WO2017183583A1 - 液晶表示素子用シール剤、液晶表示素子用シール剤の製造方法、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、液晶表示素子用シール剤の製造方法、上下導通材料、及び、液晶表示素子 Download PDFInfo
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- WO2017183583A1 WO2017183583A1 PCT/JP2017/015318 JP2017015318W WO2017183583A1 WO 2017183583 A1 WO2017183583 A1 WO 2017183583A1 JP 2017015318 W JP2017015318 W JP 2017015318W WO 2017183583 A1 WO2017183583 A1 WO 2017183583A1
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- liquid crystal
- crystal display
- meth
- bisphenol
- epoxy resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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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 is excellent in adhesiveness and light-shielding part curability and that can reduce the burden on the environment. Moreover, this invention relates to the manufacturing method of this sealing compound for liquid crystal display elements, and the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
- a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
- a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. .
- heating is performed to perform main curing, and a liquid crystal display element is manufactured.
- a liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.
- the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
- the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
- An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in adhesiveness and light-shielding part sclerosis
- Another object of the present invention is to provide a manufacturing method of the sealing agent for liquid crystal display elements, and a vertical conduction material and a liquid crystal display element using the sealing agent for liquid crystal display elements.
- the present invention is a liquid crystal display element sealing agent comprising a curable resin and a polymerization initiator and / or a thermosetting agent, wherein the curable resin is a bisphenol A type epoxy resin and / or (meth) acrylic. It is a sealing agent for liquid crystal display elements that contains a modified bisphenol A type epoxy resin and the content of bisphenol A is 50 ppm or less.
- the present invention is described in detail below.
- the present inventors have formulated a chemically and physically excellent bisphenol A type epoxy resin and / or (meth) acryl-modified bisphenol A type epoxy resin as the curable resin contained in the liquid crystal display element sealant. investigated. However, when such a curable resin is used, there is a problem that sufficient light-shielding part curability may not be obtained. The inventors of the present invention have the reason that the light-shielding part curability is deteriorated because bisphenol A slightly present in the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy resin inhibits the polymerization reaction. I thought that there was to be.
- the present inventors have found that by making the content of bisphenol A not more than a specific value, it is possible to obtain a sealing agent for a liquid crystal display element that is excellent in adhesiveness and light-shielding part curability. It came to complete. Moreover, since the sealing agent for liquid crystal display elements of this invention has reduced content of bisphenol A, the environmental load by this bisphenol A can be reduced.
- the sealing agent for liquid crystal display elements of this invention contains curable resin.
- the curable resin contains a bisphenol A type epoxy resin and / or a (meth) acryl-modified bisphenol A type epoxy resin.
- the sealing agent for liquid crystal display elements of the present invention has excellent adhesiveness.
- the “(meth) acryl” means acryl or methacryl.
- the (meth) acryl-modified bisphenol A type epoxy resin may be a completely (meth) acryl-modified bisphenol A type epoxy resin obtained by (meth) acryl-modifying all the epoxy groups of the bisphenol A type epoxy resin, A partial (meth) acryl-modified bisphenol A type epoxy resin in which a part of epoxy groups is (meth) acryl-modified may be used.
- the liquid crystal display element sealant of the present invention has a bisphenol A content of 50 ppm or less.
- the content of the bisphenol A is set to 50 ppm or less, whereby the liquid crystal display element seal of the present invention is used.
- the agent is excellent in adhesiveness and light-shielding part curability, and can reduce the burden on the environment.
- the content of bisphenol A can be quantitatively measured using liquid chromatography by extracting bisphenol A from a sealing agent using an arbitrary solution such as a dimethyl sulfoxide solution.
- the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy resin can be removed by washing with pure water.
- the purification method include a method of purification by physical adsorption removal of bisphenol A using an adsorbent.
- a method for producing a sealing agent for a liquid crystal display device comprising: a step and a step of mixing a purified bisphenol A type epoxy resin and / or a (meth) acryl-modified bisphenol A type epoxy resin with at least a polymerization initiator and / or a thermosetting agent.
- a step of purifying bisphenol A type epoxy resin and / or (meth) acryl-modified bisphenol A type epoxy resin by physical adsorption removal of bisphenol A using an adsorbent a purified bisphenol A type epoxy resin and / or Or (meth) acryl-modified bisphenol A type epoxy
- Method of manufacturing a liquid crystal display device for sealing agent and a step of mixing with a resin at least a polymerization initiator and / or thermal curing agent is also one of the present invention, respectively.
