WO2017130786A1 - Agent de scellement pour élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides - Google Patents

Agent de scellement 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
WO2017130786A1
WO2017130786A1 PCT/JP2017/001347 JP2017001347W WO2017130786A1 WO 2017130786 A1 WO2017130786 A1 WO 2017130786A1 JP 2017001347 W JP2017001347 W JP 2017001347W WO 2017130786 A1 WO2017130786 A1 WO 2017130786A1
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Prior art keywords
liquid crystal
crystal display
compound
meth
acrylate
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PCT/JP2017/001347
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English (en)
Japanese (ja)
Inventor
大輝 山脇
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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 KR1020177033055A priority Critical patent/KR20180101166A/ko
Priority to JP2017503643A priority patent/JP7048314B2/ja
Priority to CN201780001988.5A priority patent/CN107710060B/zh
Publication of WO2017130786A1 publication Critical patent/WO2017130786A1/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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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 sealant for a liquid crystal display element that is excellent in light-shielding part curability 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 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 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. . Thereafter, heating is performed at the time of liquid crystal annealing to perform main curing, and a liquid crystal display element is manufactured. If the substrates are bonded together under reduced pressure, a liquid crystal display element can be manufactured with extremely high efficiency, and this dripping method is currently the mainstream method for manufacturing liquid crystal display elements.
  • the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
  • Patent Document 3 discloses that a highly sensitive photopolymerization initiator is blended with a sealant. However, liquid crystal contamination could not be sufficiently suppressed in the light-shielding part only by blending a highly sensitive photopolymerization initiator.
  • An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in sclerosis
  • hardenability of light-shielding part, and can suppress liquid-crystal contamination. Another object of the present invention is to provide a vertical conduction material and a liquid crystal display element using the sealing agent for a liquid crystal display element.
  • the present invention relates to a sealing agent for a liquid crystal display element comprising a curable resin and a radical photopolymerization initiator, the curable resin comprising a compound having a molecular weight of 100 or more and less than 500, and a compound having a molecular weight of 500 to 3000
  • the radical photopolymerization initiator is a sealing agent for liquid crystal display elements, which is a compound having a carbazole skeleton.
  • the present inventor has examined the use of a compound having a carbazole skeleton as a particularly sensitive photoradical polymerization initiator.
  • a radical photopolymerization initiator even when such a radical photopolymerization initiator is used, there is a problem that the light-shielding part is not sufficiently cured and liquid crystal contamination is likely to occur.
  • the present inventor believes that although the compound having a carbazole skeleton used as the radical photopolymerization initiator is highly sensitive, the light-curing part curability could not be sufficiently improved due to low solubility in the curable resin. It was.
  • the present inventor not only uses a compound having a carbazole skeleton as a radical photopolymerization initiator, but also has excellent light-shielding part curability by using a combination of a compound having a specific molecular weight as a curable resin, and The present inventors have found that a sealing agent for liquid crystal display elements that can suppress liquid crystal contamination can be obtained, and have completed the present invention.
  • the sealing agent for liquid crystal display elements of this invention contains curable resin.
  • the curable resin contains a compound having a molecular weight of 100 or more and less than 500 and a compound having a molecular weight of 500 to 3000.
  • the compound having a carbazole skeleton as a radical photopolymerization initiator can be sufficiently dissolved.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability and can suppress liquid crystal contamination.
  • the “molecular weight” is a molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of polymerization degree and a compound whose modification site is unspecified. , Sometimes expressed using weight average molecular weight.
  • the above “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
  • the curable resin contains a compound having a molecular weight of 100 or more and less than 500.
  • the compound having a molecular weight of 100 or more and less than 500 preferably has a molecular weight of 300 or more and less than 500 from the viewpoint of the solubility of the compound having a carbazole skeleton.
  • the curable resin preferably contains a (meth) acrylic compound as the compound having a molecular weight of 100 or more and less than 500.
  • a (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, glycerin tri (meth) acrylate, penta Examples include erythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, and the like.
  • 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 diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol.
  • diglycidyl ether hydrogenated bisphenol E diglycidyl ether, resorcinol diglycidyl ether, biphenyl-4,4′-diylbis (glycidyl ether), 1,6-naphthalenediylbis (glycidyl ether), ethylene glycol diglycidyl ether, 1 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, and the like.
  • 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.
