WO2018037861A1 - Sealing agent for liquid crystal display elements, vertically conducting material, and liquid crystal display element - Google Patents
Sealing agent for liquid crystal display elements, vertically conducting material, and liquid crystal display element Download PDFInfo
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- WO2018037861A1 WO2018037861A1 PCT/JP2017/028030 JP2017028030W WO2018037861A1 WO 2018037861 A1 WO2018037861 A1 WO 2018037861A1 JP 2017028030 W JP2017028030 W JP 2017028030W WO 2018037861 A1 WO2018037861 A1 WO 2018037861A1
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- liquid crystal
- crystal display
- meth
- acrylate
- filler
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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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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- 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
Definitions
- the present invention relates to a sealant for a liquid crystal display element that can achieve both adhesiveness and moisture permeation prevention properties of a cured product. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using 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.
- liquid crystal display elements are increasingly required to have moisture resistance reliability when driving in high-temperature and high-humidity environments, and the sealant prevents water from entering from the outside.
- the sealant prevents water from entering from the outside.
- the adhesion of the sealing agent to the substrate, etc. is improved, and the moisture permeability of the sealing agent is prevented. It is necessary to improve the performance.
- a method for improving the moisture permeation preventive property of the sealing agent for example, a method of blending a filler such as talc can be considered.
- a filler such as talc is added in this way, when a strict moisture resistance reliability test is performed, there is a problem that display unevenness occurs in the liquid crystal display element.
- An object of this invention is to provide the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened
- the present invention contains a curable resin, a polymerization initiator and / or a thermosetting agent, and a filler, the filler includes a filler having a group having a reactive double bond on the surface, It is a sealing compound for liquid crystal display elements whose content is 55 to 100 weight part with respect to 100 weight part of said curable resin.
- the present invention is described in detail below.
- the inventor has surprisingly improved adhesion and curing by blending a filler including a filler having a group having a reactive double bond on the surface so that the content of the entire filler is in a specific range.
- the present inventors have found that a sealing agent for liquid crystal display elements that can achieve both moisture permeation preventive properties can be obtained, and have completed the present invention.
- the sealing agent for liquid crystal display elements of this invention contains a filler.
- the filler includes a filler having a group having a reactive double bond on the surface.
- the sealing compound for liquid crystal display elements of this invention becomes excellent in both adhesiveness and the moisture-permeation prevention property of hardened
- the sealing agent for liquid crystal display elements of the present invention can achieve both adhesiveness and moisture permeation preventive property of the cured product. It is considered that this is because a group having a reactive double bond on the surface of the filler reacts with the curable resin when the sealing agent is cured.
- the preferable lower limit of the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface is 2 ⁇ eq / g, and the preferable upper limit is 50 ⁇ eq / g.
- the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface thereof is within this range, the adhesive property of the obtained sealing agent for liquid crystal display elements and the moisture permeation preventive property of the cured product are improved. The effect of achieving both can be further improved.
- the more preferable lower limit of the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface thereof is 5 ⁇ eq / g
- the more preferable upper limit is 30 ⁇ eq / g
- the still more preferable lower limit is 8 ⁇ eq / g
- the more preferable upper limit is 20 ⁇ eq / g.
- the “reactive double bond equivalent of a filler having a group having a reactive double bond on the surface” means a value determined from an iodine value measured by a method according to JIS K 0070.
- the group having a reactive double bond is preferably a (meth) acryloyl group.
- the “(meth) acryloyl” means acryloyl or methacryloyl.
- the filler having a group having a reactive double bond on the surface can be obtained by a method of surface-treating base particles with a surface treatment agent capable of imparting a group having a reactive double bond.
- the base particles include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide.
- Organic particles such as inorganic particles such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, etc. Particles.
- a silane coupling agent having a group having a reactive double bond is preferably used because the group having the reactive double bond can be more reliably introduced to the filler surface.
- the silane coupling agent having a group having a reactive double bond include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and 3-methacrylic acid.
- Examples include loxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-methacryloxypropyltriethoxysilane.
- Examples of the method for surface-treating the substrate particles with the surface treatment agent include, for example, a method of spraying a mixed solution of water and the surface treatment agent on the fluidized substrate particles, alcohol, toluene, and the like. Examples include a method in which the base particles are added to the organic solvent, the surface treatment agent and water are further added, and then the water and the organic solvent are evaporated and dried by an evaporator.
