WO2014185374A1 - Agent d'étanchéité pour processus de remplissage goutte à goutte, matériau à conduction verticale et élément d'affichage à cristaux liquides - Google Patents

Agent d'étanchéité pour processus de remplissage goutte à goutte, matériau à conduction verticale et élément d'affichage à cristaux liquides Download PDF

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Publication number
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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Prior art keywords
liquid crystal
weight
meth
manufactured
acrylate
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PCT/JP2014/062574
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English (en)
Japanese (ja)
Inventor
勝則 西出
雄一 尾山
沙織 上田
山口　真史
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積水化学工業株式会社
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Priority to JP2014524603A priority Critical patent/JP5685346B1/ja
Priority to KR1020157006367A priority patent/KR101593381B1/ko
Priority to CN201480002608.6A priority patent/CN104756004B/zh
Publication of WO2014185374A1 publication Critical patent/WO2014185374A1/fr

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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention a pour objet un agent d'étanchéité qui est destiné à un processus de remplissage goutte à goutte, qui présente une excellente dureté, qui empêche l'apparition d'une rupture d'étanchéité et la contamination des cristaux liquides et dans lequel une défaillance se produit rarement. La présente invention a également pour objet un matériau à conduction verticale et un élément d'affichage à cristaux liquides qui sont produits à l'aide de l'agent d'étanchéité destiné à un processus de remplissage goutte à goutte. La présente invention est un agent d'étanchéité destiné à un processus de remplissage goutte à goutte qui est utilisé lors de la production d'éléments d'affichage à cristaux liquides à l'aide d'un processus de remplissage goutte à goutte. L'agent d'étanchéité contient une résine polymérisable, un initiateur de polymérisation et/ou un agent thermodurcissable, ainsi que des particules molles. La taille maximum des particules molles est égale à au moins 100 % de l'espace entre les cellules de l'élément d'affichage à cristaux liquides et elle se situe dans la plage comprise entre 5 et 20 µm.
PCT/JP2014/062574 2013-05-15 2014-05-12 Agent d'étanchéité pour processus de remplissage goutte à goutte, matériau à conduction verticale et élément d'affichage à cristaux liquides WO2014185374A1 (fr)

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JP2014524603A JP5685346B1 (ja) 2013-05-15 2014-05-12 液晶滴下工法用シール剤、上下導通材料、及び、液晶表示素子
KR1020157006367A KR101593381B1 (ko) 2013-05-15 2014-05-12 액정 적하 공법용 시일제, 상하 도통 재료, 및, 액정 표시 소자
CN201480002608.6A CN104756004B (zh) 2013-05-15 2014-05-12 液晶滴下工艺用密封剂、上下导通材料以及液晶显示元件

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JP2013-103185 2013-05-15
JP2013103185 2013-05-15
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JP2013-155738 2013-07-26

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JP2015079077A (ja) * 2013-10-16 2015-04-23 日本化薬株式会社 液晶シール剤及びそれを用いた液晶表示セル
KR20170002632A (ko) 2014-07-24 2017-01-06 미쓰이 가가쿠 가부시키가이샤 액정 시일제, 및 액정 표시 패널의 제조 방법
JPWO2017131002A1 (ja) * 2016-01-26 2018-11-15 積水化学工業株式会社 液晶表示素子用遮光シール剤、上下導通材料、及び、液晶表示素子

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WO2017061255A1 (fr) * 2015-10-09 2017-04-13 積水化学工業株式会社 Agent d'étanchéité pour éléments d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides
JP6837781B2 (ja) * 2016-08-31 2021-03-03 日本化薬株式会社 液晶シール剤及びそれを用いた液晶表示セル
KR102106760B1 (ko) * 2016-12-27 2020-05-06 세키스이가가쿠 고교가부시키가이샤 액정 표시 소자용 시일제, 상하 도통 재료 및 액정 표시 소자
KR102106761B1 (ko) * 2017-01-25 2020-05-06 세키스이가가쿠 고교가부시키가이샤 액정 표시 소자용 시일제, 상하 도통 재료, 액정 표시 소자, 및 경화물

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KR101593381B1 (ko) 2016-02-11
TW201500529A (zh) 2015-01-01
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