- the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy resin When purifying the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy resin by washing and removing bisphenol A with pure water, the bisphenol A type epoxy resin and In addition, the above (meth) acryl-modified bisphenol A type epoxy resin and pure water are added, and the mixture can be purified by repeatedly performing a washing operation for separating pure water after stirring while heating.
- the removal by washing with water is preferably performed using hot water of 40 ° C. to 50 ° C.
- the adsorbent used include charcoal, Carbon-based porous materials such as coal, activated carbon and carbon black, inorganic porous materials such as silica gel, alumina and magnesia, zirconia crosslinked material, alumina crosslinked material, chromium oxide crosslinked material, titanium oxide crosslinked material, iron oxide crosslinked material And clay-based porous bodies, porous glasses, zeolites, styrene-divinylbenzene copolymers, polyacrylic ester-based crosslinked bodies, and ion exchange resins obtained by chemically modifying these.
- charcoal Carbon-based porous materials such as coal, activated carbon and carbon black
- inorganic porous materials such as silica gel, alumina and magnesia, zirconia crosslinked material, alumina crosslinked material, chromium oxide crosslinked material, titanium oxide crosslinked material, iron oxide crosslinked material
- the curable resin may contain other curable resins in addition to the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy resin.
- the other curable resins include other (meth) acryl compounds other than the complete (meth) acryl-modified bisphenol A epoxy resin, the bisphenol A epoxy resin, and the partial (meth) acryl-modified bisphenol A epoxy.
- examples include other epoxy compounds other than resins.
- the curable resin contains the complete (meth) acryl-modified bisphenol A type epoxy resin and / or the other (meth) acrylic compound (these are also simply referred to as “(meth) acrylic compounds”). It is preferable to do.
- Examples of the other (meth) acrylic compounds include, for example, (meth) acrylic acid ester compounds obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and bisphenol A type epoxy resin Other complete (meth) acryl-modified epoxy resins obtained by reacting with an epoxy compound, urethane (meth) acrylate obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group, etc. .
- the “(meth) acrylate” means acrylate or methacrylate.
- 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, pentaerythritol tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl Phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaeryth Penta (meth) acrylate, dipentaeryth
- the other complete (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy compound other than bisphenol A type epoxy resin with (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. And the like.
- Examples of the epoxy compound used as a raw material for synthesizing the other complete (meth) acryl-modified epoxy resin include, for example, bisphenol F type epoxy resin, bisphenol S type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type.
- 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 epoxy resins include Epicoat 630 (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 resins 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.), Epicoat 1031 and Epicoat 1032. (All manufactured by Mitsubishi Chemical), EXA-7120 (manufactured by DIC), TEPIC (manufactured by Nissan Chemical) and the like.
- the urethane (meth) acrylate is obtained, 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. be able to.
- 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
- 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, which is a raw material of the urethane (meth) acrylate include, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, and 1,4-butane.
- Mono (meth) acrylates of dihydric alcohols such as diols and polyethylene glycols
- mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane, glycerin, and others mentioned above Complete (meth) acryl-modified epoxy resin 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.), EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8803, EBECRYL8807, EBECRYL9260, EBECRYL1290, EBECRYL5129, EBECRYL4842, EBECRYL210, EBECRYL4827, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700, EBECRYL6700 , Art resin N-1255, Art Resin UN-330, Art Resin UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U-
- the (meth) acrylic compound preferably has a hydrogen-bonding unit such as —OH group, —NH— group, and —NH 2 group from the viewpoint of suppressing adverse effects on the liquid crystal.
- the upper limit with the preferable ratio of the epoxy group with respect to the total amount of the epoxy group and (meth) acryloyl group in the said whole curable resin is 50 mol%.
- the ratio of the epoxy group is 50 mol% or less, the resulting liquid crystal display element sealant is less soluble in the liquid crystal and the liquid crystal contamination is lower. It will be excellent.
- a more preferable upper limit of the ratio of the epoxy group is 20 mol%.
- Examples of the other epoxy compounds include, for example, the epoxy compounds mentioned as raw materials for synthesizing the other complete (meth) acryl-modified epoxy resins, and portions other than the partial (meth) acryl-modified bisphenol A type epoxy resins ( And a (meth) acryl-modified epoxy resin.
- the sealing agent for liquid crystal display elements of the present invention contains the other curable resin, the bisphenol A type epoxy resin and / or the (meth) acryl-modified bisphenol A type epoxy in 100 parts by weight of the curable resin as a whole.
