2A more preferable upper limit of 25m2/g。
The volume resistance of the titanium black is preferably 0.5 Ω · cm at the lower limit and 3 Ω · cm at the upper limit, more preferably 1 Ω · cm at the lower limit and 2.5 Ω · cm at the upper limit.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, and a preferable lower limit is 1nm and a preferable upper limit is 5 μm. By setting the primary particle size of the light-shading agent in this range, the coating property can be further improved without significantly increasing the viscosity and thixotropy of the obtained sealant for a liquid crystal display element. The lower limit of the primary particle diameter of the light-shading agent is more preferably 5nm, the upper limit is more preferably 200nm, the lower limit is more preferably 10nm, and the upper limit is more preferably 100 nm.
The primary PARTICLE size of the light-shading agent can be measured using a PARTICLE size distribution analyzer (for example, "NICOMP 380 ZLS", manufactured by PARTICLE SIZING SYSTEMS).
The preferable lower limit of the content of the light-shading agent in 100 parts by weight of the sealant for a liquid crystal display element of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. By setting the content of the light-shading agent within this range, the effect of further improving the light-shielding property can be exhibited without lowering the adhesiveness, strength after curing, and drawability of the obtained sealant for a liquid crystal display element. The content of the light-shading agent is more preferably 10 parts by weight at the lower limit, more preferably 70 parts by weight at the upper limit, still more preferably 30 parts by weight at the lower limit, and still more preferably 60 parts by weight at the upper limit.
The sealant for a liquid crystal display element of the present invention may further contain additives such as a stress relaxation agent, a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, and a leveling agent, as required.
Examples of the method for producing the sealant for a liquid crystal display element of the present invention include a method of mixing a curable resin, a polymerization initiator and/or a heat-curing agent, and an additive such as a silane coupling agent added as necessary, using a mixer such as a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll machine.
In the sealant for a liquid crystal display element of the present invention, the lower limit of the adhesive strength of the cured product to the glass substrate is 290N/cm2. By setting the above adhesive strength to 290N/cm2As described above, the obtained liquid crystal display device has excellent impact resistance. The preferable lower limit of the adhesive strength is 310N/cm2More preferably, the lower limit is 330N/cm2。
The higher the bonding strength, the better, there is no preferable upper limit, but the substantial upper limit is 400N/cm2。
The adhesion strength of the cured product to the glass substrate can be measured by the following method.
First, a sealant for a liquid crystal display element was applied to a glass substrate, and another glass substrate was placed thereon to spread the sealant for a liquid crystal display element, and the resultant was irradiated with 100mW/cm2After 30 seconds, the resultant was heated at 120 ℃ for 1 hour to prepare an adhesion test piece. Next, the adhesion strength of the cured product to the glass substrate was measured by using a tensiometer for the obtained adhesion test piece.
The sealant for a liquid crystal display element of the present invention is suitable for curing at high temperature, and is preferably used by curing at 100 ℃ or higher, and more preferably used by curing at 110 ℃ or higher.
By adding conductive fine particles to the sealant for a liquid crystal display element of the present invention, a vertical conduction material can be produced. The vertical conduction material comprising the sealant for liquid crystal display element of the present invention and conductive fine particles is also one aspect of the present invention.
As the conductive fine particles, fine particles in which a conductive metal layer is formed on the surface of a metal ball or a resin fine particle, or the like can be used. Among these, fine particles in which a conductive metal layer is formed on the surface of resin fine particles are preferable because of their excellent elasticity, and thus conductive connection can be performed without damaging the transparent substrate or the like.
A liquid crystal display element produced using the sealant for a liquid crystal display element of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
The sealant for a liquid crystal display element of the present invention can suppress the occurrence of an afterimage or the like even when the aperture ratio of the sealant for a liquid crystal display element obtained is low, and is excellent in display performance of the liquid crystal display element, and therefore, can be suitably used for a liquid crystal display element having a low aperture ratio of the sealant. Specifically, the sealant for a liquid crystal display element of the present invention is suitably used for a liquid crystal display element having an aperture ratio of 50% or less, and more suitably used for a liquid crystal display element having an aperture ratio of 30% or less.
