WO2017119407A1 - Produit d'étanchéité destiné à un élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides - Google Patents

Produit d'étanchéité destiné à un élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides Download PDF

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Publication number
WO2017119407A1
WO2017119407A1 PCT/JP2017/000005 JP2017000005W WO2017119407A1 WO 2017119407 A1 WO2017119407 A1 WO 2017119407A1 JP 2017000005 W JP2017000005 W JP 2017000005W WO 2017119407 A1 WO2017119407 A1 WO 2017119407A1
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WIPO (PCT)
Prior art keywords
liquid crystal
meth
crystal display
acrylate
display element
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PCT/JP2017/000005
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English (en)
Japanese (ja)
Inventor
祐美子 寺口
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to KR1020177034601A priority Critical patent/KR20180103680A/ko
Priority to CN201780001989.XA priority patent/CN107683435B/zh
Priority to JP2017502914A priority patent/JP6978311B2/ja
Publication of WO2017119407A1 publication Critical patent/WO2017119407A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Definitions

  • the present invention relates to a sealing agent for liquid crystal display elements that is excellent in adhesiveness and can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements.
  • a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing.
  • a liquid crystal micro-droplet is dropped on the entire surface of the transparent substrate frame in a state where the sealant is uncured, and the other transparent substrate is immediately overlaid, and the seal portion is irradiated with light such as ultraviolet rays for temporary curing. .
  • heating is performed to perform main curing, and a liquid crystal display element is manufactured.
  • a liquid crystal display element can be manufactured with extremely high efficiency by bonding the substrates under a reduced pressure, and this dropping method is currently the mainstream method for manufacturing liquid crystal display elements.
  • the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
  • the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
  • This invention is the sealing compound for liquid crystal display elements containing curable resin containing the compound represented by following formula (1), and a thermosetting agent.
  • l, m, and n are each 0 to 6, and Y is 1 to 20.
  • Y is 1 to 20.
  • This inventor examined using bisphenol S diglycidyl ether excellent in adhesiveness and low liquid-contamination property as curable resin mix
  • bisphenol S diglycidyl ether excellent in adhesiveness and low liquid-contamination property as curable resin mix
  • the present inventors can obtain a sealing agent for liquid crystal display elements that is excellent in adhesiveness and can suppress liquid crystal contamination by using a bisphenol S type epoxy resin having a specific structure. As a result, the present invention has been completed.
  • the sealing agent for liquid crystal display elements of this invention contains curable resin.
  • the said curable resin contains the compound represented by the said Formula (1).
  • the sealing agent for liquid crystal display elements of the present invention is excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
  • l, m, and n are each 0 to 6. Each of l, m and n is preferably 1 to 6, more preferably 1 to 3, respectively.
  • Y is 1-20. Y is preferably from 1 to 10, and more preferably from 1 to 4.
  • the value of l, m, n, and Y in the said Formula (1) is an average value.
  • the case where l, m, or n is 0 means that the ethylene oxide structure part to which l, m, or n is attached becomes a bond.
  • Examples of the method for producing the compound represented by the above formula (1) include a method in which bisphenol S or ethylene oxide-modified bisphenol S and epichlorohydrin are subjected to a condensation polymerization reaction.
  • the content of the compound represented by the above formula (1) in the sealant for liquid crystal display elements of the present invention is preferably 1% by weight or more and less than 30% by weight.
  • the content of the compound represented by the formula (1) is within this range, the obtained sealing agent for liquid crystal display elements suppresses adhesion and liquid crystal contamination without deteriorating applicability and moisture permeation prevention. It will be superior to the effect of doing.
  • the more preferable lower limit of the content of the compound represented by the formula (1) is 5% by weight, the more preferable upper limit is 25% by weight, the still more preferable lower limit is 10% by weight, and the still more preferable upper limit is 20% by weight.
  • the curable resin preferably contains other curable resin in addition to the compound represented by the formula (1).
  • the other curable resin include (meth) acrylic compounds and epoxy compounds other than the compound represented by the above formula (1).
  • Examples of the (meth) acrylic compound include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid and an epoxy compound, and (meth) acrylic acid obtained by reacting a compound having a hydroxyl group.
  • examples thereof include urethane (meth) acrylates obtained by reacting (meth) acrylic acid ester compounds and isocyanate compounds with (meth) acrylic acid derivatives having a hydroxyl group.
  • epoxy (meth) acrylate is preferable.
  • the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in the molecule because of its high reactivity.
  • (meth) acrylate means acrylate or methacrylate
  • epoxy (meth) acrylate means that all epoxy groups in the epoxy compound are reacted with (meth) acrylic acid. Represents a compound.
  • Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
  • Examples of the epoxy compound used as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E 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 type epoxy resin, orthocresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl Novolak type epoxy 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 2,2′-diallylbisphenol A type epoxy resins include RE-810NM (manufactured by Nippon Kayaku Co., Ltd.). As what is marketed among the said hydrogenated bisphenol type
  • Examples of commercially available propylene oxide-added bisphenol A type epoxy resins include EP-4000S (manufactured by ADEKA).
  • Examples of commercially available resorcinol type epoxy resins include EX-201 (manufactured by Nagase ChemteX Corporation). Examples of commercially available biphenyl type epoxy resins include jER YX-4000H (manufactured by Mitsubishi Chemical Corporation).
