CN110168440B - 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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Publication number
CN110168440B
CN110168440B CN201880006074.2A CN201880006074A CN110168440B CN 110168440 B CN110168440 B CN 110168440B CN 201880006074 A CN201880006074 A CN 201880006074A CN 110168440 B CN110168440 B CN 110168440B
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liquid crystal
crystal display
meth
display element
acrylate
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CN110168440A (en
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山胁大辉
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Abstract

The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent adhesion, moisture permeation prevention, and low liquid crystal contamination, and which can provide a liquid crystal display element having excellent impact resistance. 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, which contains a curable resin, a non-reactive polymer having high compatibility with the curable resin and having no functional group capable of reacting with the curable resin, and further contains a polymerization initiator and/or a thermal curing agent.

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 has excellent adhesiveness, moisture permeation prevention, and low liquid crystal contamination, and which can provide a liquid crystal display element having excellent impact resistance. 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 such as a liquid crystal display unit, a method called a liquid crystal dropping method using a photo-thermal curable sealing agent as disclosed in patent documents 1 and 2 has been used from the viewpoints of shortening of a tact time, optimization of a liquid crystal usage amount, and the like.
In the liquid crystal dropping process, first, a frame-shaped seal pattern is formed by dispensing on one of 2 substrates with electrodes. Then, in a state where the sealant is not cured, fine droplets of liquid crystal are dropped into a sealing frame of the substrate, another substrate is stacked under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform precuring. Thereafter, the liquid crystal display element is manufactured by heating and main curing. Currently, this one drop fill process is the mainstream of a method for manufacturing a liquid crystal display element.
However, in recent years in which various mobile devices with liquid crystal panels, such as mobile phones and portable game machines, have become widespread, miniaturization of the devices is the most sought-after problem. As a method for downsizing, narrowing of the edge of the liquid crystal display portion is exemplified, and for example, the position of the sealing portion is arranged under the black matrix (hereinafter, also referred to as "narrow-edge design"). With such a narrow-edge design, the distance from the pixel region to the sealant is reduced, and the sealant itself is drawn to be thin, and therefore, the conventional sealant is insufficient in adhesiveness, and there is a problem that a display failure of the liquid crystal display element is easily caused by moisture permeation, liquid crystal contamination, or the like.
Further, along with the spread of mobile terminals, impact resistance is increasingly required for liquid crystal display elements, and higher adhesiveness is required for a sealant so that peeling or the like of a panel is not caused even when an impact from the outside is received by dropping or the like of the liquid crystal display elements. However, it is difficult for conventional sealants to achieve both of such high adhesiveness and moisture permeation prevention and low liquid crystal contamination.
Documents of the prior art
Patent document
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
The purpose of the present invention is to provide a sealing agent for a liquid crystal display element, which has excellent adhesion, moisture permeation prevention, and low liquid crystal contamination, and which can provide a liquid crystal display element having excellent impact resistance. Further, the present invention aims 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: the curable resin composition further comprises a polymerization initiator and/or a thermal curing agent, and a non-reactive polymer which has high compatibility with the curable resin and does not have a functional group capable of reacting with the curable resin.
The present invention will be described in detail below.
The present inventors studied: by blending a plasticizer in the sealant for a liquid crystal display element, the adhesiveness of the sealant and the flexibility of the cured product are improved, and the impact resistance of the liquid crystal display element is improved. However, the obtained sealant has a problem of poor moisture permeation resistance. Therefore, the present inventors have conducted intensive studies and, as a result, have found that: the present inventors have found that a sealant for a liquid crystal display element, which is excellent in adhesiveness, moisture permeation resistance and low liquid crystal contamination and can provide a liquid crystal display element excellent in impact resistance, can be obtained by blending a specific non-reactive polymer into the sealant, 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 preferably contains a (meth) acrylic compound and/or an epoxy compound.
In the present specification, the "(meth) acrylic" means an acrylic or a methacrylic, the "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" means an acryloyl group or a methacryloyl group.
Examples of the (meth) acrylic compound include: (meth) acrylate compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Among them, epoxy (meth) acrylates are 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 "(meth) acrylate" means an acrylate or a methacrylate, and the "epoxy (meth) acrylate" means a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
Examples of the monofunctional compound in the (meth) acrylate compound 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, methoxyglycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and mixtures thereof, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-trifluoroethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropylphthalate, 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, 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) oxypropyl acrylate, carbonate diol di (meth) acrylate, polyether glycol di (meth) acrylate, polycaprolactone di (meth) acrylate, and the use thereof, polybutadiene diol di (meth) acrylate, and the like.
