Classifications

• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
• • 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
• • 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 display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment.
• the present invention also relates to a vertically conductive material and a display element using the sealant for the display element.
• liquid crystal display elements organic EL display elements, and the like have been widely used as display elements having features such as thinness, light weight, and low power consumption.
• the liquid crystal display, the light emitting layer, and the like are usually sealed with a sealing agent made of a curable resin composition.
• a liquid crystal display element a liquid crystal display element using a photothermally curable sealant as disclosed in Patent Document 1 and Patent Document 2 from the viewpoint of shortening the tact time and optimizing the amount of liquid crystal used. It has been disclosed.
• the display element is also required to have high reliability in driving in a high temperature and high humidity environment, and to have performance corresponding to a pressure cooker test (PCT) under the conditions of 121 ° C., 100% RH, and 2 atm.
• PCT pressure cooker test
• the present invention contains a curable resin and a polymerization initiator and / or a thermosetting agent, and the curable resin does not have (A) an epoxy group and has three (meth) acryloyl groups in one molecule.
• a sealant for a display element containing at least one selected from the group consisting of compounds having a total of three or more groups. The present invention will be described in detail below.
• the present inventor confirmed a display element that had a display defect when driven in a PCT (121 ° C., 100% RH, 2 atm) environment. It was confirmed that the peeling had occurred. Therefore, the present inventor has studied the use of a (meth) acrylic compound having a specific number of functional groups or more and an epoxy compound in combination as a curable resin. As a result, the obtained sealant for a display element can suppress the infiltration of moisture and the peeling of the substrate due to the generation of air bubbles, and can obtain a display element having excellent reliability in a high temperature and high humidity environment. It was found that this was the case, and the present invention was completed.
• the effect of being able to obtain a display element having excellent reliability in a high temperature and high humidity environment in the sealant for a display element of the present invention is when the sealant for a display element of the present invention is used as a sealant for a liquid crystal display element ( In particular, it is remarkably exhibited when it is applied on an alignment film formed of polyimide or the like as a sealing agent for a liquid crystal dropping method.
• the sealant for a display element of the present invention contains a curable resin.
• the curable resin has (A) a compound having no epoxy group and having three or more (meth) acryloyl groups in one molecule (hereinafter, also referred to as "(meth) acrylic compound (A) according to the present invention”. )including. Further, the curable resin does not have a (B-1) (meth) acryloyl group, but has a compound having three or more epoxy groups in one molecule and (B-2) a (meth) acryloyl group in one molecule. And at least one selected from the group consisting of compounds having a total of 3 or more epoxy groups.
• epoxy compound (B-1) a compound having no (B-1) (meth) acryloyl group and having three or more epoxy groups in one molecule
• epoxy compound (B-2) A compound having a total of three or more (meth) acryloyl groups and epoxy groups in one molecule is also referred to as "epoxy compound (B-2) according to the present invention.
• the sealing agent for a display element of the present invention is a group consisting of the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention.
• the above-mentioned “(meth) acryloyl” means acryloyl or methacrylic acid
• the above-mentioned “(meth) acrylic” means acrylic or methacrylic acid.
• the above-mentioned “having a total of 3 or more (meth) acryloyl groups and epoxy groups in one molecule” contains (meth) acryloyl groups and epoxy groups in one molecule, respectively, and the total number is three. It means that it is the above.
• the (meth) acrylic compound (A) according to the present invention has three or more (meth) acryloyl groups in one molecule. Among them, from the viewpoint of suppressing shrinkage due to curing, the (meth) acrylic compound (A) according to the present invention preferably has 3 or more and 6 or less (meth) acryloyl groups in one molecule.
• the preferred lower limit of the molecular weight of the (meth) acrylic compound (A) according to the present invention is 100, and the preferred upper limit is 5000.
• the molecular weight of the (meth) acrylic compound (A) according to the present invention is in this range, the obtained sealant for a display element is excellent in coatability and curability.
• the more preferable lower limit of the molecular weight of the (meth) acrylic compound (A) according to the present invention is 200, and the more preferable upper limit is 3000.
• the above-mentioned "molecular weight” is the molecular weight obtained from the structural formula for a compound whose molecular structure is specified, but for a compound having a wide distribution of degree of polymerization and a compound having an unspecified modification site. It may be expressed using the weight average molecular weight.