- the preferable lower limit of the resin content is 10 parts by weight, and the preferable upper limit is 100 parts by weight.
- the content of the bisphenol A-type epoxy resin and / or the (meth) acryl-modified bisphenol A-type epoxy resin is within this range, the obtained sealing agent for liquid crystal display elements has adhesiveness, applicability, and low liquid crystal contamination.
- the minimum with more preferable content of the said bisphenol A type epoxy resin and / or the said (meth) acryl modified bisphenol A type epoxy resin is 20 weight part, and a more preferable upper limit is 90 weight part.
- the sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
- a radical polymerization initiator is preferably used from the viewpoint of curing speed and the like.
- the sealing agent for liquid crystal display elements of the present invention has such an extremely small content of bisphenol A that it inhibits such curing inhibition. It suppresses and becomes excellent in light-shielding part curability.
- the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
- photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, 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 ), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), 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 initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
- 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.
- 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 polymers 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 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When 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.
- the minimum with more preferable content of the said polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
- 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 thermosetting property can be further improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal display elements obtained will become high, and applicability
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, improving moisture permeability of cured products, and the like. preferable.
- the 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.
- the minimum with preferable content of the said filler in the sealing compound for liquid crystal display elements of this invention is 10 weight%, and a preferable upper limit is 70 weight%.
- a preferable upper limit is 70 weight%.
- the more preferable lower limit of the content of the filler is 20% by weight, and the more preferable upper limit is 60% by weight.
- 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.
- the minimum with preferable content of the said silane coupling agent in the sealing compound for liquid crystal display elements of this invention is 0.1 weight%, and a preferable upper limit is 10 weight%.
- a preferable upper limit is 10 weight%.
- the minimum with more preferable content of the said silane coupling agent is 0.3 weight%, and a more preferable upper limit is 5 weight%.
- 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 minimum with preferable content of the said light-shielding agent in the sealing compound for liquid crystal display elements of this invention is 5 weight%, and a preferable upper limit is 80 weight%.
- the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can.
- the more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
- the sealing agent for liquid crystal display elements of the present invention is further added as necessary, stress relieving agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc.
- An agent or the like 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 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 preferable lower limit of 50,000 mPa ⁇ s and a preferable upper limit of 700,000 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 100,000 mPa ⁇ s, and a more preferable upper limit is 500,000 mPa ⁇ s.
- As the E-type viscometer for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.
- 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 sealing compound for liquid crystal display elements which is excellent in adhesiveness and light-shielding part sclerosis
- the manufacturing method of this sealing compound for liquid crystal display elements, and 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 5 and Comparative Examples 1 and 2 According to the mixing ratio described in Table 1, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Nertaro”), and then further mixed using three rolls. To 5 and Comparative Examples 1 and 2 were prepared.
- Each liquid crystal display element sealing agent obtained in Examples and Comparative Examples was prepared to be a 0.1 wt / vol% dimethyl sulfoxide solution and shaken for 2 hours. Subsequently, the obtained solution was diluted 10-fold with methanol, filtered through a 0.2 ⁇ m filter, and the content of bisphenol A was measured by liquid chromatography using an external standard method.
- the adhesive strength was measured using the tension gauge.
- the resulting value obtained by dividing measured values (kgf) in the seal coating cross sectional area (cm 2) is a case was 35 kgf / cm 2 or more " ⁇ " was 30 kgf / cm 2 or more 35 kgf / cm less than 2 where " ⁇ ", the case was 25 kgf / cm 2 or more 30 kgf / cm less than 2 " ⁇ ", and evaluated the adhesiveness of the case was less than 25 kgf / cm 2 as " ⁇ ".
- the obtained sealant is applied to the central part of the substrate A (boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded, the sealant is sufficiently applied.
- 100 mW / cm 2 ultraviolet rays were irradiated for 5 seconds from the substrate A side using a metal halide lamp.
- the substrates A and B are peeled off using a cutter, and the spectrum is measured by a microscopic IR method for the sealant on a point 50 ⁇ m away from the direct ultraviolet irradiation part (the part shielded from light by chromium vapor deposition).
- the conversion rate of the inside (meth) acryloyl group was calculated
- the conversion rate was 90% or more, “ ⁇ ”, 70% or more, but less than 90%, “ ⁇ ”, 50% or more, less than 70%, “ ⁇ ”, less than 50%.
- the curability of the light-shielding part was evaluated with “ ⁇ ” as the sample.
