WO2016190398A1 - 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子 - Google Patents
液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子 Download PDFInfo
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- WO2016190398A1 WO2016190398A1 PCT/JP2016/065631 JP2016065631W WO2016190398A1 WO 2016190398 A1 WO2016190398 A1 WO 2016190398A1 JP 2016065631 W JP2016065631 W JP 2016065631W WO 2016190398 A1 WO2016190398 A1 WO 2016190398A1
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- liquid crystal
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- acrylate
- crystal dropping
- sealing agent
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/542—Macromolecular compounds
- C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
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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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0881—Titanium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2003/1034—Materials or components characterised by specific properties
- C09K2003/1059—Heat-curable materials
-
- 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
- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/02—Inorganic compounds
- C09K2200/0239—Oxides, hydroxides, carbonates
Definitions
- the present invention relates to a sealant for a liquid crystal dropping method having excellent light shielding properties and adhesiveness in a high temperature and high humidity environment. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
- 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.
- Patent Documents 1 to 3 disclose a sealant containing titanium black material, carbon black material, or other light-shielding fine particles as a light-shielding agent.
- these light-shielding agents insulating properties are disclosed. Titanium black material having a high thickness is preferred.
- liquid crystal display elements with high contrast and excellent display performance.
- liquid crystal display elements are required to have moisture resistance reliability in driving under high temperature and high humidity environments.
- Sealing agents containing a large amount of titanium black are There was a problem that the adhesiveness was remarkably lowered when exposed to a humid environment.
- An object of this invention is to provide the sealing agent for liquid crystal dropping methods which is excellent in light-shielding property and adhesiveness in a high-temperature, high-humidity environment. Moreover, an object of this invention is to provide the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods.
- the present invention contains a curable resin, a radical polymerization initiator and / or a thermosetting agent, and titanium black, and the content of titanium dioxide in the titanium black is 10% by weight or less. It is an agent.
- the present invention is described in detail below.
- Titanium black is usually produced by heating and reducing white titanium dioxide powder in a vacuum or in the presence of ammonia.
- the present inventor has found that generally used titanium black obtained by such a production method is not sufficiently reduced and a large amount of titanium dioxide remains. Therefore, the present inventor reduced the content of titanium dioxide contained in the titanium black to a specific value or less by further reducing the titanium black, and the obtained titanium black contained a large amount in the sealant. It has been found that sufficient light shielding properties can be exhibited without blending, and the present invention has been completed.
- the sealing agent for liquid crystal dropping method of the present invention has sufficient light-shielding properties even without containing a large amount of the titanium black, it has excellent adhesiveness in a high temperature and high humidity environment.
- the sealing agent for liquid crystal dropping method of the present invention contains titanium black.
- the titanium black has a role as a light shielding agent.
- a liquid crystal display device manufactured using the sealing agent for liquid crystal dropping method of the present invention containing the above-described titanium black as a light-shielding agent has no leakage of light, has high contrast, and has excellent image display quality. .
- 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 light shielding properties to the sealing agent for liquid crystal dropping method of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
- a shading agent Therefore, by using a photo radical polymerization initiator that will be described later that can start the reaction with light having a wavelength (370 to 450 nm) that increases the transmittance of the titanium black, the sealing agent for the liquid crystal dropping method of the present invention can be used. Photocurability can be further increased.
- the upper limit of the content of titanium dioxide in the titanium black is 10% by weight. When the content of titanium dioxide exceeds 10% by weight, it is necessary to blend a large amount of the titanium black in order to exhibit sufficient light-shielding properties, and the obtained sealing agent for liquid crystal dropping method has a high temperature and high humidity environment. It becomes inferior to the adhesiveness and drawing property below.
- the upper limit of the titanium dioxide content is preferably 8% by weight, more preferably 5% by weight, and still more preferably 1% by weight, and most preferably no titanium dioxide is contained.
- the content of titanium dioxide in the titanium black is derived from the area ratio of titanium dioxide-derived peaks (diffraction angle (2 ⁇ ) around 25 °, around 27 °) when titanium black is measured by X-ray diffraction. Can do.
- the measurement conditions of the X-ray diffraction measurement in the present invention are as follows.