• the above-mentioned "weight average molecular weight” is a value obtained by measuring with THF as a solvent in gel permeation chromatography (GPC) and converting it into polystyrene. 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 KK) and the like.
• Examples of the (meth) acrylic compound (A) according to the present invention include isocyanuric acid tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, trimethylol propanetri (meth) acrylate, and ethylene oxide-added trimethyl propanetri.
• the epoxy compound (B-1) according to the present invention has three or more epoxy groups in one molecule. Among them, from the viewpoint of storage stability, the epoxy compound (B-1) according to the present invention preferably has 3 or more and 10 or less epoxy groups in one molecule.
• the preferable lower limit of the molecular weight of the epoxy compound (B-1) according to the present invention is 100, and the preferred upper limit is 5000.
• the molecular weight of the epoxy compound (B-1) according to the present invention is in this range, the obtained sealant for a display element is excellent in coatability and curability.
• the more preferable lower limit of the molecular weight of the epoxy compound (B-1) according to the present invention is 200, and the more preferable upper limit is 3000.
• Examples of the epoxy compound (B-1) according to the present invention include trimethylolpropane triglycidyl ether, ethylene oxide-added trimethylol propanetriglycidyl ether, propylene oxide-added trimethylol propanetriglycidyl ether, and caprolactone-modified trimethylol propanetriglycidyl ether.
• Glycerin triglycidyl ether propylene oxide-added glycerin triglycidyl ether, pentaerythritol triglycidyl ether, ditrimethylol propanetetraglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol pentaglycidyl ether, dipentaerythritol hexaglycidyl ether, phenol novolac type Examples thereof include an epoxy compound, an orthocresol novolak type epoxy compound, a dicyclopentadiene novolak type epoxy compound, and a biphenyl novolak type epoxy compound.
• the epoxy compound (B-2) according to the present invention has a total of three or more (meth) acryloyl groups and epoxy groups in one molecule.
• the epoxy compound (B-2) according to the present invention has a total of 3 or more and 10 or less (meth) acryloyl groups and epoxy groups in one molecule. Is preferable.
• the preferable lower limit of the molecular weight of the epoxy compound (B-2) according to the present invention is 100, and the preferred upper limit is 5000.
• the molecular weight of the epoxy compound (B-2) according to the present invention is in this range, the obtained sealant for a display element is excellent in coatability and curability.
• the more preferable lower limit of the molecular weight of the epoxy compound (B-2) according to the present invention is 200, and the more preferable upper limit is 3000.
• Examples of the epoxy compound (B-2) according to the present invention include a compound obtained by reacting a part of the epoxy group of the epoxy compound (B-1) according to the present invention described above with (meth) acrylic acid. Can be mentioned.
• the curable resin contains both the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention, the (meth) acrylic compound (A) according to the present invention and the present invention.
• the preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention in the total of the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention is 20% by weight.
• the preferred upper limit is 80% by weight.
• the content ratio of the (meth) acrylic compound (A) according to the present invention is 80% by weight or less, the obtained sealing agent for a display element becomes more excellent in substrate adhesiveness.
• the more preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention is 30% by weight, and the more preferable upper limit is 70% by weight.
• the curable resin contains only the epoxy compound (B-1) according to the present invention among the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention, the present invention.
• the preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention in the total of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-1) according to the present invention is 20% by weight.
• the preferred upper limit is 80% by weight.
• the content ratio of the (meth) acrylic compound (A) according to the present invention is 80% by weight or less, the obtained sealing agent for a display element becomes more excellent in substrate adhesiveness.
• the more preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention is 30% by weight, and the more preferable upper limit is 70% by weight.
• the curable resin contains only the epoxy compound (B-2) according to the present invention among the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention, the present invention.
• the preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention in the total of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-2) according to the present invention is 20% by weight.
• the preferred upper limit is 80% by weight.
• the content ratio of the (meth) acrylic compound (A) according to the present invention is 80% by weight or less, the obtained sealing agent for a display element becomes more excellent in substrate adhesiveness.
• the more preferable lower limit of the content ratio of the (meth) acrylic compound (A) according to the present invention is 30% by weight, and the more preferable upper limit is 70% by weight.
• the curable resin is curable other than the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention. It is preferable to contain a resin. When the curable resin contains both the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention, the curable resin is contained.
