WO2014185374A1 - Sealing agent for one drop fill process, vertically conducting material, and liquid crystal display element - Google Patents
Sealing agent for one drop fill process, vertically conducting material, and liquid crystal display element Download PDFInfo
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- WO2014185374A1 WO2014185374A1 PCT/JP2014/062574 JP2014062574W WO2014185374A1 WO 2014185374 A1 WO2014185374 A1 WO 2014185374A1 JP 2014062574 W JP2014062574 W JP 2014062574W WO 2014185374 A1 WO2014185374 A1 WO 2014185374A1
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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
- G02F1/1341—Filling or closing of cells
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- G02F1/1341—Filling or closing of cells
- G02F1/13415—Drop filling process
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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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
- G02F1/13398—Spacer materials; Spacer properties
Definitions
- the present invention relates to a sealing agent for a liquid crystal dropping method that has excellent curability, suppresses the occurrence of seal break and liquid crystal contamination, and hardly causes gap defects. 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.
- Patent Document 1 and Patent Document 2 a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
- a photocurable resin, a photopolymerization initiator, a thermosetting resin, and a liquid crystal dropping method called a dropping method using a light and heat combined curing type sealant containing a thermosetting agent are being replaced.
- 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 with the sealant being uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays to perform temporary curing.
- heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
- An object of this invention is to provide the sealing agent for liquid crystal dropping methods which is excellent in sclerosis
- the present invention is a liquid crystal dropping method sealing agent used in the production of a liquid crystal display element by a liquid crystal dropping method, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and flexible particles,
- the maximum particle diameter of the particles is 100% or more of the cell gap of the liquid crystal display element and is a sealing agent for liquid crystal dropping method having a size of 5 ⁇ m to 20 ⁇ m.
- the inventor has a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element, and a flexible particle having a specific range is blended with the sealant to bond the substrates of the liquid crystal display element.
- the soft particles are partially crushed by the substrate laminating pressure in the sealant to partially form an immovable dam, thereby causing the occurrence of seal break and liquid crystal contamination due to the flow of the liquid sealant component.
- the inventors have found that it can be suppressed, and have completed the present invention.
- the sealant for a liquid crystal dropping method of the present invention is used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
- the sealing agent for liquid crystal dropping method of the present invention contains flexible particles having a maximum particle size of 100% or more of the cell gap of the liquid crystal display device and 5 ⁇ m to 20 ⁇ m.
- the flexible particles serve as a barrier between the other sealing agent component and the liquid crystal, preventing the liquid crystal from being inserted into the sealing agent and the sealing agent from being eluted into the liquid crystal. Have a role to play.
- the maximum particle diameter of the flexible particles is 100% or more of the cell gap, it can cause springback.
- a liquid crystal display element can be manufactured without any problem.
- the cell gap of the liquid crystal display element is not limited because it varies depending on the display element, but the cell gap of a general liquid crystal display element is 2 ⁇ m to 10 ⁇ m.
- the lower limit of the maximum particle size of the flexible particles is 100% of the cell gap of the liquid crystal display element and 5 ⁇ m. That is, when the cell gap of the liquid crystal display element is 5 ⁇ m or less, the lower limit of the maximum particle diameter of the flexible particles is 5 ⁇ m, and when the cell gap of the liquid crystal display element exceeds 5 ⁇ m, the lower limit of the maximum particle diameter of the flexible particles Is 100% of the cell gap of the liquid crystal display element.
- the upper limit of the maximum particle size of the flexible particles is 20 ⁇ m.
- a preferable upper limit of the maximum particle size of the flexible particles is 15 ⁇ m. Further, the maximum particle size of the flexible particles is preferably 2.6 times or less of the cell gap. When the maximum particle size of the flexible particles exceeds 2.6 times the cell gap, a springback occurs, and the obtained liquid crystal dropping method sealant is inferior in adhesiveness or the obtained liquid crystal display element has a gap defect. May occur.
- a more preferable upper limit of the maximum particle diameter of the flexible particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.
- the maximum particle size of the flexible particles and the average particle size described below are values obtained by measuring the particles before blending with the sealant using a laser diffraction particle size distribution measuring device.
- a laser diffraction type distribution measuring device Mastersizer 2000 (manufactured by Malvern) or the like can be used.
- the content ratio of the particles having a particle diameter of 5 ⁇ m or more in the particle size distribution of the flexible particles measured by the laser diffraction type distribution measuring device is 60% or more by volume frequency.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more is less than 60% in terms of volume frequency, seal breakage and liquid crystal contamination may not be sufficiently suppressed.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more is more preferably 80% or more.
- the flexible particles contain 100% or more of the cell gap of the liquid crystal display element by 70% or more of the particle size distribution in the entire flexible particles from the viewpoint of further exerting the effect of suppressing the occurrence of seal break and liquid crystal contamination. It is preferable that the liquid crystal display element is composed only of particles having a cell gap of 100% or more.
- the preferable lower limit of the average particle diameter of the flexible particles is 2 ⁇ m, and the preferable upper limit is 15 ⁇ m. If the average particle size of the flexible particles is less than 2 ⁇ m, the elution of the sealing agent into the liquid crystal may not be sufficiently prevented. When the average particle diameter of the flexible particles exceeds 15 ⁇ m, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness, or a gap defect may occur in the obtained liquid crystal display element.
- the more preferable lower limit of the average particle diameter of the flexible particles is 4 ⁇ m, and the more preferable upper limit is 12 ⁇ m.
- two or more kinds of flexible particles having different maximum particle diameters may be mixed and used as long as the overall maximum particle diameter is in the above-described range. That is, a soft particle having a maximum particle diameter of less than 100% of the cell gap of the liquid crystal display element and a soft particle having a maximum particle diameter of 100% or more of the cell gap of the liquid crystal display element may be mixed and used.
- the coefficient of variation (hereinafter also referred to as CV value) of the flexible particles is preferably 30% or less.
- CV value of the particle diameter of the flexible particles exceeds 30%, a cell gap defect may be caused.
- the CV value of the particle diameter of the flexible particles is more preferably 28% or less.
- the CV value of the particle diameter is a numerical value obtained by the following formula.
- CV value of particle diameter (%) (standard deviation of particle diameter / average particle diameter) ⁇ 100
- the maximum particle size, the average particle size, or the CV value is set within the above-mentioned range by classification.
- flexible particles having a particle size of less than 100% of the cell gap of the liquid crystal display element do not contribute to the suppression of the occurrence of seal break and liquid crystal contamination, and may increase the thixo value when blended with a sealant. It is preferable to remove by classification.
- the method for classifying the flexible particles include wet classification and dry classification. Of these, wet classification is preferable, and wet sieving classification is more preferable.
- the flexible particles include silicone particles, vinyl particles, urethane particles, fluorine particles, and nitrile particles. Of these, silicone particles and vinyl particles are preferable.
- the silicone-based particles are preferably silicone rubber particles from the viewpoint of dispersibility in the resin.
- examples of commercially available silicone particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Silicone), Trefil E-506S. EP-9215 (manufactured by Toray Dow Corning), etc., which can be classified and used.
- grains may be used independently and 2 or more types may be used together.
- (Meth) acrylic particles are preferably used as the vinyl particles.
- the (meth) acrylic particles can be obtained by polymerizing monomers as raw materials by a known method. Specifically, for example, a method in which a monomer is suspension-polymerized in the presence of a radical polymerization initiator, and a seed particle is swollen by absorbing the monomer into a non-crosslinked seed particle in the presence of a radical polymerization initiator. And a seed polymerization method.
- the “(meth) acryl” means “acryl or methacryl”.
- Examples of the monomer that is a raw material for forming the (meth) acrylic particles include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth).
- Alkyl (meth) such as acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc.
- oxygen-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc.
- (meth) nitrile and containing monomers such as acrylonitrile, trifluoromethyl (meth) acrylate, monofunctional monomer such as a fluorine-containing (meth) acrylates such as pentafluoroethyl (meth) acrylate.
- alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the deformation amount when a 1 g load is applied can be increased.
- the “(meth) acrylate” means “acrylate or methacrylate”.
- tetramethylol methane tetra (meth) acrylate tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylol propane tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, ( Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isocyanuric acid
- the preferable lower limit is 1% by weight and the preferable upper limit is 90% by weight in the whole monomer.
- the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when kneaded with various sealant raw materials, problems such as swelling do not occur, and it is easy to disperse uniformly.
- the amount of the crosslinkable monomer used is 90% or less, the recovery rate can be lowered, and problems such as springback are less likely to occur.
- a more preferable lower limit of the amount of the crosslinkable monomer used is 3%, and a more preferable upper limit is 80%.
- styrene monomers such as styrene and ⁇ -methylstyrene
- vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and propyl vinyl ether, vinyl acetate, vinyl butyrate, and laurin.
- Acid vinyl esters such as vinyl acid and vinyl stearate, unsaturated hydrocarbons such as ethylene, propylene, isoprene and butadiene, halogen-containing monomers such as vinyl chloride, vinyl fluoride and chlorostyrene, triallyl (iso ) Using monomers such as cyanurate, triallyl trimellitate, divinylbenzene, diallylphthalate, diallylacrylamide, diallyl ether, ⁇ - (meth) acryloxypropyltrimethoxysilane, trimethoxysilylstyrene, vinyltrimethoxysilane Good .
- vinyl particles for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles and the like may be used.
- urethane-based particles examples include Art Pearl (manufactured by Negami Kogyo Co., Ltd.), Dimic Beads (manufactured by Dainichi Seika Kogyo Co., Ltd.), and the like, which can be classified and used. .
- the preferable lower limit of the hardness of the flexible particles is 10, and the preferable upper limit is 50.
- the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness, or a gap defect may occur in the obtained liquid crystal display element.
- the more preferable lower limit of the hardness of the soft particles is 20, and the more preferable upper limit is 40.
