WO2012137749A1 - Agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, matière conductrice du haut en bas et élément d'affichage à cristaux liquides - Google Patents

Agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, matière conductrice du haut en bas et élément d'affichage à cristaux liquides Download PDF

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WO2012137749A1
WO2012137749A1 PCT/JP2012/059023 JP2012059023W WO2012137749A1 WO 2012137749 A1 WO2012137749 A1 WO 2012137749A1 JP 2012059023 W JP2012059023 W JP 2012059023W WO 2012137749 A1 WO2012137749 A1 WO 2012137749A1
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Prior art keywords
light
liquid crystal
meth
crystal display
shielding
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PCT/JP2012/059023
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English (en)
Japanese (ja)
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啓己 新井
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積水化学工業株式会社
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Priority to CN201280002167.0A priority Critical patent/CN103026292B/zh
Priority to KR1020127033525A priority patent/KR101321694B1/ko
Priority to JP2012519643A priority patent/JP5238909B2/ja
Publication of WO2012137749A1 publication Critical patent/WO2012137749A1/fr

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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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

  • An object of this invention is to provide the light-shielding sealant for liquid crystal display elements which is excellent in the adhesive strength with respect to a board
  • a liquid crystal display element such as a liquid crystal display cell is formed by forming a cell by facing two transparent substrates with electrodes facing each other at a predetermined interval and sealing the periphery with a sealing agent.
  • the liquid crystal was injected from the liquid crystal injection port into the cell, and the liquid crystal injection port was manufactured by a method called a vacuum injection method in which a sealing agent or a sealing agent was sealed.
  • a seal pattern having a liquid crystal injection port using a thermosetting sealant is formed by screen printing on one of two transparent substrates with electrodes, and prebaked at 60 to 100 ° C. The solvent in the sealant is dried.
  • the two substrates are opposed to each other with the spacer interposed therebetween, aligned, bonded, and subjected to hot pressing at 110 to 220 ° C. for 10 to 90 minutes to adjust the gap near the seal, and then in an oven at 110 to 220 ° C. To cure for 10 to 120 minutes.
  • liquid crystal was injected from the liquid crystal injection port, and finally, the liquid crystal injection port was sealed using a sealing agent to produce a liquid crystal display element.
  • liquid crystal display elements such as liquid crystal display cells
  • photo radical resin such as acrylic resin and photo radical polymerization
  • a liquid crystal dropping method called a dripping method using a sealing agent made of a light and heat curable resin composition containing an agent and a thermosetting resin such as an epoxy resin and a thermosetting agent.
  • liquid crystal dropping method first, a seal pattern is formed on one of the two substrates with electrodes. Next, a liquid crystal micro-droplet is dropped on the entire surface of the substrate frame in an uncured state of the sealant, the other substrate is superposed under vacuum, and after returning to normal pressure, the seal portion is irradiated with ultraviolet rays to be photocurable. The resin is cured (temporary curing step). Thereafter, the thermosetting resin is cured by heating to produce a liquid crystal display element.
  • the conventional sealant is transparent or milky white, the light that passes through the sealant cannot be shielded even with a black matrix that should originally suppress light leakage, resulting in a decrease in contrast. It was.
  • Patent Documents 1 to 3 disclose a sealant containing a titanium black material, a carbon black material, or other light shielding fine particles as a light shielding component.
  • a titanium black material having high insulating properties is preferable as the light shielding agent contained in the sealant.
  • An object of this invention is to provide the light-shielding sealant for liquid crystal display elements which is excellent in the adhesive strength with respect to a board
  • Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element manufactured using the light-shielding sealant for liquid crystal display elements.
  • the present invention is a curable resin containing a curable compound having an unsaturated double bond, a radical polymerization initiator, and a light shielding sealant for a liquid crystal dropping method containing a light shielding agent, wherein the curable resin is
  • the hydrogen-bonding functional group value is 0.5 ⁇ 10 ⁇ 3 to 3.0 ⁇ 10 ⁇ 3 mol / g, and is a light-shielding sealant for liquid crystal display elements containing titanium black as the light-shielding agent.
  • the present inventor has found that the hydrogen bonding functional group value of a curable resin containing a curable compound having an unsaturated double bond in a light-shielding sealant for liquid crystal display elements containing titanium black is 0.5 ⁇ 10 ⁇ When it is 3 to 3.0 ⁇ 10 ⁇ 3 mol / g, it has been found that a decrease in adhesive strength after high-temperature and high-humidity treatment can be suppressed, and the present invention has been completed.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains titanium black as a light-shielding agent.
