WO2017038611A1 - Produit d'étanchéité pour élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides - Google Patents

Produit d'étanchéité pour 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
WO2017038611A1
WO2017038611A1 PCT/JP2016/074778 JP2016074778W WO2017038611A1 WO 2017038611 A1 WO2017038611 A1 WO 2017038611A1 JP 2016074778 W JP2016074778 W JP 2016074778W WO 2017038611 A1 WO2017038611 A1 WO 2017038611A1
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Prior art keywords
liquid crystal
crystal display
meth
acrylate
display element
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PCT/JP2016/074778
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English (en)
Japanese (ja)
Inventor
秀幸 林
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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 CN201680009718.4A priority Critical patent/CN107209425B/zh
Priority to KR1020177020730A priority patent/KR101804108B1/ko
Priority to JP2016555795A priority patent/JP6097454B1/ja
Publication of WO2017038611A1 publication Critical patent/WO2017038611A1/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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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 adhesion and moisture permeation prevention 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.
  • Patent Document 1 and Patent Document 2 a method for manufacturing a liquid crystal display element such as a liquid crystal display cell has been disclosed in, for example, Patent Document 1 and Patent Document 2 from the conventional vacuum injection method from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
  • a liquid crystal dropping method called a dripping method using such a photothermal combined curing type sealant has become the mainstream.
  • 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 at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency.
  • liquid crystal display elements are increasingly required to have moisture resistance reliability in driving in high-temperature and high-humidity environments, and the performance of sealing agents to prevent water from entering from the outside. Is further demanded.
  • it is necessary to improve the adhesion between the sealing agent and the substrate and to make the cured product of the sealing agent excellent in moisture permeation prevention.
  • it has been difficult to achieve both adhesiveness and moisture permeation preventive properties in the sealing agent.
  • the present invention is a liquid crystal display element sealing agent containing a curable resin and a polymerization initiator and / or a thermosetting agent, and the curable resin has three or more polymerizable functional groups in one molecule. And a sealant for a liquid crystal display element containing a compound having a ring-opening structure of one or more ⁇ -caprolactone and having no cyclic structure.
  • the present invention is described in detail below.
  • the present inventors use a compound having 3 or more polymerizable functional groups and 1 or more ⁇ -caprolactone ring-opening structure in one molecule and having no cyclic structure as a curable resin.
  • a sealing agent for liquid crystal display elements that is excellent in adhesiveness and moisture permeation prevention properties and can suppress liquid crystal contamination can be obtained, thereby completing the present invention.
  • the sealing agent for liquid crystal display elements of this invention contains curable resin.
  • the curable resin is a compound having 3 or more polymerizable functional groups and 1 or more ⁇ -caprolactone ring-opening structure in one molecule and having no cyclic structure (hereinafter referred to as “the present invention”). Also referred to as “polymerizable compound”.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in adhesiveness and moisture permeation prevention properties and can suppress liquid crystal contamination.
  • the polymerizable compound according to the present invention has three or more polymerizable functional groups in one molecule.
  • a polymeric functional group which the polymeric compound concerning this invention has a (meth) acryloyl group, an epoxy group, an episulfide group etc. are mentioned, for example.
  • the polymeric compound concerning this invention has a (meth) acryloyl group as a polymeric functional group, and it is more preferable that all the polymeric functional groups to have are a (meth) acryloyl group.
  • the “(meth) acryloyl” means acryloyl or methacryloyl.
  • the polymerizable compound according to the present invention preferably has 4 to 8 polymerizable functional groups in one molecule from the viewpoint of achieving both curability and moisture permeation prevention properties. Most preferably, it has a polymerizable functional group.
  • the polymerizable compound according to the present invention has one or more ⁇ -caprolactone ring-opening structures in one molecule.
  • the polymerizable compound according to the present invention is excellent in adhesiveness.
  • the polymerizable compound according to the present invention preferably has two or more ⁇ -caprolactone ring-opening structures in one molecule, and more preferably has four or more ⁇ -caprolactone ring-opening structures in one molecule. It is more preferable to have 4 to 8 ⁇ -caprolactone ring-opening structures in one molecule, and it is most preferable to have 6 ⁇ -caprolactone ring-opening structures in one molecule.
  • the polymerizable compound according to the present invention does not have a cyclic structure, an increase in viscosity after blending can be suppressed, and the obtained sealing agent for liquid crystal display elements has excellent workability.