• a preferable lower limit of the total content of the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention in the resin Is 5% by weight, and the preferable upper limit is 60% by weight.
• the total content of the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention is 5% by weight or more. Therefore, the obtained sealant for a display element is more excellent in the effect of suppressing the invasion of air bubbles and the peeling of the substrate.
• the total content of the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention is 60% by weight or less. As a result, the obtained sealant for the display element becomes more excellent in the adhesiveness of the cured product.
• a more preferable lower limit of the total content of the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the epoxy compound (B-2) according to the present invention is 15 weight. %, A more preferred upper limit is 50% by weight.
• the above-mentioned curable resin is the epoxy compound according to the present invention among the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention.
• the preferable lower limit of the total content ratio of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-1) according to the present invention in the curable resin is 5% by weight
• the preferred upper limit is 60% by weight.
• the obtained sealing agent for a display element is a cured product.
• the flexibility is better.
• a more preferable lower limit of the total content ratio of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-1) according to the present invention is 15% by weight, and a more preferable upper limit is 50% by weight.
• the above-mentioned curable resin is the epoxy compound according to the present invention among the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention.
• the preferable lower limit of the total content ratio of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-2) according to the present invention in the curable resin is 5% by weight, the preferred upper limit is 60% by weight.
• the total content of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-2) according to the present invention is 5% by weight or more, the obtained sealing agent for a display element invades bubbles.
• the obtained sealing agent for a display element is a cured product.
• the flexibility is better.
• a more preferable lower limit of the total content ratio of the (meth) acrylic compound (A) according to the present invention and the epoxy compound (B-2) according to the present invention is 15% by weight, and a more preferable upper limit is 50% by weight.
• Examples of the other curable resin include other (meth) acrylic compounds other than the (meth) acrylic compound (A) according to the present invention, the epoxy compound (B-1) according to the present invention, and the present invention. Examples thereof include other epoxy compounds other than the epoxy compound (B-2).
• Examples of the other (meth) acrylic compound include epoxy (meth) acrylate, (meth) acrylic acid ester compound, urethane (meth) acrylate, and the like, which have two or less (meth) acryloyl groups in one molecule. Things can be mentioned.
• epoxy (meth) acrylate which is the other (meth) acrylic compound
• an epoxy compound having two or less epoxy groups in one molecule and (meth) acrylic acid are reacted in the presence of a basic catalyst according to a conventional method. It can be obtained by letting it.
• Examples of the epoxy compound having two or less epoxy groups in one molecule include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2'-diallyl bisphenol A type epoxy compound, and water.
• the epoxy compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds and the like, those having two or less epoxy groups in one molecule can be mentioned.
• monofunctional ones include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.
• bifunctional ones include, for example, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di.
• Methyloldicyclopentadienyldi (meth) acrylate ethylene oxide-modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonatediol di (meth) acrylate, polyether Examples thereof include diol di (meth) acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, and polybutadiene diol di (meth) acrylate.
• the urethane (meth) acrylate can be obtained, for example, by reacting a (meth) acrylic acid derivative having a hydroxyl group with respect to a bifunctional isocyanate compound in the presence of a catalytic amount of a tin-based compound.
• bifunctional isocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), and the like.
• MDI diphenylmethane-4,4'-diisocyanate
• examples thereof include hydrogenated MDI, polypeptide MDI, 1,5-naphthalenediocyanate, norbornan diisocyanate, trizine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, and lysine diisocyanate.
• bifunctional isocyanate compound a chain-extended bifunctional isocyanate compound obtained by reacting a polyol with an excess bifunctional isocyanate compound can also be used.
• the polyol include ethylene glycol, propylene glycol, glycerin, sorbitol, trimethylolpropane, carbonate diol, polyether diol, polyester diol, and polycaprolactone diol.
• Examples of the (meth) acrylic acid derivative having a hydroxyl group include hydroxyalkyl mono (meth) acrylates and mono (meth) acrylates of divalent alcohols.
• Examples of the hydroxyalkyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
• Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol and the like.
• Examples of the above-mentioned other epoxy compounds include the above-mentioned epoxy compounds having two or less epoxy groups in one molecule.
• examples of the other curable resin include compounds having one (meth) acryloyl group and one epoxy group in one molecule.