- a preferable lower limit is 40 parts by weight and a preferable upper limit is 100 parts by weight with respect to 100 parts by weight of the substrate particles.
- the amount of the surface treatment agent used is within this range, the resulting sealant for a liquid crystal display element is more excellent in the effect of achieving both the adhesiveness and the moisture permeation preventing property of the cured product.
- the minimum with the more preferable usage-amount of the said surface treating agent is 55 weight part, and a more preferable upper limit is 85 weight part.
- the minimum with a preferable average particle diameter of the filler which has the group which has the said reactive double bond on the surface is 0.1 micrometer, and a preferable upper limit is 2 micrometers.
- the average particle size of the filler having a group having a reactive double bond on the surface thereof is within this range, so that the adhesive property and the cured product can be obtained without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. It is excellent due to the effect of achieving both moisture permeation prevention.
- the average particle size of the filler having a group having a reactive double bond on the surface is the particle size of 10 particles observed at a magnification of 5000 times using the above-mentioned scanning electron microscope ( Mean value of major axis).
- the sealant for a liquid crystal display element of the present invention may be used in combination with a filler having a group having a reactive double bond on the surface thereof and other fillers as long as the object of the present invention is not impaired.
- a filler having a methyl group on the surface or a filler having an epoxy group on the surface a filler having a group having the reactive double bond on the surface. You may use together.
- the minimum with preferable content of the filler which has the group which has the said reactive double bond in the whole said filler on the surface is 75 weight%.
- the content of the filler having a group having a reactive double bond on the surface thereof is 75% by weight or more, the obtained sealing agent for a liquid crystal display element achieves both adhesion and moisture permeation prevention of a cured product. It will be more effective.
- the more preferable lower limit of the content of the filler having a group having the reactive double bond on the surface is 85% by weight, and the sealing agent for liquid crystal display elements of the present invention has the reactive double bond as the filler. Most preferably, it contains only fillers having groups on the surface.
- the content of the whole filler is 55 parts by weight for the lower limit and 100 parts by weight for the upper limit with respect to 100 parts by weight of the curable resin.
- the adhesive and the moisture permeation preventive property of the cured product are both excellent without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. It becomes.
- the minimum with preferable content of the said whole filler is 60 weight part, a preferable upper limit is 75 weight part, and a more preferable upper limit is 70 weight part.
- 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) acryl” means acryl or methacryl
- the “(meth) acryl compound” means a compound having a (meth) acryloyl group.
- “Meth) acryloyl” means acryloyl or methacryloyl.
- the (meth) acrylic compound examples include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable.
- the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
- the “(meth) acrylate” means acrylate or methacrylate
- the “epoxy (meth) acrylate” refers to all the epoxy groups in the epoxy compound and (meth) acrylic acid. It represents the reacted compound.
- 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).
- epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
- Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRY370R ), 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 80MF 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, Denacol acrylate DA-3
- urethane (meth) acrylate for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtainable.
- isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated MDI, polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylylene diene Isocyanate, 1,6,11-undecane triisocyanate and the like.
- MDI diphenylmethane-4,4′-diisocyanate
- XDI
- the isocyanate compound is obtained by, for example, reacting a polyol such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and an excess isocyanate compound. It is also possible to use chain-extended isocyanate compounds.
- Examples of the (meth) acrylic acid derivative having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- hydroxyalkyl mono (meth) acrylates such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like mono (meta) )
- Epoxy (meth) acrylates such as acrylate, mono (meth) acrylate or di (meth) acrylate of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy acrylate Etc. The.
- 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 said curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the sealing compound for liquid crystal display elements obtained.
- an epoxy compound the epoxy compound used as a raw material for synthesize
- 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.
- UVACURE1561 made by Daicel Ornex
- 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 to the epoxy group is within this range, the resulting sealant for a liquid crystal display element is more excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.
- the curable resin preferably has a hydrogen bonding unit such as —OH group, —NH— group, and —NH 2 group from the viewpoint of suppressing liquid crystal contamination.
- the sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
- a polymerization initiator a photo radical polymerization initiator or a thermal radical polymerization initiator can be used.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an azo initiator made of an azo compound is preferred, and a polymer azo initiator made of a polymer azo compound is more preferred.
- the “polymer azo compound” 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. To do.
- 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
- Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
- Examples of the 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 the polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) and terminal amino acid. And a polycondensate of polydimethylsiloxane having a group.