  • Examples of commercially available sulfide type epoxy resins include YSLV-50TE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
  • Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
  • Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
  • Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
  • Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
  • Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC). As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, epiclone HP7200 (made by DIC) etc. are mentioned, for example.
  • Examples of commercially available biphenyl novolac epoxy resins include NC-3000P (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available naphthalene phenol novolac type epoxy resins include ESN-165S (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
  • Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
  • Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
  • Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
  • Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
  • Other commercially available epoxy compounds include, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by NS Also, Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and the like.
  • Examples of commercially available epoxy (meth) acrylates include EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRY3702, EBECRY3703, EBECRYL3701, EBECRYL3701.
  • 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 Xyester 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, Denacol acrylate DA-314, Denacol acrylate DA-911 (all manufactured by Nagase ChemteX Corporation) and the like.
  • Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
  • those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditri Methylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate DOO, dipentaerythri
  • urethane (meth) acrylate for example, by reacting 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. Obtainable.
  • isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
  • MDI '-Diisocyanate
  • hydrogenated MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylene diisocyanate, 1,6,11-undecanetriiso Aneto and the like.
  • Examples of the isocyanate compound that is a raw material for the urethane (meth) acrylate include, for example, polyols such as ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol. Chain-extended isocyanate compounds obtained by reaction with excess isocyanate compounds can also be used.
  • Examples of the (meth) acrylic acid derivative having a hydroxyl group as a raw material for the urethane (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Hydroxyalkyl (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.
  • Mono (meth) acrylates of dihydric alcohols mono (meth) acrylates or di (meth) acrylates of trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, and bisphenol A type epoxy alcohol Epoxy (meth) acrylate of rate, and the like.
  • Examples of commercially available urethane (meth) acrylates include M-1100, M-1200, M-1210, M-1600 (all manufactured by Toagosei Co., Ltd.), EBECRYL210, EBECRYL220, EBECRYL230, EBECRYL270, EBECRYL1290, EBECRYL2220, EBECRYL4827, EBECRYL4842, EBECRYL4858, EBECRYL5129, EBECRYL6700, EBECRYL8402, EBECRYL8803, EBECRYL8804, EBECRYL8804 , Art resin N-1255, Art Resin UN-3320HB, Art Resin UN-7100, Art Resin UN-9000A, Art Resin UN-9000H (all manufactured by Negami Industrial Co., Ltd.), U-2HA, U-2PHA, U-3HA, U- 4HA, U-6H, U-6HA, U-6LPA, U-10H, U-15HA, U
  • the epoxy compound that is the other curable resin examples include, for example, an epoxy compound that is a raw material for synthesizing the epoxy (meth) acrylate other than the compound represented by the formula (1), and a partial (meth) An acrylic modified epoxy resin etc. are mentioned.
  • the partial (meth) acryl-modified epoxy resin means a compound having one or more epoxy groups and (meth) acryloyl groups in one molecule, for example, two in one molecule. It can be obtained by reacting a part of the epoxy group having an epoxy group with (meth) acrylic acid.
  • Examples of commercially available partial (meth) acrylic-modified epoxy resins include UVACURE 1561 (manufactured by Daicel Ornex).
  • the minimum with preferable content of the compound represented by the said Formula (1) in 100 weight part of curable resin whole is 5 weight part, and a preferable upper limit is 25 weight part.
  • the content of the compound represented by the above formula (1) is within this range, the obtained sealing agent for a liquid crystal display element has an effect of suppressing applicability, adhesiveness, moisture permeation prevention, and liquid crystal contamination. It will be better.
  • the minimum with more preferable content of the compound represented by said Formula (1) is 10 weight part, and a more preferable upper limit is 20 weight part.
  • the content ratio of the (meth) acryloyl group and the epoxy group in the curable resin is 50:50 in terms of molar ratio. It is preferable to set it to 95: 5.
  • the sealing agent for liquid crystal display elements of this invention contains a thermosetting agent.
  • the thermosetting agent preferably contains a trifunctional or higher functional thermosetting agent from the viewpoint of reactivity.
  • the “trifunctional or higher functional thermosetting agent” means a thermosetting agent made of a compound having three or more functional groups in one molecule which is activated by heating and acts on the curing reaction of the curable resin.
  • thermosetting agent examples include citric acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3,5-tris (2-carboxyethyl) isocyanurate, and the like.
  • thermosetting agent examples include organic acid dihydrazide, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid dihydrazide is preferably used.
  • organic acid dihydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • organic acid dihydrazides examples include SDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), Amicure VDH, Amicure VDH-J, Amicure UDH, Amicure UDH-J (all Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.
  • the content of the thermosetting agent is preferably 1 part by weight with respect to 100 parts by weight of the curable resin, and 50 parts by weight with respect to the preferable upper limit.
  • the upper limit with more preferable content of the said thermosetting agent is 30 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a radical polymerization initiator.
  • the radical polymerization initiator include a photo radical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
  • photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
  • photo radical polymerization initiators examples include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, all manufactured by Rusilin TPO ), NCI-930 (manufactured by ADEKA), SPEEDCURE EMK (manufactured by Nippon Sebel Hegner), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.) and the like.
  • thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
  • an initiator made of a polymer azo compound (hereinafter also referred to as “polymer azo initiator”) is preferable.
  • the polymer azo compound means a compound having an azo group and generating a radical capable of curing a (meth) acryloyl group by heat and having a number average molecular weight of 300 or more.
  • the preferable lower limit of the number average molecular weight of the polymeric azo initiator is 1000, and the preferable upper limit is 300,000.
  • the more preferable lower limit of the number average molecular weight of the polymeric azo initiator is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 90,000.
  • the said number average molecular weight is a value calculated
  • polymer azo initiator examples include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
  • polymer azo initiator having a structure in which a plurality of units such as polyalkylene oxide are bonded via the azo group those having a polyethylene oxide structure are preferable.
  • Examples of such a polymer azo initiator include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) Examples thereof include polycondensates of polydimethylsiloxane having a terminal amino group, such as VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all of which are Wako Pure Chemical Industries, Ltd.) Manufactured) and the like.
  • Examples of azo compounds that are not polymers include V-65 and V-501 (both manufactured by Wako Pure Chemical Industries, Ltd.).
  • organic peroxide examples include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
  • the content of the radical polymerization initiator is preferably 0.01 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the radical polymerization initiator is within this range, the obtained sealing agent for liquid crystal display elements is excellent in storage stability and curability while suppressing liquid crystal contamination.
  • the minimum with more preferable content of the said radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, improving moisture permeability of cured products, and the like. preferable.
  • the filler examples include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide,
  • Organic fillers such as calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, and calcium silicate, and organic materials such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles A filler is mentioned.
  • the minimum with preferable content of the said filler in the sealing compound for liquid crystal display elements of this invention is 10 weight%, and a preferable upper limit is 70 weight%.
  • a preferable upper limit is 70 weight%.
  • the more preferable lower limit of the content of the filler is 20% by weight, and the more preferable upper limit is 60% by weight.
  • the sealing compound for liquid crystal display elements of this invention contains a silane coupling agent.
  • the silane coupling agent mainly has a role as an adhesion assistant for favorably bonding the sealing agent and the substrate.
  • silane coupling agent since it is excellent in the effect which improves adhesiveness with a board
  • -Aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used.
  • the minimum with preferable content of the said silane coupling agent in the sealing compound for liquid crystal display elements of this invention is 0.1 weight%, and a preferable upper limit is 10 weight%.
  • a preferable upper limit is 10 weight%.
  • the minimum with more preferable content of the said silane coupling agent is 0.3 weight%, and a more preferable upper limit is 5 weight%.
  • the sealing agent for liquid crystal display elements of the present invention may contain a light shielding agent.
  • the sealing compound for liquid crystal display elements of this invention can be used suitably as a light shielding sealing agent.
  • Examples of the light-shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferable.
  • Titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 to 450 nm, compared to the average transmittance for light having a wavelength of 300 to 800 nm. That is, the above-described titanium black sufficiently shields light having a wavelength in the visible light region, thereby providing a light shielding property to the sealing agent for liquid crystal display elements of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
  • the light shielding agent contained in the liquid crystal display element sealant of the present invention is preferably a highly insulating material, and titanium black is also preferred as the highly insulating light shielding agent.
  • the above-mentioned titanium black exhibits a sufficient effect even if it is not surface-treated, but the surface is treated with an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, oxidized Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide can also be used. Especially, what is processed with the organic component is preferable at the point which can improve insulation more.
  • the liquid crystal display element produced using the sealing agent for liquid crystal display elements of the present invention containing the above-described titanium black as a light-shielding agent has sufficient light-shielding properties, and therefore has high contrast without light leakage A liquid crystal display element having excellent image display quality can be realized.
  • titanium black examples include 12S, 13M, 13M-C, 13R-N, 14M-C (all manufactured by Mitsubishi Materials Corporation), Tilak D (manufactured by Ako Kasei Co., Ltd.), and the like. Can be mentioned.
  • the preferable lower limit of the specific surface area of the titanium black is 13 m 2 / g, the preferable upper limit is 30 m 2 / g, the more preferable lower limit is 15 m 2 / g, and the more preferable upper limit is 25 m 2 / g.
  • the preferred lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferred lower limit is 1 ⁇ ⁇ cm, and the more preferred upper limit is 2.5 ⁇ ⁇ cm.
  • the primary particle diameter of the said light-shielding agent will not be specifically limited if it is below the distance between the board
  • the more preferable lower limit of the primary particle diameter of the light shielding agent is 5 nm
  • the more preferable upper limit is 200 nm
  • the still more preferable lower limit is 10 nm
  • the still more preferable upper limit is 100 nm.
  • the primary particle size of the light shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICS SIZING SYSTEMS) and dispersing the light shielding agent in a solvent (water, organic solvent, etc.).