• the compound having one (meth) acryloyl group and one epoxy group in one molecule for example, one epoxy group of an epoxy compound having two epoxy groups in one molecule is (meth).
• examples thereof include a partial (meth) acrylic-modified epoxy compound obtained by reacting with acrylic acid.
• the sealant for a display element of the present invention contains a polymerization initiator and / or a thermosetting agent.
• the polymerization initiator include radical polymerization initiators, cationic polymerization initiators and the like.
• radical polymerization initiator examples include a photoradical polymerization initiator that generates radicals by light irradiation, a thermal radical polymerization initiator that generates radicals by heating, and the like.
• photoradical polymerization initiator examples include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanosen compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds and the like.
• Specific examples of the photoradical polymerization initiator include 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, and 2- (dimethylamino).
• thermal radical polymerization initiator examples include those composed of an azo compound, an organic peroxide and the like. Of these, a polymer azo initiator composed of a polymer azo compound is preferable.
• the polymer azo compound means a compound having an azo group and having a number average molecular weight of 300 or more, which generates a radical capable of curing the (meth) acryloyloxy group by heat.
• 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 number average molecular weight of the polymer azo compound is in this range, it can be easily mixed with the curable resin, and when the obtained sealant for a display element is used for a liquid crystal display element, it has an adverse effect on the liquid crystal display. Can be prevented.
• 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 further preferable lower limit is 10,000, and the further preferable upper limit is 90,000.
• the number average molecular weight is a value obtained by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converting it into polystyrene.
• GPC gel permeation chromatography
• Examples of the column for measuring the number average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK) and the like.
• 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.
• 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.
• Specific examples of the polymer azo compound include a polycondensate of 4,4'-azobis (4-cyanopentanoic acid) and polyalkylene glycol, and 4,4'-azobis (4-cyanopentanoic acid). And a polycondensate of polydimethylsiloxane having a terminal amino group and the like.
• Examples of commercially available polymer azo compounds include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and the like. Be done.
• Examples of commercially available azo compounds that are not polymers include V-65 and V-501 (both manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• organic peroxide examples include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates and the like.
• a photocationic polymerization initiator can be preferably used as the cationic polymerization initiator.
• the photocationic polymerization initiator is not particularly limited as long as it generates protonic acid or Lewis acid by light irradiation, and may be an ionic photoacid generation type or a nonionic photoacid generation type. May be.
• Examples of the photocationic polymerization initiator include onium salts such as aromatic diazonium salt, aromatic halonium salt and aromatic sulfonium salt, and organic metal complexes such as iron-allene complex, titanosen complex and arylsilanol-aluminum complex. Can be mentioned.
• photocationic polymerization initiators examples include ADEKA PTOMER SP-150 and ADEKA PTOMER SP-170 (both manufactured by ADEKA).
• the above-mentioned polymerization initiator may be used alone or in combination of two or more.
• the content of the polymerization initiator has a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 30 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the polymerization initiator is 0.1 part by weight or more, the obtained sealant for a display element becomes more excellent in curability.
• the content of the polymerization initiator is 30 parts by weight or less, the obtained sealant for a display element becomes more excellent in storage stability.
• the more preferable lower limit of the content of the polymerization initiator is 1 part by weight, the more preferable upper limit is 10 parts by weight, and the further preferable upper limit is 5 parts by weight.
• heat-curing agent examples include organic acid hydrazide, imidazole derivative, amine compound, polyvalent phenolic compound, acid anhydride and the like. Of these, solid organic acid hydrazide is preferably used.
• the thermosetting agent may be used alone or in combination of two or more.
• Examples of the solid organic acid hydrazide include 1,3-bis (hydrazinocarboethyl) -5-isopropylhydrandine, sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, malonic acid dihydrazide and the like.
• Examples of commercially available organic acid hydrazides include organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd., organic acid hydrazides manufactured by Japan Finechem Co., Ltd., and organic acid hydrazides manufactured by Ajinomoto Fine Techno Co., Ltd.
• Examples of the organic acid hydrazide manufactured by Otsuka Chemical Co., Ltd. include SDH and ADH.
• Examples of the organic acid hydrazide manufactured by Japan Finechem Co., Ltd. include MDH and the like.