- Examples of commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). It is done.
- Examples of the azo initiator other than the polymer azo initiator 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 polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination.
- a more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.
- thermosetting agent examples 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 upper limit with more preferable content of the said thermosetting agent is 30 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 for example, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like are preferably used. It is done. These are excellent in the effect of improving the adhesion to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin. 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.
- the content of the silane coupling agent is within this range, the obtained sealing agent for liquid crystal display elements is excellent in adhesiveness while suppressing the occurrence of liquid crystal contamination.
- 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 a sufficient light-shielding property, and thus 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
- a preferable minimum is 1 nm and a preferable upper limit is 5000 nm.
- the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements is greatly increased, and workability may be deteriorated.
- the primary particle diameter of the light-shielding agent exceeds 5000 nm, applicability of the obtained sealing agent for liquid crystal display elements to the substrate may be deteriorated.
- 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, and 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 effect of improving the light-shielding property while suppressing deterioration of the adhesiveness, strength after curing, and drawing property of the obtained sealing agent for liquid crystal display elements is excellent. It will be a thing.
- 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.
- the sealing agent for liquid crystal display elements of the present invention may further include a reactive diluent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, a polymerization inhibitor, organic fine particles, and other coupling agents as necessary.
- An additive may be contained.
- 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 roll, a curable resin, and a polymerization
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
- examples thereof include a method of mixing an initiator and / or a thermosetting agent, a filler, and 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 preferred lower limit of 100,000 mPa ⁇ s and a preferred upper limit of 500,000 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.
- the more preferable lower limit of the viscosity is 200,000 mPa ⁇ s, and the more preferable upper limit is 400,000 mPa ⁇ s.
- a vertical conduction material can be produced by blending conductive fine particles with the sealing agent for liquid crystal display elements 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 are not particularly limited, and metal balls, those obtained by forming a conductive metal layer on the surface of resin fine particles, and the like can be used. Among them, 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. Specific examples include a method having the following steps. First, a step of forming a frame-shaped seal pattern on one of two transparent substrates having electrodes such as an ITO thin film by screen printing, dispenser application, or the like is performed. Next, a step of applying droplets of liquid crystal onto the entire surface of the frame of the seal pattern and applying the other substrate under vacuum is performed. Thereafter, a liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealing agent and a method of heating and temporarily curing the temporarily cured sealing agent. it can.
- the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal display elements can be provided.
- silica having methacryloyl group on the surface 100 parts by weight of silica particles having an average particle diameter of 0.7 ⁇ m synthesized by the sol-gel method are put in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-methacryloxypropyltrimethoxysilane are stirred while stirring in a nitrogen atmosphere. Sprayed, heated at 260 ° C. for 80 minutes and then cooled. Then, it was pulverized with a ball mill to prepare methacryloyl group-treated silica (average particle size 0.7 ⁇ m).
- silica having acryloyl group on the surface 100 parts by weight of silica particles having an average particle diameter of 0.7 ⁇ m synthesized by the sol-gel method are placed in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-acryloxypropyltrimethoxysilane are added while stirring in a nitrogen atmosphere. Sprayed, heated at 260 ° C. for 80 minutes and then cooled. Thereafter, the mixture was crushed with a ball mill to prepare acryloyl group-treated silica (average particle size 0.7 ⁇ m).
- silica having methyl groups on the surface 100 parts by weight of silica particles having an average particle diameter of 0.7 ⁇ m synthesized by the sol-gel method are put in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of hexamethyldisilazane are sprayed while stirring in a nitrogen atmosphere. The mixture was heated at 80 ° C. for 80 minutes and then cooled. Thereafter, the mixture was crushed with a ball mill to prepare hexamethyldisilazane-treated silica (average particle size: 0.7 ⁇ m).
- silica having epoxy group on the surface 100 parts by weight of silica particles having an average particle diameter of 0.7 ⁇ m synthesized by the sol-gel method are placed in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-glycidoxypropyltrimethoxysilane are stirred in a nitrogen atmosphere. Was sprayed, heated at 260 ° C. for 80 minutes, and then cooled. Thereafter, the mixture was crushed by a ball mill to prepare epoxy group-treated silica (average particle size 0.7 ⁇ m).
- Examples 1 to 8, Comparative Examples 1 to 6 According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls Sealants for liquid crystal display elements of Examples 1 to 8 and Comparative Examples 1 to 6 were prepared.
