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WO2023163113A1 - Encapsulant for organic el display element, organic el display device, and method for producing organic el display device - Google Patents

Encapsulant for organic el display element, organic el display device, and method for producing organic el display device Download PDF

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Publication number
WO2023163113A1
WO2023163113A1 PCT/JP2023/006769 JP2023006769W WO2023163113A1 WO 2023163113 A1 WO2023163113 A1 WO 2023163113A1 JP 2023006769 W JP2023006769 W JP 2023006769W WO 2023163113 A1 WO2023163113 A1 WO 2023163113A1
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WO
WIPO (PCT)
Prior art keywords
organic
compound
mass
group
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Application number
PCT/JP2023/006769
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French (fr)
Japanese (ja)
Inventor
宙 宮尾
航太郎 舘野
Original Assignee
三井化学株式会社
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Publication date
Application filed by 三井化学株式会社 filed Critical 三井化学株式会社
Priority to JP2024503264A priority Critical patent/JPWO2023163113A1/ja
Priority to KR1020247022513A priority patent/KR20240113961A/en
Priority to CN202380016073.7A priority patent/CN118511673A/en
Publication of WO2023163113A1 publication Critical patent/WO2023163113A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08G59/40—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 curing agents used
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/1201—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers

Definitions

  • the present invention relates to a sealing material for an organic EL display element, an organic EL display device, and a method for manufacturing an organic EL display device.
  • an organic EL display has been known as an image display device equipped with optical elements.
  • the optical elements are sealed with a sealing layer in order to prevent deterioration of the optical elements due to moisture in the atmosphere.
  • the sealing layer is formed, for example, by embedding an optical element in a sealing composition and then curing the sealing composition by light irradiation.
  • a sealing composition for example, a sealant for an organic EL display element containing a cationic polymerizable compound, a polymerization initiator, and a benzotriazole compound has been proposed (for example, the implementation of Patent Document 1 See Example 1).
  • the sealant for organic EL display elements of Patent Document 1 acid is generated from the polymerization initiator (photoacid generator) even under weak light such as from a fluorescent lamp. Then, the acid is not deactivated as it is, and the polymerization (curing) of the sealant for organic EL display elements progresses and the viscosity increases. In other words, the sealant for organic EL display elements of Patent Document 1 has a problem of low stability against white light.
  • a cured product of such a sealing composition is required to have reliability.
  • the present invention provides a sealing material for an organic EL display element that is excellent in stability against white light and reliability after curing, and an organic sealing layer comprising a cured product of the sealing material for an organic EL display element.
  • An EL display device and a method for manufacturing an organic EL display device are provided.
  • the present invention [1] includes a cationic polymerizable compound, a cationic polymerization initiator, an ultraviolet absorber, and a compound having a phenolic hydroxyl group, and the mass of the compound having a phenolic hydroxyl group relative to the ultraviolet absorber.
  • the encapsulant for organic EL display elements has a ratio (compound having a phenolic hydroxyl group/ultraviolet absorber) of 0.01 or more and less than 1.00.
  • the present invention [2] includes the sealant for organic EL display elements according to the above [1], wherein the cationic polymerizable compound is an epoxy compound and/or an oxetane compound.
  • the present invention [3] includes the encapsulant for organic EL display elements according to the above [1] or [2], wherein the ultraviolet absorber is a benzotriazole compound or a benzophenone compound.
  • the present invention [4] is the organic EL display element according to any one of the above [1] to [3], wherein the content of the ultraviolet absorber is 0.1% by mass or more and 2% by mass or less. Contains an encapsulant for
  • the present invention [5] is according to any one of the above [1] to [4], wherein the content of the compound having a phenolic hydroxyl group is 0.01% by mass or more and 0.5% by mass or less. of organic EL display element sealing material.
  • the present invention [6] is for an organic EL display element according to any one of the above [1] to [5], which is liquid at 25° C. and has a solvent content of 0.05% by mass or less. Contains encapsulant.
  • the present invention [7] is the sealing material for organic EL display elements according to any one of the above [1] to [6], wherein the viscosity at 25° C. is 5 mPa ⁇ s or more and 50 mPa ⁇ s or less. contains.
  • the present invention [8] comprises a substrate, an organic EL element mounted on one side in the thickness direction of the substrate, and a sealing layer covering the organic EL element, wherein the sealing layer comprises the above [1]
  • An organic EL display device comprising a cured product of the sealing material for an organic EL display device according to any one of [7].
  • the present invention [9] comprises a first step of preparing a substrate, a second step of mounting an organic EL element on one side in the thickness direction of the substrate, and a sealing layer covering the organic EL element by an inkjet method. and a third step of forming the organic EL display, wherein the sealing layer is made of a cured product of the sealing material for an organic EL display element according to any one of [1] to [7] above. It includes a method of manufacturing the device.
  • the mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber is 0.01 to 1.00. is less than In this sealing material for an organic EL display element, since the mass ratio is 0.01 or more, the stability against white light can be improved. Moreover, in this sealing material for organic EL display elements, since the mass ratio is less than 1.00, the reliability after curing can be improved.
  • the organic EL element is covered with a sealing layer made of a cured product of the organic EL display element sealing material of the present invention. Therefore, it is highly reliable.
  • the organic EL element is coated by an inkjet method, and a sealing layer made of a cured product of the sealing material for an organic EL display element of the present invention is formed. Therefore, an organic EL display device with excellent reliability can be manufactured.
  • FIG. 1 shows a cross-sectional view of one embodiment of the organic EL display device of the present invention.
  • 2A to 2C are schematic diagrams showing an embodiment of the method for manufacturing an organic EL display device of the present invention.
  • FIG. 2A shows the first step of preparing the substrate.
  • FIG. 2B shows the second step of mounting the organic EL element on one surface in the thickness direction of the substrate.
  • FIG. 2C shows the third step of forming the sealing layer 3 covering the organic EL element 2 by the inkjet method.
  • a sealing material for an organic EL display element contains a cationic polymerizable compound, a cationic polymerization initiator, an ultraviolet absorber, and a compound having a phenolic hydroxyl group.
  • Cationically polymerizable compounds include, for example, epoxy compounds and oxetane compounds. That is, the cationically polymerizable compound is preferably an epoxy compound and/or an oxetane compound. More preferably, the cationically polymerizable compounds are epoxy compounds and oxetane compounds.