  • 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 the light shielding sealant of the present invention with light shielding properties, while having a property of transmitting light having a wavelength near the ultraviolet region. It is.
  • the photo-curing property of the light-shielding sealant of the present invention can be obtained by using a photo-radical polymerization initiator, which will be described later, that can start the reaction with light having a wavelength (370 to 450 nm) that increases the transmittance of the titanium black. Can be further increased.
  • the light shielding agent contained in the light shielding sealant of the present invention is preferably a highly insulating material, and titanium black is also suitable as the highly insulating light shielding agent.
  • the titanium black preferably has an optical density (OD value) per ⁇ m of 3 or more, more preferably 4 or more. The higher the light shielding property of the titanium black, the better. There is no particular upper limit to the OD value of the titanium black, but it is usually 5 or less.
  • the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
  • the liquid crystal display element manufactured using the light-shielding sealant of the present invention is a liquid crystal having excellent image display quality with high contrast without light leakage because the light-shielding sealant has sufficient light shielding properties. A display element can be realized.
  • the titanium black is not particularly limited, but specific examples of commercially available products include “12S”, “13M”, “13M-C”, “13R-N” (all manufactured by Mitsubishi Materials Corporation), “Tilack”. D ”(manufactured by Ako Kasei Co., Ltd.) and the like.
  • 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 preferable lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferable upper limit is 3 ⁇ ⁇ cm, the more preferable lower limit is 1 ⁇ ⁇ cm, and the more preferable 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 light-shielding sealant are greatly increased, and workability may be deteriorated.
  • the primary particle diameter of the light-shielding agent exceeds 5 ⁇ m, the applicability of the obtained light-shielding sealant to 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
  • the still more preferable upper limit is 100 nm.
  • the content of the light-shielding agent in the light-shielding sealant of the present invention is not particularly limited, but a preferred lower limit is 5% by weight and a preferred upper limit is 80% by weight. If the content of the light shielding agent is less than 5% by weight, sufficient light shielding properties may not be obtained. When the content of the light-shielding agent exceeds 80% by weight, the adhesion of the obtained light-shielding sealant 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% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
  • the light shielding sealant of the present invention contains a curable resin.
  • the curable resin contains a curable compound having an unsaturated double bond. That is, the light-shielding sealant of the present invention contains a curable compound having an unsaturated double bond and a radical polymerization initiator described later, and initiates the reaction by light and / or heat. Specifically, it can be cured by ultraviolet irradiation and / or heating.
  • the hydrogen bonding functional group value of the curable resin is 0.5 ⁇ 10 ⁇ 3 to 3.0 ⁇ 10 ⁇ 3 mol / g.
  • the hydrogen bonding functional group value of the curable resin is less than 0.5 ⁇ 10 ⁇ 3 mol / g, the resin component is likely to be eluted into the liquid crystal, resulting in liquid crystal contamination.
  • the hydrogen bondable functional group value of the curable resin exceeds 3.0 ⁇ 10 ⁇ 3 mol / g, the adhesive strength after high-temperature and high-humidity treatment in the obtained light-shielding sealant is remarkably reduced.
  • the preferable lower limit of the hydrogen bonding functional group value of the curable resin is 0.7 ⁇ 10 ⁇ 3 mol / g, the preferable upper limit is 2.5 ⁇ 10 ⁇ 3 mol / g, and the more preferable lower limit is 2.0 ⁇ 10 ⁇ . 3 mol / g.
  • the hydrogen bondable functional group value of curable resin is computed as a hydrogen bondable functional group value per unit weight.
  • the curable resin is a compound A (hydrogen bonding functional group value ⁇ mol / g), a bg compound B (hydrogen bonding functional group value ⁇ mol / g), and a cg compound C (hydrogen bonding functional group value).
  • the hydrogen bonding functional group is not particularly limited as long as it is a functional group or a residue having hydrogen bonding properties, for example, —OH group, —NH 2 group, —NHR group (R is aromatic or aliphatic Group hydrocarbons and derivatives thereof), those having a functional group such as —COOH group, —CONH 2 group, —NHOH group, and —NHCO— bond, —NH— bond, —CONHCO— And those having a residue such as a bond or —NH—NH— bond.
  • the hydrogen bonding functional group value may be adjusted to the above range by mixing two or more kinds even if the hydrogen bonding functional group value is in the above range alone. Also good. That is, the average value of the hydrogen bonding functional group value of the compound having a hydrogen bonding functional group to be used may be in the above range.