- the hardness of the said flexible particle means the durometer A hardness measured by the method based on JISK6253.
- the content of the flexible particles is preferably 15% by weight and preferably 50% by weight with respect to the whole sealing agent for liquid crystal dropping method. If the content of the flexible particles is less than 15% by weight, the occurrence of seal breaks or liquid crystal contamination may not be sufficiently suppressed. When the content of the flexible particles exceeds 50% by weight, the obtained liquid crystal dropping method sealing agent may be inferior in adhesiveness.
- a more preferable lower limit of the content of the flexible particles is 20% by weight, and a more preferable upper limit is 40% by weight.
- the sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
- the curable resin preferably contains a (meth) acrylic resin, and more preferably contains a (meth) acrylic resin having an isocyanuric skeleton or an epoxy (meth) acrylate.
- the “(meth) acrylic resin” means a resin having a (meth) acryloyl group
- the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
- the “epoxy (meth) acrylate” means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
- Examples of the (meth) acrylic resin having an isocyanuric skeleton include, for example, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxy). And ethyl) isocyanurate.
- Examples of commercially available (meth) acrylic resins having an isocyanuric skeleton include Aronix M-315 and Aronix M-327 (both manufactured by Toagosei Co., Ltd.).
- Examples of the epoxy (meth) acrylate include those obtained by reacting (meth) acrylic acid and an epoxy resin in the presence of a basic catalyst according to a conventional method.
- Examples of the epoxy resin used as a raw material for synthesizing the epoxy (meth) acrylate include, for example, 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, ortho-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Emissions phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy resin, glycidyl ester compounds, bisphenol A type episulfide resins.
- Examples of commercially available bisphenol A type epoxy resins include Epicoat 828EL, Epicoat 1001, Epicoat 1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like.
- Epicoat 806, Epicoat 4004 all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
- Epicron EXA1514 made by DIC Corporation
- Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku 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).
- 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).
- alkyl polyol type epoxy resins examples 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.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
- Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
- Examples of commercially available bisphenol A type episulfide resins include Epicoat YL-7000 (manufactured by Mitsubishi Chemical Corporation).
- Other commercially available 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.
- Examples of commercially available epoxy (meth) acrylates include, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy Ester 200PA, epoxy ester 80MFA Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
- Examples of other (meth) acrylic resins other than the (meth) acrylic resin having an isocyanuric skeleton and epoxy (meth) acrylate are ester compounds obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, Examples thereof include urethane (meth) acrylate obtained by reacting isocyanate with a (meth) acrylic acid derivative having a hydroxyl group.
- examples of monofunctional compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (Meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydroph Furyl (meth) acrylate, benzyl (
- bifunctional ester compound examples include 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (me ) Acrylate, propylene oxide-added bisphenol A di (meth) acrylate
- ester compound having three or more functional groups examples include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri.
- 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 a compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Can do.
- Examples of the isocyanate used as a raw material for the urethane (meth) acrylate include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4 ′.
- MDI Diisocyanate
- polymeric MDI polymeric MDI
- 1,5-naphthalene diisocyanate norbornane diisocyanate
- tolidine diisocyanate xylylene diisocyanate (XDI)
- hydrogenated XDI lysine diisocyanate
- triphenylmethane triisocyanate tris (isocyanate) Phenyl) thiophosphate
- tetramethylxylene diisocyanate 1,6,10-undecane triisocyanate Doors and the like.
- isocyanate examples include, for example, a reaction between a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- a polyol such as ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate.
- the resulting chain-extended isocyanate compound
- Examples of the (meth) acrylic acid derivative having a hydroxyl group, which is a raw material of the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth).
- acrylate and 2-hydroxybutyl (meth) acrylate and dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and polyethylene glycol Epoxy (meth) acrylates such as mono (meth) acrylate or di (meth) acrylate of trivalent alcohols such as mono (meth) acrylate, trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy acrylate Etc.
- dihydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol
- Epoxy (meth) acrylates such as mono (meth) acrylate or di (meth) acrylate of trivalent alcohols such as mono (meth) acrylate, trimethylolethane
- 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-122P, U-108A, U-340P,
- the (meth) acrylic resin preferably has a hydrogen-bonding unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing adverse effects on the liquid crystal.
- the said curable resin may contain an epoxy resin for the purpose of improving the adhesiveness of the sealing agent for liquid crystal dropping methods obtained.
- said epoxy resin the epoxy resin used as the raw material for synthesize
- the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the resin having a reaction with (meth) acrylic acid.
- Examples of commercially available compounds obtained by reacting a part of the epoxy groups of a compound having two or more epoxy groups with acrylic acid include UVACURE 1561 (manufactured by Daicel Ornex Co., Ltd.).
- a preferable upper limit of the ratio of the epoxy group to the total amount of the (meth) acryloyl group and the epoxy group in the entire curable resin is 50 mol%.
- the ratio of the epoxy group exceeds 50 mol%, the resulting liquid crystal dropping method sealing agent is highly soluble in liquid crystals, causing liquid crystal contamination, and the resulting liquid crystal display element may be inferior in display performance. is there.
- a more preferable upper limit of the ratio of the epoxy group is 20 mol%.
- the sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent. Especially, it is preferable to contain a radical polymerization initiator as a polymerization initiator.
- the springback is influenced not only by the maximum particle size of the soft particles but also by the curing rate of the sealant. Since the radical polymerization initiator can significantly increase the curing rate as compared with the thermosetting agent, the effect of suppressing the occurrence of springback that is likely to occur due to the flexible particles by using in combination with the flexible particles. It can be further improved.
- the radical polymerization initiator examples include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.
- the radical polymerization initiator has a much faster curing rate than the thermosetting agent. Therefore, by using the radical polymerization initiator, it is possible to suppress the occurrence of seal breaks and liquid crystal contamination, and the flexible Springback that is easily generated by particles can also be suppressed.
- the sealing agent for liquid crystal dropping methods obtained can be hardened
- thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
- a polymer azo initiator composed of a polymer azo compound is preferable.
- the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy 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 number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal.
- the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult.
- 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
- GPC gel permeation chromatography
- Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
- 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.
- 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, thioxanthones, and the like.
- photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE OXE01, DAROCUR TPO, Benzylin TPO, Benzylin TPO, Benzylin TPO, and Lucyrin TPO
- examples include ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).
- the content of the polymerization initiator is preferably 0.1 parts by weight and preferably 30 parts by weight with respect to 100 parts by weight of the curable resin.
- the content of the polymerization initiator is less than 0.1 parts by weight, the polymerization of the obtained liquid crystal dropping method sealing agent may not sufficiently proceed.
- content of the said polymerization initiator exceeds 30 weight part, many unreacted polymerization initiators remain
- a more preferable lower limit of the content of the polymerization initiator is 1 part by weight, a more preferable upper limit is 10 parts by weight, and a still more preferable upper limit is 5 parts by weight.
- thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Among these, solid organic acid hydrazide is preferably used.
- Examples of the solid organic acid hydrazide include 1,3-bis [hydrazinocarboethyl-5-isopropylhydantoin], sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
- Examples thereof include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co., Ltd.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), 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 less than 1 part by weight, the sealing agent for liquid crystal dropping method of the present invention may not be sufficiently cured.
- content of the said thermosetting agent exceeds 50 weight part, the viscosity of the sealing compound for liquid crystal dropping methods of this invention will become high, and coating property may deteriorate.
- 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 preferably contains a curing accelerator.
- the sealing agent can be sufficiently cured without heating at a high temperature.
- Examples of the curing accelerator include polyvalent carboxylic acids having an isocyanuric ring skeleton and epoxy resin amine adducts. Specific examples include tris (2-carboxymethyl) isocyanurate, tris (2-carboxyl). And ethyl) isocyanurate, tris (3-carboxypropyl) isocyanurate, and bis (2-carboxyethyl) isocyanurate.
- the content of the curing accelerator is preferably 0.1 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. If the content of the curing accelerator is less than 0.1 parts by weight, the resulting liquid crystal dropping method sealing agent may not be sufficiently cured, or heating at a high temperature may be required for curing. is there. When content of the said hardening accelerator exceeds 10 weight part, the sealing compound for liquid crystal dropping methods obtained may become inferior to adhesiveness.
- 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 due to the stress dispersion effect, improving the coefficient of linear expansion, and further improving the moisture resistance of the cured product. preferable.
- the filler examples 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 thereof include organic fillers such as polymer 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 agents for liquid crystal dropping methods of this invention is 5 weight part, and a preferable upper limit is 70 weight part.
- a preferable upper limit is 70 weight part.
- content of the filler is less than 5 parts by weight, effects such as improvement of adhesiveness may not be sufficiently exhibited.
- content of the said filler exceeds 70 weight part, the viscosity of the sealing compound for liquid crystal dropping methods obtained will become high, and applicability
- 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.
- As said silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
- 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 20 weight part.
- a preferable upper limit is 20 weight part.
- the content of the silane coupling agent is less than 0.1 parts by weight, the effect of blending the silane coupling agent may not be sufficiently exhibited.
- content of the said silane coupling agent exceeds 20 weight part, the sealing compound for liquid crystal dropping methods obtained may cause liquid-crystal contamination.
- the minimum with more preferable content of the said silane coupling agent is 0.5 weight part, and a more preferable upper limit is 10 weight part.
- the sealing agent for liquid crystal dropping method of the present invention may contain a light shielding agent.
- the sealing compound for liquid crystal dropping methods 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 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 As the light-shielding agent contained in the liquid crystal dropping method sealing agent of the present invention, a highly insulating material is preferable, and titanium black is also preferable 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 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 a sufficient light-shielding property, and thus has a 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 light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m.
- the primary particle diameter of the light-shielding agent is less than 1 nm, the viscosity and thixotropy of the obtained liquid crystal dropping method sealing agent are greatly increased, and workability may be deteriorated.
