WO2017131002A1 - Agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, matériau à conduction verticale et élément d'affichage à cristaux liquides - Google Patents

Agent d'étanchéité protégeant de la lumière pour 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
WO2017131002A1
WO2017131002A1 PCT/JP2017/002461 JP2017002461W WO2017131002A1 WO 2017131002 A1 WO2017131002 A1 WO 2017131002A1 JP 2017002461 W JP2017002461 W JP 2017002461W WO 2017131002 A1 WO2017131002 A1 WO 2017131002A1
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Prior art keywords
liquid crystal
crystal display
light
meth
acrylate
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PCT/JP2017/002461
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English (en)
Japanese (ja)
Inventor
柴田　大輔
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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 JP2017505597A priority Critical patent/JP6918693B2/ja
Priority to CN201780002156.5A priority patent/CN107710061B/zh
Priority to KR1020177034666A priority patent/KR20180103681A/ko
Publication of WO2017131002A1 publication Critical patent/WO2017131002A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds
    • C09K19/544—Macromolecular compounds as dispersing or encapsulating medium around the liquid crystal
    • 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 light-shielding sealant for liquid crystal display elements that is excellent in curability and storage stability and that can suppress liquid crystal contamination. Moreover, this invention relates to the vertical conduction material and liquid crystal display element which use this light-shielding sealing agent for liquid crystal display elements.
  • a liquid crystal dropping method called a dropping method using a photothermal combined curing type sealing agent containing a polymerization initiator and a thermosetting agent is used.
  • a rectangular seal pattern is formed on one of the two substrates with electrodes by dispensing.
  • liquid crystal microdrops are dropped into the sealing frame of the substrate in a state where the sealing agent is uncured, the other substrate is superposed under vacuum, and the sealing portion is irradiated with light such as ultraviolet rays to perform temporary curing. Thereafter, heating is performed to perform main curing, and a liquid crystal display element is manufactured.
  • this dripping method has become the mainstream method for manufacturing liquid crystal display elements.
  • a narrow frame of the liquid crystal display unit can be cited.
  • the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
  • the sealing agent is arranged directly under the black matrix, when the dripping method is performed, the light irradiated when photocuring the sealing agent is blocked, and it is difficult for the light to reach the inside of the sealing agent.
  • the conventional sealant is insufficiently cured.
  • 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, and the contrast is lowered. It was. Therefore, a light-shielding agent is added to the sealant to give it light-shielding properties. In particular, in the case of a sealant with such light-shielding properties, the curing is insufficient and it is not cured. There was a problem that the sealing agent component of the liquid crystal was dissolved in the liquid crystal, and liquid crystal contamination was likely to occur.
  • An object of this invention is to provide the light-shielding sealing agent for liquid crystal display elements which is excellent in sclerosis
  • Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the light-shielding sealant for the liquid crystal display element.
  • the present invention contains a curable resin, a photoradical polymerization initiator, an amine adduct compound, and a light shielding agent, and the photoradical polymerization initiator has a concentration of 0.1 mg / mL. It is a light-shielding sealant for liquid crystal display elements having an extinction coefficient at a wavelength of 365 nm measured in acetonitrile mixed with a polymerization initiator of 5000 mL / g ⁇ cm or more.
  • the present invention is described in detail below.
  • This inventor examined improving the sclerosis
  • simply adding a high-sensitivity photopolymerization initiator may not allow the sealant to be fully cured to the depth, or may reduce storage stability.
  • a sensitizer is used, There is a problem that liquid crystal contamination is likely to occur due to the sensitizer.
  • the present inventor has excellent curability and storage stability by combining a long-wavelength photoradical polymerization initiator having an absorption coefficient at a wavelength of 365 nm of a specific value or more and an amine adduct compound. And it discovered that the light-shielding sealant for liquid crystal display elements which can suppress liquid-crystal contamination could be obtained, and came to complete this invention.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains a photoradical polymerization initiator.