Examples of the 3-or more-functional compound in the (meth) acrylate compound 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, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound to be used as a raw material for synthesizing the epoxy (meth) acrylate include: bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2' -diallylbisphenol a type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol a type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenol novolac type epoxy resin, naphthol novolac type epoxy resin, glycidylamine type epoxy resin, alkyl polyhydric alcohol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, and the like.
Examples of commercially available products of the bisphenol A epoxy resin include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON 850CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products of the bisphenol F type epoxy resin include: jER806 and jER4004 (both manufactured by Mitsubishi chemical Co., ltd.), and the like.
Examples of commercially available products of the bisphenol S type epoxy resin include EPICLON EXA1514 (available from DIC).
Examples of commercially available products of the 2,2' -diallylbisphenol A-type epoxy resin include RE-810NM (manufactured by Nippon chemical Co., ltd.).
Examples of commercially available products of the above hydrogenated bisphenol epoxy resins include EPICLON EXA7015 (available from DIC).
Examples of commercially available products of the above propylene oxide-added bisphenol A epoxy resin include EP-4000S (manufactured by ADEKA).
Examples of commercially available products of the above resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX).
Examples of the commercially available biphenyl-type epoxy resin include jER YX-4000H (manufactured by mitsubishi chemical corporation).
Examples of commercially available products of the thioether-type epoxy resins include YSLV-50TE (manufactured by Nippon Tekken chemical Co., ltd.).
Examples of commercially available products of the above-mentioned diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Tekken chemical Co., ltd.).
Examples of commercially available products of the above-mentioned dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Commercially available products of the naphthalene epoxy resin include EPICLON HP4032 and EPICLON EXA-4700 (both produced by DIC).
Examples of the commercially available phenol novolac epoxy resin include EPICLON-770 (available from DIC).
Examples of the commercially available products of the o-cresol novolac-type epoxy resin include EPICLON-670-EXP-S (available from DIC).
Examples of commercially available products of the dicyclopentadiene phenol type epoxy resin include EPICLON HP7200 (manufactured by DIC).
Examples of the commercially available products of the above-mentioned diphenolaldehyde type epoxy resin include NC-3000P (manufactured by Nippon chemical Co., ltd.).
Examples of the commercially available products of the naphthol novolac type epoxy resins include ESN-165S (manufactured by Nissian chemical Co., ltd.).
Among the glycidyl amine type epoxy resins, commercially available products include, for example: jeR630 (manufactured by Mitsubishi chemical corporation), EPICLON 430 (manufactured by DIC corporation), TETRAD-X (manufactured by Mitsubishi gas chemical corporation), and the like.
Examples of commercially available products of the above-mentioned alkyl polyol type epoxy resin include: ZX-1542 (Nippon Tekken chemical Co., ltd.), EPICLON 726 (DIC Co., ltd.), eplight 80MFA (Kyoeisha chemical Co., ltd.), DENACOL EX-611 (Nagase ChemteX Co., ltd.), and the like.
Among the rubber-modified epoxy resins, commercially available products include, for example: YR-450, YR-207 (both manufactured by Nippon Tekken chemical Co., ltd.), epolead PB (manufactured by Daiiol Co., ltd.), and the like.
Examples of commercially available products of the glycidyl ester compounds include DENACOL EX-147 (manufactured by Nagase ChemteX).
Examples of other commercially available products of the above epoxy compounds include: YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Tekken chemical Co., ltd.), XAC4151 (manufactured by Asahi Kasei Chemicals Co., ltd.), jER1031, jER1032 (all 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 commercially available products of the above epoxy (meth) acrylates include: epoxy (meth) acrylate manufactured by DAICEL-ALLNEX, epoxy (meth) acrylate manufactured by Xinzhongcun chemical industries, epoxy (meth) acrylate manufactured by Kyowa Kagaku chemical industries, epoxy (meth) acrylate manufactured by Nagase ChemteX, and the like.
Examples of the epoxy (meth) acrylate manufactured by DAICEL-ALLNEX include: EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, EBECRYL RDX63182 and the like.
Examples of the epoxy (meth) acrylate produced by the above-mentioned Nikamura chemical industries include: EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020, etc.
Examples of the epoxy (meth) acrylate produced by Kyoeisha chemical company include: EPOXY ESTER M-600A, EPXY ESTER 40EM, EPXY ESTER 70PA, EPXY ESTER 200PA, EPXY ESTER 80MFA, EPXY ESTER 3002M, EPXY ESTER 3002A, EPXY ESTER 1600A, EPXY ESTER 3000M, EPXY ESTER 3000A, EPXY ESTER 200EA, EPXY ESTER 400EA, and the like.