- the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the coating property of the obtained liquid crystal dropping method sealing agent on the substrate may be deteriorated.
- the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm, the more preferable upper limit is 200 nm, the still more preferable lower limit is 10 nm, and the still more preferable upper limit is 100 nm.
- the preferable lower limit of the content of the light shielding agent in 100 parts by weight of the sealing agent for liquid crystal dropping method of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight. If the content of the light shielding agent is less than 5 parts by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent exceeds 80 parts by weight, the adhesion of the obtained sealing agent for liquid crystal dropping method to the substrate and the strength after curing may be lowered, or the drawing property may be lowered.
- the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
- the sealing agent for liquid crystal dropping method of the present invention further comprises a reactive diluent for adjusting the viscosity, a spacer such as polymer beads for adjusting the panel gap, 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea and isocyanuric carboxylic acid, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent.
- a reactive diluent for adjusting the viscosity
- a spacer such as polymer beads for adjusting the panel gap
- 3-P-chlorophenyl-1,1- You may contain additives, such as hardening accelerators, such as a dimethyl urea and isocyanuric carboxylic acid, an antifoamer, a leveling agent, a polymerization inhibitor, and another coupling agent.
- the method for producing the sealing agent for liquid crystal dropping method of the present invention is not particularly limited, and for example, a curable resin using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll. And a method of mixing a polymerization initiator and / or a thermosetting agent, flexible particles, and an additive such as a silane coupling agent added as necessary.
- the preferred lower limit of the viscosity measured at 25 ° C. and 1 rpm using an E-type viscometer is 50,000 Pa ⁇ s
- the preferred upper limit is 500,000 Pa ⁇ s.
- a more preferable upper limit of the viscosity is 400,000 Pa ⁇ s.
- 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 using the sealing agent for liquid crystal dropping method of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
- the sealing agent for the liquid crystal dropping method of the present invention is applied to one of two transparent substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate.
- the process of forming a rectangular seal pattern by screen printing, dispenser application, etc., the liquid crystal drop method sealing agent of the present invention is uncured, and liquid crystal microdrops are dropped on the entire surface of the transparent substrate and applied immediately.
- a method of superposing another substrate and a step of heating and curing the sealing agent for liquid crystal dropping method of the present invention is a method for producing the liquid crystal display element of the present invention.
- the sealing compound for liquid crystal dropping methods which is excellent in sclerosis
- the vertical conduction material and liquid crystal display element which are manufactured using this sealing compound for liquid crystal dropping methods can be provided.
- Silicone rubber particles (manufactured by Shin-Etsu Silicone Co., Ltd., “KMP-601”) are dispersed in methanol and classified by wet sieving with sieves of 12 ⁇ m, 10 ⁇ m, 8 ⁇ m and 5 ⁇ m, and those passing through the sieve are collected and dried. A classified product of silicone rubber particles was obtained.
- As the sieve a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used.
- the particle diameter was measured using a laser diffraction type distribution measuring device (manufactured by Malvern, “Mastersizer 2000”).
- KMP-594, KMP-598, and KMP-600 classified products were obtained in the same manner using a sieve with an opening of 8 ⁇ m, and the particle size was measured.
- the average particle size is 8.5 ⁇ m for KMP-601 classified with a 12 ⁇ m sieve, 7.6 ⁇ m for 10 ⁇ m sieve, 6.5 ⁇ m for 8 ⁇ m sieve and 5 ⁇ m sieve for 8 ⁇ m sieve Is classified to be in the range of 5 to 8 ⁇ m is 7.1 ⁇ m, KMP-594 is classified with an 8 ⁇ m sieve and 4.7 ⁇ m, and KMP-598 is classified with an 8 ⁇ m sieve.
- KMP-600 classified by an 8 ⁇ m sieve was 4.9 ⁇ m.
- the CV value of the particle size is 27% for KMP-601 classified by 12 ⁇ m sieve, 26% for 10 ⁇ m sieve, 26% for 8 ⁇ m sieve, 8 ⁇ m sieve and 5 ⁇ m sieve. 25% is classified to a range of 5 to 8 ⁇ m, 28% is KMP-594 classified by an 8 ⁇ m sieve, and 28% is KMP-598 classified by an 8 ⁇ m sieve. 27% was obtained by classifying KMP-600 with an 8 ⁇ m sieve.
- the content ratio of particles having a particle diameter of 5 ⁇ m or more was determined by volume frequency, 99% for KMP-601 classified by a 12 ⁇ m sieve, 98.5% by 10 ⁇ m sieve, and 88.5 ⁇ m by a 8 ⁇ m sieve. 97.7%, 8% and 5 ⁇ m sieves are classified to be in the range of 5-8 ⁇ m, 100%, KMP-594 is classified by 8 ⁇ m sieves, 48%, KMP- The product obtained by classifying 598 with an 8 ⁇ m sieve was 98.1%, and the product obtained by classifying KMP-600 with an 8 ⁇ m sieve was 46%.
- the sealing agent for liquid crystal dropping methods of an Example and a comparative example shall be used for manufacture of the liquid crystal display element whose cell gap is 4.7 micrometers.
- the average particle diameter of the obtained acrylic particles B is 7.3 ⁇ m, the CV value of the particle diameter is 22%, the CV value of the particle diameter is 21%, and the content ratio of particles having a particle diameter of 5 ⁇ m or more is 71 in volume frequency. %Met.
- Example 1 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 12 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimeth
- KBM-573 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
- Example 2 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 20 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 12 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimeth
- KBM-573 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
- Example 3 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 10 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrime
- KBM-573 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
- Example 4 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by an 8 ⁇ m sieve), 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.), N-phenyl-3-aminopropyltrimethoxysilane
- Example 5 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a bisphenol A type epoxy acrylate (“EBECRYL 3700” manufactured by Daicel Ornex Co., Ltd.), and synthesis 17 parts by weight of the partially acryl-modified biphenyl ether type epoxy resin, 1 part by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., “V-501”) as a thermal radical polymerization initiator, and malonic acid as a thermosetting agent 2 parts by weight of dihydrazide (manufactured by Nippon Finechem Co., Ltd., “MDH”), 45 parts by weight of a silicone rubber particle classification product (KMP-601 classified by a 10 ⁇ m sieve), silica as a filler (manufactured by Nippon Shokubai Co
- Example 6 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight, 1 part by weight of a radical photopolymerization initiator (BASF Japan, "DAROCUR TPO"), 2 parts by weight of malonic acid dihydrazide (manufactured by Nippon Finechem, "MDH”) as a thermosetting agent, and silicone rubber particles 45 parts by weight of KMP-601 (classified with a 12 ⁇ m sieve), 20 parts by weight of silica (Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N—as the silane coupling agent Phenyl-3-aminopropyltrimethoxysi
- Example 7 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 Parts by weight, 0.5 part by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., “VPE0201”) as a thermal radical polymerization initiator, and tris (3-carboxypropyl) isocyanurate ground product (as a curing accelerator) 3 parts by weight of “C3-CIC acid” manufactured by Shikoku Kasei Kogyo Co., Ltd., pulverized to an average particle size of 1.5 ⁇ m by a jet mill) and malonic acid dihydrazide (manufactured by Nippon Finechem Co., “MDH”)
- Example 8 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Part by weight, 45 parts by weight of silicone rubber particle-classified product (KMP-601 classified so as to be in the range of 5 to 8 ⁇ m with 8 ⁇ m sieve and 5 ⁇ m sieve), and core-shell acrylate copolymer particles (filler) 20 parts by weight of “F351N” manufactured by Ganz and N-phenyl as
- Example 9 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of silicone rubber particle classified product (classified with a 12 ⁇ m sieve), 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and silane coupling agent N-phenyl-3-aminopropyltrimeth
- Example 10 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-594 classified by an 8 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimeth
- Example 11 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-598 classified by an 8 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimeth
- Example 12 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classification product (KMP-600 classified by an 8 ⁇ m sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysi
- Example 13 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of acrylic particles A, 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent (Shin-
- Example 14 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of acrylic particles B, 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent (Shin-
- (Comparative Example 2) 25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Part by weight, unclassified silicone rubber particles (manufactured by Shin-Etsu Silicone Co., Ltd., “KMP-598”, maximum particle size 30.5 ⁇ m, average particle size 13.0 ⁇ m, particle size CV value 38%, particles having a particle size of 5 ⁇ m or more
- the content ratio is 45 parts by weight of 99
- the adhesive strength was measured using the tension gauge. Further, an imide resin (“# 7942”, manufactured by Nissan Chemical Industries, Ltd.) was applied to the above-mentioned Corning glass 1737 by spin coating, prebaked at 80 ° C., and then baked at 230 ° C. to form the alignment film. In the same manner, an adhesive test piece was prepared, and the adhesive strength was measured in the same manner. The case where the adhesive strength was 200 N / cm 2 or more was “ ⁇ ”, the case where the adhesive strength was 100 N / cm 2 or more and less than 200 N / cm 2 was “ ⁇ ”, and the adhesive strength was less than 100 N / cm 2 . The case was evaluated as “x”, and the adhesion to ITO and the adhesion to the alignment film were evaluated.
- a one-round sealant (dummy seal) was applied to the outer periphery. Thereafter, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were dropped and applied with a liquid crystal dropping device, and the other transparent substrate was bonded with a vacuum bonding device under a vacuum of 5 Pa.
- the cell after bonding was irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a high-pressure mercury lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, thereby obtaining a liquid crystal display element.
- the cell gap of the obtained liquid crystal display element was measured, the case where the inside of the cell was uniformly 4 to 5 ⁇ m was “ ⁇ ”, and the case where there was a part where the gap was not 4 to 5 ⁇ m was present. “ ⁇ ”, the cell gap was evaluated as “x” when the cell could not be formed.