  • the curable compound having the unsaturated double bond is not limited, and examples thereof include resins having a vinyl group, an allyl group, a cinnamoyl group, a cinnamylidene group, a maleimide group, a (meth) acryloyloxy group, and the like. From the viewpoint of reactivity, a resin having a (meth) acryloyloxy group is preferable, and a resin having 2 to 3 (meth) acryloyloxy groups in the molecule is more preferable.
  • the “(meth) acryloyloxy group” means “acryloyloxy group or methacryloyloxy group”.
  • the resin having the (meth) acryloyloxy group is not particularly limited.
  • an ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, (meth) acrylic acid and an epoxy compound are reacted.
  • examples thereof include completely (meth) acryl-modified epoxy resins obtained by the above, urethane (meth) acrylates obtained by reacting isocyanates with (meth) acrylic acid derivatives having a hydroxyl group, and the like.
  • the “(meth) acryl” means “acryl or methacryl”
  • the “(meth) acrylate” means “acrylate or methacrylate”.
  • the “complete (meth) acryl-modified epoxy resin” represents a compound obtained by reacting all epoxy groups in the epoxy resin with (meth) acrylic acid.
  • the ester compound obtained by reacting the above (meth) acrylic acid with a compound having a hydroxyl group is not particularly limited, and 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, Lahydrofurfuryl (meth) acrylate, benzyl
  • bifunctional 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 (meth) acrylate, Lopylene oxide-added bisphenol A di (meth) acrylate, ethylene
  • tri- or higher functional group examples include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added trimethylolpropane tri (meth).
  • the complete (meth) acryl-modified epoxy resin obtained by reacting the (meth) acrylic acid and the epoxy compound is not particularly limited.
  • an epoxy resin and (meth) acrylic acid can be converted into a basic catalyst according to a conventional method. And the like obtained by reacting in the presence of.
  • the epoxy compound that is a raw material for synthesizing the complete (meth) acryl-modified epoxy resin is not particularly limited.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, 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 type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin Carboxymethyl resins, naphthalene phenol novolac-type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
  • Examples of commercially available bisphenol A type epoxy resins include Epicoat 828EL, 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.).
  • Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel 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).
  • epiclone HP7200 made by DIC
  • examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.).
  • examples of commercially available naphthalenephenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel 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 Chemical Co., Ltd.), Epicron 726 (manufactured by DIC Corporation), 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 Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corp.), and the like.
  • Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
  • Other commercially available epoxy resins include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Co., Ltd.), Epicoat 1031, Epicoat 1032 (all manufactured by Mitsubishi Chemical Corporation), EXA-7120 (manufactured by DIC Corporation), TEPIC (manufactured by Nissan Chemical Industries, Ltd.) and the like.
  • a complete (meth) acryl-modified epoxy resin obtained by reacting the (meth) acrylic acid with an epoxy compound is specifically a resorcinol type epoxy resin (“EX-201” manufactured by Nagase ChemteX Corporation). 360 parts by weight, 2 parts by weight of p-methoxyphenol as a polymerization inhibitor, 2 parts by weight of triethylamine as a reaction catalyst, and 210 parts by weight of acrylic acid were refluxed and stirred at 90 ° C. while feeding air, and reacted for 5 hours. A completely acrylic-modified resorcinol type epoxy resin can be obtained.
  • EX-201 manufactured by Nagase ChemteX Corporation
  • the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is, for example, a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of a compound having two isocyanate groups. Two equivalents can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
  • Isocyanate that is a raw material for urethane (meth) acrylate obtained by reacting the above-mentioned isocyanate with a (meth) acrylic acid derivative having a hydroxyl group is not particularly limited.
  • Examples of the isocyanate used as a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a (meth) acrylic acid derivative having a hydroxyl group include, for example, ethylene glycol, glycerin, sorbitol, trimethylolpropane, (poly) Chain-extended isocyanate compounds obtained by reaction of polyols such as propylene glycol, carbonate diol, polyether diol, polyester diol, polycaprolactone diol and excess isocyanate can also be used.
  • the (meth) acrylic acid derivative having a hydroxyl group which is a raw material for the urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative, is not particularly limited.
  • 2-hydroxyethyl Commercial products such as (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, Mono (meth) acrylates of divalent alcohols such as 1,3-butanediol, 1,4-butanediol and polyethylene glycol, mono (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin or Di (meth) acrylate, epoxy (meth) acrylates such as bisphenol A type epoxy (meth) acrylate.
  • the urethane (meth) acrylate obtained by reacting the isocyanate with a hydroxyl group-containing (meth) acrylic acid derivative is, for example, 134 parts by weight of trimethylolpropane, 0.2 part by weight of BHT as a polymerization inhibitor,
  • reaction catalysts 0.01 parts by weight of dibutyltin dilaurate and 666 parts by weight of isophorone diisocyanate were added and reacted at 60 ° C. with stirring under reflux for 2 hours.
