CN113924351A - Sealing agent for display element, vertical conduction material and display element - Google Patents
Sealing agent for display element, vertical conduction material and display element Download PDFInfo
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- CN113924351A CN113924351A CN202080040561.8A CN202080040561A CN113924351A CN 113924351 A CN113924351 A CN 113924351A CN 202080040561 A CN202080040561 A CN 202080040561A CN 113924351 A CN113924351 A CN 113924351A
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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- 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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
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- Electroluminescent Light Sources (AREA)
- Epoxy Resins (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The purpose of the present invention is to provide a sealing agent for a display element, which can provide a display element having excellent reliability in a high-temperature and high-humidity environment. Further, the present invention aims to provide a vertical-conduction material and a display element using the sealant for a display element. The sealing agent for a display element comprises a curable resin and a polymerization initiator and/or a thermal curing agent, wherein the glass transition temperature of a cured product is 125 ℃ or higher, and the cure shrinkage rate after a high-temperature high-humidity test in which the cured product is exposed for 48 hours in an environment of 121 ℃, 100% RH and 2atm is 5% or lower.
Description
Technical Field
The present invention relates to a sealing agent for a display element, which can provide a display element having excellent reliability in a high-temperature and high-humidity environment. The present invention also relates to a vertical-conduction material and a display element using the sealant for a display element.
Background
In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having features such as thin thickness, light weight, and low power consumption. In these display elements, sealing of a liquid crystal, a light emitting layer, and the like is generally performed by a sealant using a curable resin composition.
For example, from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used, liquid crystal display elements using a photo-thermal curable sealant as disclosed in patent documents 1 and 2 are disclosed.
Further, as high reliability in driving under a high-temperature and high-humidity environment, a display device is required to have performance corresponding to a Pressure Cooker Test (PCT) under conditions of 121 ℃, 100% RH, and 2 atm. In order to obtain a highly reliable display element, it is necessary to make the sealant excellent in moist heat resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication 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 display element, which can provide a display element having excellent reliability in a high-temperature and high-humidity environment. Further, the present invention aims to provide a vertical-conduction material and a display element using the sealant for a display element.
Means for solving the problems
The present invention is a sealing agent for a display element, which contains a curable resin and a polymerization initiator and/or a thermal curing agent, wherein the glass transition temperature of a cured product is 125 ℃ or higher, and the cure shrinkage rate after a high-temperature high-humidity test in which the cured product is exposed to an environment of 121 ℃, 100% RH, and 2atm for 48 hours is 5% or lower.
The present invention will be described in detail below.
The present inventors confirmed that a display element in which a display failure occurred during driving in a high-temperature and high-humidity environment had entered air bubbles. Therefore, the present inventors have studied that the glass transition temperature of a cured product of a sealing agent for a display element is a specific value or more, and the cure shrinkage rate of the cured product after exposure to a high-temperature and high-humidity test for 48 hours in an environment of 121 ℃, 100% RH, and 2atm is a specific value or less. As a result, they have found that a sealing agent for a display element, which can suppress the intrusion of bubbles and can obtain a display element having excellent reliability under a high-temperature and high-humidity environment, can be obtained, and have completed the present invention.
The effect of the sealant for a display element of the present invention that a display element having excellent reliability in a high-temperature and high-humidity environment can be obtained is particularly exhibited when the sealant for a display element of the present invention is used as a sealant for a liquid crystal display element.
The lower limit of the glass transition temperature of the cured product of the sealing agent for a display element of the present invention is 125 ℃. When the glass transition temperature of the cured product is 125 ℃ or higher and the cure shrinkage ratio described later is 5% or less, the obtained sealing agent for a display element has an excellent effect of suppressing the intrusion of bubbles in a high-temperature and high-humidity environment. The glass transition temperature of the cured product preferably has a lower limit of 130 ℃ and a more preferred lower limit of 135 ℃.
From the viewpoint of adhesiveness, the preferable upper limit of the glass transition temperature of the cured product is 160 ℃.
In the present specification, the "glass transition temperature" means: the maximum value of the loss tangent (tan δ) obtained by the dynamic viscoelasticity measurement is a temperature at which a maximum value due to the micro brownian motion appears. The glass transition temperature can be measured by a conventionally known method using a dynamic viscoelasticity measuring apparatus or the like.
As a cured product for measuring the glass transition temperature, the following cured products were used: the sealant was irradiated with a metal halide lamp for 30 seconds at 100mW/cm2The ultraviolet ray (wavelength: 365nm) of (A) was then heated at 120 ℃ for 1 hour to cure the resin composition.