Examples of the epoxy (meth) acrylate produced by Nagase ChemteX include: DENACOL ACRYLATE DA-141, DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911, and the like.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with an isocyanate compound in the presence of a catalytic amount of a tin compound.
Examples of the isocyanate compound include: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene 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.
Further, as the above isocyanate compound, a chain-extended isocyanate compound obtained by a reaction of a polyol with an excess amount of an isocyanate compound may also be used.
Examples of the polyol include: ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol, and the like.
Examples of the (meth) acrylic acid derivative having a hydroxyl group include: hydroxyalkyl mono (meth) acrylates, mono (meth) acrylates of diols, mono (meth) acrylates or di (meth) acrylates of triols, epoxy (meth) acrylates, and the like.
Examples of the hydroxyalkyl mono (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Examples of the above-mentioned dihydric alcohol include: ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, polyethylene glycol, and the like.
Examples of the trihydric alcohol include: trimethylolethane, trimethylolpropane, glycerol, etc.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylates.
Among the above urethane (meth) acrylates, commercially available ones include, for example: urethane (meth) acrylate manufactured by Toyo Synthesis, urethane (meth) acrylate manufactured by DATCEL-ALLNEX, urethane (meth) acrylate manufactured by Yokohama chemical industries, urethane (meth) acrylate manufactured by Xinzhou chemical industries, urethane (meth) acrylate manufactured by Kyowa chemical industries, and the like.
Examples of the urethane (meth) acrylate produced by the above-mentioned east asian synthesis company include: m-1100, M-1200, M-1210, M-1600 and the like.
Examples of the urethane (meth) acrylate produced by the DAICEL-ALLNEX company include: EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807, EBECRYL9260 and the like.
Examples of the urethane (meth) acrylate produced by the above-mentioned industrial company include: art Resin UN-330, art Resin SH-500B, art Resin UN-1200TPK, art Resin UN-1255, art Resin UN-3320HB, art Resin UN-7100, art Resin UN-9000A, art Resin UN-9000H and the like.
Examples of the urethane (meth) acrylate produced by the above-mentioned Nikamura chemical industries include: u-2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U-108A, U-122P, U-324A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200, UA-W2A, and the like.
Examples of the urethane (meth) acrylate produced by Kyoeisha chemical company include: AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, etc.
Examples of the epoxy compound include: epoxy compounds and partially (meth) acrylic acid-modified epoxy resins which are raw materials for synthesizing the epoxy (meth) acrylate.
In the present specification, the partially (meth) acrylic-modified epoxy resin means a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in each molecule, and can be obtained, for example, by reacting a part of epoxy groups of an epoxy compound having 2 or more epoxy groups in 1 molecule with (meth) acrylic acid.
Examples of commercially available products of the partially (meth) acrylic-modified epoxy resin include UVACURE1561 (manufactured by DAICEL-ALLNEX).
When the sealant for a liquid crystal display element of the present invention contains the (meth) acrylic compound and the epoxy compound, the ratio of the (meth) acryloyl group in the total of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 30 mol% or more and 95 mol% or less. By setting the ratio of the (meth) acryloyl group in this range, the occurrence of liquid crystal contamination is suppressed, and the obtained sealant for a liquid crystal display element is more excellent in adhesiveness.
From the viewpoint of further suppressing liquid crystal contamination, the curable resin preferably has-OH group, -NH-group, or-NH group 2 Hydrogen bonding units such as radicals.
The sealant for a liquid crystal display element of the present invention contains a non-reactive polymer having high compatibility with the curable resin and having no functional group capable of reacting with the curable resin (hereinafter, also referred to as "non-reactive polymer of the present invention"). The liquid crystal display element sealant of the present invention can achieve both excellent adhesion and excellent moisture permeation prevention by containing the non-reactive polymer of the present invention.
In the present specification, the above-mentioned "high compatibility with a curable resin" means the following state.
Specifically, first, 30 parts by weight of a non-reactive polymer was mixed with 100 parts by weight of a curable resin at 25 ℃ and then mixed with a stirrer (manufactured by Thinky corporation, "12354\ 1243192929226
Figure BDA0002120162220000091
Tarar ARE-310 ") was stirred at 1000rpm for 10 minutes. Thereafter, the mixture was left to stand for 10 minutes, and then the mixture was equally divided into 5 containers, and when the components contained in the containers were analyzed by LC-MS, the composition ratio of the components contained in the containers and the composition ratio of the components at the time of mixing were determinedThe difference in the composition ratio is all within 2%.