  • the polymerizable compound according to the present invention is excellent in the effect of suppressing liquid crystal contamination, it is preferable to have one or more hydrogen-bonding functional groups in one molecule.
  • the hydrogen bonding functional group include a hydroxyl group (—OH), a primary amino group (—NH 2 ), a secondary amino group (—NHR (R represents an aromatic or aliphatic hydrocarbon, and derivatives thereof). )), Carboxyl group (—COOH), primary amide group (—CONH 2 ), hydroxyamino group (—NHOH), amide bond (—NHCO—), imino bond (—NH—), imide bond (—CONHCO) -), Hydrazo bond (-NH-NH-) and the like. Of these, a hydroxyl group is preferred.
  • a method for producing the polymerizable compound according to the present invention for example, a method of modifying ⁇ -caprolactone with (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule and having no cyclic structure.
  • Etc. the term “(meth) acrylate” means acrylate or methacrylate, and the term “(meth) acrylate is modified with ⁇ -caprolactone” means an alcohol-derived site of (meth) acrylate and (meth) It means introducing a ring-opened product or a ring-opened polymer of ⁇ -caprolactone between the acryloyl group.
  • the ⁇ -caprolactone-modified alcohol is then synthesized.
  • -A method of esterifying a caprolactone-modified alcohol and (meth) acrylic acid in the presence of an acidic catalyst using a dehydrating solvent, or a reaction of (meth) acrylic acid with ⁇ -caprolactone to modify ⁇ -caprolactone examples thereof include a method of esterifying the ⁇ -caprolactone-modified (meth) acrylic acid and alcohol after synthesizing (meth) acrylic acid.
  • the “(meth) acryl” means acryl or methacryl.
  • the polymerizable compound according to the present invention preferably has a dendrimer structure in which a plurality of molecular chains are regularly branched from a central atom or a central molecule.
  • l, m, n, o, p, and q each independently represents an integer of 1 to 12.
  • l, m, n, o, p, and the resulting liquid crystal display element sealant are excellent in all of adhesiveness, moisture permeation prevention, and low liquid crystal contamination.
  • Each q is preferably 1 or 2, and most preferably 1.
  • the curable resin may contain other polymerizable compounds in addition to the polymerizable compound according to the present invention.
  • the preferred lower limit of the content of the polymerizable compound according to the present invention is 1 part by weight and the preferred upper limit is 80 parts by weight with respect to 100 parts by weight of the entire curable resin.
  • the content of the polymerizable compound according to the present invention is 1 part by weight or more, the obtained sealing agent for liquid crystal display elements is more excellent in adhesiveness.
  • the content of the polymerizable compound according to the present invention is 80 parts by weight or less, the obtained sealing agent for liquid crystal display elements is more excellent in moisture permeation prevention.
  • the more preferred lower limit of the content of the polymerizable compound according to the present invention is 10 parts by weight, the more preferred upper limit is 70 parts by weight, the still more preferred lower limit is 30 parts by weight, and the still more preferred upper limit is 60 parts by weight.
  • Examples of the other epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2′-diallyl bisphenol A type epoxy resin, and hydrogenated bisphenol type.
  • 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.
  • the said curable resin may contain the compound which has an epoxy group and a (meth) acryloyl group in 1 molecule as said other epoxy compound.
  • examples of such a compound include a partial (meth) acryl-modified epoxy resin obtained by reacting a part of an epoxy group having two or more epoxy groups with (meth) acrylic acid.
  • UVACURE 1561 manufactured by Daicel Ornex.
  • Examples of the other (meth) acrylic compounds include epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy compound, and (meth) acrylic acid by reacting a compound having a hydroxyl group.
  • examples thereof include urethane (meth) acrylate obtained by reacting the obtained (meth) acrylic acid ester compound and an isocyanate compound with a (meth) acrylic acid derivative having a hydroxyl group.
  • epoxy (meth) acrylate is preferable.
  • the other (meth) acrylic compounds are preferably those having two or more (meth) acryloyl groups in the molecule because of their high reactivity.
  • the “epoxy (meth) acrylate” refers to a compound obtained by reacting all epoxy groups in an epoxy compound with (meth) acrylic acid.
  • 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 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, 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
  • the content ratio of the (meth) acryloyl group and the epoxy group in the curable resin is preferably 50:50 to 95: 5.
  • the sealing agent for liquid crystal display elements of this invention contains a polymerization initiator and / or a thermosetting agent.
  • the polymerization initiator include radical polymerization initiators and cationic polymerization initiators.
  • radical polymerization initiator examples 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.
  • a photocationic polymerization initiator can be suitably used as the cationic polymerization initiator.
  • the cationic photopolymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be of an ionic photoacid generation type or a nonionic photoacid generation type. It may be.
  • Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, organometallic complexes such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Is mentioned.
  • photocationic polymerization initiators examples include Adekaoptomer SP-150 and Adekaoptomer SP-170 (both manufactured by ADEKA).