  • the photoradical polymerization initiator has an extinction coefficient of 5000 mL / g ⁇ cm or more at a wavelength of 365 nm measured in acetonitrile mixed with the photoradical polymerization initiator so that the concentration becomes 0.1 mg / mL.
  • a photoradical polymerization initiator having an absorption coefficient of 5000 mL / g ⁇ cm or more at a wavelength of 365 nm measured in acetonitrile mixed so as to have a concentration of 0.1 mg / mL is referred to as “long wavelength initiator according to the present invention”. Also called.
  • the light-shielding sealant for liquid crystal display elements of the present invention is excellent in storage stability and curability (particularly deep curability), and liquid crystal Contamination can be suppressed.
  • the above extinction coefficient can be calculated from the absorbance measured using an ultraviolet-visible spectrophotometer (for example, Cary-5 spcphotometer manufactured by Varian).
  • the resulting light-shielding liquid crystal display device The sealing agent is inferior in curability (particularly deep curability).
  • the extinction coefficient at a wavelength of 365 nm of the long wavelength initiator according to the present invention is preferably 6000 mL / g ⁇ cm or more, and more preferably 7000 mL / g ⁇ cm or more.
  • the long wavelength initiator according to the present invention preferably has an extinction coefficient of 30,000 mL / g ⁇ cm or less at the wavelength of 365 nm.
  • an oxime ester compound satisfying the above-mentioned definition of the extinction coefficient is preferable, and O-acetyl-1- (6- (2-methylbenzoyl) -9-ethyl-9H-carbazole- 3-yl) ethanone oxime is most preferred.
  • IRGACURE OXE02 made by BASF Corporation
  • the content of the long wavelength initiator according to the present invention 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 long wavelength initiator according to the present invention is in this range, the obtained light-shielding sealant for liquid crystal display elements is more excellent in storage stability and curability.
  • the more preferable lower limit of the content of the long wavelength initiator according to the present invention is 0.1 parts by weight, and the more preferable upper limit is 5 parts by weight.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains an amine adduct compound.
  • the amine adduct compound can advance the curing of the sealant by heating at a low temperature without deteriorating the storage stability of the sealant during storage. Therefore, by containing the amine adduct compound in combination with the long wavelength initiator according to the present invention, the light-shielding sealant for a liquid crystal display device of the present invention is excellent in storage stability and curability (particularly deep curability), In addition, liquid crystal contamination can be suppressed.
  • the amine adduct compound has a very low liquid-contamination property because the time until the start of curing after heating is short.
  • the amine adduct compound is preferably solid at 25 ° C.
  • fusing point of the said amine adduct compound is 50 degreeC, and a preferable upper limit is 100 degreeC.
  • the melting point of the amine adduct compound is in this range, the obtained light-shielding sealant for liquid crystal display elements is more excellent in the effect of achieving both storage stability and quick curing at low temperatures.
  • Examples of the amine adduct compound include adducts of an amine compound such as an imidazole compound or a primary to tertiary amine and an epoxy compound.
  • Examples of the commercially available amine adduct compounds include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, and Amicure PN-40J.
  • a preferable upper limit of the average particle size of the amine adduct compound is 3 ⁇ m.
  • the average particle diameter of the amine adduct compound is 3 ⁇ m or less, the obtained liquid crystal display element is more excellent in gap retention.
  • the substantial lower limit is 0.1 ⁇ m.
  • the average particle diameter can be reduced to 3 ⁇ m or less by performing treatments such as pulverization and classification.
  • the average particle size of the amine adduct compound and the maximum particle size described below are obtained by measuring the amine adduct compound before blending with the sealant using a laser diffraction particle size distribution analyzer.
  • a preferable upper limit of the maximum particle size of the amine adduct compound is 5 ⁇ m.
  • the maximum particle size of the amine adduct compound is 5 ⁇ m or less, the obtained liquid crystal display device is more excellent in gap retention.