- the sealing compound for liquid crystal dropping methods which is excellent in sclerosis
- 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
しかしながら、滴下工法で狭額縁設計の液晶表示素子を製造すると、ブラックマトリックスによりシール部に光の当たらない箇所が存在するため、充分に光照射されず硬化が進行しない光硬化性樹脂の部分が生じ、未硬化のシール剤が液晶と接するため、液晶がシール剤に差し込み、シールブレイクが発生して液晶が漏れ出してしまうことや、シール剤が液晶に溶出することにより、液晶が汚染されることがあるという問題があった。 By the way, in the present age when mobile devices with various liquid crystal panels such as mobile phones and portable game machines are widespread, downsizing of devices is the most demanded issue. As a technique for miniaturization, there is a narrow frame of the liquid crystal display unit, and for example, the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
However, when a liquid crystal display element with a narrow frame design is manufactured by the dropping method, there is a portion where the light does not shine on the seal part due to the black matrix. Because the uncured sealant comes into contact with the liquid crystal, the liquid crystal is inserted into the sealant, causing a seal break and leaking the liquid crystal. There was a problem that there was.
以下に本発明を詳述する。 The present invention is a liquid crystal dropping method sealing agent used in the production of a liquid crystal display element by a liquid crystal dropping method, which contains a curable resin, a polymerization initiator and / or a thermosetting agent, and flexible particles, The maximum particle diameter of the particles is 100% or more of the cell gap of the liquid crystal display element and is a sealing agent for liquid crystal dropping method having a size of 5 μm to 20 μm.
The present invention is described in detail below.
本発明の液晶滴下工法用シール剤は、最大粒子径が、液晶表示素子のセルギャップの100%以上であり、かつ、5μm~20μmである柔軟粒子を含有する。上記柔軟粒子は、液晶表示素子を製造する際に、他のシール剤成分と液晶との間の障壁となって、液晶がシール剤に差し込むこと、及び、シール剤が液晶へ溶出することを防止する役割を有する。
また、上記柔軟粒子は、最大粒子径がセルギャップの100%以上であるため、スプリングバックを起こし得るが、上記柔軟粒子の最大粒子径を20μm以下とすることにより、スプリングバックによるギャップ不良を引き起こすことなく液晶表示素子を作製できる。
液晶表示素子のセルギャップは、表示素子により異なるため限定されないが、一般的な液晶表示素子のセルギャップは、2μm~10μmである。 The sealant for a liquid crystal dropping method of the present invention is used for manufacturing a liquid crystal display element by a liquid crystal dropping method.
The sealing agent for liquid crystal dropping method of the present invention contains flexible particles having a maximum particle size of 100% or more of the cell gap of the liquid crystal display device and 5 μm to 20 μm. When the liquid crystal display device is manufactured, the flexible particles serve as a barrier between the other sealing agent component and the liquid crystal, preventing the liquid crystal from being inserted into the sealing agent and the sealing agent from being eluted into the liquid crystal. Have a role to play.
Moreover, since the maximum particle diameter of the flexible particles is 100% or more of the cell gap, it can cause springback. However, when the maximum particle diameter of the flexible particles is 20 μm or less, gap failure due to springback is caused. A liquid crystal display element can be manufactured without any problem.
The cell gap of the liquid crystal display element is not limited because it varies depending on the display element, but the cell gap of a general liquid crystal display element is 2 μm to 10 μm.
また、上記柔軟粒子の最大粒子径の上限は20μmである。上記柔軟粒子の最大粒子径が20μmを超えると、スプリングバックを起こし、得られる液晶滴下工法用シール剤が接着性に劣るものとなったり、得られる液晶表示素子にギャップ不良が生じたりする。上記柔軟粒子の最大粒子径の好ましい上限は15μmである。
更に、上記柔軟粒子の最大粒子径は、セルギャップの2.6倍以下であることが好ましい。上記柔軟粒子の最大粒子径がセルギャップの2.6倍を超えると、スプリングバックを起こし、得られる液晶滴下工法用シール剤が接着性に劣るものとなったり、得られる液晶表示素子にギャップ不良が生じたりすることがある。上記柔軟粒子の最大粒子径のより好ましい上限はセルギャップの2.2倍、更に好ましい上限はセルギャップの1.7倍である。
なお、本明細書において、上記柔軟粒子の最大粒子径及び後述する平均粒子径は、シール剤に配合する前の粒子について、レーザー回折式粒度分布測定装置を用いて測定することにより得られる値を意味する。上記レーザー回折式分布測定装置としては、マスターサイザー2000(マルバーン社製)等を用いることができる。 The lower limit of the maximum particle size of the flexible particles is 100% of the cell gap of the liquid crystal display element and 5 μm. That is, when the cell gap of the liquid crystal display element is 5 μm or less, the lower limit of the maximum particle diameter of the flexible particles is 5 μm, and when the cell gap of the liquid crystal display element exceeds 5 μm, the lower limit of the maximum particle diameter of the flexible particles Is 100% of the cell gap of the liquid crystal display element. When the maximum particle size of the flexible particles is less than the above lower limit value of 5 μm and 100% of the cell gap of the liquid crystal display element, seal breakage and liquid crystal contamination cannot be sufficiently suppressed. .
The upper limit of the maximum particle size of the flexible particles is 20 μm. When the maximum particle diameter of the flexible particles exceeds 20 μm, spring back occurs, and the obtained liquid crystal dropping method sealant is inferior in adhesiveness, or a gap defect occurs in the obtained liquid crystal display element. A preferable upper limit of the maximum particle size of the flexible particles is 15 μm.
Further, the maximum particle size of the flexible particles is preferably 2.6 times or less of the cell gap. When the maximum particle size of the flexible particles exceeds 2.6 times the cell gap, a springback occurs, and the obtained liquid crystal dropping method sealant is inferior in adhesiveness or the obtained liquid crystal display element has a gap defect. May occur. A more preferable upper limit of the maximum particle diameter of the flexible particles is 2.2 times the cell gap, and a more preferable upper limit is 1.7 times the cell gap.
In the present specification, the maximum particle size of the flexible particles and the average particle size described below are values obtained by measuring the particles before blending with the sealant using a laser diffraction particle size distribution measuring device. means. As the laser diffraction type distribution measuring device, Mastersizer 2000 (manufactured by Malvern) or the like can be used.
なお、本明細書において粒子径のCV値とは、下記式により求められる数値のことである。
粒子径のCV値(%)=(粒子径の標準偏差/平均粒子径)×100 The coefficient of variation (hereinafter also referred to as CV value) of the flexible particles is preferably 30% or less. When the CV value of the particle diameter of the flexible particles exceeds 30%, a cell gap defect may be caused. The CV value of the particle diameter of the flexible particles is more preferably 28% or less.
In the present specification, the CV value of the particle diameter is a numerical value obtained by the following formula.
CV value of particle diameter (%) = (standard deviation of particle diameter / average particle diameter) × 100
上記柔軟粒子を分級する方法としては、例えば、湿式分級、乾式分級等の方法が挙げられる。なかでも、湿式分級が好ましく、湿式篩分級がより好ましい。 Even if the above-mentioned flexible particles are those having a maximum particle size, an average particle size, or a CV value outside the above-mentioned ranges, the maximum particle size, the average particle size, or the CV value is set within the above-mentioned range by classification. Can do. In addition, flexible particles having a particle size of less than 100% of the cell gap of the liquid crystal display element do not contribute to the suppression of the occurrence of seal break and liquid crystal contamination, and may increase the thixo value when blended with a sealant. It is preferable to remove by classification.
Examples of the method for classifying the flexible particles include wet classification and dry classification. Of these, wet classification is preferable, and wet sieving classification is more preferable.
上記シリコーン系粒子のうち市販されているものとしては、例えば、KMP-594、KMP-597、KMP-598、KMP-600、KMP-601、KMP-602(信越シリコーン社製)、トレフィルE-506S、EP-9215(東レ・ダウコーニング社製)等が挙げられ、これらを分級して用いることができる。上記シリコーン系粒子は、単独で用いられてもよいし、2種以上が併用されてもよい。 The silicone-based particles are preferably silicone rubber particles from the viewpoint of dispersibility in the resin.
Examples of commercially available silicone particles include KMP-594, KMP-597, KMP-598, KMP-600, KMP-601, KMP-602 (manufactured by Shin-Etsu Silicone), Trefil E-506S. EP-9215 (manufactured by Toray Dow Corning), etc., which can be classified and used. The said silicone type particle | grains may be used independently and 2 or more types may be used together.
上記(メタ)アクリル粒子は、原料となる単量体を公知の方法により重合させることで得ることができる。具体的には例えば、ラジカル重合開始剤の存在下で単量体を懸濁重合する方法、ラジカル重合開始剤の存在下で非架橋の種粒子に単量体を吸収させることにより種粒子を膨潤させてシード重合する方法等が挙げられる。
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。 (Meth) acrylic particles are preferably used as the vinyl particles.
The (meth) acrylic particles can be obtained by polymerizing monomers as raw materials by a known method. Specifically, for example, a method in which a monomer is suspension-polymerized in the presence of a radical polymerization initiator, and a seed particle is swollen by absorbing the monomer into a non-crosslinked seed particle in the presence of a radical polymerization initiator. And a seed polymerization method.
In the present specification, the “(meth) acryl” means “acryl or methacryl”.
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。 Examples of the monomer that is a raw material for forming the (meth) acrylic particles include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth). Alkyl (meth) such as acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. ) Acrylates, oxygen-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, etc. And, (meth) nitrile and containing monomers such as acrylonitrile, trifluoromethyl (meth) acrylate, monofunctional monomer such as a fluorine-containing (meth) acrylates such as pentafluoroethyl (meth) acrylate. Among these, alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the deformation amount when a 1 g load is applied can be increased.
