WO2017061255A1 - 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 - Google Patents
液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 Download PDFInfo
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- WO2017061255A1 WO2017061255A1 PCT/JP2016/077419 JP2016077419W WO2017061255A1 WO 2017061255 A1 WO2017061255 A1 WO 2017061255A1 JP 2016077419 W JP2016077419 W JP 2016077419W WO 2017061255 A1 WO2017061255 A1 WO 2017061255A1
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1062—UV-curable materials
Definitions
- the present invention relates to a sealant for a liquid crystal display element that is excellent in photocurability and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
- a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
- a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing.
- liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured.
- this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
- a narrow frame of the liquid crystal display unit can be cited.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealing agent is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing agent is blocked, and it is difficult for the light to reach the inside of the sealing agent.
- the conventional sealant is insufficiently cured. As described above, when the sealant is insufficiently cured, there is a problem in that the uncured sealant component is eluted in the liquid crystal and easily causes liquid crystal contamination.
- the present invention is a sealing agent for a liquid crystal display element containing a curable resin and a photo radical polymerization initiator, wherein the photo radical polymerization initiator is a compound represented by the following formula (1-1) and / or Or it is a sealing compound for liquid crystal display elements containing the compound represented by the following formula (1-2).
- X represents an alkyl group having 1 to 8 carbon atoms, or a 2-cyclopentylethyl group in which at least one hydrogen of a cyclopentyl ring may be substituted with a methyl group or an ethyl group
- R represents a methyl group or an ethyl group
- Y represents an alkyl group having 2 to 8 carbon atoms, or a 2-cyclopentylethyl group in which at least one hydrogen of the cyclopentyl ring may be substituted with a methyl group or an ethyl group
- R represents a methyl group or an ethyl group.
- the inventors of the present invention have a liquid crystal display element seal that is excellent in photocurability and can suppress liquid crystal contamination by blending a compound having a specific structure as a photo radical polymerization initiator.
- the present inventors have found that an agent can be obtained and have completed the present invention.
- the sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator.
- the photo radical polymerization initiator is a compound represented by the above formula (1-1) and / or a compound represented by the above formula (1-2) (hereinafter referred to as “the photo radical polymerization initiator according to the present invention”). Contain).
- the sealing agent for liquid crystal display elements of the present invention is highly sensitive and excellent in photocurability (particularly light-curing part curability) and suppresses liquid crystal contamination. Will be able to.
- the sealing agent for liquid crystal display elements of the present invention may contain a compound represented by the following formula (2) and / or a compound represented by the following formula (3) as a photo radical polymerization initiator according to the present invention.
- it contains a compound represented by the following formula (2).
- Examples of commercially available radical photopolymerization initiators according to the present invention include PBG-314 and PBG-304 (both manufactured by Changzhou Strong Electronic New Materials Co., Ltd.).
- the content of the radical photopolymerization initiator according to the present invention is preferably 0.2 parts by weight with respect to 100 parts by weight of the curable resin, and 8 parts by weight with respect to the preferable upper limit.
- the content of the radical photopolymerization initiator according to the present invention is 0.2 parts by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in photocurability.
- the content of the radical photopolymerization initiator according to the present invention is 8 parts by weight or less, the obtained sealing agent for liquid crystal display elements is more excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
- the more preferable lower limit of the content of the radical photopolymerization initiator according to the present invention is 0.5 parts by weight, and the more preferable upper limit is 5 parts by weight.
- the preferable minimum of content of the radical photopolymerization initiator concerning this invention in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 5 weight part.
- the content of the photoradical polymerization initiator according to the present invention is 0.1 parts by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in photocurability.
- the radical photopolymerization initiator according to the present invention is 5 parts by weight or less, the obtained sealing agent for a liquid crystal display element is more excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
- the more preferred lower limit of the content of the radical photopolymerization initiator according to the present invention is 0.3 parts by weight, the more preferred upper limit is 3 parts by weight, the still more preferred lower limit is 0.5 parts by weight, and the still more preferred upper limit is 1 part by weight. .
- the sealing agent for liquid crystal display elements of this invention contains curable resin.
- the curable resin preferably contains a (meth) acrylic compound.
- the (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
- examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable.