- TN liquid crystal manufactured by Chisso Corporation, “JC-5001LA”
- JC-5001LA fine droplets of TN liquid crystal
- the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell.
- the obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
- the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “ ⁇ ”, slight display unevenness was confirmed.
- the display performance of the liquid crystal display element (low liquid crystal contamination 1) was evaluated with “ ⁇ ” as the case, “ ⁇ ” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed. Note that the liquid crystal display elements evaluated as “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
- the sealing compound for liquid crystal display elements which is excellent in adhesiveness and light-shielding part sclerosis
- the manufacturing method of this sealing compound for liquid crystal display elements, and the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
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Abstract
Description
しかしながら、狭額縁設計ではシール剤がブラックマトリックスの直下に配置されるため、滴下工法を行うと、シール剤を光硬化させる際に照射した光が遮られ、シール剤の内部まで光が到達せず硬化が不充分となるという問題があった。このようにシール剤の硬化が不充分となると、未硬化のシール剤成分が液晶中に溶出し、溶出したシール剤成分による硬化反応が液晶中において進行することで液晶汚染が発生するという問題があった。
以下に本発明を詳述する。
上記硬化性樹脂は、ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を含有する。上記ビスフェノールA型エポキシ樹脂及び/又は上記(メタ)アクリル変性ビスフェノールA型エポキシ樹脂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、接着性に優れるものとなる。
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する。また、上記(メタ)アクリル変性ビスフェノールA型エポキシ樹脂は、ビスフェノールA型エポキシ樹脂の全てのエポキシ基を(メタ)アクリル変性した完全(メタ)アクリル変性ビスフェノールA型エポキシ樹脂であってもよいし、一部のエポキシ基を(メタ)アクリル変性した部分(メタ)アクリル変性ビスフェノールA型エポキシ樹脂であってもよい。
本発明の液晶表示素子用シール剤は、ビスフェノールAの含有量が50ppm以下である。硬化性樹脂として上記ビスフェノールA型エポキシ樹脂及び/又は上記(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を用いつつ、上記ビスフェノールAの含有量を50ppm以下とすることにより、本発明の液晶表示素子用シール剤は、接着性及び遮光部硬化性に優れ、かつ、環境への負荷を低減できるものとなる。
なお、上記ビスフェノールAの含有量は、シール剤から、ジメチルスルホキシド溶液等の任意の溶液を用いてビスフェノールAを抽出し、液体クロマトグラフィーを用いて定量測定することができる。
本発明の液晶表示素子用シール剤を製造する方法であって、ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を、純水を用いたビスフェノールAの水洗除去により精製する工程と、精製したビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を少なくとも重合開始剤及び/又は熱硬化剤と混合する工程とを有する液晶表示素子用シール剤の製造方法、並びに、ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を、吸着剤を用いたビスフェノールAの物理的吸着除去により精製する工程と、精製したビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を少なくとも重合開始剤及び/又は熱硬化剤と混合する工程とを有する液晶表示素子用シール剤の製造方法もまた、それぞれ本発明の1つである。
また、上記水洗除去は、40℃~50℃の温水を用いて行うことが好ましい。
上記その他の硬化性樹脂としては、上記完全(メタ)アクリル変性ビスフェノールA型エポキシ樹脂以外のその他の(メタ)アクリル化合物や、上記ビスフェノールA型エポキシ樹脂及び上記部分(メタ)アクリル変性ビスフェノールA型エポキシ樹脂以外のその他のエポキシ化合物等が挙げられる。なかでも、上記硬化性樹脂は、上記完全(メタ)アクリル変性ビスフェノールA型エポキシ樹脂及び/又は上記その他の(メタ)アクリル化合物(これらを併せて単に「(メタ)アクリル化合物」ともいう)を含有することが好ましい。
上記その他の(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)アクリル酸とビスフェノールA型エポキシ樹脂以外のエポキシ化合物とを反応させることにより得られるその他の完全(メタ)アクリル変性エポキシ樹脂、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する。