In the present specification, the “(meth) acrylate” means “acrylate or methacrylate”.
なお、本明細書において上記柔軟粒子の硬度は、JIS K 6253に準拠した方法により測定されるデュロメータA硬さを意味する。 The preferable lower limit of the hardness of the flexible particles is 10, and the preferable upper limit is 50. When the hardness of the flexible particles exceeds 50, the obtained sealing agent for liquid crystal dropping method may be inferior in adhesiveness, or a gap defect may occur in the obtained liquid crystal display element. The more preferable lower limit of the hardness of the soft particles is 20, and the more preferable upper limit is 40.
In addition, in this specification, the hardness of the said flexible particle means the durometer A hardness measured by the method based on JISK6253.
上記硬化性樹脂としては、(メタ)アクリル樹脂を含有することが好ましく、イソシアヌル骨格を有する(メタ)アクリル樹脂やエポキシ(メタ)アクリレートを含有することがより好ましい。
なお、本明細書において、上記「(メタ)アクリル樹脂」とは、(メタ)アクリロイル基を有する樹脂を意味し、上記「(メタ)アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味する。また、上記「エポキシ(メタ)アクリレート」とは、エポキシ樹脂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意味する。 The sealing agent for liquid crystal dropping method of the present invention contains a curable resin.
The curable resin preferably contains a (meth) acrylic resin, and more preferably contains a (meth) acrylic resin having an isocyanuric skeleton or an epoxy (meth) acrylate.
In the present specification, the “(meth) acrylic resin” means a resin having a (meth) acryloyl group, and the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group. The “epoxy (meth) acrylate” means a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
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、エピコート806、エピコート4004(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、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(ダイセル化学工業社製)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。
上記ビスフェノールA型エピスルフィド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YL-7000(三菱化学社製)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。 Examples of commercially available bisphenol A type epoxy resins include Epicoat 828EL, Epicoat 1001, Epicoat 1004 (all manufactured by Mitsubishi Chemical Corporation), Epicron 850-S (manufactured by DIC Corporation), and the like.
As what is marketed among the said bisphenol F type epoxy resins, Epicoat 806, Epicoat 4004 (all are Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
As what is marketed among the said bisphenol S-type epoxy resins, Epicron EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
As what is marketed among the said hydrogenated bisphenol type | mold epoxy resins, Epicron EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available biphenyl type epoxy resins include Epicoat YX-4000H (manufactured by Mitsubishi Chemical Corporation).
Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
Examples of commercially available glycidylamine 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.) and Epolide PB (manufactured by Daicel Chemical Industries, Ltd.).
Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
Examples of commercially available bisphenol A type episulfide resins include Epicoat YL-7000 (manufactured by Mitsubishi Chemical Corporation).
Other commercially available 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.
上記エポキシ樹脂としては、例えば、上記エポキシ(メタ)アクリレートを合成するための原料となるエポキシ樹脂や、部分(メタ)アクリル変性エポキシ樹脂等が挙げられる。
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つ以上有する樹脂を意味し、例えば、2つ以上のエポキシ基を有する樹脂の一部分のエポキシ基を(メタ)アクリル酸と反応させることによって得ることができる。 The said curable resin may contain an epoxy resin for the purpose of improving the adhesiveness of the sealing agent for liquid crystal dropping methods obtained.
As said epoxy resin, the epoxy resin used as the raw material for synthesize | combining the said epoxy (meth) acrylate, a partial (meth) acryl modified epoxy resin, etc. are mentioned, for example.
In the present specification, the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two or more epoxy groups. It can be obtained by reacting a part of the epoxy group of the resin having a reaction with (meth) acrylic acid.
なかでも、重合開始剤としてラジカル重合開始剤を含有することが好ましい。スプリングバックは、上記柔軟粒子の最大粒子径の影響だけでなくシール剤の硬化速度にも影響を受ける。上記ラジカル重合開始剤は、熱硬化剤に比べて硬化速度が格段に速くすることができるため、上記柔軟粒子と組み合わせて用いることにより、上記柔軟粒子により発生しやすいスプリングバックの発生を抑制する効果に更に優れるものとすることができる。 The sealing agent for liquid crystal dropping method of the present invention contains a polymerization initiator and / or a thermosetting agent.
Especially, it is preferable to contain a radical polymerization initiator as a polymerization initiator. The springback is influenced not only by the maximum particle size of the soft particles but also by the curing rate of the sealant. Since the radical polymerization initiator can significantly increase the curing rate as compared with the thermosetting agent, the effect of suppressing the occurrence of springback that is likely to occur due to the flexible particles by using in combination with the flexible particles. It can be further improved.
上述したように、上記ラジカル重合開始剤は熱硬化剤に比べて硬化速度が格段に速いため、ラジカル重合開始剤を用いることにより、シールブレイクや、液晶汚染の発生を抑制し、かつ、上記柔軟粒子により発生しやすいスプリングバックも抑制できる。
なかでも、得られる液晶滴下工法用シール剤を熱により速やかに硬化させることができるため、上記ラジカル重合開始剤は、熱ラジカル重合開始剤を含有することが好ましい。 Examples of the radical polymerization initiator include a thermal radical polymerization initiator that generates radicals by heating, a photo radical polymerization initiator that generates radicals by light irradiation, and the like.
As described above, the radical polymerization initiator has a much faster curing rate than the thermosetting agent. Therefore, by using the radical polymerization initiator, it is possible to suppress the occurrence of seal breaks and liquid crystal contamination, and the flexible Springback that is easily generated by particles can also be suppressed.
Especially, since the sealing agent for liquid crystal dropping methods obtained can be hardened | cured rapidly with a heat | fever, it is preferable that the said radical polymerization initiator contains a thermal radical polymerization initiator.
なお、本明細書において高分子アゾ開始剤とは、アゾ基を有し、熱によって(メタ)アクリロイルオキシ基を硬化させることができるラジカルを生成する、数平均分子量が300以上の化合物を意味する。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example. Among these, a polymer azo initiator composed of a polymer azo compound is preferable.
In the present specification, the polymer azo initiator means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. .
なお、本明細書において、上記数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)で測定を行い、ポリスチレン換算により求められる値である。GPCによってポリスチレン換算による数平均分子量を測定する際のカラムとしては、例えば、Shodex LF-804(昭和電工社製)等が挙げられる。 The preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000. When the number average molecular weight of the polymer azo initiator is less than 1000, the polymer azo initiator may adversely affect the liquid crystal. When the number average molecular weight of the polymeric azo initiator exceeds 300,000, mixing with the curable resin may be difficult. The more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
In addition, in this specification, the said number average molecular weight is a value calculated | required by polystyrene conversion by measuring with gel permeation chromatography (GPC). Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK).
上記アゾ基を介してポリアルキレンオキサイド等のユニットが複数結合した構造を有する高分子アゾ開始剤としては、ポリエチレンオキサイド構造を有するものが好ましい。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。 Examples of the polymer azo initiator include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
As the polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group, those having a polyethylene oxide structure are preferable. Examples of 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.
上記シランカップリング剤としては、基板等との接着性を向上させる効果に優れ、硬化性樹脂と化学結合することにより液晶中への硬化性樹脂の流出を抑制することができることから、例えば、N-フェニル-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-イソシアネートプロピルトリメトキシシラン等が好適に用いられる。これらのシランカップリング剤は単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 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.
As said silane coupling agent, since it is excellent in the effect which improves adhesiveness with a board | substrate etc. and it can suppress the outflow of curable resin in a liquid crystal by chemically bonding with curable resin, it is N, for example. -Phenyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, etc. are preferably used . These silane coupling agents may be used alone or in combination of two or more.
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滴下工法用シール剤を用いて製造した液晶表示素子は、充分な遮光性を有するため、光の漏れ出しがなく高いコントラストを有し、優れた画像表示品質を有する液晶表示素子を実現することができる。 The above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
In addition, the liquid crystal display 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 a sufficient light-shielding property, and thus has a high contrast without light leakage. A liquid crystal display element having excellent image display quality can be realized.
また、上記チタンブラックの体積抵抗の好ましい下限は0.5Ω・cm、好ましい上限は3Ω・cmであり、より好ましい下限は1Ω・cm、より好ましい上限は2.5Ω・cmである。 The preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
Further, the preferred lower limit of the volume resistance of the titanium black is 0.5 Ω · cm, the preferred upper limit is 3 Ω · cm, the more preferred lower limit is 1 Ω · cm, and the more preferred upper limit is 2.5 Ω · cm.
レゾルシノール型エポキシ樹脂(ナガセケムテックス製、「デナコールEX-201」)1000重量部、重合禁止剤としてp-メトキシフェノール2重量部、反応触媒としてトリエチルアミン2重量部、及び、アクリル酸649重量部を、空気を送り込みながら90℃で5時間還流撹拌して反応させた。得られた樹脂100重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物(ホフマンミネラル社製、「シリチンV85」)10重量部が充填されたカラムで濾過し、レゾルシノール型エポキシアクリレートを得た。 (Synthesis of resorcinol type epoxy acrylate)
1000 parts by weight of resorcinol type epoxy resin (manufactured by Nagase ChemteX, “Denacol EX-201”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 649 parts by weight of acrylic acid, The reaction was carried out by stirring at 90 ° C. for 5 hours while feeding air. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). Resorcinol type epoxy acrylate was obtained.