  • 51 parts by weight of 2-hydroxyethyl acrylate was added and air was fed. It can be obtained by stirring at 90 ° C. under reflux and reacting for 2 hours.
  • urethane (meth) acrylates include, for example, M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), Evecryl 230, Evekril 270, Evekril 4858.
  • the curable resin may contain another resin such as a resin having an epoxy group.
  • the resin having the epoxy group is not particularly limited, and examples thereof include an epoxy compound that is a raw material for synthesizing the complete (meth) acryl-modified epoxy resin and a partial (meth) acryl-modified epoxy resin.
  • the partial (meth) acryl-modified epoxy resin means a resin having one or more epoxy groups and (meth) acryloyloxy groups in one molecule, for example, two or more epoxy resins. It can be obtained by reacting an epoxy group of a part of the resin having a group with (meth) acrylic acid.
  • the partial (meth) acryl-modified epoxy resin can be obtained, for example, by reacting an epoxy resin and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method. Specifically, for example, 190 g of phenol novolac type epoxy resin N-770 (manufactured by DIC) is dissolved in 500 mL of toluene, and 0.1 g of triphenylphosphine is added to this solution to obtain a uniform solution, and acrylic acid is added to this solution. 35 g of the mixture was added dropwise under reflux stirring for 2 hours, followed by further refluxing stirring for 6 hours. Next, by removing toluene, 50 mol% of the epoxy group reacted with (meth) acrylic acid, partially acryl-modified phenol novolak. Type epoxy resin can be obtained (in this case 50% partially acrylated).
  • Examples of the commercially available partial (meth) acryl-modified epoxy resin include UVACURE 1561 (manufactured by Daicel Cytec).
  • a resin having no (meth) acryloyloxy group as a reactive functional group and having only an epoxy group is a cause of liquid crystal contamination. Therefore, it is preferable not to mix, but for the purpose of improving adhesiveness, it may be added within a range that does not affect liquid crystal contamination.
  • the content of the resin having only the epoxy group is preferably 10% by weight with respect to 100 parts by weight of the entire curable resin. When the content of the resin having only the epoxy group exceeds 10% by weight, the obtained light-shielding sealant for liquid crystal display elements may cause liquid crystal contamination.
  • the ratio of the (meth) acryloyloxy group and the epoxy group of the curable resin is a molar ratio. It is preferable to blend a resin having a (meth) acryloyloxy group and a resin having an epoxy group so that the ratio becomes 50:50 to 95: 5. If the ratio of the (meth) acryloyloxy group is less than 50%, a large amount of uncured epoxy resin component may be present even if radical polymerization by the radical polymerization initiator described later is completed, and the liquid crystal may be contaminated. When the ratio of the (meth) acryloyloxy group exceeds 95%, the effect of improving the adhesive strength may not be sufficiently obtained.
  • the light-shielding sealant of the present invention contains a radical polymerization initiator.
  • the radical polymerization initiator is one that generates radicals by external stimulation such as ultraviolet irradiation or heating
  • the light-shielding sealant for a liquid crystal display element of the present invention is a photo radical polymerization initiator that generates radicals by ultraviolet irradiation, and / or Alternatively, it contains a thermal radical polymerization initiator that generates radicals by heating.
  • the light-shielding sealant of the present invention preferably contains a thermal radical polymerization initiator.
  • the liquid crystal display device to be manufactured can be reliably cured by heat even if there is a seal portion in a place where no light is irradiated by a black matrix or the like. Since it is possible, the occurrence of liquid crystal contamination is extremely low.
  • the above thermal radical polymerization initiator has a preferred lower limit of 10 hours half-life temperature of 50 ° C. and a preferred upper limit of 90 ° C.
  • the 10-hour half-life temperature of the thermal radical polymerization initiator is less than 50 ° C., the storage stability of the obtained light-shielding sealant for liquid crystal display elements may be deteriorated.
  • the 10-hour half-life temperature of the thermal radical polymerization initiator exceeds 90 ° C., it takes a long time to cure the light-shielding sealant for liquid crystal display elements of the present invention, which may affect panel productivity. is there.
  • the 10-hour half-life temperature refers to the concentration of the thermal radical polymerization initiator before the reaction when the thermal decomposition reaction is carried out at a constant temperature for 10 hours in the presence of an inert gas. It is the temperature at which it halves.
  • the thermal radical polymerization initiator is not particularly limited, and examples thereof include azo compounds and organic peroxides. Of these, 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 the curable resin with heat and having a molecular weight of 300 or more.