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、エピコート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、エピコート630(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。
上記エポキシ樹脂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)、エピコート1031、エピコート1032(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。
上記重合開始剤としては、硬化速度等の観点からラジカル重合開始剤が好適に用いられる。上記ラジカル重合開始剤を用いた場合、ビスフェノールAによる硬化阻害が特に生じやすくなるが、本発明の液晶表示素子用シール剤は、該ビスフェノールAの含有量が極めて少ないため、このような硬化阻害を抑制し、遮光部硬化性に優れるものとなる。
上記ラジカル重合開始剤としては、光照射によりラジカルを発生する光ラジカル重合開始剤や、加熱によりラジカルを発生する熱ラジカル重合開始剤等が挙げられる。
なお、本明細書において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。
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。
なお、上記E型粘度計としては、例えば、5XHBDV-III+CP(ブルックフィールド社製、ローターNo.CP-51)等を用いることができる。
フラスコに10%水酸化ナトリウム水溶液1000重量部、ビスフェノールA230重量部、及び、エピクロルヒドリン180重量部を投入し、窒素雰囲気で80℃で3時間撹拌を行った。次いで、メチルイソブチルケトン600重量部を加えて反応物を溶解した後、静置し、水層を分離除去した。その後、0.1mol/Lの塩酸水溶液300重量部を投入し、撹拌を行った後、水層を分離除去し、ビスフェノールA型エポキシ樹脂溶液を得た。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液に純水500重量部を加えて50℃で30分間加熱撹拌を行った後に純水を分離除去する水洗操作を行った。更に、この水洗操作を4回繰り返した後、減圧蒸留により溶媒を取り除き、ビスフェノールA型エポキシ樹脂A(精製品)を得た。なお、上記水洗操作に用いた純水は、40℃~50℃の温水である。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液に、吸着剤としてキョーワード2000(協和化学工業社製、酸化アルミニウム・酸化マグネシウム固溶体)を10重量部加えて50℃で30分間加熱撹拌を行い、濾過によりキョーワード2000を分離した後、減圧蒸留により溶媒を取り除き、ビスフェノールA型エポキシ樹脂B(精製品)を得た。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液から減圧蒸留によりメチルイソブチルケトンを取り除き、ビスフェノールA型エポキシ樹脂C(未精製品)を得た。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液に純水500重量部を加えて50℃で30分間加熱撹拌を行った後に純水を分離除去する水洗操作を行った。更に、この水洗操作を2回繰り返した後、減圧蒸留により溶媒を取り除き、ビスフェノールA型エポキシ樹脂A(精製品)を得た。なお、上記水洗操作に用いた純水は、40℃~50℃の温水である。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液に純水500重量部を加えて50℃で30分間加熱撹拌を行った後に純水を分離除去する水洗操作を行った。次いで、減圧蒸留により溶媒を取り除き、ビスフェノールA型エポキシ樹脂A(精製品)を得た。なお、上記水洗操作に用いた純水は、40℃~50℃の温水である。
「(ビスフェノールA型エポキシ樹脂溶液の作製)」で得られたビスフェノールA型エポキシ樹脂溶液にアクリル酸150重量部及びトリエチルベンジルアンモニウムクロリド5重量部を投入し、窒素雰囲気で80℃で3時間撹拌を行った。次いで、純水800重量部及びジエチルエ-テル800重量部を投入して撹拌した後に水層を分離除去する水洗操作を行った。更に、この水洗操作を4回繰り返した後、減圧蒸留により溶媒を取り除き、アクリル変性ビスフェノールA型エポキシ樹脂(精製品)を得た。なお、上記水洗操作に用いた純水は、40℃~50℃の温水である。
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1~5、及び、比較例1、2の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を、0.1wt/vol%のジメチルスルホキシド溶液となるように調製し、2時間振とうした。次いで、得られた溶液をメタノールで10倍に希釈した後、0.2μmフィルターでろ過し、外部標準法にて液体クロマトグラフィーを用いてビスフェノールAの含有量を測定した。
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重量部に対して平均粒子径5μmのスペーサー粒子(積水化学工業社製、「ミクロパールSP-2050」)1重量部を遊星式撹拌装置によって均一に分散させ、極微量をコーニングガラス1737(20mm×50mm×厚さ0.7mm)の中央部に取り、同型のガラスをその上に重ね合わせて液晶表示素子用シール剤を押し広げ、メタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を硬化させ、接着試験片を得た。