- Measuring instrument X'Pert-PRO-MPD (Spectris) Target: Cu Scanning angle: 5 ° -60 ° Scanning speed: 2 ° / distributor voltage: 40 kV Tube current: 30 mA
- Incident side slit 0.04 ° solar slit, automatic variable divergence slit, AS1 ° Receiving side slit: 0.04 °
- the detection limit under this condition is 0.1%.
- the content of titanium dioxide in the titanium black can be reduced by a method of reducing the titanium black containing titanium dioxide.
- titanium black is produced by heating a powder such as titanium dioxide at a high temperature of about 550 to 1100 ° C. in a vacuum or in the presence of ammonia.
- this alone is not sufficient for reduction and contains a large amount of titanium dioxide.
- Examples of a method for sufficiently reducing titanium black by sufficiently reducing titanium black include a method for increasing the reduction efficiency by increasing the heating rate during the reduction process, and the specific surface area of titanium dioxide used as a raw material. And a method of performing a two-step reduction treatment in which a reduction treatment is performed again on titanium black once reduced.
- a commercially available product can be used as the titanium black before the second reduction.
- Examples of such commercially available products include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilac D (manufactured by Ako Kasei Co., Ltd.), and the like.
- titanium black exerts 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, germanium oxide, aluminum oxide, zirconium oxide, oxidized Surface-treated titanium black such as one coated with an inorganic component such as magnesium can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
- an organic component such as a coupling agent, silicon oxide, germanium oxide, aluminum oxide, zirconium oxide, oxidized
- an inorganic component such as magnesium
- the preferable lower limit of the optical density (OD value) per 1 ⁇ m of the above-mentioned titanium black is 3.3.
- the OD value of the titanium black is 3.3 or more, an excellent light-shielding property can be exhibited without blending a large amount of the titanium black. It will be more excellent in adhesiveness and drawability in a wet environment.
- a more preferable lower limit of the OD value of the titanium black is 4.0. The higher the OD value of titanium black is, the better. There is no particular upper limit, but the substantial upper limit is 5.5.
- the OD value of the titanium black can be measured by using an optical densitometer (for example, “X-rite 360T ( ⁇ )” manufactured by X-rite).
- the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g
- the preferable upper limit is 80 m 2 / g
- the more preferable lower limit is 15 m 2 / g
- the more preferable upper limit is 75 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
- the more preferred upper limit is 2.5 ⁇ ⁇ cm.
- the primary particle diameter of the titanium black is not particularly limited as long as it is equal to or less than the distance between the substrates of the liquid crystal display element, the preferable lower limit is 1 nm and the preferable upper limit is 5000 nm.
- the primary particle diameter of the titanium black is 1 nm or more, the viscosity of the obtained liquid crystal dropping method sealing agent does not increase excessively, and the workability is improved.
- the primary particle diameter of the titanium black is 5000 nm or less, the obtained sealing agent for liquid crystal dropping method is excellent in applicability to the substrate.
- the more preferable lower limit of the primary particle diameter of the titanium black 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 diameter of the titanium black can be measured by dispersing the titanium black in a solvent (water, organic solvent, etc.) using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS).
- the content of the titanium black is preferably 5 parts by weight and preferably 55 parts by weight with respect to 100 parts by weight of the curable resin.
- the obtained sealing agent for liquid crystal dropping method has excellent light shielding properties.
- the content of the titanium black is 55 parts by weight or less, the obtained liquid crystal dropping method sealing agent is excellent in adhesiveness and drawing property in a high temperature and high humidity environment.
- the more preferable lower limit of the titanium black content is 10 parts by weight, the more preferable upper limit is 50 parts by weight, and the still more preferable lower limit is 20 parts by weight.
- the preferable minimum of content of the said titanium black in the whole sealing compound for liquid crystal dropping methods of this invention is 1 weight%, and a preferable upper limit is 50 weight%.
- the obtained liquid crystal dropping method sealing agent is more excellent in light shielding properties.
- the content of the titanium black is 50% by weight or less, the obtained sealing agent for liquid crystal dropping method is superior in adhesiveness and drawing property in a high temperature and high humidity environment.
- a more preferable lower limit of the titanium black content is 5% by weight, and a more preferable upper limit is 40% by weight.