  • the minimum with preferable content of the said light-shielding agent in the sealing compound for liquid crystal display elements of this invention is 5 weight%, and a preferable upper limit is 80 weight%.
  • the content of the light-shielding agent is within this range, the liquid crystal display element sealant can exhibit better light-shielding properties without reducing the adhesion to the substrate, the strength after curing, and the drawability. it can.
  • the more preferable lower limit of the content of the light-shielding agent is 10% by weight, the more preferable upper limit is 70% by weight, the still more preferable lower limit is 30% by weight, and the still more preferable upper limit is 60% by weight.
  • the sealing agent for liquid crystal display elements of the present invention is further added as necessary, stress relieving agent, reactive diluent, thixotropic agent, spacer, curing accelerator, antifoaming agent, leveling agent, polymerization inhibitor, etc.
  • An agent or the like may be contained.
  • a method for producing the sealing agent for liquid crystal display elements of the present invention for example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin, and a polymerization
  • examples thereof include a method of mixing an initiator and / or a thermosetting agent and an additive such as a silane coupling agent added as necessary.
  • the sealing agent for liquid crystal display elements of the present invention has a preferable lower limit of 50,000 mPa ⁇ s and a preferable upper limit of 700,000 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is within this range, the obtained sealing agent for liquid crystal display elements has excellent coating properties.
  • a more preferable lower limit of the viscosity is 100,000 mPa ⁇ s, and a more preferable upper limit is 500,000 mPa ⁇ s.
  • As the E-type viscometer for example, 5XHBDV-III + CP (manufactured by Brookfield, rotor No. CP-51) can be used.
  • a vertical conducting material can be produced by blending conductive fine particles with the liquid crystal display element sealant of the present invention.
  • Such a vertical conduction material containing the sealing agent for liquid crystal display elements of the present invention and conductive fine particles is also one aspect of the present invention.
  • the conductive fine particles a metal ball, a resin fine particle formed with a conductive metal layer on the surface, or the like can be used.
  • the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the conductive connection is possible without damaging the transparent substrate due to the excellent elasticity of the resin fine particles.
  • the liquid crystal display element using the sealing agent for liquid crystal display elements of this invention or the vertical conduction material of this invention is also one of this invention.
  • a liquid crystal dropping method is preferably used.
  • the liquid crystal display element sealant of the present invention is applied to one of two substrates such as a glass substrate with electrodes such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, or the like.
  • the sealing compound for liquid crystal display elements which is excellent in adhesiveness and can suppress liquid-crystal contamination can be provided.
  • the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
  • Examples 1 to 8 and Comparative Examples 1 and 2 According to the mixing ratio described in Table 1, each material was mixed using a planetary stirrer (manufactured by Shinky Co., Ltd., “Awatori Nertaro”), and then further mixed using three rolls.
  • the sealing agents for liquid crystal display elements of 1 to 8 and Comparative Examples 1 and 2 were prepared.
  • the adhesive strength was measured using the tension gauge.
  • the resulting value obtained by dividing measured values (kgf) in the seal coating cross sectional area (cm 2) is a case was 35 kgf / cm 2 or more " ⁇ " was 30 kgf / cm 2 or more 35 kgf / cm less than 2 where " ⁇ ", the case was 25 kgf / cm 2 or more 30 kgf / cm less than 2 " ⁇ ", and evaluated the adhesiveness of the case was less than 25 kgf / cm 2 as " ⁇ ".
  • TN liquid crystal manufactured by Chisso Corporation, “JC-5001LA”
  • JC-5001LA fine droplets of TN liquid crystal
  • the other transparent electrode substrate is 5 Pa with a vacuum bonding device. Bonding was performed under vacuum to obtain a cell.
  • the obtained cell was irradiated with 100 mW / cm 2 of ultraviolet rays for 30 seconds using a metal halide lamp, and then heated at 120 ° C. for 1 hour to cure the sealant to obtain a liquid crystal display element.
  • the display unevenness generated in the liquid crystal (especially the corner portion) around the seal portion was visually observed, and when the display unevenness was not confirmed, “ ⁇ ”, slight display unevenness was confirmed.
  • the display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “ ⁇ ” as the case, “ ⁇ ” when the display unevenness was clearly confirmed, and “X” when the severe display unevenness was confirmed. Note that the liquid crystal display elements evaluated as “ ⁇ ” and “ ⁇ ” are at a level that causes no problem in practical use.
  • the sealing compound for liquid crystal display elements which is excellent in adhesiveness and can suppress liquid-crystal contamination can be provided.
  • the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne un produit d'étanchéité destiné à un élément d'affichage à cristaux liquides, ledit produit d'étanchéité présentant une adhérence supérieure, tout en étant apte à rendre minimale la contamination de cristaux liquides. L'invention concerne également un matériau à conduction verticale et un élément d'affichage à cristaux liquides qui sont obtenus au moyen dudit produit d'étanchéité destiné à un élément d'affichage à cristaux liquides. Le produit d'étanchéité destiné à un élément d'affichage à cristaux liquides comprend un agent de durcissement thermique et une résine durcissable, ladite résine durcissable comprenant un composé exprimé dans la formule (1). Dans la formule (1), l, m, et n sont chacun compris entre 0 et 6, et Y est compris entre 1 et 20.
PCT/JP2017/000005 2016-01-07 2017-01-04 Produit d'étanchéité destiné à un élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides WO2017119407A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020177034601A KR20180103680A (ko) 2016-01-07 2017-01-04 액정 표시 소자용 시일제, 상하 도통 재료 및 액정 표시 소자
CN201780001989.XA CN107683435B (zh) 2016-01-07 2017-01-04 液晶显示元件用密封剂、上下导通材料及液晶显示元件
JP2017502914A JP6978311B2 (ja) 2016-01-07 2017-01-04 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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016001916 2016-01-07
JP2016-001916 2016-01-07