  • the said polymeric azo initiator decomposes
  • 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.
  • polymer azo initiator examples include those having a structure in which a plurality of units such as polydimethylsiloxane and polyalkylene oxide are bonded via an azo group.
  • a structure in which a plurality of units such as polyalkylene oxide are bonded those having a polyethylene oxide structure are preferable.
  • polymeric azo initiators include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) with terminal groups.
  • Examples thereof include polycondensates of polydimethylsiloxane having an amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.). ) And the like.
  • polymer azo initiator a polymer azo compound represented by the following general formula (I) described in JP-A-2008-50572 and JP-A-2003-12784 is also preferably used. Can do.
  • R 12 , R 13 , R 22 and R 23 each independently represents an alkyl group having 1 to 10 carbon atoms or a cyano group, and a and b are each independently a number of 0 to 4 A 11 and A 12 are polymer chains, and Y 11 and Y 12 are each independently —CO—O—, —O—CO—, —NH—CO—, —CO—NH—, -O- or -S-.
  • examples of the alkyl group having 1 to 10 carbon atoms represented by R 12 , R 13 , R 22 and R 23 include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, and n-decyl.
  • the polymer chains represented by A 11 and A 12 are not particularly limited.
  • compounds in which Y 11 is —O—CO— and Y 12 is —CO—O— are preferred, and the polymer chains represented by A 11 and A 12 are polyether chains and polyester chains. Those are more preferred because they are particularly inexpensive and easy to manufacture.
  • the compound represented by the following general formula (II) has good solubility and the molecular weight of the polymerization initiator. Since control is easy, it is more preferable.
  • R 12 , R 13 , R 22 , R 23 , a and b are the same as those in the general formula (I), and R 11 and R 21 each independently has 1 to 24 carbon atoms.
  • Z 11 , Z 12 , Z 21 and Z 22 each independently represents an alkylene group having 1 to 4 carbon atoms, and m, n, s and t are each independently 0 to 1000 The sum of m + n and the sum of s + t are each independently 2 or more.
  • examples of the alkylene group having 1 to 4 carbon atoms represented by Z 11 , Z 12 , Z 21 and Z 22 include methylene, ethylene, trimethylene, propylene, propylidene, isopropylidene, tetra Examples include methylene, butylene, isobutylene, ethylethylene, dimethylethylene and the like.
  • Examples of the alkyl group having 1 to 24 carbon atoms represented by R 11 and R 21 include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t- Examples include amyl, hexyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, lauryl, stearyl, behenyl, etc. It is done.
  • the alkyl groups having 1 to 24 carbon atoms represented by R 11 and R 21 those having 1 to 4 carbon atoms are preferable because of high reactivity.
  • the compound represented by the following general formula (III) has good solubility and excellent water resistance. Therefore, it is preferable.
  • R 12 , R 13 , R 22 , R 23 , a and b are the same as those in the general formula (I), and Z 13 and Z 23 each independently have 1 to 18 carbon atoms.
  • R 31 and R 41 each independently represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms, and p and u are each independently a number from 1 to 1000.
  • Examples of the alkyl group having 1 to 24 carbon atoms represented by R 31 and R 41 include those exemplified as R 11 and R 21 in the general formula (II).
  • the alkyl group having 1 to 24 carbon atoms represented by R 31 and R 41 is preferably an alkyl group having 1 to 4 carbon atoms because of high reactivity.
  • the organic peroxide is not particularly limited, and examples thereof include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxy ester, diacyl peroxide, and peroxydicarbonate.
  • a preferable minimum is 0.1 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 30 weight part.
  • the content of the thermal radical polymerization initiator is less than 0.1 part by weight, the obtained light shielding sealant may not sufficiently cure.
  • the content of the thermal radical polymerization initiator exceeds 30 parts by weight, the viscosity of the obtained light-shielding sealant for liquid crystal display elements is increased, which may adversely affect application workability.
  • the minimum with more preferable content of the said thermal radical polymerization initiator is 0.5 weight part, and a more preferable upper limit is 10 weight part.
  • the light-shielding sealant of the present invention preferably contains a radical photopolymerization initiator. Since the light-shielding sealant of the present invention contains a titanium black material, the light-radical polymerization initiator contains the light-shielding property and the photo-curing property.
  • the radical photopolymerization initiator is preferably one that can be exposed to light having a wavelength range of 370 to 450 nm as described above, but light having a wavelength of less than 370 nm or light having a wavelength of more than 450 nm. It may be one that can be exposed to light.