- the sealing agent for liquid crystal dropping method of the present invention may contain other light-shielding agent in addition to the titanium black as long as the object of the present invention is not impaired.
- the other light-shielding agents include iron oxide, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black.
- the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
- the curable resin preferably contains a (meth) acrylic compound.
- the (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
- examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable.
- the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule from the viewpoint of reactivity.
- the “(meth) acryl” means acryl or methacryl
- the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter, “(meth) acryloyl”).
- a compound having a group) means acrylate or methacrylate.
- the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid.
- Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
- those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
- Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
- Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
- Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
- Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
- Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
- Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
- Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
- Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
- Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- 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
- 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 as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth).
- Hydroxyalkyl mono (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol Mono (meth) acrylates of dihydric alcohols such as mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy Epoxy (meth) acrylates such as acrylate and the like.
- Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U
- the said curable resin may contain an epoxy compound for the purpose of improving the adhesiveness of the sealing agent for liquid crystal dropping methods 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 in one molecule. It can be obtained by reacting a part of the epoxy group having an epoxy group with (meth) acrylic acid.
- UVACURE1561 made by Daicel Ornex
- the liquid crystal dropping method sealing agent of the present invention contains the (meth) acryl compound and the epoxy compound
- the ratio of the (meth) acryloyl group to the epoxy group is 30:70 to 95: 5. It is preferable to blend the (meth) acrylic compound and the epoxy compound.
- the ratio of the (meth) acryloyl group is 30% or more, the obtained sealing agent for a liquid crystal dropping method is excellent in low liquid crystal contamination.
- the ratio of the (meth) acryloyl group is 95% or less, the obtained sealing agent for liquid crystal dropping method is superior in adhesiveness.
- the curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
- the sealing agent for liquid crystal dropping method of the present invention contains a radical polymerization initiator and / or a thermosetting agent.
- a radical polymerization initiator a thermal radical polymerization initiator or a photo radical polymerization initiator can be used.
- the sealing compound for liquid crystal dropping methods of this invention contains a thermal radical polymerization initiator.
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- an initiator composed of an azo compound (hereinafter also referred to as “azo initiator”) is preferable, and an initiator composed of a polymer azo compound (hereinafter referred to as “polymer azo initiator”). 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
- 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 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.
- 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.
- the content of the radical 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 radical polymerization initiator is within this range, the liquid crystal dropping method sealant is obtained by curability while suppressing the occurrence of liquid crystal contamination due to the unreacted radical polymerization initiator and the deterioration of weather resistance. It will be excellent.
- the minimum with more preferable content of the said radical polymerization initiator is 1 weight part, A more preferable upper limit is 10 weight part, Furthermore, a 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 content of the thermosetting agent is 1 part by weight or more, the obtained liquid crystal dropping method sealing agent is more excellent in thermosetting.
- the content of the thermosetting agent is 50 parts by weight or less, the viscosity of the obtained sealing agent does not become too high, and the coating property is excellent.
- the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a filler for the purpose of improving the viscosity, improving the adhesiveness by the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. Good.
- Examples of the filler include talc, asbestos, silica, diatomaceous earth, smectite, bentonite, calcium carbonate, magnesium carbonate, alumina, montmorillonite, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, water Inorganic fillers such as aluminum oxide, glass beads, silicon nitride, barium sulfate, gypsum, calcium silicate, sericite, activated clay, aluminum nitride, polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, core shell acrylate Examples include organic fillers such as copolymer fine particles. These fillers may be used alone or in combination of two or more.
- the minimum with preferable content of the said filler in 100 weight part of sealing compounds for liquid crystal dropping methods of this invention is 10 weight part, and a preferable upper limit is 70 weight part.
- the content of the filler is 10 parts by weight or more, the effect such as improvement of adhesiveness is excellent.
- the content of the filler is 70 parts by weight or less, the viscosity of the obtained liquid crystal dropping method sealing agent does not become too high, and the coating property is excellent.
- the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
- the sealing agent for liquid crystal dropping method of the present invention preferably 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.
- the silane coupling agent is excellent in the effect of improving adhesion to a substrate or the like, and can be prevented from flowing out of the curable resin into the liquid crystal by chemically bonding with the curable resin.
- Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
- These silane coupling agents may be used alone or in combination of two or more.