  • Examples include '-diisocyanate (MDI), hydrogenated MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, and tetramethylxylylene diisocyanate.
  • MDI '-diisocyanate
  • XDI xylylene diisocyanate
  • XDI hydrogenated XDI
  • lysine diisocyanate lysine diisocyanate
  • tetramethylxylylene diisocyanate examples include tetramethylxylylene diisocyanate.
  • 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). Divalents such as hydroxyalkyl (meth) acrylates such as acrylate and 4-hydroxybutyl (meth) acrylate, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, etc. And mono (meth) acrylates of alcohols.
  • the curable resin preferably contains an epoxy compound as a compound having a molecular weight of 100 or more and less than 500 from the viewpoint of adhesion and solubility of the compound having a carbazole skeleton.
  • an epoxy compound the epoxy compound used as a raw material for synthesize
  • 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 curable resin contains a compound having a molecular weight of 500 to 3000.
  • the preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 600, and the preferable upper limit is 2500.
  • the molecular weight of the compound having a molecular weight of 500 to 3000 is 600 or more, the solubility of the compound having a carbazole skeleton is improved.
  • the molecular weight of the compound having a molecular weight of 500 to 3000 is 2500 or less, the obtained sealing agent for liquid crystal display elements is more excellent in low liquid crystal contamination.
  • the more preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 3000 is 1000, and the more preferable upper limit is 2000.
  • the compound having a molecular weight of 500 to 3000 is preferably an oligomer compound, and more preferably an oligomer compound having a polymerization degree of 3 to 6.
  • the compound having a molecular weight of 500 to 3000 is preferably a polyfunctional compound having two or more epoxy groups and / or (meth) acryloyl groups in one molecule, which increases the crosslinking density and further suppresses elution. Since it can do, it is more preferable that it is a polyfunctional compound which has a comb-shaped structure like a novolak-type structure.
  • the compound having a molecular weight of 500 to 3000 include, for example, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, dicyclopentadiene novolac type epoxy resins, biphenyl novolac type epoxy resins, and naphthalene phenol novolac type epoxy resins.
  • 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, 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, dicyclopentadi Reaction of oligomeric epoxy resins such as ene-type epoxy resins, naphthalene-type epoxy resins, glycidylamine-type epoxy resins, alkyl polyol-type epoxy resins, rubber-modified epoxy resins, and these oligomer-type epoxy resins with (meth) acrylic acid Examples thereof include oligomer-type epoxy (meth) acrylates and oligomer-type partial (meth) acryl-modified epoxy resins. Among these, oligomer type epoxy (meth) acrylate is preferable.
  • the preferable lower limit of the content of the compound having the molecular weight of 500 to 3000 in the total of 100 parts by weight of the compound having the molecular weight of 100 or more and less than 500 and the compound having the molecular weight of 500 to 3000 is 10 parts by weight, and the preferable upper limit is 30 parts by weight. Part.
  • the content of the compound having a molecular weight of 500 to 3000 is within this range, the obtained sealing agent for liquid crystal display elements is more excellent in the light-shielding part curability and the effect of suppressing liquid crystal contamination.
  • a more preferable lower limit of the content of the compound having a molecular weight of 500 to 3000 is 12 parts by weight, and a more preferable upper limit is 20 parts by weight.
  • the sealing agent for liquid crystal display elements of this invention contains radical photopolymerization initiator.
  • the photo radical polymerization initiator is a compound having a carbazole skeleton.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in light-shielding part curability.
  • the minimum with a preferable molecular weight of the compound which has the said carbazole skeleton is 300, and a preferable upper limit is 1000.
  • a preferable molecular weight of the compound having the carbazole skeleton is within this range, the solubility in the curable resin is improved.
  • the more preferable lower limit of the molecular weight of the compound having a carbazole skeleton is 400, and the more preferable upper limit is 700.
  • the compound having a carbazole skeleton preferably has an aromatic ring other than the aromatic ring contained in the carbazole skeleton from the viewpoint of solubility in the curable resin. Moreover, since the compound having the carbazole skeleton is more excellent in light-shielding part curability, it preferably has a nitrogen atom other than the nitrogen atom contained in the carbazole skeleton, and more preferably has an oxime ester bond.
  • the compound having the carbazole skeleton preferably has an absorption coefficient of 50 mL / g ⁇ cm or more at a wavelength of 365 nm measured in acetonitrile mixed with the compound having the carbazole skeleton so that the concentration becomes 0.1 mg / mL.