• Examples of the organic acid hydrazide manufactured by Ajinomoto Fine-Techno Co., Ltd. include Amicure VDH, Amicure VDH-J, and Amicure UDH.
• the content of the thermosetting agent is preferably 1 part by weight and a preferable upper limit of 50 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the thermosetting agent is 1 part by weight or more, the obtained sealant for a display element becomes more excellent in thermosetting property.
• the content of the thermosetting agent is 50 parts by weight or less, the obtained sealant for a display element is excellent in coatability and storage stability.
• a more preferable upper limit of the content of the thermosetting agent is 30 parts by weight.
• the sealant for a display element of the present invention preferably contains a filler for the purpose of adjusting the viscosity, improving the adhesiveness by the stress dispersion effect, improving the coefficient of linear expansion, improving the moisture resistance of the cured product, and the like.
• an inorganic filler or an organic filler can be used as the filler.
• the inorganic filler include silica, talc, glass beads, asbestos, gypsum, diatomaceous soil, smectite, bentonite, montmorillonite, sericite, active white clay, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide and titanium oxide. , Calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum nitride, silicon nitride, barium sulfate, calcium silicate and the like.
• the organic filler include polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and the like.
• the preferable lower limit of the content of the filler in 100 parts by weight of the sealant for a display element of the present invention is 10 parts by weight, and the preferable upper limit is 70 parts by weight.
• the more preferable lower limit of the content of the filler is 20 parts by weight, and the more preferable upper limit is 60 parts by weight.
• the sealing agent for a display element of the present invention preferably contains a silane coupling agent.
• the silane coupling agent mainly has a role as an adhesive auxiliary for satisfactorily adhering the sealant to the substrate or the like.
• silane coupling agent for example, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isoxapropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane and the like are preferably used. Be done. These silane coupling agents have an excellent effect of improving the adhesiveness with a substrate or the like, and when the obtained sealant for a display element is used for a liquid crystal display element, the outflow of the curable resin into the liquid crystal display is suppressed. Can be done.
• the silane coupling agent may be used alone or in combination of two or more.
• the preferable lower limit of the content of the silane coupling agent in 100 parts by weight of the sealant for a display element of the present invention is 0.1 parts by weight, and the preferable upper limit is 10 parts by weight.
• the content of the silane coupling agent is in this range, the obtained sealant for a display element becomes more excellent in adhesiveness, and when the obtained sealant for a display element is used for a liquid crystal display element, it is contaminated with liquid crystal. The occurrence can be suppressed.
• the more preferable lower limit of the content of the silane coupling agent is 0.3 parts by weight, and the more preferable upper limit is 5 parts by weight.
• the sealing agent for a display element of the present invention may contain the above-mentioned light-shielding agent.
• the sealant for a display element of the present invention can be suitably used as a light-shielding sealant.
• 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 preferable.
• the light-shielding agent may be used alone or in combination of two or more.
• the titanium black is a substance having a higher transmittance in the vicinity of the ultraviolet region, particularly for light having a wavelength of 370 nm or more and 450 nm or less, as compared with the average transmittance for light having a wavelength of 300 nm or more and 800 nm or less. That is, the titanium black has a property of imparting light-shielding property to the sealant for a display element of the present invention by sufficiently blocking light having a wavelength in the visible light region, while transmitting light having a wavelength in the vicinity of the ultraviolet region. It is a light-shielding agent.
• the light-shielding agent contained in the sealant for a display element of the present invention a substance having a high insulating property is preferable, and as a light-shielding agent having a high insulating property, titanium black is suitable.
• the above titanium black exerts 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, and oxidation.
• an organic component such as a coupling agent, silicon oxide, titanium oxide, germanium oxide, aluminum oxide, and oxidation.
• Surface-treated titanium black such as those coated with an inorganic component such as zirconium or magnesium oxide, can also be used. Among them, those treated with an organic component are preferable in that the insulating property can be further improved.
• the display element manufactured by using the sealant for a display element of the present invention containing the titanium black as a light-shielding agent has a sufficient light-shielding property, so that there is no light leakage and a high contrast is obtained, which is excellent. A display element having image display quality can be realized.
• Examples of commercially available titanium blacks include titanium black manufactured by Mitsubishi Materials Corporation and titanium black manufactured by Ako Kasei Co., Ltd. Examples of the titanium black manufactured by Mitsubishi Materials Corporation include 12S, 13M, 13M-C, 13RN, 14M-C and the like. Examples of the titanium black manufactured by Ako Kasei Co., Ltd. include Tyrac D and the like.