Publications (1)

Publication Number Publication Date
WO2017119407A1 true WO2017119407A1 (fr) 2017-07-13

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JP (1) JP6978311B2 (fr)
KR (1) KR20180103680A (fr)
CN (1) CN107683435B (fr)
TW (1) TWI717446B (fr)
WO (1) WO2017119407A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015200729A (ja) * 2014-04-07 2015-11-12 日本化薬株式会社 放射線硬化型樹脂組成物、その硬化物及びその用途

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
JP2002212268A (ja) * 2001-01-19 2002-07-31 Japan Epoxy Resin Kk 半導体封止用エポキシ樹脂組成物
CA2521615A1 (fr) * 2003-04-08 2004-10-21 Nippon Kayaku Kabushiki Kaisha Agent d'etancheite pour cristaux liquides et cellule d'affichage a cristaux liquides faisant appel a ce dernier
JP5433438B2 (ja) * 2010-01-22 2014-03-05 日本化薬株式会社 熱硬化型液晶滴下工法用液晶シール剤及びそれを用いた液晶表示セル
CN105900003B (zh) * 2014-05-23 2019-07-19 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
JP2016109997A (ja) * 2014-12-10 2016-06-20 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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015200729A (ja) * 2014-04-07 2015-11-12 日本化薬株式会社 放射線硬化型樹脂組成物、その硬化物及びその用途

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TW201736564A (zh) 2017-10-16
TWI717446B (zh) 2021-02-01
KR20180103680A (ko) 2018-09-19
JP6978311B2 (ja) 2021-12-08
CN107683435B (zh) 2022-01-04
JPWO2017119407A1 (ja) 2018-10-25
CN107683435A (zh) 2018-02-09

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