  • Epoxy compounds include, for example, alicyclic epoxy resins, aliphatic epoxy resins, and aromatic epoxy resins, preferably alicyclic epoxy resins and aliphatic epoxy resins. More preferably, the epoxy compound comprises an alicyclic epoxy resin and an aliphatic epoxy resin, and even more preferably, the epoxy compound consists of an alicyclic epoxy resin and an aliphatic epoxy resin.
  • the alicyclic epoxy resin is a curable resin (photocurable resin, preferably ultraviolet curable resin) having an epoxy group and an alicyclic ring (alicyclic skeleton) and no aromatic ring.
  • alicyclic epoxy resins examples include glycidyl group-containing alicyclic epoxy resins, glycidyl ether group-containing alicyclic epoxy resins, and epoxycyclo structure-containing epoxy resins.
  • a glycidyl group-containing alicyclic epoxy resin has, for example, a glycidyl group bonded to an alicyclic ring.
  • Such a glycidyl group-containing alicyclic epoxy resin is represented, for example, by the following general formula (1).
  • R1 represents a monovalent organic group and n represents the degree of polymerization. Further, a substituent such as an alkyl group may be bonded to the carbon atoms constituting the cyclohexane ring.
  • glycidyl group-containing alicyclic epoxy resin represented by the general formula (1) specifically, 1,2-epoxy-4-(2-oxiranyl of 2,2-bis(hydroxymethyl)-1-butanol ) cyclohexane adducts.
  • a commercially available product can also be used as the glycidyl group-containing alicyclic epoxy resin represented by the general formula (1).
  • Examples of commercially available products of the glycidyl group-containing alicyclic epoxy resin represented by the general formula (1) include EHPE3150 (epoxy equivalent: 170 to 190 g/eq., manufactured by Daicel).
  • a glycidyl ether group-containing alicyclic epoxy resin has a glycidyl ether unit bonded to an alicyclic ring.
  • the glycidyl ether group-containing alicyclic epoxy resin is a polyglycidyl ether-containing alicyclic epoxy resin having a plurality of glycidyl ether units bonded to an alicyclic ring.
  • glycidyl ether-containing alicyclic epoxy resins examples include bifunctional glycidyl ether-containing alicyclic epoxy resins.
  • Bifunctional glycidyl ether-containing alicyclic epoxy resins include, for example, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hexahydrophthalic acid diglycidyl ester.
  • the epoxy cyclo structure-containing epoxy resin has an epoxy cyclo structure having an epoxy group composed of two adjacent carbon atoms forming an alicyclic ring and one oxygen atom bonded to the two carbon atoms. .
  • epoxy cyclo structure-containing epoxy resins examples include epoxy cyclohexane structure-containing epoxy resins (hereinafter referred to as ECH structure-containing epoxy resins).
  • ECH structure-containing epoxy resins examples include epoxy resins containing one ECH structure represented by the following chemical formula (2), epoxy resins containing two ECH structures represented by the following general formula (3), and their Modified products are mentioned.
  • X represents a linking group (a divalent group having one or more atoms).
  • m represents 0 or 1;
  • R2 represents one atom or substituent selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, a furyl group and a thienyl group.
  • Two R2's in formula (3) may be the same or different.
  • the epoxy resin containing two ECH structures represented by the general formula (3) (hereinafter referred to as the ECH structure-containing epoxy resin represented by the general formula (3)) has an ECH structure (epoxycyclohexyl group) in the molecule It has two epoxycyclohexyl groups at both ends, and two epoxycyclohexyl groups are linked via a linking group (a carbon-carbon bond when m is 0).
  • the epoxycyclohexyl group is a functional group containing a cyclohexane ring, an epoxy group composed of two adjacent carbon atoms forming the cyclohexane ring, and one oxygen atom bonded to the two carbon atoms. is.
  • the alkyl group represented by R2 in the general formula (3) includes, for example, a linear or branched alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.).
  • fluoroalkyl group represented by R2 in the general formula (3) for example, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms (e.g., perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, etc.).
  • Examples of the aryl group represented by R2 in the above general formula (3) include aryl groups having 6 to 18 carbon atoms (eg, phenyl group, naphthyl group, etc.).
  • Examples of the linking group represented by X in the general formula (3) include an oxygen atom, a sulfur atom, a divalent hydrocarbon group, a polyoxyalkylene group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, Examples include amide groups and groups in which these groups are linked. Note that when m is 0, two ECH structures are linked via a carbon-carbon bond.
  • divalent hydrocarbon groups examples include linear or branched alkylene groups having 1 to 20 carbon atoms (e.g., methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, butylene group, etc.), linear or branched unsaturated hydrocarbon groups having 1 to 20 carbon atoms (eg, propenylene group, methylpropenylene group, butenylene group, etc.), and the like.
  • linear or branched alkylene groups having 1 to 20 carbon atoms e.g., methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, butylene group, etc.
  • linear or branched unsaturated hydrocarbon groups having 1 to 20 carbon atoms eg, propenylene group, methylpropenylene group, butenylene group, etc.
  • polyoxyalkylene groups include linear or branched polyoxyalkylene groups having 1 to 120 carbon atoms (eg, polyoxyethylene groups, polyoxypropylene groups, etc.).
  • ECH structure-containing epoxy resins represented by general formula (3) include (3,3′,4,4′-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1, 2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 3,4-epoxycyclohexylmethyl (3,4-epoxy) Cyclohexanecarboxylate and ⁇ -caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, preferably (3,3′,4,4′-diepoxy)bicyclohexyl (In formula (3) above, m represents 0 and R2 represents a hydrogen atom.).
  • a commercially available product can also be used as the ECH structure-containing epoxy resin represented by the general formula (3).
  • Examples of commercially available ECH structure-containing epoxy resins represented by the general formula (3) include Celoxide 8000, Celoxide 8010, Celoxide 2021P, and Celoxide 2081 (manufactured by Daicel Corporation).
  • the ECH structure-containing epoxy resin preferably includes the ECH structure-containing epoxy resin represented by the above general formula (3).
  • an epoxy cyclo structure-containing epoxy resin is preferably used.
  • the weight average molecular weight of the alicyclic epoxy resin is, for example, 200 or more and, for example, 1000 or less, preferably 500 or less.
  • the weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) using polystyrene as a standard (the same applies hereinafter).