- the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
- the “(meth) acryl” means acryl or methacryl
- the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter, “(meth) acryloyl”).
- the “(meth) acrylate” means acrylate or methacrylate.
- the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid.
- Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
- those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
- Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy compound 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, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
- Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy Ester 200PA, epoxy ester 80MFA Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
- Examples of the urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative with the isocyanate compound include, for example, (meth) acrylic having a hydroxyl group with respect to 1 equivalent of an isocyanate compound having two isocyanate groups. Two equivalents of the acid derivative can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
- isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
- MDI '-Diisocyanate
- hydrogenated MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.
- MDI '-Diisocyanate
- XDI xylylene diisocyanate
- XDI hydrogenated XDI
- lysine diisocyanate triphenylmethane triisocyanate
- tris (isocyanate) Phenyl) thiophosphate tetramethylxylylene diisocyanate, 1,6,11-und
- Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate include, for example, polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Chain-extended isocyanate compounds obtained by reaction with excess isocyanate compounds can also be used.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.
- Mono (meth) acrylates of dihydric alcohols mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy alcohol Epoxy (meth) acrylate of rate, and the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U
- the curable resin preferably further contains an epoxy compound for the purpose of improving the adhesiveness of the obtained sealing agent for liquid crystal display elements.
- an epoxy compound for the purpose of improving the adhesiveness of the obtained sealing agent for liquid crystal display elements.
- combining the said epoxy (meth) acrylate, a partial (meth) acryl modified epoxy resin, etc. are mentioned, for example.
- the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
- the sealing agent for liquid crystal display elements of the present invention contains the (meth) acryl compound and the epoxy compound
- the ratio of the (meth) acryloyl group to the epoxy group is 30:70 to 95: 5. It is preferable to blend the (meth) acrylic compound and the epoxy compound.
- the ratio of the (meth) acryloyl group is 30% or more, the obtained sealing agent for liquid crystal display elements is excellent in the effect of suppressing liquid crystal contamination.
- the ratio of the (meth) acryloyl group is 95% or less, the obtained sealing agent for liquid crystal display elements is more excellent in adhesiveness.
- the curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
- the sealing agent for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
- a thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
- the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
- the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
- the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
- the said number average molecular weight is a value calculated
- polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
- Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
- Examples of azo compounds that are not a polymer include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
- organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
- the content of the thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the thermal radical polymerization initiator is within this range, the liquid crystal display element sealing agent obtained is more excellent in curability while suppressing the occurrence of liquid crystal contamination due to the unreacted radical polymerization initiator.
- the minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
- the sealing compound for liquid crystal display elements of this invention contains a thermosetting agent.
- the thermosetting agent include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
- organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- organic acid hydrazides examples include, for example, SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
- the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
- the content of the thermosetting agent is 1 part by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in thermosetting.
- the content of the thermosetting agent is 50 parts by weight or less, the viscosity of the obtained sealing agent does not become too high, and the applicability is excellent.
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for a liquid crystal display element of the present invention preferably contains a filler for the purpose of improving the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, improving the moisture resistance of the cured product, and the like.
- filler examples 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,
- Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned. These fillers may be used independently and may use 2 or more types together.
- the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
- the content of the filler is 10 parts by weight or more, the effect such as improvement in adhesiveness is excellent.
- the content of the filler is 70 parts by weight or less, the viscosity of the obtained sealing agent for liquid crystal display elements does not become too high, and the coating property is excellent.
- the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
- the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent.
- the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
- silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
- -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
- These silane coupling agents may be used alone or in combination of two or more.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing compounds for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
- a preferable upper limit is 10 weight part.
- the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
- Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
- Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
- the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
- titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
- the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm
- the more preferable upper limit is 200 nm
- the still more preferable lower limit is 10 nm
- the still more preferable upper limit is 100 nm.
- the primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
- the preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
- the content of the light-shielding agent is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in light-shielding properties while maintaining excellent drawing properties, adhesiveness, and strength after curing.
- the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
- a method for producing the sealing agent for liquid crystal display elements of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roller, etc.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roller, etc.
- examples thereof include a method of mixing the radical photopolymerization initiator according to the invention with an additive such as a silane coupling agent added as necessary.
- the sealing agent for liquid crystal display elements of the present invention has a preferable lower limit of 100,000 mPa ⁇ s and a preferable upper limit of 600,000 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal display elements has excellent coating properties.