• 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 preferable lower limit of the volume resistance of the titanium black is 0.5 ⁇ ⁇ cm, the preferred upper limit is 3 ⁇ ⁇ cm, the more preferable lower limit is 1 ⁇ ⁇ cm, and the more preferable upper limit is 2.5 ⁇ ⁇ cm.
• the primary particle size of the light-shielding agent is not particularly limited as long as it is equal to or less than the distance between the substrates of the display element, but the preferable lower limit is 1 nm and the preferable upper limit is 5000 nm.
• the primary particle size of the light-shielding agent is in this range, the light-shielding property can be improved without deteriorating the drawing property of the obtained sealant for a display element.
• 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 further preferable lower limit is 10 nm
• the further preferable upper limit is 100 nm.
• the primary particle size of the light-shielding agent can be measured by using NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS) to disperse 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 a display element 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, it is more excellent in the effect of improving the light-shielding property while suppressing the deterioration of the adhesiveness, the strength after curing, and the drawing property of the obtained sealant for display elements.
• a more preferable lower limit of the content of the light-shielding agent is 10 parts by weight, a more preferable upper limit is 70 parts by weight, a further preferable lower limit is 30 parts by weight, and a further preferable upper limit is 60 parts by weight.
• the sealant for a display element of the present invention further contains additives such as a reactive diluent, a spacer, a curing accelerator, a defoaming agent, a leveling agent, a polymerization inhibitor, and other coupling agents, if necessary. You may.
• a curable resin for example, a curable resin, a polymerization initiator and / or a thermosetting agent, a silane coupling agent to be added as necessary, and the like using a mixer are used.
• a method of mixing with and the like can be mentioned.
• the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, a three-roll, and the like.
• the preferable lower limit of the storage elastic modulus of the cured product at 121 ° C. is 0.1 GPa.
• the sealant for a display element of the present invention is more excellent in moisture and heat resistance.
• a more preferable lower limit of the storage elastic modulus of the cured product at 121 ° C. is 0.4 GPa.
• the preferable upper limit of the storage elastic modulus of the cured product at 121 ° C. is 2.0 GPa.
• the cured product for measuring the storage elastic modulus As the cured product for measuring the storage elastic modulus, a sealant that has been irradiated with ultraviolet rays of 100 mW / cm 2 for 30 seconds and then heated at 120 ° C. for 1 hour to be cured is used. Further, the storage elastic modulus was measured by using a dynamic viscoelasticity measuring device to measure the cured product at 0 ° C. under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a grip width of 25 mm, a heating rate of 10 ° C./min, and a frequency of 5 Hz. It can be measured as a value at each measurement temperature when the temperature is raised to 200 ° C.
• Examples of the dynamic viscoelasticity measuring device include DVA-200 (manufactured by IT Measurement Control Co., Ltd.) and the like.
• DVA-200 manufactured by IT Measurement Control Co., Ltd.
• a method for adjusting the storage elastic modulus at 121 ° C. and the storage elastic modulus at 25 ° C. described later a method for adjusting the type and content of the above-mentioned curable resin, polymerization initiator, thermosetting agent and the like is used. Suitable.
• the sealant for a display element of the present invention has a preferable upper limit of the storage elastic modulus of the cured product at 25 ° C. of 5.0 GPa.
• the storage elastic modulus of the cured product at 25 ° C. is 5.0 GPa or less
• the sealant for a display element of the present invention can obtain a display element having excellent adhesiveness, and the alignment film of the liquid crystal display element can be obtained. Even when it is placed on the top, it is possible to suppress panel peeling and the like.
• a more preferable upper limit of the storage elastic modulus of the cured product at 25 ° C. is 4.5 GPa.
• the preferable lower limit of the storage elastic modulus at 25 ° C. of the cured product is 3.0 GPa, and the more preferable lower limit is 3.5 GPa.
• a vertically conductive material By blending conductive fine particles with the sealant for a display element of the present invention, a vertically conductive material can be manufactured.
• a vertically conductive material containing such a sealing agent for a display element and conductive fine particles of the present invention is also one of the present inventions.