- the minimum with preferable content of the said silane coupling agent in 100 weight part of sealing agents for liquid crystal dropping methods of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
- a preferable upper limit is 10 weight part.
- the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
- the sealing agent for the liquid crystal dropping method 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, if necessary.
- An additive may be contained.
- Examples of the method for producing the sealing agent for liquid crystal dropping method of the present invention include a curable resin and a radical using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll.
- a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll.
- Examples include a method of mixing a polymerization initiator and / or a thermosetting agent, titanium black, and an additive such as a silane coupling agent added as necessary.
- the sealing agent for liquid crystal dropping method 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 dropping method 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.
- Examples of the E-type viscometer include a product name “5XH BDV-III + CP” manufactured by Brookfield, rotor No. CP-51 or the like can be used.
- the optical density (OD value) of the cured product obtained by curing the sealing agent for liquid crystal dropping method of the present invention is preferably 2.0 or more when the thickness of the cured product is 2 to 7 ⁇ m.
- the OD value of the cured body is more preferably 2.5 or more, and further preferably 3.0 or more.
- the cured body for measuring the OD value was made uniform with a sealant sandwiched between glass substrates in the range of 2 to 7 ⁇ m, and irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp. By heating at 120 ° C. for 60 minutes to cure the sealant, a cured product having a uniform thickness is obtained between the glass substrates.
- the OD value of the cured body is determined by using an optical densitometer (for example, “X-rite 360T ( ⁇ )” manufactured by X-rite) for an optical test piece in which the obtained cured body is sandwiched between glass substrates. It can be measured by using.
- an optical densitometer for example, “X-rite 360T ( ⁇ )” manufactured by X-rite
- a vertical conduction material can be manufactured by mix
- Such a vertical conduction material containing the sealing agent for liquid crystal dropping method 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 which has the sealing compound for liquid crystal dropping methods of this invention or the vertical conduction material of this invention is also one of this invention.
- the liquid crystal dropping method sealing agent of the present invention is applied to one of two transparent substrates having electrodes such as an ITO thin film by screen printing and dispenser application.
- Examples of the method include a step of irradiating and temporarily curing the sealant, and a step of heating and temporarily curing the temporarily cured sealant.
- the sealing compound for liquid crystal dropping methods excellent in light-shielding property and the adhesiveness in a high-temperature, high-humidity environment can be provided.
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
- a commercially available titanium black (Mitsubishi Materials Co., “13M-C”) is further heated in the presence of ammonia at 550 to 1100 ° C. to perform a second reduction process, thereby obtaining a highly reduced titanium black A. Obtained.
- the obtained highly reduced titanium black A was subjected to X-ray diffraction measurement under the conditions described above, and as a result, it was confirmed that it did not contain titanium dioxide.
- the obtained highly reduced titanium black A had an optical density (OD value) of 4 ⁇ m as measured using an optical densitometer (X-rite 360T ( ⁇ ), manufactured by X-rite). 0.
- Titanium dioxide was heated at 550 to 1100 ° C. in the presence of ammonia and subjected to a reduction treatment for a long time to obtain highly reduced titanium black B.
- the obtained highly reduced titanium black B was subjected to X-ray diffraction measurement under the above-mentioned conditions, and as a result, it was confirmed that it contained 5% by weight of titanium dioxide.
- the optical density (OD value) per 1 ⁇ m measured using an optical densitometer (“X-rite 360T ( ⁇ )” manufactured by X-rite) was 3. 6.
- Examples 1 to 6, Comparative Examples 1 to 5 In accordance with the blending ratios described in Tables 1 and 2, after mixing each material using a planetary stirrer ("Shinky Co., Ltd.,” Awatori Netaro), further mixing using three rolls Thus, sealants for the liquid crystal dropping method of Examples 1 to 6 and Comparative Examples 1 to 5 were prepared.
- the untreated titanium black used in the comparative example (Mitsubishi Materials Co., Ltd., “13M-C”) was measured in the same manner as the reduction-treated titanium black. As a result, the titanium dioxide content was 15% by weight.
- the optical density (OD value) per 1 ⁇ m was 3.2.
- the “EBECRYL 3700 partially modified product” is a compound having an acryloyl group and an epoxy group.
