Classifications

• • 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
• • 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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• 2017
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