WO2018062164A1 - Agent d'étanchéité pour écran à cristaux liquides, matériau à conduction verticale et écran à cristaux liquides - Google Patents

Agent d'étanchéité pour écran à cristaux liquides, matériau à conduction verticale et écran à cristaux liquides Download PDF

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Publication number
WO2018062164A1
WO2018062164A1 PCT/JP2017/034711 JP2017034711W WO2018062164A1 WO 2018062164 A1 WO2018062164 A1 WO 2018062164A1 JP 2017034711 W JP2017034711 W JP 2017034711W WO 2018062164 A1 WO2018062164 A1 WO 2018062164A1
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Prior art keywords
meth
liquid crystal
acrylate
crystal display
compound
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PCT/JP2017/034711
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English (en)
Japanese (ja)
Inventor
慶枝 松井
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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 CN201780014067.2A priority Critical patent/CN108780247A/zh
Priority to JP2017553431A priority patent/JP7007196B2/ja
Priority to KR1020187025323A priority patent/KR102466030B1/ko
Publication of WO2018062164A1 publication Critical patent/WO2018062164A1/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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • 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 curability and stability under reduced pressure. 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 photothermal combined curing type seal as disclosed in Patent Document 1 and Patent Document 2 is used from the viewpoint of shortening tact time and optimizing the amount of liquid crystal used.
  • a liquid crystal dropping method called a dropping method using an agent is used. In the dropping method, first, a rectangular seal pattern is formed on one of two transparent substrates with electrodes by dispensing. Next, 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. .
  • the position of the seal portion is arranged under the black matrix (hereinafter also referred to as a narrow frame design).
  • the sealant is placed directly under the black matrix, so when the dripping method is used, the light irradiated when photocuring the sealant is blocked, and the light does not reach the inside of the sealant. There was a problem that the curing was insufficient. If the sealant is insufficiently cured in this manner, the uncured sealant component is eluted in the liquid crystal, and the curing reaction by the eluted sealant component proceeds in the liquid crystal, resulting in liquid crystal contamination. there were.
  • An object of this invention is to provide the sealing compound for liquid crystal display elements which is excellent in sclerosis
  • hardenability and stability under reduced pressure. 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 contains a curable resin, a maleimide compound, and a radical polymerization initiator, the curable resin contains a compound having a molecular weight of 500 to 1500, and the molecular weight in 100 parts by weight of the curable resin is 500.
  • This inventor examined improving the stability of the sealing agent under reduced pressure by using a compound having a specific range of molecular weight as the curable resin used for the sealing agent.
  • the obtained sealing agent is excellent in stability under reduced pressure, there is a problem that it is inferior in reactivity (curability).
  • the content of the compound having a molecular weight in the specific range or the content of the polymerization initiator is adjusted, it is difficult to achieve both curability and stability under reduced pressure. Therefore, as a result of further intensive studies, the present inventors have determined that the content of the compound having the molecular weight in the specific range is a specific ratio, and that the maleimide compound is used in addition to the curable resin, so that the curability and the pressure can be reduced. It has been found that a sealing agent for liquid crystal display elements that can achieve both stability and stability can be obtained, and the present invention has been completed.
  • 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 500 to 1500.
  • the sealing agent for liquid crystal display elements of the present invention is excellent in stability under reduced pressure.
  • the preferable lower limit of the molecular weight of the compound having a molecular weight of 500 to 1500 is 600, the preferable upper limit is 1300, the more preferable lower limit is 700, and the more preferable upper limit is 1000.
  • 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). Further, as will be described later, in the present invention, the maleimide compound is not included in the curable resin.
  • the curable resin preferably contains a (meth) acrylic compound having a molecular weight of 500 to 1500 as the compound having a molecular weight of 500 to 1500.
  • the (meth) acrylic compound having a molecular weight of 500 to 1500 is preferably an epoxy (meth) acrylate having a molecular weight of 500 to 1500 obtained by reacting (meth) acrylic acid with an epoxy compound.
  • the (meth) acrylic compound having a molecular weight of 500 to 1500 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.
  • the (meth) acrylic compound having a molecular weight of 500 to 1500 include, for example, phenol novolac type epoxy (meth) acrylate, orthocresol novolac type epoxy (meth) acrylate, and dicyclopentadiene novolac type epoxy (meth) acrylate.