  • the compound having the carbazole skeleton has an extinction coefficient of 50 mL / g ⁇ cm or more, the obtained sealing agent for liquid crystal display elements is more excellent in light-shielding part curability.
  • the light absorption coefficient of the compound having a carbazole skeleton is more preferably 100 mL / g ⁇ cm or more. Further, there is no particular upper limit of the light absorption coefficient of the compound having a carbazole skeleton, but the substantial upper limit is 1000 mL / g ⁇ cm.
  • the compound having the carbazole skeleton include, for example, O-acetyl-1- (6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl) ethanone oxime, 3,6 -Bis- (2methyl-2morpholino-propionyl) -9-N-octylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-benzoylcarbazole, 3,6-bis (2-methyl) -2-morpholinopropionyl) -9-n-butylcarbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 2- (Nn-butyl-3′-carbazolyl) ) -4,6-bis (trichloromethyl) -s-triazine and the like.
  • Examples of commercially available compounds having the carbazole skeleton include IRGACURE OXE02 (manufactured by BASF).
  • the content of the compound having a carbazole skeleton is preferably 0.5 parts by weight and preferably 10 parts by weight with respect to 100 parts by weight of the curable resin.
  • the content of the compound having the carbazole skeleton is within this range, the obtained sealing agent for liquid crystal display elements is excellent in light-shielding part curability, weather resistance, storage stability, and the effect of suppressing liquid crystal contamination.
  • the more preferable lower limit of the content of the compound having a carbazole skeleton is 1 part by weight, and the more preferable upper limit is 3 parts by weight.
  • the sealing agent for liquid crystal display elements of the present invention may contain other photoradical polymerization initiator as the photoradical polymerization initiator in addition to the compound having the carbazole skeleton, but the light-shielding part curability and the liquid crystal From the viewpoint of achieving both the effect of suppressing contamination, it is preferable that no other radical photopolymerization initiator is contained.
  • the sealing agent for liquid crystal display elements of the present invention may contain a sensitizer.
  • the sealing agent for liquid crystal display elements of this invention can obtain the sealing agent for liquid crystal display elements which is more sensitive and is excellent in light-shielding part curability by containing the said sensitizer.
  • the sensitizer preferably has a sufficient light absorption band in the ultraviolet / visible region, a compound having a benzophenone skeleton, a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, a compound having a coumarin skeleton, a thioxanthone skeleton And at least one compound selected from the group consisting of compounds having a phthalocyanine skeleton, and a group consisting of a compound having an anthracene skeleton, a compound having an anthraquinone skeleton, and a compound having a thioxanthone skeleton More preferably, it is at least one compound selected.
  • Examples of the compound having a benzophenone skeleton include benzophenone, 2,4-dichlorobenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like.
  • Examples of the compound having an anthracene skeleton include 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, and 9,10-dibutoxyanthracene.
  • Examples of the compound having an anthraquinone skeleton include 1-methylanthraquinone, 2-ethylanthraquinone, 1,4-dihydroxyanthraquinone, 2- (2-hydroxyethoxy) anthraquinone and the like.
  • Examples of the compound having a coumarin skeleton include 7-diethylamino-4-methylcoumarin.
  • Examples of the compound having a thioxanthone skeleton include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propylthioxanthone, and the like.
  • Examples of the compound having a phthalocyanine skeleton include phthalocyanine.
  • phthalocyanine examples include phthalocyanine.
  • 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis ( At least one of diethylamino) benzophenone is preferred.
  • the content of the sensitizer is such that a preferred lower limit is 2 parts by weight and a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator.
  • a preferred lower limit is 2 parts by weight
  • a preferred upper limit is 50 parts by weight with respect to 100 parts by weight of the radical photopolymerization initiator.
  • the content of the sensitizer is within this range, the obtained sealing agent for a liquid crystal display element is more excellent in light-shielding part curability while suppressing liquid crystal contamination.
  • the minimum with more preferable content of the said sensitizer is 5 weight part, and a more preferable upper limit is 40 weight part.
  • the sealing agent for liquid crystal display elements of the present invention may contain a thermal radical polymerization initiator.
  • 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 compound means a compound having an azo group and generating a radical 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 a polymer 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 thermal 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 thermal 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 thermosetting agent.