- a more preferable lower limit of the viscosity is 150,000 mPa ⁇ s, and a more preferable upper limit is 450,000 mPa ⁇ s.
- a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
- Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
- the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
- the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
- the liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
- a liquid crystal dropping method is preferably used.
- the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like.
- the step of forming a frame-shaped seal pattern, the liquid crystal display element sealant of the present invention is uncured, and a liquid crystal micro-droplet is dropped into the frame of the substrate seal pattern, and another substrate is formed under vacuum.
- a step of irradiating the seal pattern portion of the sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and heating the temporarily cured sealant examples thereof include a method having a step of main curing.
- the sealing compound for liquid crystal display elements which is excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
- Examples 1 to 7, Comparative Examples 1 to 4 According to the blending ratio described in Table 1, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), and then mixed using three rolls. The sealing agents for liquid crystal display elements 1 to 7 and Comparative Examples 1 to 4 were prepared.
- a glass substrate was prepared by dispersing 1 part by weight of spacer fine particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI-H050”) in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples.
- a glass substrate of the same size was applied to the substrate, and then a 100 mW / cm 2 light was irradiated for 10 seconds using a metal halide lamp to prepare a photocurable test piece. Light irradiation was carried out in two patterns with no cut filter and with a cut filter of 380 nm or less, and three test pieces were prepared for each.
- Photocurability was evaluated by measuring the amount of change of the (meth) acryloyl group-derived peak before and after light irradiation using an infrared spectroscope (manufactured by BIORAD, “FTS3000”). “ ⁇ ” when the peak derived from the (meth) acryloyl group decreases by 95% or more after light irradiation, “ ⁇ ” when the peak derived from the (meth) acryloyl group decreases by 80% or more but less than 95% after the light irradiation, light The case where the peak derived from the (meth) acryloyl group is reduced by 70% or more and less than 80% after the irradiation is “ ⁇ ”, and the case where the decrease in the peak derived from the (meth) acryloyl group after the light irradiation is less than 70% is “ ⁇ ” The photocurability was evaluated as “ In addition, the variation
- Liquid crystal contamination 1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and then two rubbing is performed. It applied with a dispenser so that it might become a frame shape with a line width of 1 mm to one of a finished alignment film and a substrate with a transparent electrode. Subsequently, liquid crystal (Chisso, “JC-5004LA”) microdrops are applied to the entire surface of the sealant frame of the substrate with the transparent electrode, and the other substrate with the transparent electrode is immediately bonded to the sealant part.
- spacer fine particles 1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is dispersed in 100 parts by weight of the sealant for each liquid crystal display element obtained in Examples and Comparative Examples, and then two rubbing is performed. It
- the metal halide lamp was used to irradiate 100 mW / cm 2 of light for 10 seconds to cure the sealant, and further heated at 120 ° C. for 1 hour to obtain a liquid crystal display element.
- Light irradiation was carried out in two patterns with no cut filter and with a cut filter of 380 nm or less, and three liquid crystal display elements were produced for each.
- the liquid-crystal contamination of the sealant vicinity after making it into a voltage application state at 60 degreeC for 1000 hours was confirmed visually. Liquid crystal contamination is determined by the color unevenness of the three liquid crystal display elements.
- ⁇ indicates that there is no color unevenness for all the liquid crystal display elements, and at least one liquid crystal
- ⁇ when at least one liquid crystal display element had slight color unevenness, “ ⁇ ”, and at least one liquid crystal display element had considerable color unevenness.
- the case was evaluated as “x” to evaluate the liquid crystal contamination. Note that the liquid crystal display elements with the evaluations “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
- the sealing compound for liquid crystal display elements which is excellent in photocurability and can suppress liquid crystal contamination can be provided.