The "aperture ratio of the sealant" is a ratio of a portion of the sealant not hidden by the wiring or the like, and can be measured by observing the shape of the metal wiring disposed on the upper portion of the sealant using an optical microscope.
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 one drop fill process.
Specific examples of the method for manufacturing a liquid crystal display element of the present invention by a liquid crystal dropping method include a method including the following steps: a step of forming a frame-shaped seal pattern by applying the sealant for a liquid crystal display element of the present invention on a substrate by screen printing, dispenser application, or the like; a step of applying a liquid crystal in a dropwise manner to the entire inner surface of the frame of the transparent substrate in an uncured state with the sealant for a liquid crystal display element of the present invention or the like, and immediately superposing the other substrate; and a step of pre-curing the sealant by irradiating the seal pattern portion of the sealant for a liquid crystal display element of the present invention with light such as ultraviolet rays; and a step of heating the precured sealant to primarily cure the sealant.
Effects of the invention
According to the present invention, a sealant for a liquid crystal display element which can provide a liquid crystal display element having excellent adhesiveness, low liquid crystal contamination, and excellent display performance can be provided. Further, according to the present invention, a vertical conduction material and a liquid crystal display element, which are produced using the sealant for a liquid crystal display element, can be provided.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(preparation of curable resin A)
2-hydroxyethyl acrylate 116 parts by weight, beta-propiolactone 114 parts by weight, and hydroquinone 0.3 part by weight as a polymerization inhibitor were charged into a reaction flask, and stirred at 90 ℃ for 5 hours using a cap electric heater, and then phthalic anhydride 148 parts by weight was added and further stirred for 5 hours. Subsequently, 170 parts by weight of bisphenol a diglycidyl ether was added to the obtained reaction product, and the mixture was stirred at 90 ℃ for 5 hours, thereby obtaining a curable resin a.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin A was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the following formula (3), R4Is a structure derived from bisphenol a diglycidyl ether represented by the following formula (4), X is a ring-opening structure of β -propiolactone represented by the following formula (5), n is 2, and a is 2).
Figure BDA0001634135730000161
In the formula (3), the symbol denotes a bonding site.
Figure BDA0001634135730000171
In the formula (4), the symbol "X" represents a bonding site.
Figure BDA0001634135730000172
In the formula (5), the symbol denotes a bonding site.
(preparation of curable resin B)
Curable resin B was obtained in the same manner as in the above "(production of curable resin a)" except that the loading of β -propiolactone was changed to 360 parts by weight.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that the curable resin B was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2A group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4Is a structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of β -propiolactone represented by the above formula (5), n is 5, and a is 2).
(preparation of curable resin C)
Curable resin C was obtained in the same manner as in the above "(production of curable resin a)" except that 200 parts by weight of γ -valerolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13The curable resin C was confirmed to be a compound (R) represented by the above formula (1) by C-NMR and FT-IR analyses1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by formula (4) above, X is a ring-opening structure of γ -valerolactone represented by formula (6) below, n is 2, and a is 2).
Figure BDA0001634135730000173
In the formula (6), the symbol "X" represents a bonding site.
(preparation of curable resin D)
Curable resin D was obtained in the same manner as in the above "(production of curable resin a)" except that 500 parts by weight of γ -valerolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin D was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of γ -valerolactone represented by the above formula (6), n is 5, and a is 2).
(preparation of curable resin E)
Curable resin E was obtained in the same manner as in the above "(production of curable resin a)" except that 114 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin E was represented by the above formula (1)Compound (R)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of ∈ -caprolactone represented by the following formula (7), n is 1, and a is 2).
Figure BDA0001634135730000181
In the formula (7), the symbol denotes a bonding site.
(preparation of curable resin F)
A curable resin F was obtained in the same manner as in the above "(production of curable resin a)" except that 228 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13The C-NMR and FT-IR analyses confirmed that the curable resin F was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of ∈ -caprolactone represented by the above formula (7), n is 2, and a is 2).