  • a more preferable upper limit of the maximum particle size of the amine adduct compound is 4.5 ⁇ m.
  • the content ratio of particles having a particle diameter of 3 ⁇ m or less in the particle size distribution of the amine adduct compound measured by the laser diffraction particle size distribution analyzer is preferably 99% or more by volume frequency.
  • the content ratio of the particles having a particle diameter of 3 ⁇ m or less in the amine adduct compound is 99% or more by volume frequency, the obtained liquid crystal display element is more excellent in gap retention.
  • the content ratio of particles having a particle diameter of 3 ⁇ m or less in the amine adduct compound is most preferably 100%.
  • the content of the amine adduct compound is preferably 0.1 parts by weight and preferably 70 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the amine adduct compound is within this range, the obtained light-shielding sealant for liquid crystal display elements is excellent in storage stability, curability, and the effect of suppressing liquid crystal contamination.
  • the minimum with more preferable content of the said amine adduct compound is 0.5 weight part, and a more preferable upper limit is 40 weight part.
  • the light-shielding sealant for liquid crystal display elements of the present invention may contain other thermosetting agents in addition to the amine adduct compound as long as the object of the present invention is not impaired.
  • curing agent an imidazole type hardening
  • hydrazide-based curing agents are preferably used.
  • hydrazide-based curing agent examples include 1,3-bis (hydrazinocarboethyl-5-isopropylhydantoin), sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • examples thereof include Amicure VDH, Amicure UDH (all manufactured by Ajinomoto Fine Techno Co.), SDH, IDH, ADH (all manufactured by Otsuka Chemical Co., Ltd.), MDH (manufactured by Nippon Finechem Co., Ltd.), and the like.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains a curable resin.
  • the curable resin preferably contains a (meth) acrylic compound and an epoxy compound.
  • (meth) acrylic compound for example, (meth) acrylic acid ester compound obtained by reacting (meth) acrylic acid with a compound having a hydroxyl group, (meth) acrylic acid and epoxy compound are reacted.
  • examples include epoxy (meth) acrylates obtained, urethane (meth) acrylates obtained by reacting an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group. Of these, epoxy (meth) acrylate is preferable.
  • the (meth) acrylic compound preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
  • the “(meth) acryl” means acryl or methacryl
  • the “(meth) acryl compound” means an acryloyl group or a methacryloyl group (hereinafter referred to as “(meth) acryloyl group”). Also referred to as).
  • the “(meth) acrylate” means acrylate or methacrylate.
  • the “epoxy (meth) acrylate” represents a compound obtained by reacting all epoxy groups in the epoxy compound with (meth) acrylic acid.
  • Examples of the monofunctional compounds among the (meth) acrylic acid ester compounds include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
  • Examples of the bifunctional compound among the (meth) acrylic acid ester compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexane.
  • those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri ( (Meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra Meth) acrylate, dipentaerythritol pen
  • Examples of the epoxy (meth) acrylate include those obtained by reacting an epoxy compound and (meth) acrylic acid in the presence of a basic catalyst according to a conventional method.
  • Examples of the epoxy compound as a raw material for synthesizing the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 2,2′-diallyl bisphenol A type epoxy resin. , Hydrogenated bisphenol type epoxy resin, propylene oxide added bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol Novolac epoxy resin, orthocresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, naphtha Ren phenol novolak type epoxy resin, glycidyl amine type epoxy resin, alkyl polyol type epoxy resin, rubber-modified epoxy resins, glycidyl ester compounds.
  • Examples of commercially available diphenyl ether type epoxy resins include YSLV-80DE (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
  • Examples of commercially available dicyclopentadiene type epoxy resins include EP-4088S (manufactured by ADEKA).
  • Examples of commercially available naphthalene type epoxy resins include Epicron HP4032, Epicron EXA-4700 (both manufactured by DIC) and the like.
  • Examples of commercially available phenol novolac epoxy resins include Epicron N-770 (manufactured by DIC).