The upper limit of the cure shrinkage after the high-temperature high-humidity test in which a cured product is exposed to an environment of 121 ℃, 100% RH, and 2atm for 48 hours is 5%. By setting the cure shrinkage to 5% or less and the glass transition temperature of the cured product to 125 ℃ or more, the obtained sealing agent for a display element has an excellent effect of suppressing the intrusion of bubbles in a high-temperature and high-humidity environment. The upper limit of the cure shrinkage is preferably 4.8%, and more preferably 4.5%.
The lower limit of the cure shrinkage is not particularly limited, and the lower limit is substantially 3%.
In the present specification, the "curing shrinkage" is a specific gravity of the sealant for display element before curing at 25 ℃ represented by GAG represents a specific gravity of a cured product after a high temperature and high humidity test at 25 ℃BThe value is calculated by the following formula.
Cure shrinkage (%) ═ GB-GA)/GB)×100
As a cured product subjected to the high temperature and high humidity test, a sealant was irradiated for 30 seconds at 100mW/cm2And then heated at 120 ℃ for 1 hour to cure the resin composition.
The reason why intrusion of bubbles can be suppressed by using the sealant for a display element of the present invention is considered as follows.
Namely, it is considered that: since the curing shrinkage in the high-temperature and high-humidity environment described above occurs, a path through which moisture enters the cured product is generated, and the moisture entering the path turns into water vapor to generate bubbles. The glass transition temperature of the cured product of the sealing agent for a display element of the present invention is 125 ℃ or higher, and the cure shrinkage rate after the high-temperature and high-humidity test is 5% or less, and therefore, it is estimated that the formation of such a path is suppressed.
In the sealing agent for a display element of the present invention, as a method for setting the glass transition temperature and the cure shrinkage ratio of the cured product to the above ranges, a method for adjusting the types and the content ratios of the respective components contained in the sealing agent for a display element is preferable.
As a method for adjusting the glass transition temperature of the cured product to the above range, for example, a curable resin having a hard skeleton such as a bisphenol a type skeleton, a polyfunctional curable resin for increasing the crosslinking density, a methacryl Ratio (Methacrylic Ratio) described later, and the like can be used, but the method is not limited thereto. In addition, as a method for setting the curing shrinkage ratio to the above range, for example, a method of reducing a crosslinking density of the curable resin, a method of reducing a content ratio of a (meth) acryloyl group in a total of a (meth) acryloyl group and an epoxy group in the curable resin described later, and the like are conceivable, but the method is not limited to these methods.
The sealant for a display element of the present invention contains a curable resin.
The curable resin preferably contains a compound having a (meth) acryloyl group.
By including the compound having a (meth) acryloyl group, the obtained sealant for a display element is excellent in low liquid crystal contamination property when used as a sealant for a liquid crystal display element. Among them, the curable resin more preferably contains a compound having a methacryloyl group, from the viewpoint of facilitating the setting of the glass transition temperature in the above range.
In the present specification, the "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group.
When the curable resin contains the compound having a methacryloyl group, the methacryloyl group ratio represented by the following formula (I) is preferably 0.5 or more. When the methacryl ratio is 0.5 or more, the glass transition temperature can be more easily set to the above range. The methacryl ratio is more preferably 0.6 or more.
(ii) methacryl ratio ═ WM/EM)/(WA/EA+WM/EM) (I)
In the formula (I), EAIs the acryloyl equivalent (g/mol) of the compound having an acryloyl group, EMMethacryloyl equivalent (g/mol), W, of a compound having a methacryloyl groupAIs the content (parts by weight) of a compound having an acryloyl group, WMIs the content (parts by weight) of the compound having a methacryloyl group.
The "acryloyl equivalent weight" is a value obtained by dividing the weight (g) of the compound having an acryloyl group by the number of moles (mol) of acryloyl groups contained in the compound having an acryloyl group. When the curable resin contains a plurality of the compounds having an acryloyl group (A1, A2,. cndot. cndot.), "W" in the formula (I)A/EA"means that: the sum of the values obtained by dividing the content of the compound having an acryloyl group by the equivalent weight of the acryloyl group (W) for each compound having an acryloyl groupA1/EA1+WA2/EA2+. cndot.). In the case where the curable resin does not contain the compound having an acryloyl group, the "W" in the formula (I)A/EA"is set to 0.
The "methacryloyl equivalent" is a value obtained by dividing the weight (g) of a compound having a methacryloyl group by the number of moles (mol) of methacryloyl groups contained in the compound having a methacryloyl group. When the curable resin contains a plurality of the compounds having a methacryloyl group (M1, M2,. cndot. cndot.), "W" in the formula (I)M/EM"means that: the sum of the values (W) obtained by dividing the content of the compound having a methacryloyl group by the equivalent weight of a methacryloyl group for each compound having a methacryloyl groupM1/EM1+WM2/EM2+···)。
Examples of the compound having a (meth) acryloyl group include partially (meth) acrylic-modified epoxy compounds, epoxy (meth) acrylates, (meth) acrylate compounds, urethane (meth) acrylates, and the like. Among these, the curable resin preferably contains a part of a methacrylic-modified epoxy compound, and more preferably contains a part of a methacrylic-modified bisphenol a-type epoxy compound, in order to make it easier to set the glass transition temperature and the cure shrinkage of the cured product to the respective ranges described above.