The non-reactive polymer of the present invention does not have a functional group capable of reacting with the curable resin.
The functional group capable of reacting with the curable resin depends on the type of the curable resin used, and specific examples thereof include: (meth) acryloyl, epoxy, hydroxyl, amino, carboxyl, and the like.
The non-reactive polymer of the present invention is preferably a non-functional (meth) acrylic polymer, because the obtained sealant for a liquid crystal display element is more excellent in low liquid crystal contamination.
The weight average molecular weight of the non-reactive polymer of the present invention has a preferred lower limit of 1000 and a preferred upper limit of 1 ten thousand. By making the weight average molecular weight of the non-reactive polymer of the present invention 1000 or more, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness and the obtained liquid crystal display element is more excellent in impact resistance. By making the weight average molecular weight of the non-reactive polymer of the present invention 1 ten thousand or less, the obtained sealant for a liquid crystal display element is more excellent in drawing property. A more preferred lower limit and a more preferred upper limit of the weight average molecular weight of the non-reactive polymer of the present invention is 1500, and a more preferred upper limit is 8000.
In the present specification, the weight average molecular weight is a value determined by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko K.K.).
The preferred upper limit of the glass transition temperature of the non-reactive polymer of the present invention is-30 ℃. The sealant for a liquid crystal display element of the present invention has more excellent adhesiveness when the glass transition temperature is-30 ℃ or lower. A more preferable upper limit of the glass transition temperature is-50 ℃.
From the viewpoint of moisture permeability resistance, the lower limit of the glass transition temperature of the cured product is preferably-100 ℃ and the more preferred lower limit is-80 ℃.
In the present specification, the "glass transition temperature" means a temperature at which a maximum value due to micro brownian motion appears among maximum values of loss tangent (tan δ) obtained by dynamic viscoelasticity measurement. The glass transition temperature can be measured by a conventionally known method using a viscoelasticity measuring apparatus or the like.
The content of the non-reactive polymer of the present invention has a preferable lower limit of 5 parts by weight and a preferable upper limit of 150 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the non-reactive polymer of the present invention to 5 parts by weight or more, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness. By setting the content of the non-reactive polymer of the present invention to 150 parts by weight or less, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness and moisture permeation resistance, and the cured product can be prevented from becoming brittle. A more preferable lower limit of the content of the non-reactive polymer of the present invention is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.
The content of the non-reactive polymer of the present invention in 100 parts by weight of the sealant for liquid crystal display elements of the present invention has a preferred lower limit of 5 parts by weight and a preferred upper limit of 60 parts by weight. By setting the content of the non-reactive polymer of the present invention to 5 parts by weight or more, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness. By setting the content of the non-reactive polymer of the present invention to 60 parts by weight or less, the obtained sealant for a liquid crystal display element is more excellent in adhesiveness and moisture permeation resistance, and the cured product can be prevented from becoming brittle. A more preferred lower limit of the content of the non-reactive polymer of the present invention is 15 parts by weight, and a more preferred upper limit is 45 parts by weight.
The sealant for a liquid crystal display element of the present invention contains a polymerization initiator and/or a thermal curing agent.
Examples of the polymerization initiator include: a radical polymerization initiator, a cationic polymerization initiator, and the like.
Examples of the radical polymerization initiator include: a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.
Examples of the photo radical polymerization initiator include: benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
Examples of commercially available products of the photo radical polymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1,2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholino) phenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyloxime), 2,4, 6-trimethylbenzoyldiphenyl phosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
The photo radical polymerization initiator may be used alone, or two or more of them may be used in combination.
Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides. Among them, a polymeric azo initiator containing a polymeric azo compound is preferable.
The thermal radical polymerization initiator may be used alone or in combination of two or more.
In the present specification, the macromolecular azo compound means a compound having an azo group, which generates a radical capable of curing a (meth) acryloyloxy group by heat, and having a number average molecular weight of 300 or more.
The number average molecular weight of the macromolecular azo compound has a preferred lower limit of 1000 and a preferred upper limit of 30 ten thousand. When the number average molecular weight of the macromolecular azo compound is in this range, adverse effects on liquid crystals can be prevented and the compound can be easily mixed into a curable resin. A more preferable lower limit of the number average molecular weight of the macromolecular azo compound is 5000, a more preferable upper limit is 10 ten thousand, a further more preferable lower limit is 1 ten thousand, and a further more preferable upper limit is 9 ten thousand.