  • the epoxy equivalent of the alicyclic epoxy resin is, for example, 90 g/eq. above, preferably 100 g/eq. Above, for example, 250 g/eq. Below, preferably 190 g/eq. It is below.
  • the epoxy equivalent can be measured according to JIS K7236:2001 (the same applies hereinafter).
  • Aliphatic epoxy resins include, for example, bifunctional aliphatic epoxy resins.
  • Difunctional aliphatic epoxy resins include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether, preferably neo Pentyl glycol diglycidyl ether may be mentioned.
  • the weight average molecular weight of the aliphatic epoxy resin is, for example, 150 or more and, for example, 400 or less.
  • the epoxy equivalent of the aliphatic epoxy resin is, for example, 60 g/eq. above, and for example, 250 g/eq. It is below.
  • the content of the alicyclic epoxy resin is, for example, , 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass or less.
  • the content of the alicyclic epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass, relative to the cationic polymerizable compound. It is below.
  • the content of the aliphatic epoxy resin is For example, it is 40 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less. Further, the content of the aliphatic epoxy resin is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, 50% by mass or less, preferably 40% by mass or less, relative to the cationic polymerizable compound. is.
  • Epoxy compounds can be used alone or in combination of two or more.
  • the content of the epoxy compound is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less, relative to the cationic polymerizable compound. .
  • the oxetane compound contains, for example, from 1 to 5 oxetane rings.
  • oxetane compounds include monofunctional oxetane compounds having one oxetane ring, bifunctional oxetane compounds having two oxetane rings, and trifunctional or higher oxetane compounds having three or more oxetane rings.
  • Examples of monofunctional oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 2-ethylhexyl (3 -ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl)ether, and 3-cyclohexylmethyl-3-ethyl-oxetane.
  • bifunctional oxetane compounds include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3,3′-(oxybismethylene)bis(3-ethyloxetane), 1, 4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene, 1,3-bis[(3-ethyl-3-oxetanyl)methoxy]benzene, 3,7-bis(3-oxetanyl)-5-oxa -nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,2-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxe
  • trifunctional or higher oxetane compounds include trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3 -oxetanylmethyl) ether, and dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether.
  • oxetane compounds can also be used.
  • examples of commercially available oxetane compounds include Aron oxetane OXT-221 (3,3'-(oxybismethylene)bis(3-ethyloxetane)) and Aron oxetane OXT-121 (manufactured by Toagosei Chemical Co., Ltd.). .
  • the oxetane compound preferably includes a bifunctional oxetane compound.
  • the oxetane compound can be used alone or in combination of two or more.
  • the content of the oxetane compound is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less, relative to the cationic polymerizable compound.
  • the content of the cationic polymerizable compound is, for example, 80% by mass or more, preferably 90% by mass or more, and, for example, 98% by mass or less with respect to the sealing material for organic EL display elements.
  • a cationic polymerization initiator is, for example, a photoacid generator that generates an acid upon irradiation with light.
  • the cationic polymerization initiator is not particularly limited, and known cationic polymerization initiators can be used.
  • the cationic polymerization initiator can be used alone or in combination of two or more.
  • the content of the cationic polymerization initiator is, for 100 parts by mass of the cationic polymerizable compound, for example, 0.5 parts by mass or more, preferably 0.8 parts by mass or more, more preferably 1.3 parts by mass or more, Also, for example, it is 5 parts by mass or less, preferably 2.5 parts by mass or less.
  • the content of the cationic polymerization initiator is, for example, 0.5% by mass or more, preferably 1% by mass or more, and, for example, 10% by mass or less, relative to the sealing material for organic EL display elements. Preferably, it is 5% by mass or less.
  • the ultraviolet absorber is a component that absorbs white light and suppresses the generation of acid from the cationic polymerization initiator.
  • ultraviolet absorbers examples include benzotriazole compounds, benzophenone compounds, triazine compounds, and cyanoacrylate compounds.
  • Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2,2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl, 2-(2′- hydroxy-5′-methyl-phenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-butyl-phenyl)benzotriazole, 2-(2′-hydroxy-3′-t- Butyl-5′-methyl-phenyl)-5-chloro benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-butyl-phenyl)-5-chloro benzotriazole, 2-( 2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, and 2-(2' -hydroxy-4'-n-octoxyphenyl)benzotri
  • a commercially available product can also be used as the benzotriazole compound.
  • benzotriazole compounds include Tinuvin 234 (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, manufactured by BASF Japan Ltd.). , KEMISORB71 (2-(2-hydroxy-5-methylphenyl)benzotriazole, manufactured by Chemipro Kasei Co., Ltd.), and RUVA-93 (2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl] -2H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd.).
  • benzophenone compounds include [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone, 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -methoxy benzophenone, 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5- Sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-dodecyloxy benzophenone, 2-hydroxy -4-benzyloxybenzophenone, 2,2',4,4'-tetrahydroxy benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, and 2-hydroxy-4-(2-hydroxy-3-me
  • a commercially available product can also be used as the benzophenone compound.
  • Commercially available benzophenone compounds include, for example, KEMIISORB12 (2-hydroxy-4-n-octyloxybenzophenone, manufactured by Chemipro Kasei Co., Ltd.) and Adekastab 1413 ([2-hydroxy-4-(octyloxy)phenyl](phenyl) Methanone, manufactured by ADEKA).
  • triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol and 2,4-diphenyl- 6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazines, preferably 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1, 3,5-triazines are mentioned.
  • a commercially available product can also be used as the triazine compound.
  • Examples of commercially available triazine compounds include KEMISORB102 (2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, manufactured by Chemipro Kasei).
  • cyanoacrylate compounds include ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate.
  • the UV absorber preferably a benzotriazole compound, a benzophenone compound, and a triazine compound, more preferably a benzotriazole compound and a benzophenone compound, more preferably as a UV absorber, a benzotriazole compound or benzophenone.
  • a compound is selected.
  • the UV absorber is a benzotriazole compound or a benzophenone compound, the stability against white light is even better.
  • the ultraviolet absorber is a benzotriazole compound from the viewpoint of further improving the stability against white light.
  • the ultraviolet absorbers can be used alone or in combination of two or more.
  • the content of the ultraviolet absorber is, for example, 0.05 parts by mass or more, preferably 0.4 parts by mass or more, more preferably 0.8 parts by mass or more with respect to 100 parts by mass of the cationic polymerizable compound, and , for example, 2 parts by mass or less, preferably 1.5 parts by mass or less.