- 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 100 mW / cm 2 of ultraviolet rays for 30 seconds using 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. Observe the sealant in the resulting testability evaluation test piece.
- optical density (OD value) of the obtained optical test piece was measured using an optical densitometer (“X-rite 360T ( ⁇ )” manufactured by X-rite).
- X-rite 360T ( ⁇ ) manufactured by X-rite.
- the light shielding property was evaluated with “ ⁇ ” and a value of less than 2.0 as “x”.
- the pressure cooker test (121 degreeC, 100% RH, 0.2MPa) was done for the test piece produced similarly to the initial stage adhesion test piece for 24 hours, and the adhesion test piece after the high temperature, high humidity process was obtained.
- the adhesive strength was measured using a 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 " ⁇ ", 25 kgf / cm 2 or more when 30 kgf / cm was less than 2 " ⁇ ", the adhesion of the case was less than 25 kgf / cm 2 as " ⁇ " (initial adhesion and high-temperature and high-humidity treatment Post-adhesiveness was evaluated.
- a sealing agent was applied so as to draw a frame on one of the two glass substrates with an ITO thin film.
- fine droplets of TN liquid crystal manufactured by Chisso Corp., “JC-5001LA”
- JC-5001LA fine droplets of TN liquid crystal
- the two substrates were bonded together under a reduced pressure of 5 Pa.
- the bonded cell was irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C.
- liquid crystal display element was stored for 24 hours in an environment of a temperature of 80 ° C. and a humidity of 90% RH, and then driven with a voltage of AC 3.5 V, and the presence or absence of display unevenness (color unevenness) was visually observed.
- “ ⁇ ” when no display unevenness is seen at the periphery of the liquid crystal display element “ ⁇ ” when a little thin display unevenness is seen at the periphery, and clear dark display unevenness at the periphery
- the display performance of the liquid crystal display element was evaluated by setting “ ⁇ ” as “ ⁇ ”, and “ ⁇ ” when the clear dark display unevenness spread not only to the peripheral portion but also to the central portion. Note that the liquid crystal display elements with the evaluations “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
- the sealing compound for liquid crystal dropping methods excellent in light-shielding property and the adhesiveness in a high-temperature, high-humidity environment can be provided.
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods 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。