- the two substrates were bonded together under a reduced pressure of 5 Pa with a vacuum bonding apparatus.
- the cell after bonding was irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then the sealant was thermally cured by heating at 120 ° C. for 60 minutes to prepare a drawing property evaluation test piece.
- the sealing agent in the obtained drawing property evaluation test piece was observed.
- the tension test (5 mm / sec) was done with the chuck
- the sealing compound for liquid crystal display elements which can make adhesiveness and moisture permeability prevention property of hardened
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal display elements can be provided.
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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。 In recent years, as a method of manufacturing a liquid crystal display element such as a liquid crystal display cell, a curable resin and a light as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used. 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.
In the dropping method, first, a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing. Next, 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. At present, this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
このような狭額縁設計に伴い、液晶表示素子において、画素領域からシール剤までの距離が近くなっており、シール剤によって液晶が汚染されることによる表示むらが生じやすくなっている。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for miniaturization, there is a narrow frame of the liquid crystal display unit, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
With such a narrow frame design, in the liquid crystal display element, the distance from the pixel region to the sealing agent is close, and display unevenness due to contamination of the liquid crystal by the sealing agent is likely to occur.
以下に本発明を詳述する。 The present invention contains a curable resin, a polymerization initiator and / or a thermosetting agent, and a filler, the filler includes a filler having a group having a reactive double bond on the surface, It is a sealing compound for liquid crystal display elements whose content is 55 to 100 weight part with respect to 100 weight part of said curable resin.
The present invention is described in detail below.
上記フィラーは、反応性二重結合を有する基を表面に有するフィラーを含む。上記反応性二重結合を有する基を表面に有するフィラー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、接着性と硬化物の透湿防止性との両方に優れるものとなる。
上記反応性二重結合を有する基を表面に有するフィラー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が接着性と硬化物の透湿防止性とを両立させることができる理由としては、シール剤を硬化させる際に該フィラーの表面の反応性二重結合を有する基と硬化性樹脂とが反応するためであると考えられる。 The sealing agent for liquid crystal display elements of this invention contains a filler.
The filler includes a filler having a group having a reactive double bond on the surface. By containing the filler which has the group which has the said reactive double bond on the surface, the sealing compound for liquid crystal display elements of this invention becomes excellent in both adhesiveness and the moisture-permeation prevention property of hardened | cured material.
By including a filler having a group having a reactive double bond on the surface, the sealing agent for liquid crystal display elements of the present invention can achieve both adhesiveness and moisture permeation preventive property of the cured product. It is considered that this is because a group having a reactive double bond on the surface of the filler reacts with the curable resin when the sealing agent is cured.
なお、上記「反応性二重結合を有する基を表面に有するフィラーの反応性二重結合当量」は、JIS K 0070に準拠した方法により測定されるヨウ素価から求められる値を意味する。 The preferable lower limit of the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface is 2 μeq / g, and the preferable upper limit is 50 μeq / g. When the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface thereof is within this range, the adhesive property of the obtained sealing agent for liquid crystal display elements and the moisture permeation preventive property of the cured product are improved. The effect of achieving both can be further improved. The more preferable lower limit of the reactive double bond equivalent of the filler having a group having a reactive double bond on the surface thereof is 5 μeq / g, the more preferable upper limit is 30 μeq / g, the still more preferable lower limit is 8 μeq / g, and the more preferable upper limit is 20 μeq / g.
The “reactive double bond equivalent of a filler having a group having a reactive double bond on the surface” means a value determined from an iodine value measured by a method according to JIS K 0070.
なお、本明細書において上記「(メタ)アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 The group having a reactive double bond is preferably a (meth) acryloyl group.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.
上記反応性二重結合を有する基を有するシランカップリング剤としては、例えば、3-アクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-アクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-アクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-アクリロキシプロピルトリエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン等が挙げられる。 As the surface treatment agent, a silane coupling agent having a group having a reactive double bond is preferably used because the group having the reactive double bond can be more reliably introduced to the filler surface.
Examples of the silane coupling agent having a group having a reactive double bond include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldimethoxysilane, and 3-methacrylic acid. Examples include loxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, and 3-methacryloxypropyltriethoxysilane.