In the present specification, the "(meth) acrylic acid" refers to acrylic acid or methacrylic acid. The "partially (meth) acrylic-modified epoxy compound" is a compound having 1 or more epoxy groups and 1 or more (meth) acryloyl groups in each molecule, which is obtained by reacting (meth) acrylic acid with a part of epoxy groups of a compound having 2 or more epoxy groups. 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 epoxy compound to be used as a raw material for synthesizing the partially (meth) acrylic acid-modified 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 addition bisphenol a type epoxy compounds, resorcinol type epoxy compounds, biphenyl type epoxy compounds, sulfide 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 phenol novolac type epoxy compounds, biphenol phenol novolac type epoxy compounds, naphthol novolac type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyhydric alcohol type epoxy compounds, rubber modified type epoxy compounds, glycidyl ester compounds, and the like.
Examples of commercially available products of the bisphenol A type epoxy compound include jER828EL, jER1004 (both manufactured by Mitsubishi chemical corporation), EPICLON EXA-850CRP (manufactured by DIC corporation), and the like.
Examples of commercially available products of the bisphenol F type epoxy compound include jER806 and jER4004 (both manufactured by Mitsubishi chemical corporation).
Examples of commercially available products of the bisphenol S type epoxy compounds include EPICLON EXA1514 (available from DIC).
Examples of commercially available products of the 2, 2' -diallylbisphenol A-type epoxy compounds include RE-810NM (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products of the above-mentioned hydrogenated bisphenol epoxy compounds include EPICLON EXA7015 (available from DIC).
Examples of commercially available products of the above propylene oxide-added bisphenol A type epoxy compounds include EP-4000S (manufactured by ADEKA).
Examples of commercially available products of the above resorcinol-type epoxy compounds include EX-201 (manufactured by Nagase Chemtex).
Examples of commercially available biphenyl-type epoxy compounds include jER YX-4000H (manufactured by mitsubishi chemical corporation).
Examples of commercially available products of the sulfide-type epoxy compounds include YSLV-50TE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the above diphenyl ether type epoxy compounds include YSLV-80DE (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the dicyclopentadiene type epoxy compounds include EP-4088S (manufactured by ADEKA).
Examples of commercially available products of the naphthalene epoxy compound include EPICLON HP4032 and EPICLON EXA-4700 (both available from DIC).
Examples of commercially available products of the phenol novolac type epoxy compounds include EPICLON-770 (available from DIC).
Examples of the commercially available o-cresol novolac epoxy compound include EPICLON-670-EXP-S (available from DIC).
Examples of commercially available products of the dicyclopentadiene phenol-based epoxy compound include EPICLON HP7200 (available from DIC).
Examples of the commercially available products of the above-mentioned diphenolaldehyde type epoxy compounds include NC-3000P (manufactured by Nippon chemical Co., Ltd.).
Examples of commercially available products of the naphthol phenol type epoxy compounds include ESN-165S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.).
Examples of commercially available products of the glycidyl amine type epoxy compound include JeR630 (manufactured by Mitsubishi chemical corporation), EPICLON 430 (manufactured by DIC corporation), and TETRAD-X (manufactured by Mitsubishi gas chemical corporation).
Examples of commercially available products of the above-mentioned alkyl polyol type epoxy compounds include ZX-1542(NIPPON STEEL Chemical & Material Co., Ltd.), EPICLON726(DIC Co., Ltd.), Eplight 80MFA (Kyoho Chemical Co., Ltd.), and Denacol EX-611(Nagase Chemtex Co., Ltd.).
Examples of commercially available products of the rubber-modified epoxy compound include YR-450, YR-207 (both NIPPON STEEL Chemical & Material Co., Ltd.), Epolead PB (DAICEL 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 STEEL Chemical & Material Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all manufactured by Mitsubishi Chemical Co., Ltd.), EXA-7120 (manufactured by Nissan Chemical Co., Ltd.), TEPIC (manufactured by Nissan Chemical Co., Ltd.).
Examples of commercially available products of the partially (meth) acrylic-modified epoxy compound include UVACURE1561, KRM8287 (both manufactured by DAICEL ALLNEX Co., Ltd.), and MEM-5000H (manufactured by NEO CHEMICAL Co., Ltd.).
Examples of the epoxy (meth) acrylate include: epoxy (meth) acrylates obtained by reacting an epoxy compound with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method, and the like.