しかしながら、透明や乳白色のシール剤を用いた場合、本来、光漏れを抑制するはずのブラックマトリックスでも、シール剤を透過する光は遮光することができず、得られる液晶表示素子のコントラストを下げてしまうという問題があった。
近年、コントラストが高く表示性能に優れる液晶表示素子への要求がますます高くなっており、これに応える充分な遮光性を発揮させるためには、シール剤に比較的多量のチタンブラックを配合する必要があった。一方で、タブレット端末や携帯端末の普及に伴い、液晶表示素子には高温高湿環境下での駆動等における耐湿信頼性が要求されており、多量のチタンブラックを含有するシール剤は、高温高湿の環境に曝されると接着性が著しく低下するという問題があった。
以下に本発明を詳述する。
なお、上記チタンブラック中の二酸化チタンの含有量は、チタンブラックをX線回折測定した際の二酸化チタン由来のピーク(回折角(2θ)25°付近、27°付近)の面積比から導出することができる。
本発明におけるX線回折測定の測定条件は次の通りである。
測定機器:X’Pert-PRO-MPD(スペクトリス社製)
ターゲット:Cu
走査角度:5°-60°
走査速度:2°/分
管電圧:40kV
管電流:30mA
入射側スリット:0.04°ソーラースリット、自動可変型ダイバージェンススリット、AS1°
受光側スリット:0.04°
なお、この条件における検出限界は0.1%である。
通常、チタンブラックは、二酸化チタン等の粉末を真空中やアンモニアの存在下で550~1100℃程度の高温で加熱することにより製造される。しかしながら、これだけでは還元が充分でなく、二酸化チタンを多く含有するものとなる。チタンブラックを充分に還元して二酸化チタンの含有量を充分に低減する方法としては、例えば、還元処理中の昇温速度を早くすることで還元効率を上げる方法、原料として用いる二酸化チタンの比表面積を大きくする方法、1度還元処理したチタンブラックに再び還元処理を行う2段階還元処理を行う方法等が挙げられる。
上記チタンブラックのOD値は高ければ高いほどよく、好ましい上限は特に無いが、実質的な上限は5.5である。
上記チタンブラックのOD値は、光学濃度計(例えば、X-rite社製、「X-rite360T(ν)」等)を用いることにより測定することができる。
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、上記チタンブラックの一次粒子径は、NICOMP 380ZLS(PARTICLE SIZING SYSTEMS社製)を用いて、上記チタンブラックを溶媒(水、有機溶媒等)に分散させて測定することができる。
また、本発明の液晶滴下工法用シール剤全体中における上記チタンブラックの含有量の好ましい下限は1重量%、好ましい上限は50重量%である。上記チタンブラックの含有量が1重量以上であることにより、得られる液晶滴下工法用シール剤が遮光性により優れるものとなる。上記チタンブラックの含有量が50重量%以下であることにより、得られる液晶滴下工法用シール剤が高温高湿環境下における接着性や描画性により優れるものとなる。上記チタンブラックの含有量のより好ましい下限は5重量%、より好ましい上限は40重量%である。
上記その他の遮光剤としては、例えば、酸化鉄、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。
上記硬化性樹脂は、(メタ)アクリル化合物を含有することが好ましい。
上記(メタ)アクリル化合物としては、例えば、(メタ)アクリル酸に水酸基を有する化合物を反応させることにより得られる(メタ)アクリル酸エステル化合物、(メタ)アクリル酸とエポキシ化合物とを反応させることにより得られるエポキシ(メタ)アクリレート、イソシアネート化合物に水酸基を有する(メタ)アクリル酸誘導体を反応させることにより得られるウレタン(メタ)アクリレート等が挙げられる。なかでも、エポキシ(メタ)アクリレートが好ましい。また、上記(メタ)アクリル化合物は、反応性の観点から、1分子中に(メタ)アクリロイル基を2個以上有するものが好ましい。
なお、本明細書において、上記「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、上記「(メタ)アクリル化合物」とは、アクリロイル基又はメタクリロイル基(以下、併せて「(メタ)アクリロイル基」ともいう)を有する化合物を意味する。また、上記「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。更に、上記「エポキシ(メタ)アクリレート」とは、エポキシ化合物中の全てのエポキシ基を(メタ)アクリル酸と反応させた化合物のことを表す。
上記ビスフェノールF型エポキシ樹脂のうち市販されているものとしては、例えば、jER806、jER4004(いずれも三菱化学社製)等が挙げられる。
上記ビスフェノールS型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA1514(DIC社製)等が挙げられる。
上記2,2’-ジアリルビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、RE-810NM(日本化薬社製)等が挙げられる。
上記水添ビスフェノール型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンEXA7015(DIC社製)等が挙げられる。
上記プロピレンオキシド付加ビスフェノールA型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4000S(ADEKA社製)等が挙げられる。
上記レゾルシノール型エポキシ樹脂のうち市販されているものとしては、例えば、EX-201(ナガセケムテックス社製)等が挙げられる。
上記ビフェニル型エポキシ樹脂のうち市販されているものとしては、例えば、jER YX-4000H(三菱化学社製)等が挙げられる。