  • the content of the ultraviolet absorber is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.8% by mass, relative to the sealing material for organic EL display elements. % or more, and for example, 2% by mass or less, preferably 1.5% by mass or less, more preferably 1.5% by mass or less, from the viewpoint of improving the reliability of the sealing material for organic EL display elements after curing. It is 2% by mass or less.
  • the content of the ultraviolet absorber is equal to or higher than the above lower limit, the stability against white light can be improved.
  • the content of the ultraviolet absorber is equal to or less than the above upper limit, the curability when cured by irradiation with ultraviolet rays is maintained.
  • a compound having a phenolic hydroxyl group is a component that scavenges an acid generated from a cationic polymerization initiator upon irradiation with light.
  • a compound having a phenolic hydroxyl group is a compound having one or more phenolic hydroxyl groups in the molecule. Further, the compounds having a phenolic hydroxyl group do not include the above benzotriazole compounds, the above benzophenone compounds, the above triazine compounds, and the above cyanoacrylate compounds.
  • a compound having a phenolic hydroxyl group preferably a compound having a monofunctional phenolic hydroxyl group having one benzene ring, the benzene ring having one phenolic hydroxyl group, one benzene ring and a compound having a bifunctional phenolic hydroxyl group in which the benzene ring has two phenolic hydroxyl groups, and a compound having one benzene ring, in which the benzene ring has three or more phenolic hydroxyl groups compounds having a trifunctional or higher phenolic hydroxyl group. That is, a compound having a phenolic hydroxyl group preferably has one benzene ring. This ensures excellent stability.
  • Examples of compounds having a monofunctional phenolic hydroxyl group include compounds represented by the following formula (4).
  • R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl ester group.
  • alkyl groups having 1 to 10 carbon atoms Indicates an alkyl group having 1 to 10 carbon atoms.
  • alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
  • R4 represents an alkylene group having 1 to 6 carbon atoms.
  • alkylene group having 1 to 6 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group and butylene group.
  • R5 represents an alkyl group having 1 to 10 carbon atoms.
  • alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
  • a compound having a monofunctional phenolic hydroxyl group preferably 2,6-di-tert-butyl-p-cresol (a compound in which R3 represents a methyl group in the above formula (4)), and Benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester (in the above formula (4), R3 represents an alkyl ester group, the above formula (5) , a compound in which R4 represents an ethylene group and R5 represents a heptyl group, a compound in which R4 represents an ethylene group and R5 represents an octyl group, and a compound in which R4 represents an ethylene group and R5 represents a nonyl group. mixture), preferably 2,6-di-tert-butyl-p-cresol.
  • the compound represented by formula (4) above preferably does not contain an alkyl ester group. Therefore, since the contribution of the addition amount to the stability of white light is high, it is even more excellent from the viewpoint of compatibility between the stability of white light and curability.
  • Examples of compounds having a bifunctional phenolic hydroxyl group include hydroquinone, resorcinol, tert-butylcatechol, and tert-butylhydroquinone.
  • Examples of compounds having trifunctional or higher phenolic hydroxyl groups include pyrogallol.
  • the compound having a phenolic hydroxyl group preferably a compound having a monofunctional phenolic hydroxyl group and a compound having a bifunctional phenolic hydroxyl group, more preferably a compound having both stability and curability to white light
  • a compound having a monofunctional phenolic hydroxyl group can be mentioned.
  • the molecular weight of the compound having a phenolic hydroxyl group is, for example, 94 or more, preferably 100 or more, more preferably 200 or more, and for example, 1000 or less, preferably 500 or less, stability against white light and From the viewpoint of compatibility with curability, it is more preferably 300 or less.
  • the molecular weight is low, the contribution of the amount added to the stability of white light is high, so it is even more excellent from the viewpoint of compatibility between the stability of white light and curability.
  • a compound having a phenolic hydroxyl group can be used alone or in combination of two or more.
  • the content of the compound having a phenolic hydroxyl group is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound. parts or more, more preferably 0.1 parts by mass or more, and for example, 0.5 parts by mass or less, preferably 0.3 parts by mass or less, more preferably 0.15 parts by mass or less.
  • the content of the compound having a phenolic hydroxyl group is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and for example, 0.5% by mass or less, preferably 0.3% by mass or less, more preferably 0.15% by mass or less be.
  • the content of the compound having a phenolic hydroxyl group is at least the above lower limit, the stability against white light can be improved.
  • the curability is excellent.
  • the mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber is 0.01 or more, preferably 0.03 or more, more preferably 0.03 or more. 07 or more, more preferably 0.09 or more, particularly preferably 0.1 or more, and less than 1.00, preferably 0.5 or less, more preferably 0.3 or less, further preferably 0 .2 or less.
  • the mass ratio is equal to or higher than the lower limit, the stability against white light can be improved.
  • the mass ratio is less than the lower limit, the stability against white light is lowered.
  • the mass ratio is equal to or less than the upper limit, the reliability of the sealing material for organic EL display elements is excellent.
  • a sealant for an organic EL display element To prepare a sealant for an organic EL display element, first, a cationically polymerizable compound, a cationically polymerizable compound, an ultraviolet absorber, and a compound having a phenolic hydroxyl group are mixed to prepare a mixture. Next, a cationic polymerization initiator is added to this mixture and mixed. This prepares the sealing material for organic EL display elements.
  • the sealing material for organic EL display elements can also contain an additive.
  • Additives include, for example, sensitizers, tackifiers, antioxidants, polymerization initiation aids, anti-aging agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, preservatives, and antibacterial agents.
  • the blending ratio of additives is appropriately set according to the application and purpose.
  • Additives can be used singly or in combination of two or more.
  • the organic EL display element sealing material may contain a solvent, but preferably the organic EL display element sealing material does not substantially contain a solvent.
  • the solvent content is, for example, 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less.
  • the organic EL display element sealing material is preferably liquid at 25°C. Being liquid at 25°C is defined as having a viscosity of 5 mPa ⁇ s or more and 50 mPa ⁇ s or less at 25°C. If the sealing material for organic EL display elements is liquid at 25° C., it is excellent in jettability by inkjet.