Examples of the epoxy compound to be used as a raw material for synthesizing the epoxy (meth) acrylate include the same epoxy compounds as those used as a raw material for synthesizing the partially (meth) acrylic acid-modified epoxy compound.
Examples of commercially available products of the epoxy (meth) acrylate include epoxy (meth) acrylate manufactured by DAICEL ALLNEX, epoxy (meth) acrylate manufactured by Newzhou chemical industries, epoxy (meth) acrylate manufactured by Kyowa chemical industries, and epoxy (meth) acrylate manufactured by Nagase Chemtex.
Examples of the epoxy (meth) acrylate manufactured by DAICEL ALLNEX include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3708, EBECRYL3800, EBECRYL6040, and EBECRYL RDX 63182.
Examples of the epoxy (meth) acrylate manufactured by Nippon Komura chemical industries include EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD and EMA-1020.
Examples of the Epoxy (meth) acrylate manufactured by Kyoeisha chemical company include Epoxy Ester M-600A, Epoxy Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA, Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy Ester 3000M, Epoxy Ester3000A, Epoxy Ester 200EA, and Epoxy Ester 400 EA.
Examples of the epoxy (meth) Acrylate manufactured by Nagase Chemtex include Denacol Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate DA-911.
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, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl (2-butyl (meth) acrylate, n-butyl (acrylate, n-butyl (2-butyl acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl (meth) acrylate, n-butyl acrylate, n-butyl (meth) acrylate, n-butyl (2-acrylate, n-butyl acrylate, n-acrylate, n, 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, ethylcarbitol (meth) acrylate, 2,2, 2-trifluoroethyl (meth) acrylate, 2,2,3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, N-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylcarbitol (meth) acrylate, 2,2,2, 3, 3-tetrafluoropropyl (meth) acrylate, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (meth) acrylate, and mixtures thereof, Diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, and the like.
Examples of the 2-functional compound in the (meth) acrylate compound include: 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide addition bisphenol A di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene oxide, propylene glycol di (meth) acrylate, and ethylene oxide addition bisphenol A acrylate, and the like, Propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol dicyclopentadienyl di (meth) acrylate (Japanese: ジメチロールジシクロペンタジエニルジ (メタ) アクリレート), 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.
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, tri (meth) acryloyloxyethyl phosphate, bis (trimethylolpropane) tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
The urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with a polyfunctional isocyanate compound in the presence of a catalytic amount of a tin compound.
Examples of the polyfunctional isocyanate compound include: isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, 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 polyfunctional isocyanate compound, a polyfunctional isocyanate compound having an extended chain obtained by a reaction of a polyol and an excessive amount of the polyfunctional isocyanate compound may be used.
Examples of the polyhydric alcohol 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, and 4-hydroxybutyl (meth) acrylate.
Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, 1, 4-butanediol, and polyethylene glycol.
Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, glycerol, and the like.
Examples of the epoxy (meth) acrylate include bisphenol a type epoxy acrylates.
Examples of commercially available products of the urethane (meth) acrylates include urethane (meth) acrylates manufactured by east asia synthesis company, urethane (meth) acrylates manufactured by DAICEL ALLNEX company, urethane (meth) acrylates manufactured by seiko industries, urethane (meth) acrylates manufactured by seiko chemical companies, and urethane (meth) acrylates manufactured by coyowa chemical companies.
Examples of the urethane (meth) acrylates manufactured by Toyo Synthesis Co.Ltd include M-1100, M-1200, M-1210 and M-1600.
Examples of the urethane (meth) acrylate produced by DAICEL ALLNEX include EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8807 and EBECRYL 9288060.
Examples of the urethane (meth) acrylates produced by the above-mentioned Geneva industries include ArtResin UN-330, ArtResin SH-500B, ArtResin UN-1200TPK, ArtResin UN-1255, ArtResin UN-3320HB, ArtResin UN-7100, ArtResin UN-9000A, and ArtResin UN-9000H.
Examples of the urethane (meth) acrylates produced by 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-122A, U-122P, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4000, UA-4100, UA-4200, UA-4400, UA-5201P, UA-7100, UA-7200 and UA-W2A.
Examples of the urethane (meth) acrylate manufactured by Kyoeisha chemical company include AH-600, AI-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T, and the like.
The curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the obtained sealing agent for an element, and the like. Examples of the epoxy compound include the same epoxy compounds as those used as raw materials for synthesizing the partially (meth) acrylic acid-modified epoxy compound.
When the curable resin contains the compound having a (meth) acryloyl group and the epoxy compound, the content of the (meth) acryloyl group in the total of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 50 mol% or more and 95 mol% or less.
The sealant for a 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 and a cationic polymerization initiator.
Examples of the radical polymerization initiator include a photo radical polymerization initiator which generates radicals by light irradiation, a thermal radical polymerization initiator which generates radicals by heating, and the like.