(preparation of curable resin G)
Curable resin G was obtained in the same manner as in the above "(production of curable resin a)", except that epsilon-caprolactone (342 parts by weight) was added instead of beta-propiolactone (114 parts by weight).
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin G was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4Is derived from bisphenol A diglycidyl ether represented by the above formula (4), and X is epsilon-caprolactone represented by the above formula (7)Open-loop structure, n-3, a-2).
(preparation of curable resin H)
Curable resin H was obtained in the same manner as in the above "(production of curable resin a)" except that 456 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin H was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of ∈ -caprolactone represented by the above formula (7), n is 4, and a is 2).
(preparation of curable resin I)
Curable resin I was obtained in the same manner as in the above "(production of curable resin a)", except that 570 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that curable resin I was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of ∈ -caprolactone represented by the above formula (7), n is 5, and a is 2).
(preparation of curable resin J)
Curable resin J was obtained in the same manner as in the "production of curable resin a" above except that 684 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that the curable resin J was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opening structure of ∈ -caprolactone represented by the above formula (7), n is 6, and a is 2).
(preparation of curable resin K)
A curable resin K was obtained in the same manner as in the above "(production of curable resin a)" except that 256 parts by weight of γ -heptalactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that the curable resin K was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4The structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opened structure of γ -heptalactone represented by the following formula (8), n is 2, and a is 2).
Figure BDA0001634135730000201
In the formula (8), the symbol denotes a bonding site.
(preparation of curable resin L)
A curable resin L was obtained in the same manner as in the above "(production of curable resin a)" except that 640 parts by weight of γ -heptalactone was added instead of 114 parts by weight of β -propiolactone.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that the curable resin L was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4Is a structure derived from bisphenol a diglycidyl ether represented by the above formula (4), X is a ring-opened structure of γ -heptalactone represented by the above formula (8), n is 5, and a is 2).
(preparation of curable resin M)
A curable resin M was obtained in the same manner as in the above "(production of curable resin a)" except that 342 parts by weight of ∈ -caprolactone was added instead of 114 parts by weight of β -propiolactone, and 230 parts by weight of tris (p-hydroxyphenyl) methane diglycidyl ether was added instead of 170 parts by weight of bisphenol a diglycidyl ether.
By passing1H-NMR、13C-NMR and FT-IR analyses confirmed that the curable resin M was a compound (R) represented by the above formula (1)1Is a hydrogen atom, R2Is a group represented by the above formula (2-2) (b ═ 2, c ═ 0, d ═ 0), R3Is a structure derived from phthalic anhydride represented by the above formula (3), R4Is a structure derived from tris (p-hydroxyphenyl) methane diglycidyl ether represented by the following formula (9), X is a ring-opening structure of epsilon-caprolactone represented by the above formula (7), n is 3, and a is 2.
Figure BDA0001634135730000211
In the formula (9), the symbol denotes a bonding site.
(preparation of partially acrylic acid-modified bisphenol F type epoxy resin)
Bisphenol F diglycidyl ether 312 parts by weight was dissolved in 600mL of toluene, and 0.2g of triphenylphosphine was added to the solution to prepare a uniform solution. To the resulting solution, 72 parts by weight of acrylic acid was added dropwise over 2 hours under reflux stirring, followed by reflux stirring for 6 hours. Then, toluene was removed to obtain a partially acrylic-modified bisphenol F type epoxy resin represented by the following formula (10).
Figure BDA0001634135730000212
(examples 1 to 17, comparative examples 1 to 5)
The respective materials were stirred by a planetary stirring apparatus (manufactured by Thinky, ぁわとり tylan) according to the mixing ratios shown in tables 1 to 3, and then uniformly mixed by a ceramic three-roll mill to obtain liquid crystal display element sealants of examples 1 to 17 and comparative examples 1 to 5.
< evaluation >
The following evaluations were performed on the respective liquid crystal display element sealants obtained in examples and comparative examples. The results are shown in tables 1 to 3.