得られた接着試験片について、テンションゲージを用いて接着強度を測定した。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「◎」、30kgf/cm2以上35kgf/cm2未満であった場合を「○」、25kgf/cm2以上30kgf/cm2未満であった場合を「△」、25kgf/cm2未満であった場合を「×」として接着性を評価した。
まず、厚さ0.7mmのコーニングガラスの片面半分をクロム蒸着した基板Aと、片面全体をクロム蒸着した基板Bとを準備した。次に、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重量部に対して平均粒子径5μmのスペーサー微粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤を基板Aの中央部(クロム蒸着部と非蒸着部との境界)に塗布し、基板Bを貼り合わせてからシール剤を充分に押し潰し、基板A側からメタルハライドランプを用いて100mW/cm2の紫外線を5秒照射した。
その後、カッターを用いて基板A及びBを剥がし、紫外線直接照射部の際から50μm離れた点(クロム蒸着により遮光されていた部分)上のシール剤について顕微IR法によってスペクトルを測定し、シール剤中の(メタ)アクリロイル基の転化率を以下の方法により求めた。即ち、815~800cm-1のピーク面積を(メタ)アクリロイル基のピーク面積とし、845~820cm-1のピーク面積をリファレンスピーク面積として、下記式により(メタ)アクリロイル基の転化率を算出し、転化率が90%以上であったものを「◎」、70%以上90%未満であったものを「○」、50%以上70%未満であったものを「△」、50%未満であったものを「×」として遮光部硬化性を評価した。
(メタ)アクリロイル基の転化率=(1-(紫外線照射後の(メタ)アクリロイル基のピーク面積/紫外線照射後のリファレンスピーク面積)/(紫外線照射前の(メタ)アクリロイル基のピーク面積/紫外線照射前のリファレンスピーク面積))×100
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重量部に対して平均粒子径5μmのスペーサー粒子(積水化学工業社製、「ミクロパールSI-H050」)1重量部を遊星式撹拌装置によって均一に分散させ、得られたシール剤を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、脱泡処理を行ってから、ディスペンサー(武蔵エンジニアリング社製、「SHOTMASTER300」)にて、2枚のITO薄膜付きの透明電極基板の一方にシール剤を枠状に塗布した。続いて、TN液晶(チッソ社製、「JC-5001LA」)の微小滴を液晶滴下装置にてシール剤の枠内に滴下塗布し、他方の透明電極基板を、真空貼り合わせ装置にて5Paの真空下にて貼り合わせ、セルを得た。得られたセルに、メタルハライドランプを用いて100mW/cm2の紫外線を30秒照射した後、120℃で1時間加熱してシール剤を硬化させ、液晶表示素子を得た。
得られた液晶表示素子について、シール部周辺の液晶(特にコーナー部)に生じる表示むらを目視にて観察し、表示むらが確認されなかった場合を「◎」、わずかな表示むらが確認された場合を「○」、はっきりと表示むらが確認された場合を「△」、酷い表示むらが確認された場合を「×」として液晶表示素子の表示性能(低液晶汚染性1)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。
上記「(液晶表示素子の表示性能(低液晶汚染性1))」と同様の方法で作製した液晶表示素子について、40℃、50%RHの条件で180日間放置した後、シール部周辺の液晶(特にコーナー部)に生じる表示むらを目視にて観察し、表示むらが確認されなかった場合を「◎」、わずかな表示むらが確認された場合を「○」、はっきりと表示むらが確認された場合を「△」、酷い表示むらが確認された場合を「×」として液晶表示素子の表示性能(低液晶汚染性2)を評価した。
表示性能が初期(液晶表示素子の表示性能(低液晶汚染性1))と比べて悪化したものは、シール剤中の僅かな未硬化性分が徐々に液晶中に溶出したと推測される。
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 (6)
- 硬化性樹脂と、重合開始剤及び/又は熱硬化剤とを含有する液晶表示素子用シール剤であって、
前記硬化性樹脂は、ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を含有し、
ビスフェノールAの含有量が50ppm以下である
ことを特徴とする液晶表示素子用シール剤。 - 硬化性樹脂は、(メタ)アクリル化合物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。
- 請求項1又は2記載の液晶表示素子用シール剤を製造する方法であって、
ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を、純水を用いたビスフェノールAの水洗除去により精製する工程と、
精製したビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を少なくとも重合開始剤及び/又は熱硬化剤と混合する工程とを有することを特徴とする液晶表示素子用シール剤の製造方法。 - 請求項1又は2記載の液晶表示素子用シール剤を製造する方法であって、
ビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を、吸着剤を用いたビスフェノールAの物理的吸着除去により精製する工程と、
精製したビスフェノールA型エポキシ樹脂及び/又は(メタ)アクリル変性ビスフェノールA型エポキシ樹脂を少なくとも重合開始剤及び/又は熱硬化剤と混合する工程とを有することを特徴とする液晶表示素子用シール剤の製造方法。 - 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。
- 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5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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