なお、本明細書において上記反応性二重結合を有する基を表面に有するフィラーの平均粒子径は、上述した走査型電子顕微鏡を用いて、5000倍の倍率で観察した粒子10個の粒子径(長径)の平均値を意味する。 The minimum with a preferable average particle diameter of the filler which has the group which has the said reactive double bond on the surface is 0.1 micrometer, and a preferable upper limit is 2 micrometers. The average particle size of the filler having a group having a reactive double bond on the surface thereof is within this range, so that the adhesive property and the cured product can be obtained without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements. It is excellent due to the effect of achieving both moisture permeation prevention.
In the present specification, the average particle size of the filler having a group having a reactive double bond on the surface is the particle size of 10 particles observed at a magnification of 5000 times using the above-mentioned scanning electron microscope ( Mean value of major axis).
例えば、配向膜に対する接着性を向上させるために、上記その他のフィラーとして、メチル基を表面に有するフィラーやエポキシ基を表面に有するフィラーを上記反応性二重結合を有する基を表面に有するフィラーと併用してもよい。 The sealant for a liquid crystal display element of the present invention may be used in combination with a filler having a group having a reactive double bond on the surface thereof and other fillers as long as the object of the present invention is not impaired.
For example, in order to improve the adhesion to the alignment film, as the other filler, a filler having a methyl group on the surface or a filler having an epoxy group on the surface, a filler having a group having the reactive double bond on the surface, You may use together.
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。
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、(メタ)アクリロイル基を有する化合物を意味し、上記「(メタ)アクリロイル」とは、アクリロイル又はメタクリロイルを意味する。 The sealing agent for liquid crystal display elements of this invention contains curable resin.
The curable resin preferably contains a (meth) acrylic compound.
In the present specification, the “(meth) acryl” means acryl or methacryl, and the “(meth) acryl compound” means a compound having a (meth) acryloyl group. “Meth) acryloyl” means acryloyl or methacryloyl.
なお、本明細書において、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し、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。 Examples of the (meth) acrylic compound include (meth) acrylic acid ester compounds, epoxy (meth) acrylates, urethane (meth) acrylates, and the like. Of these, epoxy (meth) acrylate is preferable. The (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” refers to all the epoxy groups in the epoxy compound and (meth) acrylic acid. It represents the reacted compound.
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。 As what is marketed among the said bisphenol A type epoxy resins, jER828EL, jER1004 (all are the Mitsubishi Chemical company make), Epiklon 850CRP (made by DIC company), etc. are mentioned, for example.
As what is marketed among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical company make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
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).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
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 Nippon Steel & Sumikin Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), jER1031, jER1032 (all Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
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。 The said curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the sealing compound for liquid crystal display elements obtained. As said epoxy compound, the epoxy compound used as a raw material for synthesize | combining the said epoxy (meth) acrylate, a partial (meth) acryl modified epoxy resin, etc. are mentioned, for example.
In the present specification, 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.
上記重合開始剤としては、光ラジカル重合開始剤や熱ラジカル重合開始剤を用いることができる。 The sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
As the polymerization initiator, a photo radical polymerization initiator or a thermal radical polymerization initiator can be used.
なお、本明細書において上記「高分子アゾ化合物」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。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, from the viewpoint of suppressing liquid crystal contamination, an azo initiator made of an azo compound is preferred, and a polymer azo initiator made of a polymer azo compound is more preferred.
In the present specification, the “polymer azo compound” 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. To do.
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。 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. When the number average molecular weight of the polymeric azo initiator is within this range, it can be easily mixed with a curable resin while suppressing liquid crystal contamination. 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.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). 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 KK).
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。
上記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る。
上記高分子アゾ開始剤のうち市販されているものとしては、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、高分子アゾ開始剤以外のアゾ開始剤の例としては、例えば、V-65、V-501(いずれも和光純薬工業社製)等が挙げられる。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the 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 the polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) and terminal amino acid. And a polycondensate of polydimethylsiloxane having a group.
Examples of commercially available polymer azo initiators include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). It is done.
Examples of the azo initiator other than the polymer azo initiator include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
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。 Examples of the organic acid hydrazide include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
Examples of commercially available organic acid hydrazides 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.
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。 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.
In addition, 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 a sufficient light-shielding property, and thus has high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
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。 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.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
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。 Although the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board | substrates of a liquid crystal display element, a preferable minimum is 1 nm and a preferable upper limit is 5000 nm. When the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained sealing agent for liquid crystal display elements is greatly increased, and workability may be deteriorated. When the primary particle diameter of the light-shielding agent exceeds 5000 nm, applicability of the obtained sealing agent for liquid crystal display elements to the substrate may be deteriorated. 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, and 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.).