ビフェニルエーテル型エポキシ樹脂(新日鉄住金化学社製、「YSLV80DE」)1000重量部、重合禁止剤としてp-メトキシフェノール2重量部、反応触媒としてトリエチルアミン2重量部、及び、アクリル酸229重量部を、空気を送り込みながら90℃で還流撹拌し、5時間反応させた。得られた樹脂100重量部を、反応物中のイオン性不純物を吸着させる為にクオルツとカオリンの天然結合物(ホフマンミネラル社製、「シリチンV85」)10重量部が充填されたカラムで濾過し、部分アクリル変性ビフェニルエーテル型エポキシ樹脂を得た。 (Synthesis of partially acrylic modified biphenyl ether type epoxy resin)
1000 parts by weight of a biphenyl ether type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YSLV80DE”), 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 229 parts by weight of acrylic acid, The mixture was refluxed and stirred at 90 ° C. for 5 hours. In order to adsorb ionic impurities in the reaction product, 100 parts by weight of the obtained resin was filtered through a column packed with 10 parts by weight of a natural combination of quartz and kaolin (manufactured by Hoffman Mineral Co., Ltd., “Siritin V85”). A partially acrylic-modified biphenyl ether type epoxy resin was obtained.
シリコーンゴム粒子(信越シリコーン社製、「KMP-601」)をメタノールに分散し12μm、10μm、8μm、5μmの目開きの篩で湿式篩分級し、篩を通過したものを回収して乾燥させ、シリコーンゴム粒子の分級処理品を得た。篩はポリイミドフィルムにレーザーで超高精度微細加工を施して得た極めて精度の高い穴を有するものを用いた。
得られたシリコーンゴム粒子の分級処理品について、レーザー回折式分布測定装置(マルバーン社製、「マスターサイザー2000」)を用いて粒子径を測定した。また、別のシリコーンゴム粒子KMP-594、KMP-598、KMP-600についても、8μmの目開きの篩を用い、同様にして分級処理品を得、粒子径を測定した。
また、平均粒子径は、KMP-601を12μm篩で分級したものが8.5μm、10μm篩で分級したものが7.6μm、8μm篩で分級したものが6.5μm、8μm篩と5μm篩とで5~8μmの範囲となるように分級したものが7.1μmであり、KMP-594を8μm篩で分級したものが4.7μmであり、KMP-598を8μm篩で分級したものが6.9μmであり、KMP-600を8μm篩で分級したものが4.9μmであった。
更に、粒子径のCV値は、KMP-601を12μm篩で分級したものが27%、10μm篩で分級したものが26%、8μm篩で分級したものが26%、8μm篩と5μm篩とで5~8μmの範囲となるように分級したものが25%であり、KMP-594を8μm篩で分級したものが28%であり、KMP-598を8μm篩で分級したものが28%であり、KMP-600を8μm篩で分級したものが27%であった。
加えて、5μm以上の粒子径の粒子の含有割合は、体積頻度で、KMP-601を12μm篩で分級したものが99%、10μm篩で分級したものが98.5%、8μm篩で分級したものが97.7%、8μm篩と5μm篩とで5~8μmの範囲となるように分級したものが100%であり、KMP-594を8μm篩で分級したものが48%であり、KMP-598を8μm篩で分級したものが98.1%であり、KMP-600を8μm篩で分級したものが46%であった。
なお、実施例及び比較例の液晶滴下工法用シール剤は、セルギャップが4.7μmの液晶表示素子の製造に用いられるものとする。 (Classification of silicone particles)
Silicone rubber particles (manufactured by Shin-Etsu Silicone Co., Ltd., “KMP-601”) are dispersed in methanol and classified by wet sieving with sieves of 12 μm, 10 μm, 8 μm and 5 μm, and those passing through the sieve are collected and dried. A classified product of silicone rubber particles was obtained. As the sieve, a polyimide film having a hole with extremely high accuracy obtained by applying ultrahigh precision fine processing with a laser was used.
About the classification treatment product of the obtained silicone rubber particles, the particle diameter was measured using a laser diffraction type distribution measuring device (manufactured by Malvern, “Mastersizer 2000”). For other silicone rubber particles KMP-594, KMP-598, and KMP-600, classified products were obtained in the same manner using a sieve with an opening of 8 μm, and the particle size was measured.
The average particle size is 8.5 μm for KMP-601 classified with a 12 μm sieve, 7.6 μm for 10 μm sieve, 6.5 μm for 8 μm sieve and 5 μm sieve for 8 μm sieve Is classified to be in the range of 5 to 8 μm is 7.1 μm, KMP-594 is classified with an 8 μm sieve and 4.7 μm, and KMP-598 is classified with an 8 μm sieve. 9 μm, and KMP-600 classified by an 8 μm sieve was 4.9 μm.
Furthermore, the CV value of the particle size is 27% for KMP-601 classified by 12 μm sieve, 26% for 10 μm sieve, 26% for 8 μm sieve, 8 μm sieve and 5 μm sieve. 25% is classified to a range of 5 to 8 μm, 28% is KMP-594 classified by an 8 μm sieve, and 28% is KMP-598 classified by an 8 μm sieve. 27% was obtained by classifying KMP-600 with an 8 μm sieve.
In addition, the content ratio of particles having a particle diameter of 5 μm or more was determined by volume frequency, 99% for KMP-601 classified by a 12 μm sieve, 98.5% by 10 μm sieve, and 88.5 μm by a 8 μm sieve. 97.7%, 8% and 5μm sieves are classified to be in the range of 5-8μm, 100%, KMP-594 is classified by 8μm sieves, 48%, KMP- The product obtained by classifying 598 with an 8 μm sieve was 98.1%, and the product obtained by classifying KMP-600 with an 8 μm sieve was 46%.
In addition, the sealing agent for liquid crystal dropping methods of an Example and a comparative example shall be used for manufacture of the liquid crystal display element whose cell gap is 4.7 micrometers.
ポリテトラメチレングリコールジアクリレート800gと、スチレン200gと、過酸化ベンゾイル40gとを混合し、均一に溶解させ、モノマー混合液を得た。得られたモノマー混合液をポリビニルアルコール1重量%水溶液の入った反応釜に投入し、2~4時間攪拌することで、モノマーの液滴が所定の粒子径になるよう、粒子径調整を行った。次いで、85℃の窒素雰囲気下で9時間反応を行い、アクリル系粒子Aを得た。得られた粒子を熱水にて数回洗浄した後、12μm篩で分級、乾燥を行った。
得られたアクリル系粒子Aの平均粒子径は7.5μm、粒子径のCV値は21%、5μm以上の粒子径の粒子の含有割合は、体積頻度で75%であった。 (Preparation of acrylic particles A)
800 g of polytetramethylene glycol diacrylate, 200 g of styrene, and 40 g of benzoyl peroxide were mixed and dissolved uniformly to obtain a monomer mixed solution. The obtained monomer mixture was put into a reaction vessel containing a 1% by weight aqueous solution of polyvinyl alcohol and stirred for 2 to 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size. . Subsequently, reaction was performed in a nitrogen atmosphere at 85 ° C. for 9 hours to obtain acrylic particles A. The obtained particles were washed several times with hot water, and then classified and dried with a 12 μm sieve.
The average particle diameter of the obtained acrylic particles A was 7.5 μm, the CV value of the particle diameter was 21%, and the content ratio of particles having a particle diameter of 5 μm or more was 75% in terms of volume frequency.
ポリテトラメチレングリコールジアクリレート700gと、エチルヘキシルメタクリレート300gと、過酸化ベンゾイル40gとを混合し、均一に溶解させ、モノマー混合液を得た。得られたモノマー混合液をポリビニルアルコール1重量%水溶液の入った反応釜に投入し、2~4時間攪拌することで、モノマーの液滴が所定の粒子径になるよう、粒子径調整を行った。次いで、85℃の窒素雰囲気下で9時間反応を行い、アクリル系粒子Bを得た。得られた粒子を熱水にて数回洗浄した後、12μm篩で分級、乾燥を行った。
得られたアクリル系粒子Bの平均粒子径は7.3μm、粒子径のCV値は22%、粒子径のCV値は21%、5μm以上の粒子径の粒子の含有割合は、体積頻度で71%であった。 (Preparation of acrylic particles B)
700 g of polytetramethylene glycol diacrylate, 300 g of ethylhexyl methacrylate, and 40 g of benzoyl peroxide were mixed and dissolved uniformly to obtain a monomer mixture. The obtained monomer mixture was put into a reaction vessel containing a 1% by weight aqueous solution of polyvinyl alcohol and stirred for 2 to 4 hours to adjust the particle size so that the monomer droplets had a predetermined particle size. . Next, the reaction was performed in a nitrogen atmosphere at 85 ° C. for 9 hours to obtain acrylic particles B. The obtained particles were washed several times with hot water, and then classified and dried with a 12 μm sieve.