  • the viscosity at 25° C. is, for example, 1 mPa s or more, preferably 5 mPa s or more, more preferably 10 mPa s or more, and for example, 50 mPa s or less, preferably , 30 mPa ⁇ s or less, more preferably 25 mPa ⁇ s or less.
  • the cured product of the sealing material for organic EL display elements preferably has transparency.
  • the total light transmittance (in accordance with JIS K 7361-1) of the cured product of the sealing material for organic EL display elements is, for example, 80% or more, preferably 85% or more, and more preferably 90% or more and, for example, 100% or less.
  • the mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber is 0.01 or more and less than 1.00. be.
  • the mass ratio is 0.01 or more, the stability against white light can be improved.
  • the mass ratio is less than 1.00, the reliability of the cured organic EL element can be improved from the viewpoint of curability.
  • a sealing material for organic EL display elements has excellent stability against white light and excellent reliability after curing, it can be suitably used as a sealing material for organic EL display elements. .
  • this organic EL display element sealing material has stability against white light, thickening is suppressed. Therefore, it can be suitably used in the inkjet method.
  • a cationically polymerizable compound, a cationically polymerizable compound, an ultraviolet absorber, and a compound having a phenolic hydroxyl group are mixed, and the mixture is After preparing this mixture, a cationic polymerization initiator is blended, but the cationic polymerization initiator can be blended together with the cationic polymerizable compound, the ultraviolet absorber, and the compound having a phenolic hydroxyl group.
  • Organic EL display device One embodiment of the organic EL display device of the present invention will be described with reference to FIG.
  • the organic EL display device 10 includes a substrate 1 , an organic EL element 2 mounted on one surface of the substrate 1 in the thickness direction, and a sealing layer 3 covering the organic EL element 2 .
  • a substrate 1 supports an organic EL element 2 .
  • Examples of the substrate 1 include glass substrates and plastic substrates, preferably glass substrates.
  • the thickness of the substrate 1 is, for example, 0.1 mm or more and, for example, 20 mm or less.
  • the organic EL element 2 is a known organic EL element and mounted on the substrate 1 .
  • the organic EL element 2 includes a cathode reflective electrode, an organic EL layer, and an anode transparent electrode (not shown).
  • the sealing layer 3 is a layer for suppressing deterioration of the organic EL element 2 due to moisture in the atmosphere.
  • the sealing layer 3 is made of a cured product of the above-described organic EL display element sealing material.
  • the thickness of the sealing layer 3 is, for example, 1 ⁇ m or more and, for example, 100 ⁇ m or less.
  • the method for manufacturing an organic EL display device includes a first step of preparing a substrate 1, a second step of mounting an organic EL element 2 on one side in the thickness direction of the substrate 1, and coating the organic EL element 2 by an inkjet method. and a third step of forming the sealing layer 3 to be formed.
  • a substrate 1 is prepared as shown in FIG. 2A.
  • the organic EL element 2 is mounted on one surface of the substrate 1 in the thickness direction by, for example, a known method (eg, vacuum deposition method).
  • the sealing layer 3 that covers the organic EL element 2 is formed by the inkjet method. According to the inkjet method, the organic EL element 2 can be reliably sealed.
  • the organic EL display element sealing material is arranged so as to cover the organic EL element 2 by an inkjet method. Thereafter, the organic EL display element sealing material is irradiated with light to cure the organic EL display element sealing material. Thus, the organic EL display device 10 is manufactured.
  • the organic EL elements 2 are covered with a sealing layer 3 made of a cured product of a highly reliable organic EL display element sealing material. Therefore, it is highly reliable.
  • the manufacturing method of the organic EL display device includes forming the sealing layer 3 which covers the organic EL element 2 and is made of a cured product of a highly reliable sealing material for an organic EL display element by an inkjet method. . Therefore, the organic EL display device 10 having excellent reliability can be manufactured.
  • the organic EL display device 10 can be provided with another sealing layer (for example, an inorganic sealing layer) on one side in the thickness direction and/or the other side in the thickness direction.
  • another sealing layer for example, an inorganic sealing layer
  • CEL8010 (3,3′,4,4′-diepoxy)bicyclohexyl, trade name “Celoxide 8010”, Daicel NPG (G): neopentyl glycol diglycidyl ether, Sakamoto Yakuhin Kogyo OXT221: 3,3 '-(Oxybismethylene)bis(3-ethyloxetane), trade name "Aronoxetane OXT-221", Tinuvin234 manufactured by Toagosei Chemical Co., Ltd.: 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)-phenol, BASF Japan Ltd.
  • KEMIISORB71 2-(2-hydroxy-5-methylphenyl) benzotriazole
  • Chemipro Kasei Co., Ltd. RUVA-93 2-[2-hydroxy- 5-[2-(Methacryloyloxy)ethyl]phenyl]-2H-benzotriazole
  • KEMIISORB12 manufactured by Otsuka Chemical Co., Ltd.: 2-hydroxy-4-n-octyloxybenzophenone
  • Adekastab 1413 manufactured by Chemipro Kasei Co., Ltd.: [2-Hydroxy-4 -(Octyloxy)phenyl](phenyl)methanone
  • ADEKA KEMIISORB102 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine
  • Chemipro Kasei BHT 2,6-di-tert-butyl-p-cresol
  • molecular weight 220 Irganox 1135 Benz
  • the stability to white light was evaluated based on the following criteria. Table 1 shows the results. Good: The viscosity increase rate was less than 20%. ⁇ : The viscosity increase rate was 20% or more and less than 50%. x: The viscosity increase rate was 50% or more.
  • the organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix).
  • the inkjet cartridge was set in an inkjet device DMP-2831 (manufactured by Fuji Film Dimatix) installed under a fluorescent light, and after adjusting the coating state, 1000 droplets were placed on a non-alkali glass of 50 mm ⁇ 50 mm at a pitch of 500 ⁇ m. applied.
  • the sealing material for an organic EL display element was left under a fluorescent lamp for 3 hours, and again, using an inkjet cartridge, 1000 droplets were applied on non-alkali glass at a pitch of 500 ⁇ m.
  • the number of droplets that could not be applied after standing for 3 hours was 98% or more of the number before standing.
  • ⁇ After standing for 3 hours, the number of droplets that could not be applied was 90% or more and less than 98% of the number before standing.
  • x After standing for 3 hours, the number of droplets that could not be applied was less than 90% of the number before standing.