本発明の液晶表示素子を製造する方法としては、液晶滴下工法が好適に用いられ、具体的には例えば、以下の各工程を有する方法等が挙げられる。
まず、ITO薄膜等の電極を有する2枚の透明基板の一方に、本発明の液晶表示素子用シール剤をスクリーン印刷、ディスペンサー塗布等により枠状のシールパターンを形成する工程を行う。次いで、液晶の微小滴をシールパターンの枠内全面に滴下塗布し、真空下で他方の基板を重ね合わせる工程を行う。その後、シールパターン部分に紫外線等の光を照射してシール剤を仮硬化させる工程、及び、仮硬化させたシール剤を加熱して本硬化させる工程を行う方法により、液晶表示素子を得ることができる。 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.
As a method for producing the liquid crystal display element of the present invention, a liquid crystal dropping method is preferably used. Specific examples include a method having the following steps.
First, a step of forming a frame-shaped seal pattern on one of two transparent substrates having electrodes such as an ITO thin film by screen printing, dispenser application, or the like is performed. Next, a step of applying droplets of liquid crystal onto the entire surface of the frame of the seal pattern and applying the other substrate under vacuum is performed. Thereafter, a liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealing agent and a method of heating and temporarily curing the temporarily cured sealing agent. it can.
ゾルゲル法で合成した平均粒子径0.7μmのシリカ粒子を260℃で80分間加熱した後に冷却し調製した。 (Preparation of untreated silica)
Silica particles with an average particle size of 0.7 μm synthesized by the sol-gel method were heated at 260 ° C. for 80 minutes and then cooled to prepare.
ゾルゲル法で合成した平均粒子径0.7μmのシリカ粒子100重量部をヘンシェルミキサーに入れ、窒素雰囲気下にて撹拌しながら水0.5重量部及び3-メタクリロキシプロピルトリメトキシシラン10重量部を噴霧し、260℃で80分間加熱した後に冷却した。その後、ボールミルで解砕して、メタクリロイル基処理シリカ(平均粒子径0.7μm)を調製した。 (Production of silica having methacryloyl group on the surface)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are put in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-methacryloxypropyltrimethoxysilane are stirred while stirring in a nitrogen atmosphere. Sprayed, heated at 260 ° C. for 80 minutes and then cooled. Then, it was pulverized with a ball mill to prepare methacryloyl group-treated silica (average particle size 0.7 μm).
ゾルゲル法で合成した平均粒子径0.7μmのシリカ粒子100重量部をヘンシェルミキサーに入れ、窒素雰囲気下にて撹拌しながら水0.5重量部及び3-アクリロキシプロピルトリメトキシシラン10重量部を噴霧し、260℃で80分間加熱した後に冷却した。その後、ボールミルで解砕して、アクリロイル基処理シリカ(平均粒子径0.7μm)を調製した。 (Production of silica having acryloyl group on the surface)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are placed in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-acryloxypropyltrimethoxysilane are added while stirring in a nitrogen atmosphere. Sprayed, heated at 260 ° C. for 80 minutes and then cooled. Thereafter, the mixture was crushed with a ball mill to prepare acryloyl group-treated silica (average particle size 0.7 μm).
ゾルゲル法で合成した平均粒子径0.7μmのシリカ粒子100重量部をヘンシェルミキサーに入れ、窒素雰囲気下にて撹拌しながら水0.5重量部及びヘキサメチルジシラザン10重量部を噴霧し、260℃で80分間加熱した後に冷却した。その後、ボールミルで解砕して、ヘキサメチルジシラザン処理シリカ(平均粒子径0.7μm)を調製した。 (Production of silica having methyl groups on the surface)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are put in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of hexamethyldisilazane are sprayed while stirring in a nitrogen atmosphere. The mixture was heated at 80 ° C. for 80 minutes and then cooled. Thereafter, the mixture was crushed with a ball mill to prepare hexamethyldisilazane-treated silica (average particle size: 0.7 μm).