  • the preferable lower limit of the content of the compound having a molecular weight of 500 to 1500 in 100 parts by weight of the curable resin is 10 parts by weight, and the preferable upper limit is 50 parts by weight.
  • the content of the compound having a molecular weight of 500 to 1500 is within this range, the obtained sealing agent for liquid crystal display elements has an excellent effect of achieving both curability and stability under reduced pressure.
  • a more preferable lower limit of the content of the compound having a molecular weight of 500 to 1500 is 20 parts by weight, and a more preferable upper limit is 30 parts by weight.
  • the curable resin contains other curable resins in addition to the compound having a molecular weight of 500 to 1500.
  • the other curable resin is preferably a compound having a molecular weight of less than 500.
  • Examples of the compound having a molecular weight of less than 500 include (meth) acrylic compounds having a molecular weight of less than 500, epoxy compounds having a molecular weight of less than 500, and the like.
  • Examples of the (meth) acrylic compound having a molecular weight of less than 500 include, for example, a (meth) acrylic acid ester compound having a molecular weight of less than 500, an epoxy (meth) acrylate having a molecular weight of less than 500, and a urethane (meth) acrylate having a molecular weight of less than 500. Etc. Of these, epoxy (meth) acrylate having a molecular weight of less than 500 is preferred.
  • the (meth) acrylic compound having a molecular weight of less than 500 preferably has two or more (meth) acryloyl groups in one molecule because of its high reactivity.
  • Examples of monofunctional compounds among the (meth) acrylic acid ester compounds having a molecular weight of less than 500 include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl ( (Meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl
  • Examples of the bifunctional one of the (meth) acrylic acid ester compounds having a molecular weight of less than 500 include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate Tetraethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Neopentyl glycol di (meta Acrylate, dimethylol dicyclopent
  • those having three or more functions include, for example, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, glycerin tri ( And (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, pentaerythritol tetra (meth) acrylate, and the like.
  • Examples of the epoxy (meth) acrylate having a molecular weight of less than 500 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 an epoxy (meth) acrylate having a molecular weight of less than 500 include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol E diglycidyl ether, and hydrogenated bisphenol A diglycidyl.
  • the urethane (meth) acrylate having a molecular weight of less than 500 is, for example, 2 equivalents of a (meth) acrylic acid derivative having a hydroxyl group with respect to 1 equivalent of an isocyanate compound having two isocyanate groups in the presence of a catalytic amount of a tin-based compound. It can be obtained by reacting.
  • isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4′-diisocyanate (MDI), hydrogenated Examples include MDI, 1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, tetramethylxylylene diisocyanate, and the like.
  • MDI isophorone diisocyanate
  • 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate
  • hexamethylene diisocyanate trimethylhexamethylene diisocyanate
  • Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl (meth) acrylate and mono (meth) acrylate of a divalent alcohol.
  • Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. It is done.
  • Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and the like.
  • the epoxy compound having a molecular weight of less than 500 examples include an epoxy compound used as a raw material for synthesizing an epoxy (meth) acrylate having a molecular weight of less than 500, a partial (meth) acryl-modified epoxy resin having a molecular weight of less than 500, and the like.
  • 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 groups. It can be obtained by reacting a part of the epoxy group of the epoxy compound having a methacrylic acid with (meth) acrylic acid.
  • the sealing agent for liquid crystal display elements of this invention contains a maleimide compound.
  • the sealing agent for liquid crystal display elements of the present invention has excellent curability.
  • the maleimide compound is not contained in either a curable resin or a radical polymerization initiator.
  • the maleimide compound is preferably a polyfunctional maleimide compound having two or more maleimide groups in one molecule from the viewpoint of reactivity.
  • a preferred lower limit of the molecular weight of the maleimide compound is 400.
  • the resulting sealant for a liquid crystal display element is more excellent in the effect of achieving both curability and stability under reduced pressure.
  • a more preferred lower limit of the molecular weight of the maleimide compound is 500.
  • the upper limit with preferable molecular weight of the said maleimide compound is 1500, and a more preferable upper limit is 1000.
  • maleimide compound a compound represented by the following formula (1) or a compound represented by the following formula (2) is preferably used.
  • R 1 represents an alkylene group having 2 to 3 carbon atoms, and n is an integer of 2 to 40.