Examples of the photo radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thioxanthone-based compounds.
Specific examples of the photo radical polymerization initiator include: 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholino) phenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethan-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, methyl-1- (4-methyl-phenyl) -2-hydroxy-2-methyl-1-propan-1-one, methyl-1-one, and mixtures thereof, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyloxime), 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators composed of azo compounds, organic peroxides, and the like. Among them, a polymeric azo initiator composed of a polymeric azo compound is preferable.
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 has 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, the compound can be easily mixed into a curable resin, and when the obtained sealant for a display element is used for a liquid crystal display element, adverse effects on the liquid crystal can be prevented. The number average molecular weight of the macromolecular azo compound is preferably 5000 at a lower limit, 10 ten thousand at a higher limit, 1 ten thousand at a higher limit, and 9 ten thousand at a higher limit.
In the present specification, the number 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 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.
Examples of commercially available products of the above-mentioned macromolecular azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Fuji film and Wako pure chemical industries, Ltd.).
Further, examples of commercially available azo compounds which are not polymers include V-65 and V-501 (both manufactured by Fuji film and Wako pure chemical industries, Ltd.).
Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacylperoxides, and peroxydicarbonates.
As the cationic polymerization initiator, a photo cationic polymerization initiator can be preferably used. The photo cation polymerization initiator is not particularly limited as long as it generates a protonic acid or a lewis acid by light irradiation, and may be an ionic photo-acid type photo cation polymerization initiator or a nonionic photo cation polymerization initiator.
Examples of the photo cation polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts and aromatic sulfonium salts, and organic metal complexes such as iron-arene complexes, titanocene complexes and aryl silanol-aluminum complexes.
Examples of commercially available products of the above-mentioned photo cation polymerization initiator include Adeka Optimer SP-150 and Adeka Optimer SP-170 (both manufactured by ADEKA Co., Ltd.).
The polymerization initiators may be used alone or in combination of 2 or more.
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 display element is more excellent in curability. By setting the content of the polymerization initiator to 30 parts by weight or less, the obtained sealing agent for a display element is more excellent in storage stability. 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 heat-curing agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyphenol compounds, and acid anhydrides. Among them, solid organic acid hydrazides are preferably used.
The thermosetting agent may be used alone, or 2 or more of them may be used in combination.
Examples of the solid organic acid hydrazide include 1, 3-bis (hydrazinocarbonylethyl (Japanese: ヒドラジノカルボエチル)) -5-isopropylhydantoin, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide, and the like.
Examples of commercially available organic acid hydrazides include those manufactured by Otsuka chemical corporation, those manufactured by Japan Finechem, and those manufactured by Ajinomoto Fine-Technio corporation.
Examples of the organic acid hydrazide available from Otsuka chemical company include SDH and ADH.
Examples of the organic acid hydrazide manufactured by Japan Finechem include MDH.
Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Technio include AMICURE VDH, AMICURE VDH-J, and AMICURE UDH.
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 to 1 part by weight or more, the obtained sealant for a display element is more excellent in thermosetting property. By setting the content of the thermosetting agent to 50 parts by weight or less, the obtained sealing agent for a display element is more excellent in coatability and storage stability. A more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
The sealant for a display element of the present invention preferably contains a filler for the purpose of adjusting viscosity, improving adhesiveness by a stress dispersion effect, improving a linear expansion coefficient, improving moisture resistance of a 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, montmorillonite, 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 fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
The lower limit of the content of the filler in 100 parts by weight of the sealant for 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 improvement in adhesiveness can be further exhibited while suppressing deterioration in 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 display element of the present invention preferably contains a silane coupling agent. 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-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. are preferably used. These silane coupling agents have an excellent effect of improving adhesion to a substrate or the like, and when the obtained sealant for a display element is used for a liquid crystal display element, outflow of a curable resin into a liquid crystal can be suppressed.
The silane coupling agents may be used alone, or 2 or more of them may be used in combination.
The preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for display elements of the present invention is 0.1 part by weight, and the preferable upper limit is 10 parts by weight. When the content of the silane coupling agent is within this range, the obtained sealant for a display element has more excellent adhesiveness, and when the obtained sealant for a display element is used for a liquid crystal display element, occurrence of liquid crystal contamination can be suppressed. 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 display element sealing agent of the present invention may contain the light-shading agent. By containing the light-shading agent, the sealant for a 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, resin-coated carbon black, and the like. Among them, titanium black is preferable.
The light-shading agent can be used alone, or can be used in combination of 2 or more.
The titanium black has a higher transmittance for light in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370nm to 450nm, than the average transmittance for light having 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 display element of the present invention can provide light-shielding properties by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. As the light-shading agent contained in the sealing agent for a display element of the present invention, a material having high insulation properties is preferable, and titanium black is also suitable as the light-shading agent having high insulation properties.