  • Examples of the ortho-cresol novolac type epoxy resin that are commercially available include epiclone N-670-EXP-S (manufactured by DIC).
  • Examples of commercially available glycidylamine type epoxy resins include jER630 (manufactured by Mitsubishi Chemical), Epicron 430 (manufactured by DIC), and TETRAD-X (manufactured by Mitsubishi Gas Chemical).
  • Examples of commercially available alkyl polyol type epoxy resins include ZX-1542 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epiklon 726 (manufactured by DIC), Epolite 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), Denacol EX-611. (Manufactured by Nagase ChemteX Corporation).
  • Examples of commercially available rubber-modified epoxy resins include YR-450, YR-207 (both manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epolide PB (manufactured by Daicel Corporation), and the like.
  • Examples of commercially available glycidyl ester compounds include Denacol EX-147 (manufactured by Nagase ChemteX Corporation).
  • 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, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRY3603 EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester M-600A, epoxy ester 40EM, epoxy ester 70PA, epoxy Ester 200PA, epoxy ester 80MFA Epoxy ester 3002M, Epoxy ester 3002A, Epoxy ester 1600A, Epoxy ester 3000M, Epoxy ester 3000A, Epoxy ester 200EA, Epoxy ester 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), Denacol acrylate DA-141, Den
  • Examples of the urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid derivative with the isocyanate compound include, for example, (meth) acrylic having a hydroxyl group with respect to 1 equivalent of an isocyanate compound having two isocyanate groups. Two equivalents of the acid derivative can be obtained by reacting in the presence of a catalytic amount of a tin-based compound.
  • isocyanate compound used as the raw material for the urethane (meth) acrylate examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and diphenylmethane-4,4.
  • MDI '-Diisocyanate
  • hydrogenated MDI polymeric MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate) Phenyl) thiophosphate, tetramethylxylylene diisocyanate, 1,6,11-undecantrie Cyanate, and the like.
  • MDI '-Diisocyanate
  • XDI xylylene diisocyanate
  • XDI hydrogenated XDI
  • lysine diisocyanate triphenylmethane triisocyanate
  • tris (isocyanate) Phenyl) thiophosphate tetramethylxylylene diisocyanate, 1,6,11-und
  • 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
  • combining the said epoxy (meth) acrylate, a partial (meth) acryl modified epoxy resin, etc. are mentioned, for example.
  • 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 or more epoxy compounds. Can be obtained by reacting a part of the epoxy group with (meth) acrylic acid.
  • the ratio of (meth) acryloyl group to epoxy group is 30:70 to 95: 5. It is preferable to blend the (meth) acrylic compound and the epoxy compound. When the ratio of the (meth) acryloyl group to the epoxy group is within this range, the obtained light-shielding sealant for liquid crystal display elements is more excellent in the effect of suppressing adhesiveness and liquid crystal contamination.
  • the curable resin preferably has a hydrogen bondable unit such as —OH group, —NH— group, —NH 2 group, etc. from the viewpoint of suppressing liquid crystal contamination.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains a light-shielding agent.
  • 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 the light-shielding sealant for the liquid crystal display element of the present invention, while transmitting light having a wavelength in the vicinity of the ultraviolet region.
  • the light-shielding agent contained in the light-shielding sealant for liquid crystal display elements of the present invention a highly insulating material is preferable, and titanium black is also preferable as a 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 manufactured using the light-shielding sealant 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 thus has high contrast without light leakage. Thus, 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
  • a preferable minimum is 1 nm and a preferable upper limit is 5000 nm.
  • 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 preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the light-shielding sealant for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 80 parts by weight.
  • the content of the light-shielding agent is within this range, the obtained light-shielding sealant for liquid crystal display elements is excellent in adhesion to the substrate, strength after curing, coating properties, and light-shielding properties.