In the present specification, the number average molecular weight is a value determined by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and in terms of polystyrene. 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 macromolecular azo compound include a macromolecular azo compound having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
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 macromolecular azo compound 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.
Among the above-mentioned polymeric azo initiators, commercially available products include, for example: VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fuji film and Wako pure chemical industries, ltd.), and the like. Examples of the non-polymer azo initiator include: v-65 and V-501 (both manufactured by Fuji film and Wako pure chemical industries, ltd.), and the like.
Examples of the organic peroxide include: ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, and the like.
As the cationic polymerization initiator, a photo cationic polymerization initiator can be suitably used. The photo cation polymerization initiator is not particularly limited as long as it generates a protonic acid or a lewis acid by irradiation with light, and may be of an ionic photo acid generation type or a nonionic photo acid generation type.
Examples of the photo cation polymerization initiator include: and organic metal complexes such as onium salts including aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes.
Examples of commercially available products of the above-mentioned photocationic polymerization initiator include: ADEKA OPTOMER SP-150, ADEKA OPTOMER SP-170 (both manufactured by ADEKA Co., ltd.), 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 curable resin. By setting the content of the polymerization initiator to 0.1 parts by weight or more, the obtained sealant for a liquid crystal display element is more excellent in curability. By setting the content of the polymerization initiator to 30 parts by weight or less, the storage stability of the obtained sealant for a liquid crystal display element is further improved. 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 further preferably 5 parts by weight.
Examples of the thermosetting agent include: organic acid hydrazide, imidazole derivative, amine compound, polyphenol compound, acid anhydride, and the like. Among them, organic acid hydrazide can be preferably used.
The heat-curing agent may be used alone or in combination of two or more.
Examples of the organic acid hydrazide include: sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide, and the like.
Examples of commercially available products of the organic acid hydrazide include: an organic acid hydrazide manufactured by Otsuka chemical company, an organic acid hydrazide manufactured by Aomoto Fine Technical company, and the like.
Examples of the organic acid hydrazide produced by Otsuka chemical company include SDH and ADH.
Examples of the organic acid hydrazide produced by the aforementioned ajinomoto fine technologies include: amicure VDH, amicure VDH-J, amicure UDH-J, and the like.
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 with respect to 100 parts by weight of the curable resin. By setting the content of the thermosetting agent within this range, the obtained sealant for a liquid crystal display element can be made more excellent in thermosetting property without deteriorating coatability and the like. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
The sealant for a liquid crystal display element of the present invention preferably contains a filler in order to adjust the viscosity, further improve the adhesiveness by the stress dispersion effect, improve the linear expansion coefficient, further improve the moisture permeation resistance of the cured product, and the like.
As the filler, an inorganic filler or an organic filler can be used.
Examples of the inorganic filler include: silica, talc, glass beads, asbestos, gypsum, diatomaceous 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, calcium silicate, and the like.
Examples of the organic filler include: polyester microparticles, polyurethane microparticles, vinyl polymer microparticles, acrylic polymer microparticles, and the like.
The fillers may be used alone or in combination of two or more.
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 effects such as further improvement in adhesiveness can be obtained without deteriorating the drawing property 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. The silane coupling agent mainly functions as an adhesion aid for better adhesion of the sealant to a substrate or the like.
As the silane coupling agent, for example, there can be suitably used: 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like. These silane coupling agents have an excellent effect of improving adhesion to a substrate or the like, and can inhibit the outflow of a curable resin into a liquid crystal by chemically bonding with the curable resin.
The silane coupling agents may be used alone or in combination of two or more.
The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the 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 in this range, the effects such as suppression of liquid crystal contamination and further improvement of adhesion are further improved. A more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and a more preferable upper limit is 5 parts by weight.
The sealant for a liquid crystal display element of the present invention may contain a light-shading agent. The inclusion of the light-shading agent makes the sealant for a liquid crystal display element of the present invention suitable for use as a light-shading sealant.
Examples of the light-shading agent include: iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, and the like. 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 370nm to 450nm, than the average transmittance for light at a wavelength of 300nm 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 provides 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 exerts a sufficient effect even without being surface-treated, but a titanium black surface-treated with an organic component such as a coupling agent may be used; 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. Among them, titanium black treated with an organic component is preferable from the viewpoint of further improving the insulation property.
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 high contrast without light leakage and excellent image display quality can be realized.