  • the content of the 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. When the content of the 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 polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
  • thermosetting agent examples include organic acid hydrazides, imidazole derivatives, amine compounds, polyhydric phenol compounds, acid anhydrides, and the like. Of these, organic acid hydrazide is preferably used.
  • organic acid hydrazide examples include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide, and the like.
  • organic acid hydrazides examples include, for example, 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 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 preferable lower limit of the content of the filler in 100 parts by weight of the sealant for liquid crystal display elements of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
  • the minimum with more preferable content of the said filler is 20 weight part, and a more preferable upper limit is 60 weight part.
  • the sealing 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 100 weight part of sealing compounds 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.
  • 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 preferable lower limit of the content of the light-shielding agent in 100 parts by weight of the 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 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 parts by weight, the more preferable upper limit is 70 parts by weight, the still more preferable lower limit is 30 parts by weight, and the still more preferable upper limit is 60 parts by weight.
  • the sealing agent for liquid crystal 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.
  • 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 which has the sealing compound 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.
  • ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and moisture-permeable prevention property, and can provide the sealing compound for liquid crystal display elements which can suppress liquid-crystal contamination. Moreover, according to this invention, the vertical conduction material and liquid crystal display element which use this sealing compound for liquid crystal display elements can be provided.
  • a polymerization inhibitor is prepared by reacting 25.4 parts by weight (0.1 mol) of dipentaerythritol with 68.4 parts by weight (0.6 mol) of ⁇ -caprolactone and 43.2 parts by weight (0.6 mol) of acrylic acid.
  • As a catalyst 0.01 part by weight of hydroquinone, 0.1 part by weight of p-toluenesulfonic acid as a catalyst, and 200 parts by weight of propylene glycol methyl ether acetate (PGMEA) as a solvent were charged in a flask and heated while flowing nitrogen. After reacting in an oil bath at 120 ° C.
  • the mixture was allowed to cool to room temperature to obtain ⁇ -caprolactone-modified dipentaerythritol hexaacrylate A as the polymerizable compound according to the present invention.
  • ⁇ -caprolactone-modified dipentaerythritol hexaacrylate A is represented by l, m, n, o, p in the above formula (1).
  • And q were confirmed to be 1.
  • ⁇ -caprolactone-modified dipentaerythritol hexaacrylate B as a polymerizable compound according to the present invention.
  • the obtained ⁇ -caprolactone-modified dipentaerythritol hexaacrylate B is represented by l, m, n, o, p in the above formula (1).
  • And q were confirmed to be 2 compounds.
  • Examples 1 to 10 and Comparative Examples 1 to 5 According to the blending ratios described in Tables 1 and 2, each material was mixed using a planetary stirrer ("Shinky”, “Awatori Nertaro”), and then mixed by using three rolls. The sealing agents for liquid crystal display elements of Examples 1 to 10 and Comparative Examples 1 to 5 were prepared.
  • the adhesive strength was measured using the tension gauge.
  • the case the adhesive strength was 330N / cm 2 or more " ⁇ ", where the adhesive strength is less than 300N / cm 2 more than 330N / cm 2 " ⁇ ", the adhesive strength of 270N / cm 2 more than 300N / cm
  • the adhesiveness was evaluated as “ ⁇ ” when less than 2 and “x” when the adhesive strength was less than 270 N / cm 2 .
  • 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, “ ⁇ ”, 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.
  • ADVANTAGE OF THE INVENTION According to this invention, it is excellent in adhesiveness and moisture-permeable prevention property, and can provide the sealing compound for liquid crystal display elements which can suppress liquid-crystal contamination. Moreover, according to this invention, 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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention vise à pourvoir à un produit d'étanchéité pour un élément d'affichage à cristaux liquides, le produit d'étanchéité présentant une excellente adhérence ainsi qu'une excellente prévention de la pénétration d'humidité et pouvant supprimer la contamination de cristaux liquides. La présente invention vise également à pourvoir à un matériau à conduction verticale, ainsi qu'à un élément d'affichage à cristaux liquides obtenu à l'aide du produit d'étanchéité pour un élément d'affichage à cristaux liquides. La présente invention concerne un produit d'étanchéité pour un élément d'affichage à cristaux liquides, qui contient une résine durcissable, et un initiateur de polymérisation et/ou un agent thermodurcissable, la résine durcissable contenant un composé ayant au moins trois groupes fonctionnels polymérisables et une ou plusieurs structures à cycle ouvert d'ε-caprolactone dans chaque molécule de ce composé et n'ayant pas de structure cyclique.
PCT/JP2016/074778 2015-09-02 2016-08-25 Produit d'étanchéité pour élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides WO2017038611A1 (fr)