  • Such photo-radical polymerization initiator is not particularly limited, for example, IRGACURE127, IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE1300, IRGACURE1700, IRGACURE1800, IRGACURE1870, IRGACURE2959, IRGACURE4265, IRGACUREOXE01, IRGACUREOXE02, CGI242, LUCIRIN TPO, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by BASF Japan), ESACURE TPO (Lamberti) ), Speedcure TPO, Speedcure TPO-L (all manufactured by LAMBSON), MICURE TPO (manufactured by MIWON), N-1414 (manufactured by ADEKA), Solvathlon BIPE, Solvathlon BI
  • a preferable minimum is 0.1 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of said curable resins. If the content of the radical photopolymerization initiator is less than 0.1 parts by weight, the photopolymerization may not proceed sufficiently or the reaction may become too slow. When the content of the radical photopolymerization initiator exceeds 10 parts by weight, workability may be deteriorated or the reaction may become uneven.
  • the minimum with more preferable content of radical photopolymerization initiator is 1 weight part, and a more preferable upper limit is 5 weight part.
  • the light-shielding sealing agent for liquid crystal display elements of this invention contains a thermosetting agent further.
  • the said thermosetting agent is not specifically limited, For example, organic acid hydrazide, an imidazole derivative, an amine compound, a polyhydric phenol type compound, an acid anhydride etc. are mentioned. Among these, organic acid hydrazide solid at room temperature is preferably used.
  • the organic acid hydrazide which is solid at room temperature is not particularly limited, and examples thereof include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
  • Examples of commercially available products include SDH (Nippon Finechem Co., Ltd.). Amicure VDH, Amicure VDH-J, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), ADH (manufactured by Otsuka Chemical Co., Ltd.) and the like.
  • thermosetting agent is not specifically limited, A preferable minimum is 1 weight part with respect to 100 weight part of said curable resin, and a preferable upper limit is 50 weight part.
  • content of the thermosetting agent is less than 1 part by weight, the effect of containing the thermosetting agent is hardly obtained.
  • content of the said thermosetting agent exceeds 50 weight part, the viscosity of the light-shielding sealing agent obtained will become high, and applicability
  • the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
  • the light-shielding sealant of the present invention preferably contains a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product.
  • the filler is not particularly limited.
  • Inorganic fillers such as magnesium, aluminum hydroxide, 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, etc.
  • organic fillers are examples of organic fillers.
  • the light shielding sealant of the present invention preferably contains a silane coupling agent.
  • the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
  • the silane coupling agent is not particularly limited, and for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane and the like are preferably used.
  • the light-shielding sealant of the present invention further comprises a reactive diluent for adjusting the viscosity, a thixotropic agent for adjusting the thixotropy, a spacer such as a polymer bead for adjusting the panel gap, if necessary. It may contain a curing accelerator such as chlorophenyl-1,1-dimethylurea, an antifoaming agent, a leveling agent, a polymerization inhibitor, and other additives.
  • a reactive diluent for adjusting the viscosity
  • a thixotropic agent for adjusting the thixotropy
  • spacer such as a polymer bead for adjusting the panel gap
  • the method for producing the light-shielding sealant of the present invention is not particularly limited.
  • the curable resin, the radical polymerization initiator, the light-shielding agent, and additives that are blended as necessary are conventionally known.
  • the method of mixing by a method is mentioned.
  • the optical density (OD value) of the cured product obtained by curing the light-shielding sealant of the present invention is preferably 2.0 or more when the thickness of the cured product is 2 to 7 ⁇ m.
  • the OD value of the cured body is more preferably 2.5 or more, and further preferably 3.0 or more. The higher the OD value of the cured body, the better.
  • the preferable upper limit of the OD value of the cured body is 5 in order to balance the blending amount of the light shielding agent.
  • the light-shielding sealant of the present invention produces an adhesive test piece formed by bonding two glass substrates in a cross shape via the light-shielding sealant for liquid crystal display elements of the present invention, and the pressure tester test ( 121 ° C., 100% RH, 0.2 MPa) for 24 hours, the adhesive strength is preferably 30 kgf / cm 2 or more. When the adhesive strength at the time of performing the pressure cooker test is less than 30 kgf / cm 2 , the obtained liquid crystal display element may be inferior in reliability in a high temperature and high humidity environment.
  • a vertical conducting material can be produced by blending conductive fine particles with the light-shielding sealant for liquid crystal display elements of the present invention.
  • the vertical conduction material containing the light-shielding sealant for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
  • the conductive fine particles 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 manufactured using the light-shielding sealant for liquid crystal display elements of the present invention and / or the vertical conduction material of the present invention is also one aspect of the present invention.