  • the organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). After setting the inkjet cartridge in an inkjet device DMP-2831 (manufactured by Fujifilm Dimatix) and adjusting the coating state, a 40 mm ⁇ 40 mm size was placed on a 50 mm ⁇ 50 mm alkali-free glass with a thickness of 10 ⁇ m after curing. was applied so as to be Thus, a coating film was obtained. Next, the coating film is left for 1 minute in an environment with a temperature of 25° C.
  • the coating film is irradiated with light from a UV-LED with a wavelength of 395 nm at an illuminance of 100 mW/cm 2 and 1500 mJ/cm 2 to cure. let me Thus, an evaluation board was manufactured.
  • P1a indicates the peak height of the wave number of 1371 cm after curing
  • P1b indicates the peak height of the wave number of 1371 cm -1 before curing
  • P2a indicates the peak height of the wave number of 831 cm -1 after curing .
  • Wavenumber peak height is indicated
  • P2b indicates the peak height of 831 cm ⁇ 1 wavenumber before curing.
  • the organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). After setting the inkjet cartridge in an inkjet device DMP-2831 (manufactured by Fuji Film Dimatix) and adjusting the ejection state, a 15 mm ⁇ 15 mm size ink was applied to a glass substrate so that the thickness after curing was 10 ⁇ m. It was applied to obtain a coating film.
  • the coating film was left for 1 minute in an environment with a temperature of 25° C. and a humidity of 50%, and then irradiated with light from a UV-LED with a wavelength of 395 nm at an illuminance of 100 mW/cm 2 and 1500 mJ/cm 2 . , cured to obtain a cured film
  • the cured film was plasma-treated for 1 minute under the conditions of 2500 W (ICP power supply), 300 W (RF power supply), DC bias of 200 V, argon (Ar) flow rate of 50 sccm, and pressure of 10 mtorr.
  • SiNx film an inorganic sealing layer with a thickness of 100 nm was formed on the cured film side by RF sputtering using a SiNx target.
  • SiNx film an inorganic sealing layer with a thickness of 100 nm was formed on the cured film side by RF sputtering using a SiNx target.
  • an organic EL element was mounted on another glass substrate to manufacture a second evaluation substrate.
  • the first evaluation substrate and the second evaluation substrate were bonded together.
  • an evaluation organic EL display device was manufactured.
  • the organic EL display device for evaluation was subjected to a reliability test at 85°C. Specifically, the emission area ratio (%) after each organic EL display device for evaluation was stored at 85° C. for 100 hours was determined by the following method. That is, using Motic Images Plus software (manufactured by Shimadzu Rika Co., Ltd.), the luminescent area in the initial state and the luminescent area after storage for 100 hours were calculated, and the luminescent area ratio was calculated based on the following formula (8).
  • Luminescent area ratio (%) Luminous area after storage for 100 hours/Luminous area in initial state x 100 (8)
  • the reliability of the organic EL device was evaluated based on the following criteria. Table 1 shows the results. ⁇ : The emission area ratio was 80% or more. ⁇ : The emission area ratio was 50% or more and less than 80%. x: Emission area ratio was less than 50%.
  • the sealing material for an organic EL display device, the organic EL display device, and the method for manufacturing an organic EL display device of the present invention are suitably used in the manufacture of an image display device.

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Abstract

This encapsulant for an organic EL display element contains a cationic-polymerizable compound, a cationic polymerization initiator, a UV absorber, and a compound having phenolic hydroxyl groups. The mass ratio of the compound having phenolic hydroxyl groups to the UV absorber (compound having phenolic hydroxyl groups/UV absorber) is 0.01 or greater but less than 1.00.

Description

有機ＥＬ用表示素子用封止材、有機ＥＬ表示装置および有機ＥＬ表示装置の製造方法Sealing material for organic EL display device, organic EL display device, and method for manufacturing organic EL display device
　本発明は、有機ＥＬ用表示素子用封止材、有機ＥＬ表示装置および有機ＥＬ表示装置の製造方法に関する。 The present invention relates to a sealing material for an organic EL display element, an organic EL display device, and a method for manufacturing an organic EL display device.
　近年、光学素子を備える画像表示装置として、例えば、有機ＥＬディスプレイが知られている。このような画像表示装置では、光学素子が大気中の水分などにより劣化することを抑制するために、光学素子が封止層によって封止されている。 In recent years, for example, an organic EL display has been known as an image display device equipped with optical elements. In such an image display device, the optical elements are sealed with a sealing layer in order to prevent deterioration of the optical elements due to moisture in the atmosphere.
　封止層は、例えば、光学素子を封止用組成物に埋め込んだ後、光照射によって、封止用組成物を硬化させることにより形成される。 The sealing layer is formed, for example, by embedding an optical element in a sealing composition and then curing the sealing composition by light irradiation.
　このような封止用組成物として、例えば、カチオン重合性化合物と、重合開始剤と、ベンゾトリアゾール化合物とを含む有機ＥＬ表示素子用封止剤が提案されている（例えば、特許文献１の実施例１参照。）。 As such a sealing composition, for example, a sealant for an organic EL display element containing a cationic polymerizable compound, a polymerization initiator, and a benzotriazole compound has been proposed (for example, the implementation of Patent Document 1 See Example 1).
国際公開２０２１／００６０７０号パンフレットWO2021/006070 Pamphlet
　一方、特許文献１の有機ＥＬ表示素子用封止剤では、蛍光灯などの弱い光でも、重合開始剤（光酸発生剤）から、酸が発生する。そして、その酸は、そのまま失活することなく、有機ＥＬ表示素子用封止剤の重合（硬化）が進行し、増粘する。つまり、特許文献１の有機ＥＬ表示素子用封止剤には、白色光に対する安定性が低いという不具合がある。 On the other hand, in the sealant for organic EL display elements of Patent Document 1, acid is generated from the polymerization initiator (photoacid generator) even under weak light such as from a fluorescent lamp. Then, the acid is not deactivated as it is, and the polymerization (curing) of the sealant for organic EL display elements progresses and the viscosity increases. In other words, the sealant for organic EL display elements of Patent Document 1 has a problem of low stability against white light.
　また、このような封止用組成物の硬化物には、信頼性が要求される。 In addition, a cured product of such a sealing composition is required to have reliability.