- the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
Abstract
Description
滴下工法では、まず、2枚の電極付き基板の一方に、ディスペンスにより長方形状のシールパターンを形成する。次いで、シール剤が未硬化の状態で液晶の微小滴を基板のシール枠内に滴下し、真空下で他方の基板を重ね合わせ、シール部に紫外線等の光を照射して仮硬化を行う。その後、加熱して本硬化を行い、液晶表示素子を作製する。現在この滴下工法が液晶表示素子の製造方法の主流となっている。
式(1-2)中、Yは、炭素数2~8のアルキル基、又は、シクロペンチル環の少なくとも1つの水素がメチル基若しくはエチル基で置換されていてもよい2-シクロペンチルエチル基を表し、Rは、メチル基又はエチル基を表す。
以下に本発明を詳述する。
上記光ラジカル重合開始剤は、上記式(1-1)で表される化合物及び/又は上記式(1-2)で表される化合物(以下、「本発明にかかる光ラジカル重合開始剤」ともいう)を含有する。本発明にかかる光ラジカル重合開始剤を含有することにより、本発明の液晶表示素子用シール剤は、高感度で光硬化性(特に遮光部硬化性)に優れ、かつ、液晶汚染を抑制することができるものとなる。
また、本発明の液晶表示素子用シール剤100重量部中における本発明にかかる光ラジカル重合開始剤の含有量の好ましい下限は0.1重量部、好ましい上限が5重量部である。上記本発明にかかる光ラジカル重合開始剤の含有量が0.1重量部以上であることにより、得られる液晶表示素子用シール剤が光硬化性により優れるものとなる。本発明にかかる光ラジカル重合開始剤が5重量部以下であることにより、得られる液晶表示素子用シール剤が、接着性及び液晶汚染を抑制する効果により優れるものとなる。本発明にかかる光ラジカル重合開始剤の含有量のより好ましい下限は0.3重量部、より好ましい上限は3重量部、更に好ましい下限は0.5重量部、更に好ましい上限は1重量部である。
上記硬化性樹脂は、(メタ)アクリル化合物を含有することが好ましい。
上記(メタ)アクリル化合物としては、例えば、(メタ)アクリル酸に水酸基を有する化合物を反応させることにより得られる(メタ)アクリル酸エステル化合物、(メタ)アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ(メタ)アクリレート、イソシアネート化合物に水酸基を有する(メタ)アクリル酸誘導体を反応させることにより得られるウレタン(メタ)アクリレート等が挙げられる。なかでも、エポキシ(メタ)アクリレートが好ましい。また、上記(メタ)アクリル化合物は、反応性の高さから分子中に(メタ)アクリロイル基を2個以上有するものが好ましい。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」とは、アクリロイル基又はメタクリロイル基(以下、併せて「(メタ)アクリロイル基」ともいう)を有する化合物を意味する。また、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。更に、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、jER YX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、jER630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ化合物のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。
なお、本明細書において上記部分(メタ)アクリル変性エポキシ樹脂とは、1分子中にエポキシ基と(メタ)アクリロイル基とをそれぞれ1つ以上有する化合物を意味し、例えば、2つ以上のエポキシ化合物の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。なかでも、高分子アゾ化合物からなる開始剤(以下、「高分子アゾ開始剤」ともいう)が好ましい。
なお、本明細書において高分子アゾ開始剤とは、アゾ基を有し、熱によって(メタ)アクリロイル基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。このような高分子アゾ開始剤としては、例えば、4,4’-アゾビス(4-シアノペンタン酸)とポリアルキレングリコールの重縮合物や、4,4’-アゾビス(4-シアノペンタン酸)と末端アミノ基を有するポリジメチルシロキサンの重縮合物等が挙げられ、具体的には例えば、VPE-0201、VPE-0401、VPE-0601、VPS-0501、VPS-1001(いずれも和光純薬工業社製)等が挙げられる。
また、高分子ではないアゾ化合物の例としてはV-65、V-501(いずれも和光純薬工業社製)等が挙げられる。
上記熱硬化剤としては、例えば、有機酸ヒドラジド、イミダゾール誘導体、アミン化合物、多価フェノール系化合物、酸無水物等が挙げられる。なかでも、有機酸ヒドラジドが好適に用いられる。
上記有機酸ヒドラジドのうち市販されているものとしては、例えば、SDH、ADH(いずれも大塚化学社製)、アミキュアVDH、アミキュアVDH-J、アミキュアUDH、アミキュアUDH-J(いずれも味の素ファインテクノ社製)等が挙げられる。