The average particle diameter of the obtained acrylic particles B is 7.3 μm, the CV value of the particle diameter is 22%, the CV value of the particle diameter is 21%, and the content ratio of particles having a particle diameter of 5 μm or more is 71 in volume frequency. %Met.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を12μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 1)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 12 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as silane coupling agent ( Koshi Silicone Co., Ltd. (“KBM-573”) 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を12μm篩で分級したもの)20重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 2)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 20 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 12 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as silane coupling agent ( Koshi Silicone Co., Ltd. (“KBM-573”) 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を10μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 3)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by a 10 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as silane coupling agent ( Koshi Silicone Co., Ltd. (“KBM-573”) 1 part by weight and 3-glycidoxypropyltrimethoxysilane (Chisso Corp., “Syra Ace S510”) 2 parts by weight are blended, and a planetary stirring device (Sinky Corp.) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を8μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 Example 4
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-601 classified by an 8 μm sieve), 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.), N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent 1 part by weight of “KBM-573” manufactured by Silicone Co., Ltd. and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso “Syra Ace S510”) After stirring with “Awatori Netaro”), the mixture was uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、ビスフェノールA型エポキシアクリレート(ダイセル・オルネクス社製、「EBECRYL3700」)58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「V-501」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を10μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 5)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a bisphenol A type epoxy acrylate (“EBECRYL 3700” manufactured by Daicel Ornex Co., Ltd.), and synthesis 17 parts by weight of the partially acryl-modified biphenyl ether type epoxy resin, 1 part by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., “V-501”) as a thermal radical polymerization initiator, and malonic acid as a thermosetting agent 2 parts by weight of dihydrazide (manufactured by Nippon Finechem Co., Ltd., “MDH”), 45 parts by weight of a silicone rubber particle classification product (KMP-601 classified by a 10 μm sieve), silica as a filler (manufactured by Nippon Shokubai Co., Ltd., "Seahoster KE-S100HG") 20 parts by weight and N-F as silane coupling agent 1 part by weight of nyl-3-aminopropyltrimethoxysilane (“KBM-573” manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso, “Syraace S510”) The mixture was stirred with a planetary stirrer (Shinky Corp., “Awatori Nertaro”), and then mixed uniformly with a ceramic three roll to obtain a sealant for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、光ラジカル重合開始剤(BASF Japan社製、「DAROCUR TPO」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を12μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 6)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight, 1 part by weight of a radical photopolymerization initiator (BASF Japan, "DAROCUR TPO"), 2 parts by weight of malonic acid dihydrazide (manufactured by Nippon Finechem, "MDH") as a thermosetting agent, and silicone rubber particles 45 parts by weight of KMP-601 (classified with a 12 μm sieve), 20 parts by weight of silica (Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N—as the silane coupling agent Phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Silico) 1 part by weight of “KBM-573” manufactured by Thon Co., Ltd. and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso “Syra Ace S510”) , “Awatori Netaro”), and then uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)0.5重量部と、硬化促進剤としてトリス(3-カルボキシプロピル)イソシアヌレート粉砕品(四国化成工業社製、「C3-CIC酸」をジェットミルで平均粒径1.5μmに粉砕したもの)3重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)20重量部と、シリコーンゴム粒子の分級処理品(KMP-601を12μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 7)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 Parts by weight, 0.5 part by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, Ltd., “VPE0201”) as a thermal radical polymerization initiator, and tris (3-carboxypropyl) isocyanurate ground product (as a curing accelerator) 3 parts by weight of “C3-CIC acid” manufactured by Shikoku Kasei Kogyo Co., Ltd., pulverized to an average particle size of 1.5 μm by a jet mill) and malonic acid dihydrazide (manufactured by Nippon Finechem Co., “MDH”) 20 Part by weight and silicone rubber particle classification product (KMP-601 classified by 12 μm sieve) 4 5 parts by weight, 20 parts by weight of silica (Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”) as filler, and N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., “ 1 part by weight of KBM-573 ”) and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation,“ Syra Ace S510 ”), and a planetary stirrer (Sinky Corporation )) And then mixed uniformly with a ceramic three roll to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-601を8μm篩と5μm篩で5~8μmの範囲となるように分級したもの)45重量部と、充填剤としてコアシェルアクリレート共重合体粒子(ガンツ社製、「F351N」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 8)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Part by weight, 45 parts by weight of silicone rubber particle-classified product (KMP-601 classified so as to be in the range of 5 to 8 μm with 8 μm sieve and 5 μm sieve), and core-shell acrylate copolymer particles (filler) 20 parts by weight of “F351N” manufactured by Ganz and N-phenyl as a silane coupling agent 1 part by weight of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, “KBM-573”) and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso, “Syra Ace S510”) After stirring with a planetary stirrer ("Shinky" manufactured by Shinky Co., Ltd.), the mixture was uniformly mixed with a three ceramic roll to obtain a sealant for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(12μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部と、遮光剤としてチタンブラック(三菱マテリアル社製、「13M-C」)20重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 Example 9
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of silicone rubber particle classified product (classified with a 12 μm sieve), 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and silane coupling agent N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd.) , “KBM-573”) and 1 part by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, “Syra Ace S510”), and titanium black (manufactured by Mitsubishi Materials Corporation, “13M-C” )) 20 parts by weight, and after stirring with a planetary stirrer (Shinky Co., “Awatori Netaro”), the mixture is uniformly mixed with three ceramic rolls to obtain a liquid crystal dropping method sealing agent. Obtained.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-594を8μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 10)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-594 classified by an 8 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent 1 part by weight of “KBM-573” manufactured by Silicone Co., Ltd. and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso “Syra Ace S510”) After stirring with “Awatori Netaro”), the mixture was uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-598を8μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 11)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classified product (KMP-598 classified by an 8 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent 1 part by weight of “KBM-573” manufactured by Silicone Co., Ltd. and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso “Syra Ace S510”) After stirring with “Awatori Netaro”), the mixture was uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、シリコーンゴム粒子の分級処理品(KMP-600を8μm篩で分級したもの)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 Example 12
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of a silicone rubber particle classification product (KMP-600 classified by an 8 μm sieve), and 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.) N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent 1 part by weight of “KBM-573” manufactured by Silicone Co., Ltd. and 2 parts by weight of 3-glycidoxypropyltrimethoxysilane (manufactured by Chisso “Syra Ace S510”) After stirring with “Awatori Netaro”), the mixture was uniformly mixed with three ceramic rolls to obtain a sealing agent for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、アクリル系粒子A45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 13)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of acrylic particles A, 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent (Shin-Etsu Silicone, “KBM-573”) 1 part by weight and 3-g 3 parts of a ceramic roll after blending with 2 parts by weight of Sidoxypropyltrimethoxysilane (manufactured by Chisso Corp., “Syra Ace S510”) and stirring with a planetary stirrer (“Shinky Corp.,“ Awatori Netaro ”) Were mixed uniformly to obtain a sealant for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、アクリル系粒子B45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Example 14)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Parts by weight, 45 parts by weight of acrylic particles B, 20 parts by weight of silica (manufactured by Nippon Shokubai Co., Ltd., “Seahoster KE-S100HG”), and N-phenyl-3-aminopropyltrimethoxysilane as a silane coupling agent (Shin-Etsu Silicone, “KBM-573”) 1 part by weight and 3-g 3 parts of a ceramic roll after blending with 2 parts by weight of Sidoxypropyltrimethoxysilane (manufactured by Chisso Corp., “Syra Ace S510”) and stirring with a planetary stirrer (“Shinky Corp.,“ Awatori Netaro ”) Were mixed uniformly to obtain a sealant for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Comparative Example 1)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (manufactured by Wako Pure Chemical Industries, “VPE0201”) and 2 parts of malonic acid dihydrazide (manufactured by Nippon Finechem, “MDH”) as a thermosetting agent Parts, 20 parts by weight of silica as a filler (“Chihoster KE-S100HG” manufactured by Nippon Shokubai Co., Ltd.), and N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone, “KBM-” as a silane coupling agent) 573 ") 1 part by weight and 3-glycidoxypropyltrimethoxysilane 2 parts by weight (manufactured by Chisso Corp., “Syra Ace S510”), and after stirring with a planetary stirrer (Shinky Corp., “Awatori Netaro”), uniformly mixed with three ceramic rolls Thus, a sealing agent for a liquid crystal dropping method was obtained.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、未分級シリコーンゴム粒子(信越シリコーン社製、「KMP-598」、最大粒子径30.5μm、平均粒子径13.0μm、粒子径のCV値38%、5μm以上の粒子径の粒子の含有割合は、体積頻度で99.3%)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Comparative Example 2)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Part by weight, unclassified silicone rubber particles (manufactured by Shin-Etsu Silicone Co., Ltd., “KMP-598”, maximum particle size 30.5 μm, average particle size 13.0 μm, particle size CV value 38%, particles having a particle size of 5 μm or more The content ratio is 45 parts by weight of 99.3% by volume frequency and silica (manufactured by Nippon Shokubai Co., Ltd. KE-S100HG "), 20 parts by weight, 1 part by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone," KBM-573 ") as a silane coupling agent and 3-glycidoxypropyltri After mixing with 2 parts by weight of methoxysilane (manufactured by Chisso Corporation, “Syra Ace S510”) and stirring with a planetary stirrer (manufactured by Shinky Co., Ltd. “Netaro Awatori”), uniformly with three ceramic rolls The mixture was mixed to obtain a sealant for liquid crystal dropping method.
硬化性樹脂としてイソシアヌル骨格を有するアクリル樹脂(東亞合成社製、「アロニックスM-315」)25重量部、合成したレゾルシノール型エポキシアクリレート58重量部、及び、合成した部分アクリル変性ビフェニルエーテル型エポキシ樹脂17重量部と、熱ラジカル重合開始剤として高分子アゾ開始剤(和光純薬工業社製、「VPE0201」)1重量部と、熱硬化剤としてマロン酸ジヒドラジド(日本ファインケム社製、「MDH」)2重量部と、未分級シリコーンゴム粒子(信越シリコーン社製、「KMP-601」、最大粒子径30.8μm、平均粒子径13.0μm、粒子径のCV値34%、5μm以上の粒子径の粒子の含有割合は、体積頻度で99.1%)45重量部と、充填剤としてシリカ(日本触媒社製、「シーホスターKE-S100HG」)20重量部と、シランカップリング剤としてN-フェニル-3-アミノプロピルトリメトキシシラン(信越シリコーン社製、「KBM-573」)1重量部及び3-グリシドキシプロピルトリメトキシシラン(チッソ社製、「サイラエースS510」)2重量部とを配合し、遊星式撹拌装置(シンキー社製、「あわとり練太郎」)にて撹拌した後、セラミック3本ロールにて均一に混合して液晶滴下工法用シール剤を得た。 (Comparative Example 3)
25 parts by weight of an acrylic resin having an isocyanuric skeleton (“Aronix M-315” manufactured by Toagosei Co., Ltd.) as a curable resin, 58 parts by weight of a synthesized resorcinol type epoxy acrylate, and a synthesized partially acrylic modified biphenyl ether type epoxy resin 17 1 part by weight of a polymer azo initiator (“VPE0201”, manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal radical polymerization initiator, and 2 parts of malonic acid dihydrazide (“MDH”, manufactured by Nippon Finechem) as a thermosetting agent Part by weight, unclassified silicone rubber particles (manufactured by Shin-Etsu Silicone, “KMP-601”, maximum particle size 30.8 μm, average particle size 13.0 μm, particle size CV value 34%, particles with a particle size of 5 μm or more The content ratio is 45 parts by weight with a volume frequency of 99.1%) and silica as a filler (manufactured by Nippon Shokubai Co., Ltd. KE-S100HG "), 20 parts by weight, 1 part by weight of N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone," KBM-573 ") as a silane coupling agent and 3-glycidoxypropyltri After mixing with 2 parts by weight of methoxysilane (manufactured by Chisso Corporation, “Syra Ace S510”) and stirring with a planetary stirrer (manufactured by Shinky Co., Ltd. “Netaro Awatori”), uniformly with three ceramic rolls The mixture was mixed to obtain a sealant for liquid crystal dropping method.