  • the light-shielding sealant for the liquid crystal display element of the present invention is rectangularly formed on one of two transparent substrates with electrodes such as an ITO thin film by screen printing, dispenser application, or the like.
  • a liquid crystal micro-droplet is applied to the entire surface of the transparent substrate with the light-shielding sealant for the liquid crystal display element of the present invention in an uncured state, and the other transparent substrate is immediately overlaid.
  • the step of irradiating the seal pattern portion such as the light-shielding sealant for the liquid crystal display element of the present invention with light such as ultraviolet rays to temporarily cure the sealant, and heating the temporarily cured sealant to Examples thereof include a method having a step of curing.
  • the present invention it is possible to provide a light-shielding sealant for a liquid crystal display element that has excellent adhesion strength to a substrate even after being exposed to a high-temperature and high-humidity environment. Moreover, the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealant for liquid crystal display elements can be provided.
  • Examples 1 to 17 and Comparative Examples 1 to 9 Each curable resin was blended according to the blending ratio described in Tables 1 to 3, and then a thermal radical polymerization initiator and / or a photo radical polymerization initiator was blended. Next, after completely dissolving the thermal radical polymerization initiator and / or the photo radical polymerization initiator, the mixture was stirred using a planetary stirrer (“Shinky Co., Ltd.“ Awatori Netaro ”), and then a light shielding agent, a thermosetting agent, A filler and a silane coupling agent were blended and further stirred with a planetary stirrer. Then, the light-shielding sealant for liquid crystal display elements of an Example and a comparative example was prepared by disperse
  • FIG. 1 is a diagram schematically showing a procedure for manufacturing a liquid crystal display element by a liquid crystal dropping method in Examples and Comparative Examples.
  • the obtained light-shielding sealant for a liquid crystal display element was applied to a substrate on which a transparent electrode and an alignment film were formed with a dispenser so as to draw a square frame.
  • liquid crystal Choso "JC-5004LA”
  • fine droplets are applied dropwise onto the entire surface of the transparent substrate frame, and the substrate on which another transparent electrode and alignment film are formed is superposed in a vacuum.
  • the outer frame seal portion was irradiated with 100 mW / cm 2 ultraviolet rays for 30 seconds using a high-pressure mercury lamp.
  • liquid crystal annealing was performed at 120 ° C. for 1 hour, and the light-shielding sealant for liquid crystal display elements was thermally cured to obtain a liquid crystal display element.
  • a very small amount of the obtained light-shielding sealant for a liquid crystal display element is placed on the center of a glass substrate (20 mm ⁇ 50 mm ⁇ 1.1 mmt), and a glass substrate of the same size is superimposed on the glass substrate so as to form a cross.
  • the sealing agent for liquid crystal display elements was expanded. In this state, 100 mW / cm 2 of ultraviolet rays were irradiated for 30 seconds, and then heated at 120 ° C. for 1 hour to obtain an initial adhesion test piece.
  • a pressure cooker test (121 ° C., 100% RH, 0.2 MPa) was performed for 24 hours on the obtained initial adhesion test piece to obtain an adhesion test piece after high-temperature and high-humidity treatment.
  • the adhesive strength (kgf / cm 2 ) was measured using a tension gauge.
  • Optical density (OD value) 1 g of a silica spacer (Sekisui Chemical Co., Ltd., “Micropearl SI”) having a diameter of 5 ⁇ m was added as a spacer to 100 g of the obtained light-shielding sealant for a liquid crystal display device, and mixed and stirred. Apply the obtained light-shielding sealant for spacer-equipped liquid crystal display elements onto a glass substrate of 20 mm x 20 mm, overlay a glass substrate of the same size on the substrate, apply a load, and crush it to the diameter of the spacer to make the thickness uniform I made it.
  • optical test piece After irradiating 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, heating was performed at 120 ° C. for 1 hour to obtain an optical test piece.
  • the optical density (OD value) of the obtained optical test piece was measured using X-rite 360T ( ⁇ ) (manufactured by X-rite).
  • the adhesive strength after the high-temperature and high-humidity test of the light-shielding sealant obtained in the examples was 30 kgf / cm 2 or more, both of which had no practical problem at all. Further, the optical density (OD value) was very high at 3.0 or more, and it had a sufficient light shielding property. Regarding the color unevenness, there was no, almost none, or a slight degree, and there was no problem in practical use at all.
  • the present invention it is possible to provide a light-shielding sealant for a liquid crystal display element that has excellent adhesion strength to a substrate even after being exposed to a high-temperature and high-humidity environment. Moreover, the vertical conduction material and liquid crystal display element which are manufactured using this light-shielding sealant for liquid crystal display elements can be provided.