Examples of commercially available products of the titanium black include: titanium black manufactured by Mitsubishi Materials, titanium black manufactured by Red spiking chemical company, and the like.
Examples of the titanium black manufactured by Mitsubishi Materials include: 12S, 13M-C, 13R-N, 14M-C, and the like.
Examples of the titanium black produced by the aforementioned gibbing chemical company include Tilack D.
The lower limit of the specific surface area of the titanium black is preferably 13m 2 A preferred upper limit is 30m 2 A more preferred lower limit is 15m 2 A more preferred upper limit is 25 m/g 2 /g。
The volume resistance of the titanium black has a preferable lower limit of 0.5 Ω · em, a preferable upper limit of 3 Ω · cm, a more preferable lower limit of 1 Ω · em, and a more preferable upper limit of 2.5 Ω · em.
The primary particle size of the light-shading agent is not particularly limited as long as it is not more than the distance between substrates of the liquid crystal display device, and a preferable lower limit is 1nm and a preferable upper limit is 5000nm. By setting the primary particle size of the light-shielding agent in this range, it is possible to obtain a liquid crystal display element sealant having more excellent light-shielding properties without deteriorating the drawing properties and the like of the sealant. A more preferable lower limit of the primary particle diameter of the light-shading agent is 5nm, a more preferable upper limit is 200nm, a further more preferable lower limit is 10nm, and a further more preferable upper limit is 100nm.
The primary PARTICLE size of the light-screening agent can be measured by dispersing the light-screening agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by part 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 obtained sealant for a liquid crystal display element can exhibit more excellent light-shielding properties without significantly reducing the adhesiveness, strength after curing, and drawing properties. The content of the light-shading agent is preferably 10 parts by weight at the lower limit, 70 parts by weight at the upper limit, 30 parts by weight at the lower limit, and 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 reactive diluent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, and a polymerization inhibitor as needed.
Examples of a method for producing the sealant for a liquid crystal display element of the present invention include a method in which a curable resin, a polymerization initiator and/or a heat-curing agent, the non-reactive polymer of the present invention, and a silane coupling agent added as needed are mixed using a mixer.
Examples of the mixer include: homogenizing disperser, homogenizing mixer, universal mixer, planetary mixer, kneading machine, three-roller machine, etc.
The sealant for a liquid crystal display element of the present invention is blended with conductive fine particles, whereby 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, metal balls, a resin fine particle having a conductive metal layer formed on the surface thereof, or the like can be used. Among these, the conductive fine particles having the conductive metal layer formed on the surface of the resin fine particles are preferable because the conductive connection can be performed without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
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.
As a method for manufacturing the liquid crystal display element of the present invention, a liquid crystal dropping method can be suitably used, and specifically, for example, a method having the following steps can be mentioned.
First, the following steps are performed: the sealing agent for a liquid crystal display element of the present invention is applied to one of 2 substrates such as a glass substrate with an electrode such as an ITO film and a polyethylene terephthalate substrate by screen printing, dispenser application, or the like to form a frame-shaped seal pattern. Next, the following steps are performed: in the uncured state of the sealant for a liquid crystal display element of the present invention, fine droplets of liquid crystal are applied dropwise to the inside of a frame of a seal pattern of a substrate, and the other substrate is stacked under vacuum. Then, a step of pre-curing the sealant by irradiating a 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 main-curing the pre-cured sealant by heating are performed, and a liquid crystal display element can be obtained by this method.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a sealant for a liquid crystal display element, which is excellent in adhesiveness, moisture permeation resistance, and low liquid crystal contamination, and which can provide a liquid crystal display element having excellent impact resistance. 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.
(examples 1 to 11 and comparative examples 1 to 3)
According to the blending ratios described in tables 1 and 2, a planetary mixer (manufactured by Thinky Co., ltd.) "あねとり
Figure BDA0002120162220000171
Taro ") were mixed, and then mixed using a three-roll mill, thereby preparing the liquid crystal display element sealants of examples 1 to 11 and comparative examples 1 to 3.
"ARUFON UP-1021" in the tables is the nonfunctional acrylic polymer having no functional group capable of reacting with a curable resin (weight average molecular weight 1600, glass transition temperature-71 ℃ C.) used in examples 1 to 5 and 11. Further, 30 parts by weight (total 260 g) of "ARUFON UP-1021" was mixed with 100 parts by weight of the curable resin at 25 ℃, and then the mixture was stirred by a stirrer (manufactured by Thinky corporation, "123549712392929212426
Figure BDA0002120162220000172
Taran ARE-310 ") at 1000rpm for 10 minutes. Thereafter, the mixture was allowed to stand for 10 minutes, and then, the mixture was equally divided into 5 containers, and when the components contained in the respective containers were analyzed by LC-MS, it was confirmed that the differences between the constituent ratios of the components contained in the respective containers and the constituent ratios of the components at the time of mixing were all within 2%.