  • the more preferable lower limit of the content of the light shielding agent is 10 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
  • the light-shielding sealant for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator as long as the object of the present invention is not impaired.
  • a 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 initiator 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 thermal radical polymerization initiator is preferably 0.05 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the thermal radical polymerization initiator is within this range, the obtained light-shielding sealant for a liquid crystal display element is more excellent in thermosetting while maintaining excellent storage stability.
  • the minimum with more preferable content of the said thermal radical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
  • the light-shielding sealant for liquid crystal display elements of the present invention contains a filler for the purpose of improving viscosity, improving adhesiveness due to stress dispersion effect, improving linear expansion coefficient, and further improving moisture resistance of the cured product. Is preferred.
  • 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. These fillers may be used independently and may use 2 or more types together.
  • the minimum with preferable content of the said filler in 100 weight part of light-shielding sealants for liquid crystal display elements of this invention is 10 weight part, and a preferable upper limit is 70 weight part.
  • the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
  • the light-shielding sealant for liquid crystal display elements 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.
  • 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.
  • These silane coupling agents may be used alone or in combination of two or more.
  • the minimum with preferable content of the said silane coupling agent in 100 weight part of light-shielding sealants for liquid crystal display elements of this invention is 0.1 weight part, and a preferable upper limit is 10 weight part.
  • a preferable upper limit is 10 weight part.
  • the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 5 weight part.
  • a method for producing the light-shielding sealant 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,
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three roll, a curable resin
  • Examples include a method of mixing a long wavelength initiator according to the present invention, an amine adduct compound, a light-shielding agent, and an additive such as a silane coupling agent added as necessary.
  • the light-shielding sealant for liquid crystal display elements of the present invention has a preferred lower limit of 100,000 mPa ⁇ s and a preferred upper limit of 600,000 mPa ⁇ s measured using an E-type viscometer at 25 ° C. and 1 rpm. When the viscosity is in this range, the obtained light-shielding sealant for liquid crystal display elements has excellent coating properties.
  • a more preferable lower limit of the viscosity is 150,000 mPa ⁇ s, and a more preferable upper limit is 450,000 mPa ⁇ s.
  • 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.
  • Such a 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 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 light-shielding sealant for liquid crystal display elements of the present invention or the vertical conduction material of the present invention is also one aspect of the present invention.
  • a liquid crystal dropping method is preferably used.
  • the light shielding sealant for the liquid crystal display element 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 liquid crystal display element light-shielding sealant of the present invention is uncured and finely applied liquid crystal droplets are dropped into the seal pattern frame of the substrate and separated under vacuum.
  • Examples thereof include a method having a step of main curing.
  • the light-shielding sealing agent for liquid crystal display elements which is excellent in sclerosis
  • the vertical conduction material and liquid crystal display element which use this light-shielding sealant for liquid crystal display elements can be provided.
  • Examples 1 to 7, Comparative Examples 1 to 6 According to the blending ratio described in Table 1, each material was mixed using a planetary stirrer (“Shinky Co., Ltd.,“ Awatori Nertaro ”), and then mixed using three rolls. The light shielding sealants for liquid crystal display elements 1 to 7 and Comparative Examples 1 to 6 were prepared.
  • Light shielding 1 part by weight of spacer fine particles (“Micropearl SI-H050” manufactured by Sekisui Chemical Co., Ltd.) is uniformly dispersed with 100% by weight of the light-shielding sealant for each liquid crystal display element obtained in the examples and comparative examples, using a planetary stirrer. Then, it was applied onto a 50 mm ⁇ 50 mm glass substrate, and the same type of glass substrate was overlaid thereon. Subsequently, after irradiating 3000 mJ / cm ⁇ 2 > light (wavelength 380 nm) with a metal halide lamp, the sealant was cured by heating at 120 [deg.] C.
  • the obtained OD value test piece was measured for the OD value using PDA-100 (manufactured by Konica), and when the OD value was 2.5 or more, “ ⁇ ”, 2.0 or more and 2.5
  • the light-shielding property was evaluated as “ ⁇ ” when it was less than “x” and “x” when it was less than 2.0.