上記スルフィド型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-50TE(新日鉄住金化学社製)等が挙げられる。
上記ジフェニルエーテル型エポキシ樹脂のうち市販されているものとしては、例えば、YSLV-80DE(新日鉄住金化学社製)等が挙げられる。
上記ジシクロペンタジエン型エポキシ樹脂のうち市販されているものとしては、例えば、EP-4088S(ADEKA社製)等が挙げられる。
上記ナフタレン型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP4032、エピクロンEXA-4700(いずれもDIC社製)等が挙げられる。
上記フェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-770(DIC社製)等が挙げられる。
上記オルトクレゾールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンN-670-EXP-S(DIC社製)等が挙げられる。
上記ジシクロペンタジエンノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、エピクロンHP7200(DIC社製)等が挙げられる。
上記ビフェニルノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、NC-3000P(日本化薬社製)等が挙げられる。
上記ナフタレンフェノールノボラック型エポキシ樹脂のうち市販されているものとしては、例えば、ESN-165S(新日鉄住金化学社製)等が挙げられる。
上記グリシジルアミン型エポキシ樹脂のうち市販されているものとしては、例えば、jER630(三菱化学社製)、エピクロン430(DIC社製)、TETRAD-X(三菱ガス化学社製)等が挙げられる。
上記アルキルポリオール型エポキシ樹脂のうち市販されているものとしては、例えば、ZX-1542(新日鉄住金化学社製)、エピクロン726(DIC社製)、エポライト80MFA(共栄社化学社製)、デナコールEX-611(ナガセケムテックス社製)等が挙げられる。
上記ゴム変性型エポキシ樹脂のうち市販されているものとしては、例えば、YR-450、YR-207(いずれも新日鉄住金化学社製)、エポリードPB(ダイセル社製)等が挙げられる。
上記グリシジルエステル化合物のうち市販されているものとしては、例えば、デナコールEX-147(ナガセケムテックス社製)等が挙げられる。
上記エポキシ化合物のうちその他に市販されているものとしては、例えば、YDC-1312、YSLV-80XY、YSLV-90CR(いずれも新日鉄住金化学社製)、XAC4151(旭化成社製)、jER1031、jER1032(いずれも三菱化学社製)、EXA-7120(DIC社製)、TEPIC(日産化学社製)等が挙げられる。
なお、本明細書において上記部分(メタ)アクリル変性エポキシ樹脂とは、1分子中にエポキシ基と(メタ)アクリロイル基とをそれぞれ1つ以上有する化合物を意味し、例えば、1分子中に2つ以上のエポキシ基を有するエポキシ化合物の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。
上記ラジカル重合開始剤としては、熱ラジカル重合開始剤や光ラジカル重合開始剤を用いることができる。なかでも、ブラックマトリックス等による遮光部が存在する場合でも充分に硬化させることができることから、本発明の液晶滴下工法用シール剤は、熱ラジカル重合開始剤を含有することが好ましい。
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。
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。
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。
なお、上記E型粘度計としては、例えば、ブルックフィールド社製、製品名「5XH BDV-III+CP」、ローターNo.CP-51等を用いることができる。
なお、上記OD値を測定する硬化体は、ガラス基板間にシール剤を挟んで厚さを2~7μmの範囲で均一とし、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60分加熱してシール剤を硬化させることにより、均一な厚さを有する硬化体としてガラス基板間に得られる。上記硬化体のOD値は、得られた硬化体がガラス基板間に挟まれてなる光学試験片について、光学濃度計(例えば、X-rite社製、「X-rite360T(ν)」等)を用いることにより測定することができる。
本発明の液晶表示素子を製造する方法としては、具体的には例えば、ITO薄膜等の電極を有する2枚の透明基板の一方に、本発明の液晶滴下工法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、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、及び、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有する方法等が挙げられる。
市販のチタンブラック(三菱マテリアル社製、「13M-C」)について、更にアンモニアの存在下で550~1100℃で加熱して2段階目の還元処理を行うことにより、高還元処理チタンブラックAを得た。
得られた高還元処理チタンブラックAについて、上述した条件でX線回折測定を行った結果、二酸化チタンを含有しないものであることを確認した。また、得られた高還元処理チタンブラックAについて、光学濃度計(X-rite社製、「X-rite360T(ν)」)を用いて測定された1μmあたりの光学濃度(OD値)は4.0であった。
二酸化チタンをアンモニアの存在下で550~1100℃で加熱して長時間の還元処理を行うことにより、高還元処理チタンブラックBを得た。