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1~3に示した。 <Evaluation>
The following evaluation was performed about each sealing compound for liquid crystal dropping methods obtained by the Example and the comparative example. The results are shown in Tables 1-3.
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重量部に対して平均粒子径4μmのスペーサー粒子(積水化学工業社製、「ミクロパールSI」)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、ITO薄膜を形成したコーニングガラス1737(20mm×50mm×厚さ1.1mm)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滴下工法用シール剤を押し広げ、高圧水銀ランプを用いて100mW/cm2の紫外線を30秒間照射した後、120℃で60分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。
また、上記のコーニングガラス1737にイミド樹脂(日産化学社製、「#7492」)をスピンコートで塗布し、80℃でプリベイクした後、230℃焼成して配向膜を形成した基板を用いて上記と同様にして接着試験片を作製し、同様にして接着強度を測定した。接着強度が200N/cm2以上であった場合を「○」、接着強度が100N/cm2以上200N/cm2未満であった場合を「△」、接着強度が100N/cm2未満であった場合を「×」として、ITOに対する接着性及び配向膜に対する接着性を評価した。 (Adhesiveness)
One part by weight of spacer particles having an average particle diameter of 4 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SI”) with respect to 100 parts by weight of each liquid crystal dropping method sealing agent obtained in Examples and Comparative Examples is a planetary stirrer. Disperse evenly and take a very small amount in the center of Corning glass 1737 (20 mm x 50 mm x thickness 1.1 mm) on which the ITO thin film is formed. The adhesive was spread and irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a high-pressure mercury lamp, and then heated at 120 ° C. for 60 minutes to cure the sealant to obtain an adhesion test piece. About the obtained adhesion test piece, the adhesive strength was measured using the tension gauge.
Further, an imide resin (“# 7942”, manufactured by Nissan Chemical Industries, Ltd.) was applied to the above-mentioned Corning glass 1737 by spin coating, prebaked at 80 ° C., and then baked at 230 ° C. to form the alignment film. In the same manner, an adhesive test piece was prepared, and the adhesive strength was measured in the same manner. The case where the adhesive strength was 200 N / cm 2 or more was “◯”, the case where the adhesive strength was 100 N / cm 2 or more and less than 200 N / cm 2 was “Δ”, and the adhesive strength was less than 100 N / cm 2 . The case was evaluated as “x”, and the adhesion to ITO and the adhesion to the alignment film were evaluated.
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重量部に対して平均粒子径4.7μmのスペーサー粒子(積水化学工業社製、「ミクロパールSI」)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うちの一方に長方形の枠を描く様にシール剤(メインシール)を塗布し、続いて、セルを真空に保持するため、更に外周に一周シール剤(ダミーシール)を塗布した。その後、TN液晶(チッソ社製、「JC-5001LA」)の微小滴を液晶滴下装置にて滴下塗布し、他方の透明基板を、真空貼り合わせ装置にて5Paの真空下にて貼り合わせた。貼り合わせた後のセルに高圧水銀ランプを用いて100mW/cm2の紫外線を30秒間照射した後、120℃で60分間加熱してシール剤を熱硬化させ、液晶表示素子を得た。
得られた液晶表示素子のセルギャップを測定し、セル内が均一に4~5μmとなっていた場合を「○」、セル内に4~5μmのギャップがとれていない箇所が存在した場合を「△」、セルが形成できなかった場合を「×」としてセルギャップを評価した。 (Cell gap)
One part by weight of spacer particles (“Micropearl SI”, manufactured by Sekisui Chemical Co., Ltd.) having an average particle size of 4.7 μm per 100 parts by weight of the sealant for each liquid crystal dropping method obtained in Examples and Comparative Examples is a planetary type. After uniformly dispersing with a stirrer, the resulting sealant is filled into a dispensing syringe (Musashi Engineering, PSY-10E), defoamed, and dispenser (Musashi Engineering, In SHOTMASTER 300 "), a sealing agent (main seal) is applied so as to draw a rectangular frame on one of the two transparent electrode substrates with an ITO thin film, and then the cell is further maintained in a vacuum. A one-round sealant (dummy seal) was applied to the outer periphery. Thereafter, fine droplets of TN liquid crystal (manufactured by Chisso Corporation, “JC-5001LA”) were dropped and applied with a liquid crystal dropping device, and the other transparent substrate was bonded with a vacuum bonding device under a vacuum of 5 Pa. The cell after bonding was irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a high-pressure mercury lamp, and then heated at 120 ° C. for 60 minutes to thermally cure the sealing agent, thereby obtaining a liquid crystal display element.
When the cell gap of the obtained liquid crystal display element was measured, the case where the inside of the cell was uniformly 4 to 5 μm was “◯”, and the case where there was a part where the gap was not 4 to 5 μm was present. “Δ”, the cell gap was evaluated as “x” when the cell could not be formed.
上記「(セルギャップ)」の評価にて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、表示むらが全く無かった場合を「◎」、表示むらがほとんど無かった場合を「○」、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又はセルが形成できなかった場合を「×」として液晶汚染性を評価した。 (Liquid crystal contamination)
Regarding the liquid crystal display element obtained by the evaluation of “(cell gap)”, the display unevenness generated in the liquid crystal (particularly the corner portion) around the seal portion was visually observed, and the case where there was no display unevenness was ”, When there is almost no display unevenness,“ △ ”when display unevenness is confirmed, and“ × ”when severe display unevenness is confirmed or when a cell cannot be formed Evaluated.
Claims (7)
- 液晶滴下工法による液晶表示素子の製造に用いる液晶滴下工法用シール剤であって、
硬化性樹脂と、重合開始剤及び/又は熱硬化剤と、柔軟粒子とを含有し、
前記柔軟粒子の最大粒子径が、液晶表示素子のセルギャップの100%以上であり、かつ、5μm~20μmであることを特徴とする液晶滴下工法用シール剤。 A liquid crystal dropping method sealing agent used for manufacturing a liquid crystal display element by a liquid crystal dropping method,
Containing a curable resin, a polymerization initiator and / or a thermosetting agent, and soft particles,
A sealing agent for a liquid crystal dropping method, wherein the flexible particles have a maximum particle diameter of 100% or more of a cell gap of a liquid crystal display element and 5 μm to 20 μm. - 柔軟粒子は、粒子径の変動係数が30%以下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。 The sealing agent for a liquid crystal dropping method according to claim 1, wherein the flexible particles have a coefficient of variation in particle diameter of 30% or less.
- 重合開始剤として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又は2記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 1 or 2, wherein a thermal radical polymerization initiator is contained as a polymerization initiator.
- 熱ラジカル重合開始剤は、高分子アゾ開始剤であることを特徴とする請求項3記載の液晶滴下工法用シール剤。 The sealing agent for liquid crystal dropping method according to claim 3, wherein the thermal radical polymerization initiator is a polymer azo initiator.
- 遮光剤を含有することを特徴とする請求項1、2、3又は4記載の液晶滴下工法用シール剤。 5. The sealing agent for liquid crystal dropping method according to claim 1, 2, 3, or 4, characterized by containing a light shielding agent.
- 請求項1、2、3、4又は5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。 A vertical conduction material comprising the sealing agent for a liquid crystal dropping method according to claim 1, and conductive fine particles.
- 請求項1、2、3、4若しくは5記載の液晶滴下工法用シール剤又は請求項6記載の上下導通材料を用いて製造されることを特徴とする液晶表示素子。 A liquid crystal display element manufactured using the sealing agent for a liquid crystal dropping method according to claim 1, 2, 3, 4 or 5, or the vertical conduction material according to claim 6.
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JP2015079077A (en) * | 2013-10-16 | 2015-04-23 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using the same |
KR20170002632A (en) | 2014-07-24 | 2017-01-06 | 미쓰이 가가쿠 가부시키가이샤 | Liquid crystal sealing agent and production method for liquid crystal display panel |
JPWO2017131002A1 (en) * | 2016-01-26 | 2018-11-15 | 積水化学工業株式会社 | Light-shielding sealing agent for liquid crystal display element, vertical conduction material, and liquid crystal display element |
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KR102164731B1 (en) * | 2013-05-24 | 2020-10-13 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal dropping methods, vertically conducting material, and liquid crystal display element |
KR102649401B1 (en) * | 2015-10-09 | 2024-03-19 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
JP6837781B2 (en) * | 2016-08-31 | 2021-03-03 | 日本化薬株式会社 | Liquid crystal sealant and liquid crystal display cell using it |
WO2018124023A1 (en) * | 2016-12-27 | 2018-07-05 | 積水化学工業株式会社 | Sealing agent for liquid crystal display elements, vertically conducting material and liquid crystal display element |
KR102106761B1 (en) * | 2017-01-25 | 2020-05-06 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for liquid crystal display element, upper and lower conduction material, liquid crystal display element, and cured product |
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