ゾルゲル法で合成した平均粒子径0.7μmのシリカ粒子100重量部をヘンシェルミキサーに入れ、窒素雰囲気下にて撹拌しながら水0.5重量部及び3-グリシドキシプロピルトリメトキシシラン10重量部を噴霧し、260℃で80分間加熱した後に冷却した。その後、ボールミルで解砕して、エポキシ基処理シリカ(平均粒子径0.7μm)を調製した。 (Preparation of silica having epoxy group on the surface)
100 parts by weight of silica particles having an average particle diameter of 0.7 μm synthesized by the sol-gel method are placed in a Henschel mixer, and 0.5 parts by weight of water and 10 parts by weight of 3-glycidoxypropyltrimethoxysilane are stirred in a nitrogen atmosphere. Was sprayed, heated at 260 ° C. for 80 minutes, and then cooled. Thereafter, the mixture was crushed by a ball mill to prepare epoxy group-treated silica (average particle size 0.7 μm).
表1、2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1~8、比較例1~6の液晶表示素子用シール剤を調製した。 (Examples 1 to 8, Comparative Examples 1 to 6)
According to the mixing ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Netaro ”), by further mixing using three rolls Sealants for liquid crystal display elements of Examples 1 to 8 and Comparative Examples 1 to 6 were prepared.
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、2に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal display elements obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
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、シリカスペーサー(積水化学工業社製、「SI-H055」)を1重量%配合し、脱泡処理をしてシール剤中の泡を取り除いた後、ディスペンス用のシリンジ(武蔵エンジニアリング社製、「PSY-10E」)に充填し、再び脱泡処理を行った。次いで、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)を用いて、2枚のITO薄膜付きガラス基板のうちの一方に長方形の枠を描く様にシール剤を塗布し、他方のITO薄膜付きガラス基板を重ね、真空貼り合わせ装置にて5Paの減圧下にて2枚の基板を貼り合わせた。貼り合わせた後のセルにメタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによってシール剤を熱硬化させ、描画性評価試験片を作製した。得られた描画性評価試験片内のシール剤を観察した。シール剤に断線不良も端部のうねりもなくきれいなラインが描けていた場合を「◎」、断線不良はないがシール剤の端部にわずかにうねりが生じていた場合を「○」、断線不良はないがシール剤の端部にはっきりとうねりが生じていた場合を「△」、断線不良が生じていた場合を「×」として描画性を評価した。 (Drawability)
In each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples, 1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) is blended, defoamed, After removing the foam, it was filled into a syringe for dispensing (“PSY-10E” manufactured by Musashi Engineering Co., Ltd.), and defoamed again. Next, using a dispenser (“SHOTMASTER 300” manufactured by Musashi Engineering Co., Ltd.), a sealing agent is applied on one of the two glass substrates with an ITO thin film so as to draw a rectangular frame, and the other glass substrate with an ITO thin film. The two substrates were bonded together under a reduced pressure of 5 Pa with a vacuum bonding apparatus. The cell after bonding was irradiated with 3000 mJ / cm 2 ultraviolet rays with a metal halide lamp, and then the sealant was thermally cured by heating at 120 ° C. for 60 minutes to prepare a drawing property evaluation test piece. The sealing agent in the obtained drawing property evaluation test piece was observed. "◎" when the sealant has drawn a clean line with no wire breakage and no waviness at the end, "○" when there is no wire breakage but slight waviness at the end of the sealant, "○" However, the drawing property was evaluated as “Δ” when the end of the sealant was clearly wavy, and “X” when the disconnection failure occurred.
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、シリカスペーサー(積水化学工業社製、「SI-H055」)を1重量%配合し、2枚のITO薄膜付きガラス基板(30×40mm)のうちの一方に微小滴下した。このITO薄膜付きガラス基板にもう一方のITO薄膜付きガラス基板を十字状に貼り合わせ、メタルハライドランプにて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによって接着性試験片を得た。得られた接着性試験片について、上下に配したチャックにて引っ張り試験(5mm/sec)を行った。得られた測定値(kgf)をシール塗布断面積(cm2)で除した値が、35kgf/cm2以上であった場合を「◎」、25kgf/cm2以上35kgf/cm2未満であった場合を「○」、15kgf/cm2以上25kgf/cm2未満であった場合を「△」、15kgf/cm2未満であった場合を「×」として接着性を評価した。 (Adhesiveness)
1% by weight of a silica spacer (“SI-H055” manufactured by Sekisui Chemical Co., Ltd.) was added to each liquid crystal display element sealing agent obtained in Examples and Comparative Examples, and two glass substrates with ITO thin film (30 × 40 mm) was finely dropped on one of them. The glass substrate with the ITO thin film is bonded to the glass substrate with the ITO thin film in a cross shape, irradiated with 3000 mJ / cm 2 of ultraviolet rays with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to thereby test the adhesion test piece. Got. About the obtained adhesive test piece, the tension test (5 mm / sec) was done with the chuck | zipper arranged up and down. The value obtained by dividing the obtained measured value (kgf) by the seal application cross-sectional area (cm 2 ) was 35 kgf / cm 2 or more, “◎”, 25 kgf / cm 2 or more and less than 35 kgf / cm 2 where "○", the case was 15 kgf / cm 2 or more 25 kgf / cm less than 2 "△", and evaluated the adhesiveness of the case was less than 15 kgf / cm 2 as "×".