  • R 2 represents a divalent aliphatic group having 1 to 40 carbon atoms.
  • R 2 preferably has 12 to 36 carbon atoms.
  • R 2 preferably has an aliphatic ring.
  • Specific examples of the compound represented by the above formula (2) include 1,20-bismaleimide-10,11-dioctyl-eicosane (compound represented by the following formula (3-1)), 1- Heptylenemaleimide-2-octylenemaleimide-4-octyl-5-heptylcyclohexane (compound represented by the following formula (3-2)), 1,2-dioctylenemaleimide-3-octyl-4-hexyl And cyclohexane (a compound represented by the following formula (3-3)). These compounds can be synthesized by the method described in US Pat. No. 5,973,166.
  • the minimum with preferable content of the said maleimide compound with respect to 100 weight part of said curable resins is 1 weight part, and a preferable upper limit is 10 weight part.
  • a preferable upper limit is 10 weight part.
  • the content of the maleimide compound is in this range, the obtained sealing agent for liquid crystal display elements is more excellent in the effect of achieving both curability and stability under reduced pressure.
  • a more preferred lower limit for the content of the maleimide compound is 3 parts by weight, and a more preferred upper limit is 8 parts by weight.
  • the sealing agent for liquid crystal display elements of the present invention contains a radical polymerization initiator.
  • a radical polymerization initiator a photo radical polymerization initiator or a thermal radical polymerization initiator can be used. Of these, a radical photopolymerization initiator is preferable. Further, as described above, in the present invention, the maleimide compound is not included in the radical polymerization initiator.
  • photo radical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthones, and the like. Of these, oxime ester compounds are preferred.
  • oxime ester compounds examples include 1- (4- (phenylthio) phenyl) -1,2-octanedione 2- (O-benzoyloxime), O-acetyl-1- (6- (2-methylbenzoyl) ) -9-ethyl-9H-carbazol-3-yl) ethanone oxime and the like.
  • Examples of commercially available photo radical polymerization initiators include IRGACURE OXE01, IRGACURE OXE02, IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE Benzo F2 Examples include ether, benzoin ethyl ether, and benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.).
  • thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
  • a polymer azo initiator composed of a polymer azo compound is preferable.
  • the “polymer azo compound” means a compound having an azo group and generating a radical capable of curing a (meth) acryloyloxy group by heat and having a number average molecular weight of 300 or more. means.
  • the preferable lower limit of the number average molecular weight of the polymer azo compound is 1000, and the preferable upper limit is 300,000.
  • the more preferable lower limit of the number average molecular weight of the polymer azo compound 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
  • Examples of the polymer azo compound include those having a structure in which a plurality of units such as polyalkylene oxide and polydimethylsiloxane are bonded via an azo group.
  • Examples of the polymer azo compound 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 compound include polycondensates of 4,4′-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4′-azobis (4-cyanopentanoic acid) and terminal. Examples thereof include polycondensates of polydimethylsiloxane having an amino group.
  • Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, and VPS-1001 (all manufactured by Wako Pure Chemical Industries, Ltd.).
  • Examples of the azo compound that is 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 radical polymerization initiator is preferably 0.1 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 radical polymerization initiator is within this range, the curability can be improved without deteriorating the storage stability of the obtained sealing agent for liquid crystal display elements.
  • the minimum with more preferable content of the said radical polymerization initiator is 0.5 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 flexible particles include silicone particles, vinyl particles, urethane particles, fluorine particles, and nitrile particles. Of these, silicone particles and vinyl particles are preferable.
  • a silicone rubber particle is preferable from a dispersible viewpoint to resin.
  • (Meth) acrylic particles are preferably used as the vinyl particles.
  • the (meth) acrylic particles can be obtained by polymerizing monomers as raw materials by a known method. Specifically, for example, a method in which a monomer is suspension-polymerized in the presence of a radical polymerization initiator, and a seed particle is swollen by absorbing the monomer into a non-crosslinked seed particle in the presence of a radical polymerization initiator. And a seed polymerization method.
  • Examples of the monomer that is a raw material for forming the (meth) acrylic particles include alkyl (meth) acrylates, oxygen atom-containing (meth) acrylates, nitrile-containing monomers, and fluorine-containing (meth) acrylates. Monofunctional monomers such as the like.