  • thermosetting agent 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 the viscosity, improving the adhesion due to the stress dispersion effect, improving the linear expansion coefficient, and further improving the moisture resistance of the cured product. 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.
  • 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 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.
  • the light-shielding agent examples include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. Of these, titanium black is preferred because of its high insulating properties.
  • 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 light-shielding agent is not particularly limited as long as it is not more than the distance between the substrates of the liquid crystal display element, but the preferred lower limit is 1 nm and the preferred upper limit is 5 ⁇ m. When the primary particle diameter of the light-shielding agent is within this range, the light-shielding property can be improved without deteriorating the applicability of the obtained sealing agent for liquid crystal display elements.
  • 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.
  • 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, or a three roll, a curable resin, a light
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three roll, a curable resin, a light
  • 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, or a three roll, a curable resin,
  • 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.
  • Examples of the method include a step of combining, and a step of irradiating light such as ultraviolet rays to the seal pattern portion of the sealant for liquid crystal display element of the present invention to photocur the sealant.
  • a step of heating and thermosetting the sealant may be performed.
  • the sealing compound for liquid crystal display elements which is excellent in light-shielding part curability 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 9, 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. Sealants for liquid crystal display elements of Examples 1 to 9 and Comparative Examples 1 to 5 were prepared.
  • the obtained sealant is applied to the central part of the substrate A (boundary between the chromium vapor deposition part and the non-deposition part), and after the substrate B is bonded, the sealant is sufficiently applied.
  • 100 mW / cm 2 ultraviolet rays were irradiated from the substrate A side using a metal halide lamp for 30 seconds.
  • the substrates A and B are peeled off using a cutter, and the spectrum is measured by a microscopic IR method for the sealant on a point 50 ⁇ m away from the direct ultraviolet irradiation part (the part shielded from light by chromium vapor deposition).
  • the conversion rate of the inside (meth) acryloyl group was calculated
  • the conversion rate was 90% or more, “ ⁇ ”, 70% or more, but less than 90%, “ ⁇ ”, 50% or more, less than 70%, “ ⁇ ”, less than 50%.
  • the curability of the light-shielding part was evaluated with “ ⁇ ” as the sample.
  • 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 light-shielding part curability 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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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention a pour objet de fournir un agent de scellement pour élément d'affichage à cristaux liquides qui présente d'excellentes propriétés de durcissement de partie écran à la lumière, et qui permet d'empêcher une contamination de cristaux liquides. L'invention a également pour objet de fournir un élément d'affichage à cristaux liquides et un matériau à conduction verticale mettant en œuvre cet agent de scellement pour élément d'affichage à cristaux liquides. L'agent de scellement pour élément d'affichage à cristaux liquides comprend une résine durcissable et un initiateur de polymérisation par voie photoradicalaire. Ladite résine durcissable comprend un composé dont la masse moléculaire est supérieure ou égale à 100 et inférieure à 500, et un composé dont la masse moléculaire est comprise entre 500 et 3000. Ledit initiateur de polymérisation par voie photoradicalaire consiste en un composé possédant un squelette de carbazole.
PCT/JP2017/001347 2016-01-26 2017-01-17 Agent de scellement pour élément d'affichage à cristaux liquides, matériau à conduction verticale, et élément d'affichage à cristaux liquides WO2017130786A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020177033055A KR20180101166A (ko) 2016-01-26 2017-01-17 액정 표시 소자용 시일제, 상하 도통 재료, 및, 액정 표시 소자
JP2017503643A JP7048314B2 (ja) 2016-01-26 2017-01-17 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
CN201780001988.5A CN107710060B (zh) 2016-01-26 2017-01-17 液晶显示元件用密封剂、上下导通材料及液晶显示元件

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JP2016-012749 2016-01-26
JP2016012749 2016-01-26

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WO2017130786A1 true WO2017130786A1 (fr) 2017-08-03

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JP (1) JP7048314B2 (fr)
KR (1) KR20180101166A (fr)
CN (1) CN107710060B (fr)
TW (1) TWI714709B (fr)
WO (1) WO2017130786A1 (fr)

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JPWO2017130786A1 (ja) 2018-11-15
CN107710060B (zh) 2021-11-12
TWI714709B (zh) 2021-01-01
CN107710060A (zh) 2018-02-16
JP7048314B2 (ja) 2022-04-05
TW201739831A (zh) 2017-11-16
KR20180101166A (ko) 2018-09-12

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