　本発明は、白色光に対する安定性、および、硬化後の信頼性に優れる有機ＥＬ用表示素子用封止材、その有機ＥＬ用表示素子用封止材の硬化物からなる封止層を備える有機ＥＬ表示装置、および、有機ＥＬ表示装置の製造方法を提供する。 The present invention provides a sealing material for an organic EL display element that is excellent in stability against white light and reliability after curing, and an organic sealing layer comprising a cured product of the sealing material for an organic EL display element. An EL display device and a method for manufacturing an organic EL display device are provided.
　本発明［１］は、カチオン重合性化合物と、カチオン重合開始剤と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とを含み、前記紫外線吸収剤に対する前記フェノール性の水酸基を有する化合物の質量比（フェノール性の水酸基を有する化合物／紫外線吸収剤）が、０．０１以上１．００未満である、有機ＥＬ用表示素子用封止材である。 The present invention [1] includes a cationic polymerizable compound, a cationic polymerization initiator, an ultraviolet absorber, and a compound having a phenolic hydroxyl group, and the mass of the compound having a phenolic hydroxyl group relative to the ultraviolet absorber. The encapsulant for organic EL display elements has a ratio (compound having a phenolic hydroxyl group/ultraviolet absorber) of 0.01 or more and less than 1.00.
　本発明［２］は、前記カチオン重合性化合物は、エポキシ化合物および／またはオキセタン化合物である、上記［１］に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [2] includes the sealant for organic EL display elements according to the above [1], wherein the cationic polymerizable compound is an epoxy compound and/or an oxetane compound.
　本発明［３］は、前記紫外線吸収剤は、ベンゾトリアゾール化合物、または、ベンゾフェノン化合物である、上記［１］または［２］に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [3] includes the encapsulant for organic EL display elements according to the above [1] or [2], wherein the ultraviolet absorber is a benzotriazole compound or a benzophenone compound.
　本発明［４］は、前記紫外線吸収剤の含有量が、０．１質量％以上２質量％以下である、上記［１］～［３］のいずれか一項に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [4] is the organic EL display element according to any one of the above [1] to [3], wherein the content of the ultraviolet absorber is 0.1% by mass or more and 2% by mass or less. Contains an encapsulant for
　本発明［５］は、前記フェノール性の水酸基を有する化合物の含有量が、０．０１質量％以上０．５質量％以下である、上記［１］～［４］のいずれか一項に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [5] is according to any one of the above [1] to [4], wherein the content of the compound having a phenolic hydroxyl group is 0.01% by mass or more and 0.5% by mass or less. of organic EL display element sealing material.
　本発明［６］は、２５℃で液状であり、溶剤含有量が、０．０５質量％以下である、上記［１］～［５］のいずれか一項に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [6] is for an organic EL display element according to any one of the above [1] to [5], which is liquid at 25° C. and has a solvent content of 0.05% by mass or less. Contains encapsulant.
　本発明［７］は、２５℃での粘度が、５ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下である、上記［１］～［６］のいずれか一項に記載の有機ＥＬ用表示素子用封止材を含んでいる。 The present invention [7] is the sealing material for organic EL display elements according to any one of the above [1] to [6], wherein the viscosity at 25° C. is 5 mPa·s or more and 50 mPa·s or less. contains.
　本発明［８］は、基板と、前記基板の厚み方向一方面に実装される有機ＥＬ素子と、前記有機ＥＬ素子を被覆する封止層とを備え、前記封止層は、上記［１］～［７］のいずれか一項に記載の有機ＥＬ用表示素子用封止材の硬化物からなる、有機ＥＬ表示装置を含んでいる。 The present invention [8] comprises a substrate, an organic EL element mounted on one side in the thickness direction of the substrate, and a sealing layer covering the organic EL element, wherein the sealing layer comprises the above [1] An organic EL display device comprising a cured product of the sealing material for an organic EL display device according to any one of [7].
　本発明［９］は、基板を準備する第１工程と、前記基板の厚み方向一方面に、有機ＥＬ素子を実装する第２工程と、インクジェット法によって、前記有機ＥＬ素子を被覆する封止層を形成する第３工程とを備え、前記封止層は、上記［１］～［７］のいずれか一項に記載の有機ＥＬ用表示素子用封止材の硬化物からなる、有機ＥＬ表示装置の製造方法を含んでいる。 The present invention [9] comprises a first step of preparing a substrate, a second step of mounting an organic EL element on one side in the thickness direction of the substrate, and a sealing layer covering the organic EL element by an inkjet method. and a third step of forming the organic EL display, wherein the sealing layer is made of a cured product of the sealing material for an organic EL display element according to any one of [1] to [7] above. It includes a method of manufacturing the device.
　本発明の有機ＥＬ用表示素子用封止材において、紫外線吸収剤に対するフェノール性の水酸基を有する化合物の質量比（フェノール性の水酸基を有する化合物／紫外線吸収剤）が、０．０１以上１．００未満である。この有機ＥＬ用表示素子用封止材において、上記質量比が、０．０１以上であるため、白色光に対する安定性を向上できる。また、この有機ＥＬ用表示素子用封止材において、上記質量比が、１．００未満であるため、硬化後の信頼性を向上できる。 In the sealing material for an organic EL display element of the present invention, the mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber (compound having a phenolic hydroxyl group/ultraviolet absorber) is 0.01 to 1.00. is less than In this sealing material for an organic EL display element, since the mass ratio is 0.01 or more, the stability against white light can be improved. Moreover, in this sealing material for organic EL display elements, since the mass ratio is less than 1.00, the reliability after curing can be improved.
　本発明の有機ＥＬ表示装置は、本発明の有機ＥＬ用表示素子用封止材の硬化物からなる封止層によって、有機ＥＬ素子が被覆されている。そのため、信頼性に優れる。 In the organic EL display device of the present invention, the organic EL element is covered with a sealing layer made of a cured product of the organic EL display element sealing material of the present invention. Therefore, it is highly reliable.
　本発明の有機ＥＬ表示装置の製造方法は、インクジェット法によって、有機ＥＬ素子を被覆し、かつ、本発明の有機ＥＬ用表示素子用封止材の硬化物からなる封止層を形成する。そのため、信頼性に優れる有機ＥＬ表示装置を製造できる。 In the method for manufacturing an organic EL display device of the present invention, the organic EL element is coated by an inkjet method, and a sealing layer made of a cured product of the sealing material for an organic EL display element of the present invention is formed. Therefore, an organic EL display device with excellent reliability can be manufactured.