  • alkyl (meth) acrylates examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • oxygen atom-containing (meth) acrylates examples include 2-hydroxyethyl (meth) acrylate, glycerol (meth) acrylate, polyoxyethylene (meth) acrylate, glycidyl (meth) acrylate, and the like.
  • nitrile-containing monomer examples include (meth) acrylonitrile. Examples thereof include trifluoromethyl (meth) acrylate and pentafluoroethyl (meth) acrylate.
  • alkyl (meth) acrylates are preferable because the Tg of the homopolymer is low and the deformation amount when a 1 g load is applied can be increased.
  • tetramethylol methane tetra (meth) acrylate tetramethylol methane tri (meth) acrylate, tetramethylol methane di (meth) acrylate, trimethylol propane tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, glycerol tri (meth) acrylate, glycerol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, ( Poly) tetramethylene di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, isocyanuric acid
  • the preferable lower limit is 1% by weight and the preferable upper limit is 90% by weight in the whole monomer as a raw material for forming the (meth) acrylic particles.
  • the amount of the crosslinkable monomer used is 1% by weight or more, the solvent resistance is improved, and when kneaded with various sealant raw materials, problems such as swelling do not occur and the particles are easily dispersed uniformly.
  • the amount of the crosslinkable monomer used is 90% by weight or less, the recovery rate can be lowered.
  • a more preferable lower limit of the amount of the crosslinkable monomer used is 3% by weight, and a more preferable upper limit is 80% by weight.
  • styrene monomers In addition to these acrylic monomers, styrene monomers, vinyl ethers, carboxylic acid vinyl esters, unsaturated hydrocarbons, halogen-containing monomers, triallyl cyanurate, triallyl isocyanurate, Monomers such as triallyl trimellitate, divinylbenzene, diallyl phthalate, diallylacrylamide, diallyl ether, ⁇ - (meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane may be used.
  • the styrene monomer include styrene, ⁇ -methylstyrene, trimethoxysilylstyrene, and the like.
  • Examples of the vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, and the like.
  • Examples of the carboxylic acid vinyl esters include vinyl acetate, vinyl butyrate, vinyl laurate, and vinyl stearate.
  • Examples of the unsaturated hydrocarbon include ethylene, propylene, isoprene, butadiene and the like.
  • Examples of the halogen-containing monomer include vinyl chloride, vinyl fluoride, chlorostyrene, and the like.
  • core-shell (meth) acrylate copolymer fine particles are also preferably used.
  • core-shell (meth) acrylate copolymer fine particles include F351 (manufactured by Zeon Kasei Co., Ltd.).
  • vinyl particles for example, polydivinylbenzene particles, polychloroprene particles, butadiene rubber particles and the like may be used.
  • the preferable lower limit of the average particle diameter of the flexible particles is 0.01 ⁇ m, and the preferable upper limit is 10 ⁇ m.
  • the more preferable lower limit of the average particle diameter of the flexible particles is 0.1 ⁇ m, and the more preferable upper limit is 8 ⁇ m.
  • the average particle diameter of the said flexible particle means the value obtained by measuring using the laser diffraction type particle size distribution measuring apparatus about the particle
  • the laser diffraction particle size distribution measuring device Mastersizer 2000 (manufactured by Malvern) or the like can be used.
  • the preferable lower limit of the hardness of the flexible particles is 10, and the preferable upper limit is 50.
  • the more preferable lower limit of the hardness of the soft particles is 20, and the more preferable upper limit is 40.
  • the hardness of the said flexible particle means the durometer A hardness measured by the method based on JISK6253.
  • the preferable lower limit of the content of the flexible particles in 100 parts by weight of the sealing agent for liquid crystal display elements of the present invention is 5 parts by weight, and the preferable upper limit is 50 parts by weight.
  • grain is 10 weight part, and a more preferable upper limit is 30 weight part.
  • the sealing agent for liquid crystal display elements of the present invention preferably contains a filler for the purpose of improving the viscosity, improving the adhesiveness due to the stress dispersion effect, improving the linear expansion coefficient, and the like.
  • Examples of the filler include inorganic fillers and organic fillers other than those contained in the flexible particles.
  • Examples of the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous earth, smectite, bentonite, montmorillonite, sericite, activated clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, and titanium oxide.