"ARUFON UP-1170" in the tables is the nonfunctional acrylic polymer having no functional group capable of reacting with a curable resin (weight average molecular weight 8000, glass transition temperature-57 ℃) used in examples 6 to 10. Further, 30 parts by weight (total 260 g) of "ARUFON UP-1170" was mixed with 100 parts by weight of the curable resin at 25 ℃, and then the mixture was stirred by a stirrer (manufactured by Thinky corporation, "123549712392929212426
Figure BDA0002120162220000173
Tarar ARE-310 ") at 1000rpm for 10 minutes. Then, after leaving to stand for 10 minutes, the mixture was equally divided into 5 containers, and when the components contained in each container were analyzed by LC-MS, it was confirmed that the differences between the constituent ratios of the components contained in the respective containers and the constituent ratio of the components at the time of mixing were all within 2%.
In the table "ARUFON UH-20Reference numeral 41 "denotes an acrylic polymer having a hydroxyl group as a functional group capable of reacting with a curable resin (weight average molecular weight 2500, glass transition temperature-50 ℃ C.) used in comparative example 2. Further, 30 parts by weight of "ARUFON UH-2041" (total 260 g) was mixed with 100 parts by weight of the curable resin at 25 ℃ and then the mixture was stirred with a stirrer (manufactured by Thinky, inc. "\ 12354971239212426
Figure BDA0002120162220000181
Tarar ARE-310 ") at 1000rpm for 10 minutes. Thereafter, the mixture was allowed to stand for 10 minutes, and then, the mixture was equally divided into 5 containers, and when the components contained in the respective containers were analyzed by LC-MS, it was confirmed that the differences between the constituent ratios of the components contained in the respective containers and the constituent ratios of the components at the time of mixing were all within 2%.
"ARUFON UG-4010" in the table is an acrylic polymer having an epoxy group as a functional group capable of reacting with a curable resin (weight average molecular weight 2900, glass transition temperature-57 ℃) used in comparative example 3. Further, 30 parts by weight (total 260 g) of "ARUFON UG-4010 was mixed with 100 parts by weight of the curable resin at 25 ℃, and then the mixture was stirred with a stirrer (manufactured by Thinky corporation," 12354\12397123921242692
Figure BDA0002120162220000182
Tarar ARE-310 ") at 1000rpm for 10 minutes. Then, after leaving to stand for 10 minutes, the mixture was equally divided into 5 containers, and when the components contained in each container were analyzed by LC-MS, it was confirmed that the differences between the constituent ratios of the components contained in the respective containers and the constituent ratio of the components at the time of mixing were all within 2%.
< evaluation >
The following evaluations were made on the sealants for liquid crystal display elements obtained in examples and comparative examples. The results are shown in tables 1 and 2.
(descriptive Properties)
1 part by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples was added to 100 parts by weight of each of the sealantsSpacer particles having an average particle diameter of 5 μm (manufactured by Water-logging chemical industries, ltd. "Micropearl SP-2050") were uniformly dispersed. Next, the sealant in which the spacer particles were dispersed was filled in a syringe for dispensing ("PSY-10E" manufactured by Musashi Engineering, inc.), and after a defoaming treatment, the sealant was applied to one of 2 transparent substrates with an ITO film by using a dispenser ("SHOTMASTER 300") so as to draw a rectangular frame. Next, another transparent substrate was bonded under a reduced pressure of 5Pa using a vacuum bonding apparatus, thereby obtaining a cell. The obtained unit was irradiated with 100mW/cm using a metal halide lamp 2 After 30 seconds, the sealant was cured by heating at 120 ℃ for 1 hour to obtain a test piece. The sealant in the obtained test piece was observed, and the drawing property was evaluated by assuming that the sealant was "excellent" in the case where the sealant drawn a perfect line without disconnection failure and fluctuation, assuming that the sealant did not have disconnection failure but slightly fluctuated, "Δ" in the case where the sealant did not have disconnection failure but largely fluctuated, "and" x "in the case where the disconnection failure occurred.