また、遮光剤として上記チタンブラックを含有する本発明の液晶表示素子用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。
なお、上記遮光剤の一次粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)を用いて、上記遮光剤を溶媒(水、有機溶媒等)に分散させて測定することができる。
表1に記載された配合比に従い、各材料を、遊星式撹拌機(シンキー社製、「あわとり練太郎」)を用いて混合した後、更に3本ロールを用いて混合することにより実施例1~7、比較例1~4の各液晶表示素子用シール剤を調製した。
実施例及び比較例で得られた各液晶表示素子用シール剤について以下の評価を行った。結果を表1に示した。
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させたものをガラス基板上に塗布し、その基板に同サイズのガラス基板を重ね合わせ、次に、メタルハライドランプを用いて100mW/cm2の光を10秒照射し、光硬化性試験片を作製した。光照射はカットフィルタ無しの場合と380nm以下カットフィルタ有りの場合の2パターンを行い、それぞれについて3枚の試験片を作製した。赤外分光装置(BIORAD社製、「FTS3000」)を用い、(メタ)アクリロイル基由来ピークの光照射前後での変化量を測定することで光硬化性の評価を行った。光照射後に(メタ)アクリロイル基由来のピークが95%以上減少した場合を「◎」、光照射後に(メタ)アクリロイル基由来のピークが80%以上95%未満減少した場合を「○」、光照射後に(メタ)アクリロイル基由来のピークが70%以上80%未満減少した場合を「△」、光照射後の(メタ)アクリロイル基由来のピークの減少が70%未満であった場合を「×」として光硬化性を評価した。
なお、(メタ)アクリロイル基由来ピークの光照射前後での変化量は、3枚の試験片から得られた平均値を取った。
実施例及び比較例で得られた各液晶表示素子用シール剤100重量部にスペーサ微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を分散させた後、2枚のラビング済み配向膜及び透明電極付き基板の一方に、線幅が1mmの枠状になるようにディスペンサーで塗布した。
続いて液晶(チッソ社製、「JC-5004LA」)の微小滴を透明電極付き基板のシール剤の枠内全面に滴下塗布し、すぐにもう一方の透明電極付き基板を貼り合わせ、シール剤部分にメタルハライドランプを用いて100mW/cm2の光を10秒照射してシール剤を硬化させ、更に、120℃で1時間加熱して液晶表示素子を得た。光照射はカットフィルタ無しの場合と380nm以下カットフィルタ有りの場合の2パターンを行い、それぞれについて3枚の液晶表示素子を作製した。
得られた液晶表示素子について、60℃で1000時間電圧印加状態とした後のシール剤付近の液晶汚染を目視によって確認した。
液晶汚染は、3枚の液晶表示素子の色むらにより判断しており、色むらの程度に応じて、全ての液晶表示素子について色むらが全くなかった場合を「◎」、少なくとも1枚の液晶表示素子に色むらが微かにあった場合を「○」、少なくとも1枚の液晶表示素子に色むらが少しあった場合を「△」、少なくとも1枚の液晶表示素子に色むらがかなりあった場合を「×」として液晶汚染性を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。
Claims (5)
- 硬化性樹脂と、光ラジカル重合開始剤とを含有する液晶表示素子用シール剤であって、
前記光ラジカル重合開始剤は、下記式(1-1)で表される化合物及び/又は下記式(1-2)で表される化合物を含有することを特徴とする液晶表示素子用シール剤。
式(1-2)中、Yは、炭素数2~8のアルキル基、又は、シクロペンチル環の少なくとも1つの水素がメチル基若しくはエチル基で置換されていてもよい2-シクロペンチルエチル基を表し、Rは、メチル基又はエチル基を表す。 - 遮光剤を含有することを特徴とする請求項1又は2記載の液晶表示素子用シール剤。
- 請求項1、2又は3記載の液晶表示素子用シール剤と、導電性微粒子とを含有することを特徴とする上下導通材料。
- 請求項1、2若しくは3記載の液晶表示素子用シール剤、又は、請求項4記載の上下導通材料を用いてなることを特徴とする液晶表示素子。
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JPWO2018207730A1 (ja) * | 2017-05-08 | 2019-06-27 | 積水化学工業株式会社 | 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子 |
CN110168441A (zh) * | 2017-05-08 | 2019-08-23 | 积水化学工业株式会社 | 液晶显示元件用密封剂、上下导通材料和液晶显示元件 |
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