得られた高還元処理チタンブラックBについて、上述した条件でX線回折測定を行った結果、二酸化チタンを5重量%含有するものであることを確認した。また、得られた高還元処理チタンブラックBについて、光学濃度計(X-rite社製、「X-rite360T(ν)」)を用いて測定された1μmあたりの光学濃度(OD値)は3.6であった。
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1~6、比較例1~5の液晶滴下工法用シール剤を調製した。
なお、比較例で用いた未処理のチタンブラック(三菱マテリアル社製、「13M-C」)について、上記還元処理チタンブラックと同様にして測定した結果、二酸化チタンの含有量は15重量%であり、1μmあたりの光学濃度(OD値)は3.2であった。
また、「EBECRYL3700部分変性品」は、アクリロイル基とエポキシ基とを有する化合物である。
実施例及び比較例で得られた各液晶滴下工法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。
実施例及び比較例で得られた各液晶滴下工法用シール剤について、E型粘度計(ブルックフィールド社製、「5XHBDV-III+CP」、ローターNo.CP-51)を用いて、25℃、1rpmの条件で粘度を測定した。
実施例及び比較例で得られた各液晶滴下工法用シール剤100重量部に、シリカスペーサー(積水化学工業社製、「ミクロパールSI」)1重量部を配合し、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を用いて100mW/cm2の紫外線を30秒照射した後、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、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。
実施例及び比較例で得られた各液晶滴下工法用シール剤100重量部にスペーサとして直径5μmのシリカスペーサ(積水化学工業社製、「ミクロパールSI」)1重量部を配合して混合撹拌を行った。
得られたスペーサ入り液晶滴下工法用シール剤を、長さ20mm、幅20mmのガラス基板上に塗布し、その基板に同サイズのガラス基板を重ね合わせ、荷重をかけ、スペーサの直径まで押しつぶして厚さを均一(5μm)にした。次に、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60分加熱を行い、光学試験片を得た。得られた光学試験片について、光学濃度計(X-rite社製、「X-rite360T(ν)」)を用いて光学濃度(OD値)を測定した。得られた測定値が、3.3以上であった場合を「◎」、2.5以上3.3未満であった場合を「○」、2.0以上2.5未満であった場合を「△」、2.0未満であった場合を「×」として遮光性を評価した。
実施例及び比較例で得られた各液晶滴下工法用シール剤をガラス基板(長さ50mm、幅20mm、厚さ1.1mm)の中央部に極微量だけ取り、その上に同じ大きさのガラス基板を十字状になるように重ね合わせて液晶滴下工法用シール剤を押し広げた。その状態で100mW/cm2の紫外線を30秒照射した後、120℃で60分加熱を行い、初期接着試験片を得た。また、初期接着試験片と同様にして作製した試験片について、プレッシャークッカー試験(121℃、100%RH、0.2MPa)を24時間行い、高温高湿処理後接着試験片を得た。得られた初期接着試験片及び高温高湿処理後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(初期接着性及び高温高湿処理後接着性)を評価した。
実施例及び比較例で得られた各液晶滴下工法用シール剤100重量部に、シリカスペーサー(積水化学工業社製、「ミクロパールSI」)1重量部を配合し、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枠を描く様にシール剤を塗布した。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を用いて100mW/cm2の紫外線を30秒照射した後、120℃で60分加熱することによってシール剤を熱硬化させ、液晶表示素子を作製した。得られた液晶表示素子を温度80℃、湿度90%RHの環境下にて24時間保管した後、AC3.5Vの電圧駆動をさせ、表示むら(色むら)の有無を目視で観察した。液晶表示素子の周辺部に表示むらが全く見られなかった場合を「◎」、周辺部に少し薄い表示むらが見えた場合を「○」、周辺部にはっきりとした濃い表示むらがあった場合を「△」、はっきりとした濃い表示むらが周辺部のみではなく、中央部まで広がっていた場合を「×」として液晶表示素子の表示性能を評価した。
なお、評価が「◎」、「○」の液晶表示素子は実用に全く問題のないレベルである。
Claims (6)
- 硬化性樹脂と、ラジカル重合開始剤及び/又は熱硬化剤と、チタンブラックとを含有し、前記チタンブラック中の二酸化チタンの含有量が10重量%以下であることを特徴とする液晶滴下工法用シール剤。
- チタンブラックは、1μmあたりの光学濃度が3.3以上であることを特徴とする請求項1記載の液晶滴下工法用シール剤。
- チタンブラックの含有量が、硬化性樹脂100重量部に対して、5~55重量部であることを特徴とする請求項1又は2記載の液晶滴下工法用シール剤。
- 熱ラジカル重合開始剤を含有することを特徴とする請求項1、2又は3記載の液晶滴下工法用シール剤。
- 請求項1、2、3又は4記載の液晶滴下工法用シール剤と導電性微粒子とを含有することを特徴とする上下導通材料。
- 請求項1、2、3若しくは4記載の液晶滴下工法用シール剤又は請求項5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。
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