  • one of two ITO glass-coated alkali glass substrates (30 ⁇ 40 mm) was finely dropped onto one, and the other alkali glass substrate was bonded in a cross shape to a metal halide lamp at 3000 mJ / After irradiation with light of cm 2 (wavelength 380 nm), the sealing agent was cured by heating at 120 ° C. for 60 minutes to obtain an adhesion test piece.
  • the obtained adhesion test piece was subjected to a high-temperature and high-humidity test that was allowed to stand for 24 hours in an environment of 60 ° C., 90% RH, and 1 atmosphere, and then a tensile test (5 mm / mm) was performed using a chuck placed above and below the adhesion test piece. sec).
  • TN liquid crystal manufactured by Chisso, “JC-5001LA”
  • JC-5001LA fine droplets of TN liquid crystal
  • the cells were pasted together to obtain a cell.
  • the obtained cell was irradiated with 3000 mJ / cm 2 light (wavelength 380 nm) with a metal halide lamp, and then heated at 120 ° C. for 60 minutes to cure the sealant, thereby obtaining 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, “ ⁇ ”, a slight display unevenness was confirmed.
  • the display performance (low liquid crystal contamination) of the liquid crystal display element was evaluated with “C” in which the case of “ ⁇ ” was observed and the case where severe display unevenness was confirmed.
  • the light-shielding sealing agent for liquid crystal display elements which is excellent in sclerosis
  • the vertical conduction material and liquid crystal display element which use this light-shielding sealant for liquid crystal display elements can be provided.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
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  • Polymerisation Methods In General (AREA)

Abstract

La présente invention a pour objet de réaliser un agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides qui présente une aptitude au durcissement et une stabilité de conservation excellentes et qui est capable de supprimer la contamination des cristaux liquides. De plus, la présente invention a pour objet de réaliser un matériau à conduction verticale et un élément d'affichage à cristaux liquides en utilisant l'agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides. La présente invention est un agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides contenant une résine durcissable, un initiateur de polymérisation photoradicalaire, un composé d'addition d'amine et un agent de protection contre la lumière. L'initiateur de polymérisation photoradicalaire présente un coefficient d'absorption égal ou supérieur à 5000 ml/g･cm à une longueur d'onde de 365 nm, le coefficient d'absorption étant mesuré dans un acétonitrile dans lequel l'initiateur de polymérisation photoradicalaire est mélangé de façon à présenter une concentration de 0,1 mg/ml.
PCT/JP2017/002461 2016-01-26 2017-01-25 Agent d'étanchéité protégeant de la lumière pour un élément d'affichage à cristaux liquides, matériau à conduction verticale et élément d'affichage à cristaux liquides WO2017131002A1 (fr)

Priority Applications (3)

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JP2017505597A JP6918693B2 (ja) 2016-01-26 2017-01-25 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
CN201780002156.5A CN107710061B (zh) 2016-01-26 2017-01-25 液晶显示元件用遮光密封剂、上下导通材料和液晶显示元件
KR1020177034666A KR20180103681A (ko) 2016-01-26 2017-01-25 액정 표시 소자용 차광 시일제, 상하 도통 재료, 및, 액정 표시 소자

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JP2016012748 2016-01-26

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WO2019193966A1 (fr) * 2018-04-03 2019-10-10 協立化学産業株式会社 Composition durcissable, agent d'étanchéité pour cristaux liquides, panneau à cristaux liquides, et procédé de production d'un panneau à cristaux liquides

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JP6918693B2 (ja) 2021-08-11
JPWO2017131002A1 (ja) 2018-11-15
TW201739833A (zh) 2017-11-16
CN107710061A (zh) 2018-02-16
TWI735523B (zh) 2021-08-11
KR20180103681A (ko) 2018-09-19

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