Priority Applications (3)

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CN201680009718.4A CN107209425B (zh) 2015-09-02 2016-08-25 液晶显示元件用密封剂、上下导通材料及液晶显示元件
KR1020177020730A KR101804108B1 (ko) 2015-09-02 2016-08-25 액정 표시 소자용 시일제, 상하 도통 재료 및 액정 표시 소자
JP2016555795A JP6097454B1 (ja) 2015-09-02 2016-08-25 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

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JP2015173014 2015-09-02
JP2015-173014 2015-09-02

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WO2020230678A1 (fr) 2019-05-10 2020-11-19 三井化学株式会社 Agent d'étanchéité à cristaux liquides, écran d'affichage à cristaux liquides l'utilisant et son procédé de production
WO2020235357A1 (fr) 2019-05-17 2020-11-26 三井化学株式会社 Agent d'étanchéité pour procédés de dépôt de cristaux liquides, écran d'affichage à cristaux liquides l'utilisant et son procédé de production

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JP2008065064A (ja) * 2006-09-07 2008-03-21 Mitsui Chemicals Inc 液晶滴下工法用シール剤組成物およびそれを用いた液晶表示パネルの製造方法
JP2009058933A (ja) * 2007-07-06 2009-03-19 Mitsui Chemicals Inc 液晶シール剤、ならびにこれに用いられる（メタ）アクリル酸エステル化合物およびその製造方法
WO2014034684A1 (fr) * 2012-08-27 2014-03-06 日本化薬株式会社 Agent d'étanchéité pour cristal liquide, et cellule d'affichage à cristaux liquides obtenue grâce à cet agent

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JP4875441B2 (ja) 2006-09-07 2012-02-15 三井化学株式会社 液晶滴下工法用シール剤組成物およびそれを用いた液晶表示パネルの製造方法
WO2009154138A1 (fr) * 2008-06-18 2009-12-23 株式会社ブリヂストン Composition d'adhésif et procédé de fabrication de dalle d'écran l'utilisant
JP5986987B2 (ja) * 2011-03-28 2016-09-06 三井化学株式会社 液晶シール剤、それを用いた液晶表示パネルの製造方法、および液晶表示パネル
WO2014199853A1 (fr) * 2013-06-11 2014-12-18 積水化学工業株式会社 Agent de scellement pour procédés de dépôt de cristaux liquides, matière à conduction verticale, et élément d'affichage à cristaux liquides
CN105683225B (zh) * 2013-12-05 2019-09-03 积水化学工业株式会社 液晶显示元件用密封剂、上下导通材料及液晶显示元件
JP6535002B2 (ja) * 2014-07-17 2019-06-26 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

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WO2006120998A1 (fr) * 2005-05-09 2006-11-16 Sekisui Chemical Co., Ltd. Materiau d’etancheite pour le procede de diffusion a cristaux liquides, materiau de transfert et dispositifs d’affichage a cristaux liquides
JP2008065064A (ja) * 2006-09-07 2008-03-21 Mitsui Chemicals Inc 液晶滴下工法用シール剤組成物およびそれを用いた液晶表示パネルの製造方法
JP2009058933A (ja) * 2007-07-06 2009-03-19 Mitsui Chemicals Inc 液晶シール剤、ならびにこれに用いられる（メタ）アクリル酸エステル化合物およびその製造方法
WO2014034684A1 (fr) * 2012-08-27 2014-03-06 日本化薬株式会社 Agent d'étanchéité pour cristal liquide, et cellule d'affichage à cristaux liquides obtenue grâce à cet agent

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JP2017090931A (ja) 2017-05-25
CN107209425B (zh) 2019-05-31
TWI716440B (zh) 2021-01-21
CN107209425A (zh) 2017-09-26
KR101804108B1 (ko) 2017-12-01
TW202112840A (zh) 2021-04-01
JP6097454B1 (ja) 2017-03-15
KR20170092700A (ko) 2017-08-11
TW201718671A (zh) 2017-06-01
JPWO2017038611A1 (ja) 2017-09-07

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