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を、平滑な離型フィルム上にコーターを用いて厚さ200~300μmとなるように塗布した。次いで、メタルハライドランプを用いて3000mJ/cm2の紫外線を照射した後、120℃で60分加熱することによって透湿度測定用フィルムを得た。JIS Z 0208の防湿包装材料の透湿度試験方法(カップ法)に準じた方法で透湿度試験用カップを作製し、得られた透湿度測定用フィルムを取り付け、温度80℃湿度90%RHの恒温恒湿オーブンに投入して透湿度を測定した。得られた透湿度の値が、50g/m2・24hr未満であった場合を「◎」、50g/m2・24hr以上65g/m2・24hr未満であった場合を「○」、65g/m2・24hr以上80g/m2・24hr未満であった場合を「△」、80g/m2・24hr以上であった場合を「×」として透湿防止性を評価した。 (Moisture permeability prevention)
Each of the sealing agents for liquid crystal display elements obtained in Examples and Comparative Examples was applied on a smooth release film using a coater so as to have a thickness of 200 to 300 μm. Subsequently, after irradiating 3000 mJ / cm < 2 > of ultraviolet-rays using a metal halide lamp, the film for moisture permeability measurement was obtained by heating at 120 degreeC for 60 minutes. A moisture permeability test cup was prepared by a method according to JIS Z 0208 for moisture-proof packaging materials (cup method), the obtained moisture permeability measurement film was attached, and the temperature was 80 ° C. and humidity was 90% RH. The moisture permeability was measured by putting in a constant humidity oven. The case where the obtained moisture permeability value is less than 50 g / m 2 · 24 hr is “◎”, and the case where it is 50 g / m 2 · 24 hr or more and less than 65 g / m 2 · 24 hr is “◯”, 65 g / m m 2 · 24 hr or where more than 80 g / m was less than 2 · 24 hr or "△", was evaluated anti-moisture permeation as "×" the case was 80g / m 2 · 24hr or more.
Claims (4)
- 硬化性樹脂と、重合開始剤及び/又は熱硬化剤と、フィラーとを含有し、
前記フィラーは、反応性二重結合を有する基を表面に有するフィラーを含み、
前記フィラー全体の含有量が、前記硬化性樹脂100重量部に対して55重量部以上100重量部以下である
ことを特徴とする液晶表示素子用シール剤。 Containing a curable resin, a polymerization initiator and / or a thermosetting agent, and a filler,
The filler includes a filler having a group having a reactive double bond on the surface,
Content of the said whole filler is 55 to 100 weight part with respect to 100 weight part of said curable resin, The sealing compound for liquid crystal display elements characterized by the above-mentioned. - 遮光剤を含有することを特徴とする請求項1記載の液晶表示素子用シール剤。 The light-shielding agent is contained, The sealing agent for liquid crystal display elements of Claim 1 characterized by the above-mentioned.
- 請求項1又は2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。 A vertical conduction material comprising the sealing agent for a liquid crystal display element according to claim 1 or 2 and conductive fine particles.
- 請求項1若しくは2記載の液晶表示素子用シール剤又は請求項3記載の上下導通材料を有することを特徴とする液晶表示素子。 A liquid crystal display element comprising the sealing agent for a liquid crystal display element according to claim 1 or 2 or the vertical conduction material according to claim 3.
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JPWO2018037861A1 (en) | 2019-06-20 |
CN108780248A (en) | 2018-11-09 |
KR20190044581A (en) | 2019-04-30 |
TW201823417A (en) | 2018-07-01 |
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