  • 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 for example, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like are preferably used. These are excellent in the effect of improving the adhesion to a substrate or the like, and can suppress the outflow of the curable resin into the liquid crystal by chemically bonding with the curable resin.
  • 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 titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black.
  • the iron oxide, titanium oxide, etc. which were mentioned as said inorganic filler can also be used as said light-shielding agent.
  • 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 a sufficient light-shielding property, and thus 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 lowering 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 further contains additives such as a reactive diluent, a thixotropic agent, a spacer, a curing accelerator, an antifoaming agent, a leveling agent, and a polymerization inhibitor, if necessary. May be.
  • Examples of the method for producing the sealing agent for liquid crystal display elements of the present invention include a curable resin and a maleimide using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
  • a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
  • the method etc. which mix a compound, a radical polymerization initiator, the silane coupling agent etc. which are added as needed are mentioned.
  • 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 as a method for producing the liquid crystal display element of the present invention.
  • a method having the following steps First, the sealant for liquid crystal display element of the present invention is applied to one of two substrates such as a glass substrate with an electrode such as an ITO thin film or a polyethylene terephthalate substrate by screen printing, dispenser application, etc. A step of forming a pattern is performed. Next, in a state where the sealant for a liquid crystal display element of the present invention is uncured, a step of applying droplets of liquid crystals into the frame of the seal pattern of the substrate and superimposing another substrate under vacuum is performed.
  • a liquid crystal display element can be obtained by the method of irradiating light, such as an ultraviolet-ray, to the seal pattern part of the sealing agent for liquid crystal display elements of this invention, and photocuring a sealing agent.
  • a step of heating and thermosetting the sealant may be performed.
  • the sealing compound for liquid crystal display elements which is excellent in sclerosis
  • 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 and Comparative Examples 1 to 6 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 6 were prepared. Note that dimaleimide acetate of polytetramethylene ether glycol (manufactured by DIC, “LUMICURE MIA200”) described in the table as a maleimide compound is a compound represented by the above formula (1).
  • the sealing compound for liquid crystal display elements which is excellent in sclerosis
  • 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)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Sealing Material Composition (AREA)
  • Liquid Crystal (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Un objectif de la présente invention est de produire un agent d'étanchéité pour un écran à cristaux liquides qui présente une excellente aptitude au durcissement et est extrêmement sûr sous pression réduite. De plus, la présente invention a pour autre objectif de produire un matériau à conduction verticale et un écran à cristaux liquides en utilisant l'agent d'étanchéité destiné à un écran à cristaux liquides. La présente invention concerne un agent d'étanchéité destiné à un écran à cristaux liquides, l'agent d'étanchéité contenant une résine durcissable, un composé maléimide, et un amorceur de polymérisation radicalaire, la résine durcissable contenant un composé ayant un poids moléculaire de 500 à 1500, et la teneur du composé ayant un poids moléculaire de 500 à 1500 est de 10 à 50 parties en poids sur la base de 100 parties en poids de la résine durcissable.
PCT/JP2017/034711 2016-09-29 2017-09-26 Agent d'étanchéité pour écran à cristaux liquides, matériau à conduction verticale et écran à cristaux liquides WO2018062164A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201780014067.2A CN108780247A (zh) 2016-09-29 2017-09-26 液晶显示元件用密封剂、上下导通材料和液晶显示元件
JP2017553431A JP7007196B2 (ja) 2016-09-29 2017-09-26 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
KR1020187025323A KR102466030B1 (ko) 2016-09-29 2017-09-26 액정 표시 소자용 시일제, 상하 도통 재료, 및 액정 표시 소자

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JP2016-191492 2016-09-29
JP2016191492 2016-09-29

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JP2010020286A (ja) * 2008-06-13 2010-01-28 Henkel Corp 液晶滴下工法用シール剤および液晶表示装置の製造方法
WO2015123824A1 (fr) * 2014-02-19 2015-08-27 Ablestik (Shanghai) Ltd. Composition de resine durcissable pour sceller un cristal liquide

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KR20190058378A (ko) 2019-05-29
JPWO2018062164A1 (ja) 2019-07-11
JP7007196B2 (ja) 2022-01-24
KR102466030B1 (ko) 2022-11-10
TWI731173B (zh) 2021-06-21
CN108780247A (zh) 2018-11-09
TW201819530A (zh) 2018-06-01

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