(storage stability)
The sealing agent for liquid crystal display elements obtained in examples and comparative examples was put in a syringe, vacuum defoamed using a vacuum defoaming device (manufactured by Thinky, inc. "ARV-200") at 1500rpm and 3 torr for 10 minutes, allowed to stand at 23 ℃ for 2 weeks under an atmosphere of a humidity of 50% RH, and then a small amount of the sealing agent was removed with a spatula and applied to a glass substrate by hand to examine whether or not the sealing agent gelled.
The storage stability was evaluated by marking "o" when the glass substrate could be easily coated without gelation, marking "Δ" when gelation occurred and coatability was deteriorated, and marking "x" when coating could not be performed.
(adhesiveness)
3 parts by weight of polymer beads having an average particle diameter of 5 μm (Micropearl SP, manufactured by Water chemical industries, Ltd.) were dispersed by a planetary stirring apparatus to 100 parts by weight of each of the liquid crystal display element sealants obtained in examples and comparative examples to prepare a uniform solution. The resulting solution was measured to a very small amount at the center of a glass substrate (20 mm. times.50 mm. times.1.1 mmt), and a glass substrate of the same type was superimposed thereon, and the sealant for a liquid crystal display element was spread. In this state, the irradiation was conducted at 100mW/cm2After 30 seconds, the resultant was heated at 120 ℃ for 1 hour to obtain an adhesion test piece.
The adhesion strength of the obtained adhesion test piece was measured by using a tensiometer.
(display Performance of liquid Crystal display element (afterimage prevention))
0.5g of a liquid crystal (JC-5001 LA, manufactured by Chisso corporation) was added to the sample bottle, 0.1g of each of the sealants for liquid crystal dropping method obtained in examples and comparative examples was added thereto, the mixture was shaken, and then heated at 120 ℃ for 1 hour to be cooled to room temperature (25 ℃).
Having a transparent electrode and an alignment film"SE 7492", manufactured by seikagaku corporation), the sealant for liquid crystal dropping process obtained in each of examples and comparative examples was applied to the alignment film of the glass substrate by a dispenser so as to form a square frame. Next, the minute droplets of the liquid crystal taken out of the sample bottle were applied dropwise to the entire surface of the frame on the substrate, and the other glass substrate was stacked in a vacuum. Removing vacuum, irradiating with 100mW/cm2After 30 seconds, the sealant was cured by heating at 120 ℃ for 1 hour to obtain a liquid crystal display element (aperture ratio of sealant: 20%).
With respect to the obtained liquid crystal display element, the occurrence of an afterimage when a 1V dc voltage was applied while an 1.5V ac voltage was applied was visually confirmed. As a result, the case where no afterimage was confirmed at all was indicated by "o", the case where a small afterimage was confirmed was indicated by "Δ", and the case where a serious afterimage was confirmed was indicated by "x", and the display performance of the liquid crystal display element (afterimage prevention property) was evaluated.
(display Performance of liquid Crystal display element (Low liquid Crystal contamination))
The sealing agent for liquid crystal dropping process obtained in each of examples and comparative examples was applied to an alignment film of a glass substrate having a transparent electrode and an alignment film (SE 7492, manufactured by nippon chemical) by a dispenser so as to form a square frame. Then, a minute droplet of liquid crystal ("JC-5001 LA" manufactured by Chisso corporation) was applied dropwise to the entire surface of the frame on the substrate, and the other glass substrate was stacked in a vacuum. The vacuum is released, and the display part is covered up by irradiating 100mW/cm2After 30 seconds, the sealant was cured by heating at 120 ℃ for 1 hour to obtain a liquid crystal display element (aperture ratio of sealant: 20%). The periphery of the sealant in the display portion of the obtained liquid crystal display element was confirmed using a polarization microscope. As a result, the display performance of the liquid crystal display element (low liquid crystal contamination) was evaluated by marking "o" as a case where no display unevenness was observed at all, marking "Δ" as a case where a small amount of display unevenness was observed, and marking "x" as a case where a serious display unevenness was observed.