The titanium black exhibits a sufficient effect without being surface-treated, but a titanium black surface-treated with an organic component such as a coupling agent, or a titanium black surface-treated 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 in terms of further improving the insulation property.
Further, since the display element produced using the sealant for a display element of the present invention containing the titanium black as a light-shielding agent has sufficient light-shielding properties, a display element which is light-tight, has high contrast, and has 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 gibberella chemical company, and the like.
Examples of the titanium black manufactured by Mitsubishi Materials include 12S, 13M-C, 13R-N and 14M-C.
Examples of the titanium black manufactured by red spike formation company include Tilack D.
The above titanium black scaleA preferred lower limit of the area is 13m2A preferred upper limit is 30m2A more preferred lower limit is 15m2A more preferred upper limit is 25m2/g。
The volume resistance of the titanium black has a preferred lower limit of 0.5 Ω · cm, a preferred upper limit of 3 Ω · cm, a more preferred lower limit of 1 Ω · cm, and a more preferred upper limit of 2.5 Ω · cm.
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 display element, and the lower limit is preferably 1nm and the upper limit is preferably 5000 nm. By setting the primary particle size of the light-shading agent in this range, the light-shading properties can be further improved without deteriorating the drawing properties and the like of the obtained sealing agent for a display element. The lower limit of the primary particle diameter of the light-shading agent is preferably 5nm, the upper limit thereof is preferably 200nm, the lower limit thereof is more preferably 10nm, and the upper limit thereof is more preferably 100 nm.
The primary PARTICLE size of the light-shading agent can be measured by dispersing the light-shading agent in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (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 display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. When the content of the light-shading agent is in this range, the obtained sealant for a display element is more excellent in the effect of improving the light-shading property while suppressing deterioration of the adhesiveness, strength after curing, and drawing property. 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 sealing agent for a display element of the present invention may further contain additives such as a reactive diluent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents, as required.
Examples of a method for producing the sealant for a display element of the present invention include a method in which a curable resin, a polymerization initiator and/or a heat-curing agent, and a silane coupling agent and the like added as necessary are mixed by using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a planetary mixer, a kneader, and a 3-roll machine.
The vertical conduction material can be produced by blending conductive fine particles in the sealing agent for a display element of the present invention. Such a vertically conducting material containing the sealing agent for a display element of the present invention and conductive fine particles is also one aspect of the present invention.
The conductive fine particles are not particularly limited, and metal spheres, fine particles having a conductive metal layer formed on the surface of resin fine particles, or the like can be used. Among these, fine particles having a conductive metal layer formed on the surface of the resin fine particles are preferable because the fine particles can be electrically connected without damaging the transparent substrate or the like due to the excellent elasticity of the resin fine particles.
A display device having a cured product of the sealant for a display device of the present invention or a cured product of the vertical conduction material of the present invention is also one aspect of the present invention. The display element of the present invention is preferably a liquid crystal display element.
As a method for manufacturing a liquid crystal display element using the sealant for a display element of the present invention, a liquid crystal dropping method is preferably used, and specifically, for example, a method having the following steps is exemplified.
First, the following steps are performed: the sealing agent for a display element of the present invention is applied to one of 2 transparent substrates having electrodes such as ITO thin films by screen printing, dispenser application, or the like to form a frame-shaped seal pattern. Next, a step of dropping fine liquid crystal droplets onto the entire inner surface of the frame of the seal pattern and laminating the other transparent substrate under vacuum is performed. Then, a liquid crystal display element can be obtained by performing a method including a step of temporarily curing the sealant by irradiating the seal pattern portion with light such as ultraviolet rays, and a step of permanently curing the temporarily cured sealant by heating.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a sealing agent for a display element, which can provide a display element having excellent reliability in a high-temperature and high-humidity environment, can be provided. Further, according to the present invention, a vertical conduction material and a display element using the sealant for a 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 5 and comparative examples 1 to 3
The materials were mixed by a planetary mixer at the mixing ratio shown in table 1, and then mixed by a 3-roll mill to prepare a sealant for a display element. As the above-mentioned planetary mixer, a deaerated Miller Taglan (manufactured by Thinky Co., Ltd.) was used.
The obtained sealant for each display element was irradiated with a metal halide lamp for 30 seconds at 100mW/cm2Then, the resulting mixture was heated at 120 ℃ for 1 hour to obtain a cured product.
The resulting cured product was measured for dynamic viscoelasticity under conditions of a test piece width of 5mm, a thickness of 0.35mm, a holding width of 25mm, a temperature rise rate of 10 ℃/min, and a frequency of 5Hz using a dynamic viscoelasticity measuring apparatus, and the temperature at which the maximum value of the loss tangent (tan. delta.) was determined as the glass transition temperature. DVA-200 (manufactured by IT measurement and control Co., Ltd.) was used as the dynamic viscoelasticity measuring apparatus. The results are shown in Table 1.