(adhesiveness)
1 part by weight of spacer particles (Micropearl SI-H050, manufactured by Water chemical industries, ltd.) were dispersed in 100 parts by weight of each of the sealants for liquid crystal display elements obtained in examples and comparative examples. The sealant in which the spacer particles were dispersed was dispenser-coated with a line width of 1mm of the sealant so that the display portion became 45mm × 55mm on one of 2 substrates (length 75mm, width 75mm, thickness 0.7 mm) with the rubbed alignment film and the transparent electrode. Then, minute droplets of liquid crystal ("JC-5004 LA", manufactured by Chisso corporation) were applied dropwise to the entire surface of the frame of the sealant coated on the substrate with the transparent electrode, and the other substrate was immediately bonded. Next, the sealant portion was irradiated with 100mW/cm using a metal halide lamp 2 30 seconds, and then heated at 120 ℃ for 1 hour, thereby producing 10 pieces of the sealing agent for liquid crystal display elements obtained in examples and comparative examples, each of which was used to prepare 10 individual liquid crystal display elementsAnd (5) Yuan.
A drop test was performed to drop each liquid crystal display element from a height of 2 m. After the drop test, the adhesiveness was evaluated by assuming that the liquid crystal was not leaked due to peeling or cracking in all the cells as "excellent", assuming that the liquid crystal was leaked in the liquid crystal display elements of 1 cell or more and less than 4 cells as "o", assuming that the liquid crystal was leaked in the liquid crystal display elements of 4 cells or more and less than 7 cells as "Δ", and assuming that the liquid crystal was leaked in the liquid crystal display elements of 7 cells or more as "x".
(moisture permeability prevention)
The sealants for liquid crystal display elements obtained in examples and comparative examples were applied in a thickness of 200 to 300 μm in a smooth release film form using a coater. Next, the applied sealant was irradiated with 100mW/cm using a metal halide lamp 2 After 30 seconds, the sealant was cured by heating at 120 ℃ for 1 hour to obtain a cured film for moisture permeability measurement. The moisture permeability test cup was prepared by the method according to the moisture permeability test method (cup method) of the moisture-proof packaging material according to JIS Z0208, the obtained cured film for moisture permeability measurement was mounted, and the film was put into a constant-temperature and constant-humidity oven at a temperature of 60 ℃ and a humidity of 90% rh to measure the moisture permeability. The moisture permeability is less than 200g/m 2 24hr is [ ], and 200g/m 2 24hr or more and less than 250g/m 2 24hr as ". Smallcircle", 250g/m 2 24hr or more and less than 300g/m 2 24hr case is designated as "Δ", and 300g/m 2 The moisture permeability resistance was evaluated by assuming that 24hr or more was "x".
(Low liquid Crystal contamination)
The sealant for liquid crystal display elements obtained in examples and comparative examples was prepared in the same manner as in the "adhesiveness" described above to prepare liquid crystal display elements.
After the obtained liquid crystal display element was subjected to a 100-hour operation test, the alignment of liquid crystal was visually observed to be disturbed in a state where a voltage was applied at 80 ℃ for 1000 hours.
The liquid crystal alignment disorder was judged from color unevenness in the peripheral portion and the display portion, and the low liquid crystal contamination was evaluated by assuming that "o" was the case where no color unevenness was present at all, "Δ" was the case where a little color unevenness was observed in the peripheral portion, and "x" was the case where the color unevenness had spread to the display portion.
[ Table 1]
Figure BDA0002120162220000211
[ Table 2]
Figure BDA0002120162220000221
Industrial applicability
The present invention provides a sealant for a liquid crystal display element, which is excellent in adhesiveness, moisture permeation resistance, and low liquid crystal contamination, and which can provide a liquid crystal display element having excellent impact resistance. 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, a non-reactive polymer which has high compatibility with the curable resin and does not have a functional group capable of reacting with the curable resin, and further comprising a polymerization initiator and/or a thermal curing agent,
the curable resin contains an epoxy (meth) acrylate.
2. The sealant for a liquid crystal display element according to claim 1, wherein the non-reactive polymer is a non-functional (meth) acrylic polymer.
3. The sealant for a liquid crystal display element according to claim 1 or 2, wherein a weight average molecular weight of the non-reactive polymer is 1000 or more and 1 ten thousand or less.
4. The sealant for a liquid crystal display element according to claim 1 or 2, wherein the glass transition temperature of the non-reactive polymer is-30 ℃ or lower.
5. The sealant for a liquid crystal display element according to claim 1 or 2, wherein a content of the non-reactive polymer is 5 parts by weight or more and 150 parts by weight or less with respect to 100 parts by weight of the curable resin.
6. A vertically conducting material comprising the sealing agent 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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