(impact resistance of liquid Crystal display device)
The respective sealants for liquid crystal display elements obtained in examples and comparative examples were prepared in the same manner as described above "(display performance of liquid crystal display element (low liquid crystal contamination))", and each of 10 cells of liquid crystal display element was prepared.
A drop test was performed to drop each liquid crystal display element from a height of 2m, and after the drop test, the case where no liquid crystal leakage occurred in all the cells due to peeling or cracking was designated as "o", the case where liquid crystal leakage occurred in the liquid crystal display elements of 1 cell or more and 9 cells or less was designated as "Δ", and the case where liquid crystal leakage occurred in all the liquid crystal display elements was designated as "x", and the impact resistance of the liquid crystal display elements was evaluated.
[ Table 1]
Figure BDA0001634135730000241
[ Table 2]
Figure BDA0001634135730000251
[ Table 3]
Figure BDA0001634135730000261
Industrial applicability
According to the present invention, a sealant for a liquid crystal display element which can provide a liquid crystal display element having excellent adhesiveness, low liquid crystal contamination, and excellent display performance can be provided. Further, according to the present invention, a vertical conduction material and a liquid crystal display element, which are produced using the sealant for a liquid crystal display element, can be provided.

Claims (7)

1. A sealant for a liquid crystal display element, comprising a curable resin and further comprising a polymerization initiator and/or a thermal curing agent, wherein,
the curable resin contains: a compound represented by the following formula (1) and a compound having 2 or more epoxy groups in 1 molecule,
the compound having 2 or more epoxy groups in 1 molecule is a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a 2, 2' -diallylbisphenol A type epoxy compound, a hydrogenated bisphenol type epoxy compound, a propylene oxide-added bisphenol A type epoxy compound, a resorcinol type epoxy compound, a biphenyl type epoxy compound, a thioether type epoxy compound, a diphenyl ether type epoxy compound, a dicyclopentadiene type epoxy compound, a naphthalene type epoxy compound, a phenol novolac type epoxy compound, an o-cresol novolac type epoxy compound, a dicyclopentadiene novolac type epoxy compound, a biphenyl novolac type epoxy compound, a naphthol novolac type epoxy compound, a glycidylamine type epoxy compound, an alkyl polyhydric alcohol type epoxy compound, a rubber-modified epoxy resin, a rubber-modified rubber, Or a compound of a glycidyl ester, or a mixture thereof,
the curable resin contains 5 to 25 parts by weight of a compound having 2 or more epoxy groups in 1 molecule per 100 parts by weight of the curable resin,
the adhesion strength of the cured product to a glass substrate was 290N/cm2In the above-mentioned manner,
Figure FDA0003159851440000011
in the formula (1), R1Represents a hydrogen atom or a methyl group, R2Represents a group represented by the following formula (2-1) or (2-2), R3Represents a structure derived from an acid anhydride, R4Represents a structure derived from an epoxy compound, X represents a lactone ring-opening structure, n represents an integer of 1 to 6, a represents an integer of 1 to 4,
Figure FDA0003159851440000021
in the formula (2-1), the symbol represents a bonding site,
in the formula (2-2), b represents an integer of 0 to 8, c represents an integer of 0 to 3, d represents an integer of 0 to 8, e represents an integer of 0 to 8, any one of b, c and d is 1 or more, and represents a bonding position.
2. The sealant for a liquid crystal display element according to claim 1, wherein the content of the compound represented by the formula (1) is 5 to 50 parts by weight in 100 parts by weight of the curable resin.
3. The sealant for a liquid crystal display element according to claim 1 or 2, which contains a polymerization inhibitor.
4. The sealant for a liquid crystal display element according to claim 1 or 2, which contains a light-screening agent.
5. The sealant for a liquid crystal display element according to claim 3, which contains a light-screening agent.
6. A vertically conducting material comprising the sealant for liquid crystal display element according to claim 1, 2, 3, 4 or 5 and conductive fine particles.
7. A liquid crystal display element produced by using the sealant for a liquid crystal display element according to claim 1, 2, 3, 4 or 5 or the vertically conducting material according to claim 6.
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