The cured product obtained was subjected to a high temperature and high humidity test in which the cured product was exposed to an atmosphere of 121 ℃, 100% RH, and 2atm for 48 hours. The specific gravity at 25 ℃ of the sealant for a display element before curing and the specific gravity at 25 ℃ of the cured product after the high temperature and high humidity test were measured, and the curing shrinkage was calculated from the above formula. The results are shown in Table 1.
< evaluation >
The following evaluations were made for each of the sealants for display elements obtained in examples and comparative examples. The results are shown in Table 1.
(reliability in high-temperature and high-humidity Environment)
In the implementation ofEach of the sealants for display elements obtained in examples and comparative examples had 1 part by weight of spacer particles uniformly dispersed therein. As the spacer, MicroPearl SI-H050 (manufactured by Water chemical industries, Ltd.) was used. The sealant in which the spacer particles are dispersed is filled in a syringe for dispensing, is subjected to defoaming treatment, and is then applied to a transparent substrate with an alignment film and an ITO thin film by a dispenser so as to draw a rectangular frame. PSY-10E (manufactured by Musashi Engineering Co., Ltd.) was used as a syringe, and SHOTMASTER300 (manufactured by Musashi Engineering Co., Ltd.) was used as a dispenser. Next, the minute droplets of the liquid crystal were dropped onto the entire surface of the frame coated with the sealant, and another transparent substrate was bonded immediately. JC-5004LA (manufactured by CHISSO) was used as the liquid crystal. Immediately after the transparent substrates were bonded, the sealant portion was irradiated with 100mW/cm for 30 seconds using a metal halide lamp2Then, the resultant was heated at 120 ℃ for 1 hour to obtain a liquid crystal display element. For each of the sealants for display elements obtained in examples and comparative examples, 20 liquid crystal display elements were produced.
The resulting liquid crystal display element was exposed to PCT conditions (121 ℃, 100% RH, 2atm) for 48 hours. The presence or absence of bubbles was confirmed by visual observation of the liquid crystal display element after exposure to the PCT condition.
Reliability in a high-temperature and high-humidity environment was evaluated by "x" in the case where no bubble was observed in any of 20 liquid crystal display elements, "o" in the case where no bubble was observed in any of 1 to 3 liquid crystal display elements, "Δ" in the case where no bubble was observed in any of 4 to 8 liquid crystal display elements, and "x" in the case where no bubble was observed in any of 9 or more liquid crystal display elements.
[ Table 1]
Industrial applicability
According to the present invention, a sealing agent for a display element, which can provide a display element having excellent reliability in a high-temperature and high-humidity environment, can be provided. Further, according to the present invention, a vertical conduction material and a display element using the sealant for a display element can be provided.
Claims (6)
1. A sealing agent for a display element, characterized by comprising a curable resin and a polymerization initiator and/or a thermal curing agent,
the glass transition temperature of the cured product is 125 ℃ or higher,
the cured product has a cure shrinkage of 5% or less after a high-temperature high-humidity test in which the cured product is exposed to an environment of 121 ℃, 100% RH, and 2atm for 48 hours.
2. The sealant for a display element according to claim 1, wherein the curable resin contains a compound having a methacryloyl group,
the ratio of the methacryl group represented by the following formula (I) is 0.5 or more,
(ii) methacryl ratio ═ WM/EM)/(WA/EA+WM/EM) (I)
In the formula (I), EAIs the acryloyl equivalent of the compound having an acryloyl group, EMIs the methacryloyl equivalent of the compound having a methacryloyl group, WAIs the content of a compound having an acryloyl group, WMIs the content of a compound having a methacryloyl group, EAAnd EMHas the unit of g/mol, WAAnd WMThe unit of (A) is part by weight.
3. The sealant for a display element according to claim 2, wherein the curable resin contains a part of a methacrylic-modified epoxy compound.
4. The sealant for a display element according to claim 3, wherein the curable resin contains a part of a methacrylic-modified bisphenol A-type epoxy compound.
5. A vertically conducting material comprising the sealing agent for display elements according to claim 1,2, 3 or 4 and conductive fine particles.
6. A display device comprising a cured product of the sealant for display devices according to claim 1,2, 3, or 4 or a cured product of the vertical conduction material according to claim 5.