• the conductive fine particles are not particularly limited, and metal balls, those having a conductive metal layer formed on the surface of the resin fine particles, and the like can be used. Among them, the one in which the conductive metal layer is formed on the surface of the resin fine particles is preferable because the excellent elasticity of the resin fine particles enables conductive connection without damaging the transparent substrate or the like.
• a display element having a cured product of the sealant for a display element of the present invention or a cured product of the vertically conductive material of the present invention is also one of the present inventions.
• a liquid crystal display element is suitable.
• a liquid crystal dropping method is preferably used, and specific examples thereof include a method having the following steps. First, a step of applying the sealant for a display element of the present invention to one of two transparent substrates having electrodes such as an ITO thin film by screen printing, dispenser application, or the like to form a frame-shaped seal pattern is performed.
• a step of dripping and applying the fine droplets of the liquid crystal on the entire surface of the frame of the seal pattern and superimposing the other transparent substrate under vacuum is performed.
• a liquid crystal display element can be obtained by a method of irradiating the seal pattern portion with light such as ultraviolet rays to temporarily cure the sealant and a step of heating the temporarily cured sealant to perform main curing. can.
• the sealing agent is often applied on an alignment film formed of polyimide or the like, but the high temperature and high temperature of the sealing agent for the display element of the present invention are used. The effect of being able to obtain a display element having excellent reliability in a humid environment is particularly remarkable when it is applied onto the alignment film in this way.
• a sealant for a display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment. Further, according to the present invention, it is possible to provide a vertically conductive material and a display element using the sealant for the display element.
• each material was mixed using a planetary stirrer, and then further mixed using three rolls to prepare a sealing agent for a display element.
• Awatori Rentaro manufactured by Shinky Co., Ltd.
• the obtained sealing agent for each display element was irradiated with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp (manufactured by Sen Special Light Source Co., Ltd., “MB1500T-3”), and then 1 at 120 ° C.
• a cured product was obtained by heating for hours.
• the obtained cured product was changed from 0 ° C to 200 ° C by using a dynamic viscoelasticity measuring device under the conditions of a test piece width of 5 mm, a thickness of 0.35 mm, a grip width of 25 mm, a heating rate of 10 ° C./min, and a frequency of 5 Hz.
• the temperature was raised and the storage elastic modulus at 25 ° C. and 121 ° C. was measured.
• Tables 1 and 2 The "total of (A) and (B-1) and / or (B-2)" in Tables 1 and 2 is as follows.
• the (meth) acrylic compound (A) according to the present invention according to the present invention. It means the total of the epoxy compound (B-1) and the epoxy compound (B-2) according to the present invention.
• the curable resin contains only the epoxy compound (B-1) according to the present invention among the epoxy compound (B-1) according to the present invention and the epoxy compound (B-2) according to the present invention, the present invention is used. It means the total of the (meth) acrylic compound (A) and the epoxy compound (B-1) according to the present invention.
• the present invention It means the total of the (meth) acrylic compound (A) and the epoxy compound (B-2) according to the present invention.
• spacer particles 1 part by weight of spacer particles was uniformly dispersed in 100 parts by weight of the sealant for each display element obtained in Examples and Comparative Examples.
• the spacer particles Micropearl SI-H050 (manufactured by Sekisui Chemical Co., Ltd.) was used.
• a sealing agent in which spacer particles are dispersed is filled in a syringe for dispensing, defoaming treatment is performed, and then a rectangular frame with a line width of about 1 mm is drawn on a transparent substrate with an alignment film and an ITO thin film with a dispenser. was applied to.
• PSY-10E manufactured by Musashi Engineering Co., Ltd.
• SHOTMASTER 300 manufactured by Musashi Engineering Co., Ltd.
• another transparent substrate was attached, and immediately after irradiating the sealant part with 100 mW / cm 2 ultraviolet rays (wavelength 365 nm) for 30 seconds using a metal halide lamp (“MB1500T-3” manufactured by Sen Special Light Source Co., Ltd.). , 120 ° C. for 1 hour to obtain a test piece.
• the obtained test piece was exposed to PCT conditions (121 ° C., 100% RH, 2 atm) for 24 hours.
• a sealant for a display element capable of obtaining a display element having excellent reliability in a high temperature and high humidity environment. Further, according to the present invention, it is possible to provide a vertically conductive material and a display element using the sealant for the display element.

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