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Abstract

La présente invention a pour but de procurer : un agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, qui peut présenter une excellente force d'adhérence à un substrat même après avoir été exposé à un environnement à haute température et à haute humidité ; et une matière conductrice du haut en bas et un élément d'affichage à cristaux liquides, chacun d'eux étant obtenu à l'aide de l'agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides. La présente invention concerne un agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides qui est un agent d'étanchéité protégeant de la lumière pour une utilisation dans un procédé de dépôt en gouttes de cristaux liquides, comprenant une résine durcissable qui contient un composé durcissable ayant une double liaison insaturée, un amorceur de polymérisation radicalaire et un agent protégeant de la lumière, la résine durcissable ayant un indice de groupe fonctionnel de liaison à hydrogène de 0,5 × 10-3 à 3,0 × 10-3 mol/g et du noir de titane étant contenu comme agent protégeant de la lumière.
PCT/JP2012/059023 2011-04-05 2012-04-03 Agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, matière conductrice du haut en bas et élément d'affichage à cristaux liquides WO2012137749A1 (fr)

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KR1020127033525A KR101321694B1 (ko) 2011-04-05 2012-04-03 액정 표시 소자용 차광 시일제, 상하 도통 재료 및 액정 표시 소자
JP2012519643A JP5238909B2 (ja) 2011-04-05 2012-04-03 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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CN109897599B (zh) * 2015-11-09 2020-09-01 积水化学工业株式会社 液晶显示元件用密封剂、上下导通材料和液晶显示元件
KR102509153B1 (ko) * 2018-07-24 2023-03-10 미쓰이 가가쿠 가부시키가이샤 액정 적하 공법용 차광 실링제, 및 이것을 이용한 액정 표시 패널의 제조 방법
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JP2006313286A (ja) * 2005-05-09 2006-11-16 Sekisui Chem Co Ltd 液晶滴下工法用遮光シール剤、上下導通材料、及び、液晶表示素子
JP2007304273A (ja) * 2006-05-10 2007-11-22 Hitachi Displays Ltd 液晶表示素子
WO2009128470A1 (fr) * 2008-04-18 2009-10-22 積水化学工業株式会社 Agent de scellement destiné à être utilisé dans un procédé d'application en gouttes de cristaux liquides, agent de scellement pour écran à cristaux liquides, matériau à conduction verticale et élément d’affichage à cristaux liquides

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JP2018077544A (ja) * 2012-11-13 2018-05-17 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、液晶表示素子、及び、ヒドラジド系熱硬化剤
JP2014115639A (ja) * 2012-11-13 2014-06-26 Sekisui Chem Co Ltd 液晶表示素子用シール剤、上下導通材料、液晶表示素子、及び、ヒドラジド系熱硬化剤
JP2014139662A (ja) * 2012-12-19 2014-07-31 Sekisui Chem Co Ltd 液晶滴下工法用シール剤、液晶滴下工法用シール剤の製造方法、上下導通材料、及び、液晶表示素子
CN105283803A (zh) * 2013-06-11 2016-01-27 积水化学工业株式会社 液晶滴下工艺用密封剂、上下导通材料及液晶显示元件
JP2015001615A (ja) * 2013-06-14 2015-01-05 積水化学工業株式会社 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
KR20160094929A (ko) * 2013-12-05 2016-08-10 세키스이가가쿠 고교가부시키가이샤 중합성 단량체, 고분자 화합물, 광경화성 수지 조성물, 액정 표시 소자용 시일제, 상하 도통 재료, 및 액정 표시 소자
KR102256146B1 (ko) * 2013-12-05 2021-05-25 세키스이가가쿠 고교가부시키가이샤 중합성 단량체, 고분자 화합물, 광경화성 수지 조성물, 액정 표시 소자용 시일제, 상하 도통 재료, 및 액정 표시 소자
JP2019091086A (ja) * 2014-06-03 2019-06-13 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
JP6078698B1 (ja) * 2015-05-28 2017-02-08 積水化学工業株式会社 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
WO2016190398A1 (fr) * 2015-05-28 2016-12-01 積水化学工業株式会社 Agent de scellement pour procédés de dépôt de cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides
JP2017082021A (ja) * 2015-10-22 2017-05-18 株式会社ブリヂストン エマルジョン粘着剤、粘着シート、エマルジョン粘着剤の製造方法、及び粘着シートの製造方法
JP6263317B1 (ja) * 2016-05-17 2018-01-17 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子
WO2017199905A1 (fr) * 2016-05-17 2017-11-23 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

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TW201245825A (en) 2012-11-16
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