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| JP2019-123019 | 2019-07-01 | ||
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| JP2019-126948 | 2019-07-08 | ||
| JP2019126948 | 2019-07-08 | ||
| PCT/JP2020/025479 WO2021002317A1 (en) | 2019-07-01 | 2020-06-29 | Sealing agent for display elements, vertically conductive material, and display element |
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| CN113924351A true CN113924351A (en) | 2022-01-11 |
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| KR (2) | KR20220027054A (en) |
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| WO2023182245A1 (en) * | 2022-03-25 | 2023-09-28 | 積水化学工業株式会社 | Liquid crystal display element sealant and liquid crystal display element |
| WO2024014379A1 (en) * | 2022-07-12 | 2024-01-18 | ソニーセミコンダクタソリューションズ株式会社 | Light-emitting device, electronic apparatus, and sealing device |
| WO2024065048A1 (en) * | 2022-09-27 | 2024-04-04 | Zeroin Foods Inc. | Sweetened fiber and methods thereof |
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| JP2000066220A (en) * | 1998-08-19 | 2000-03-03 | Sumitomo Bakelite Co Ltd | Sealing material for liquid crystal display element and liquid crystal display element using the material |
| JP2000227600A (en) * | 1998-11-30 | 2000-08-15 | Toshiba Corp | Manufacture of liquid crystal display cell |
| JP3583326B2 (en) | 1999-11-01 | 2004-11-04 | 協立化学産業株式会社 | Sealant for dripping method of LCD panel |
| JP2002069160A (en) * | 1999-12-14 | 2002-03-08 | Mitsui Chemicals Inc | Sealing agent for liquid crystal display cell, composition for sealing agent for liquid crystal display cell and liquid crystal display element |
| EP1405888A1 (en) | 2001-05-16 | 2004-04-07 | Sekisui Chemical Co., Ltd. | Curing resin composition and sealants and end-sealing materials for displays |
| JP2009134293A (en) * | 2007-11-08 | 2009-06-18 | Sekisui Chem Co Ltd | Sealing agent for liquid crystal installation method, vertical conduction material and liquid crystal display element |
| KR101950538B1 (en) * | 2011-08-10 | 2019-02-20 | 도아고세이가부시키가이샤 | Active energy ray-curable resin composition for gap filling |
| KR101716588B1 (en) * | 2012-06-20 | 2017-03-14 | 미쯔비시 레이온 가부시끼가이샤 | Method for producing laminate, laminate, and article |
| CN102888199B (en) * | 2012-09-17 | 2014-06-18 | 北京京东方光电科技有限公司 | Frame sealing glue and preparation method and application thereof |
| JP6431422B2 (en) * | 2015-03-27 | 2018-11-28 | 株式会社ジャパンディスプレイ | Liquid crystal display |
| CN109897599B (en) * | 2015-11-09 | 2020-09-01 | 积水化学工业株式会社 | Sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
| JP7388808B2 (en) * | 2017-09-19 | 2023-11-29 | 共栄社化学株式会社 | Method for producing partially esterified epoxy resin |
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2020
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- 2020-06-29 CN CN202080036217.1A patent/CN113826043A/en active Pending
- 2020-06-29 TW TW109121874A patent/TW202108694A/en unknown
- 2020-06-29 JP JP2020540840A patent/JP6905158B2/en active Active
- 2020-06-29 TW TW109121873A patent/TW202108693A/en unknown
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2021
- 2021-06-17 JP JP2021100842A patent/JP2021167416A/en active Pending
- 2021-07-06 JP JP2021112291A patent/JP2021177246A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002317172A (en) * | 2001-04-20 | 2002-10-31 | Nippon Kayaku Co Ltd | Sealing medium resin composition for liquid crystal display |
| WO2009084718A1 (en) * | 2007-12-28 | 2009-07-09 | Three Bond Co., Ltd. | Curable composition |
| JP2016012131A (en) * | 2014-06-03 | 2016-01-21 | 積水化学工業株式会社 | Sealing agent for liquid crystal display element, vertical conducting material, and liquid crystal display element |
| CN106796376A (en) * | 2015-05-08 | 2017-05-31 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display cells |
| CN108780251A (en) * | 2016-09-29 | 2018-11-09 | 积水化学工业株式会社 | Sealing material for liquid crystal display device, upper and lower conductive material and liquid crystal display element |
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| WO2021002317A1 (en) | 2021-01-07 |
| WO2021002318A1 (en) | 2021-01-07 |
| KR20220023751A (en) | 2022-03-02 |
| JP2021177246A (en) | 2021-11-11 |
| JP6905158B2 (en) | 2021-07-21 |
| TW202108693A (en) | 2021-03-01 |
| JPWO2021002318A1 (en) | 2021-09-13 |
| JPWO2021002317A1 (en) | 2021-09-13 |
| TW202108694A (en) | 2021-03-01 |
| JP2021167416A (en) | 2021-10-21 |
| CN113826043A (en) | 2021-12-21 |
| KR20220027054A (en) | 2022-03-07 |
| JP6910561B2 (en) | 2021-07-28 |
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