図１は、本発明の有機ＥＬ表示装置の一実施形態の断面図を示す。FIG. 1 shows a cross-sectional view of one embodiment of the organic EL display device of the present invention. 図２Ａ～図２Ｃは、本発明の有機ＥＬ表示装置の製造方法の一実施形態を示す概略図である。図２Ａは、基板を準備する第１工程を示す。図２Ｂは、基板の厚み方向一方面に、有機ＥＬ素子を実装する第２工程を示す。図２Ｃは、インクジェット法によって、有機ＥＬ素子２を被覆する封止層３を形成する第３工程を示す。2A to 2C are schematic diagrams showing an embodiment of the method for manufacturing an organic EL display device of the present invention. FIG. 2A shows the first step of preparing the substrate. FIG. 2B shows the second step of mounting the organic EL element on one surface in the thickness direction of the substrate. FIG. 2C shows the third step of forming the sealing layer 3 covering the organic EL element 2 by the inkjet method.
　有機ＥＬ用表示素子用封止材は、カチオン重合性化合物と、カチオン重合開始剤と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とを含む。 A sealing material for an organic EL display element contains a cationic polymerizable compound, a cationic polymerization initiator, an ultraviolet absorber, and a compound having a phenolic hydroxyl group.
＜カチオン重合性化合物＞
　カチオン重合性化合物としては、例えば、エポキシ化合物およびオキセタン化合物が挙げられる。つまり、カチオン重合性化合物は、好ましくは、エポキシ化合物および／またはオキセタン化合物である。また、より好ましくは、カチオン重合性化合物は、エポキシ化合物およびオキセタン化合物である。 <Cationically polymerizable compound>
Cationic polymerizable compounds include, for example, epoxy compounds and oxetane compounds. That is, the cationically polymerizable compound is preferably an epoxy compound and/or an oxetane compound. More preferably, the cationically polymerizable compounds are epoxy compounds and oxetane compounds.
［エポキシ化合物］
　エポキシ化合物としては、例えば、脂環式エポキシ樹脂、脂肪族エポキシ樹脂、および、芳香族エポキシ樹脂が挙げられ、好ましくは、脂環式エポキシ樹脂および脂肪族エポキシ樹脂が挙げられる。より好ましくは、エポキシ化合物は、脂環式エポキシ樹脂および脂肪族エポキシ樹脂を含み、さらに好ましくは、エポキシ化合物は、脂環式エポキシ樹脂および脂肪族エポキシ樹脂からなる。 [Epoxy compound]
Epoxy compounds include, for example, alicyclic epoxy resins, aliphatic epoxy resins, and aromatic epoxy resins, preferably alicyclic epoxy resins and aliphatic epoxy resins. More preferably, the epoxy compound comprises an alicyclic epoxy resin and an aliphatic epoxy resin, and even more preferably, the epoxy compound consists of an alicyclic epoxy resin and an aliphatic epoxy resin.
（脂環式エポキシ樹脂）
　脂環式エポキシ樹脂は、エポキシ基と脂肪族環（脂環骨格）とを有し、芳香族環を有しない硬化性樹脂（光硬化性樹脂、好ましくは、紫外線硬化性樹脂）である。 (alicyclic epoxy resin)
The alicyclic epoxy resin is a curable resin (photocurable resin, preferably ultraviolet curable resin) having an epoxy group and an alicyclic ring (alicyclic skeleton) and no aromatic ring.
　脂環式エポキシ樹脂として、例えば、グリシジル基含有脂環式エポキシ樹脂、グリシジルエーテル基含有脂環式エポキシ樹脂、および、エポキシシクロ構造含有エポキシ樹脂が挙げられる。 Examples of alicyclic epoxy resins include glycidyl group-containing alicyclic epoxy resins, glycidyl ether group-containing alicyclic epoxy resins, and epoxycyclo structure-containing epoxy resins.
（（グリシジル基含有脂環式エポキシ樹脂））
　グリシジル基含有脂環式エポキシ樹脂は、例えば、脂肪族環に結合するグリシジル基を有する。このようなグリシジル基含有脂環式エポキシ樹脂は、例えば、下記一般式（１）で示される。 ((glycidyl group-containing alicyclic epoxy resin))
A glycidyl group-containing alicyclic epoxy resin has, for example, a glycidyl group bonded to an alicyclic ring. Such a glycidyl group-containing alicyclic epoxy resin is represented, for example, by the following general formula (1).

　式（１）において、Ｒ１は、一価の有機基を示し、ｎは重合度を示す。また、シクロヘキサン環を構成する炭素原子には、アルキル基などの置換基が結合していてもよい。
In formula (1), R1 represents a monovalent organic group and n represents the degree of polymerization. Further, a substituent such as an alkyl group may be bonded to the carbon atoms constituting the cyclohexane ring.
　上記一般式（１）で示されるグリシジル基含有脂環式エポキシ樹脂として、具体的には、２，２－ビス（ヒドロキシメチル）－１－ブタノールの１，２－エポキシ－４－（２－オキシラニル）シクロヘキサン付加物が挙げられる。 As the glycidyl group-containing alicyclic epoxy resin represented by the general formula (1), specifically, 1,2-epoxy-4-(2-oxiranyl of 2,2-bis(hydroxymethyl)-1-butanol ) cyclohexane adducts.
　上記一般式（１）で示されるグリシジル基含有脂環式エポキシ樹脂は、市販品を用いることもできる。上記一般式（１）で示されるグリシジル基含有脂環式エポキシ樹脂の市販品として、例えば、ＥＨＰＥ３１５０（エポキシ当量１７０～１９０ｇ／ｅｑ．、ダイセル社製）が挙げられる。 A commercially available product can also be used as the glycidyl group-containing alicyclic epoxy resin represented by the general formula (1). Examples of commercially available products of the glycidyl group-containing alicyclic epoxy resin represented by the general formula (1) include EHPE3150 (epoxy equivalent: 170 to 190 g/eq., manufactured by Daicel).
（（グリシジルエーテル基含有脂環式エポキシ樹脂））
　グリシジルエーテル基含有脂環式エポキシ樹脂は、脂肪族環に結合するグリシジルエーテルユニットを有する。好ましくは、グリシジルエーテル基含有脂環式エポキシ樹脂は、脂肪族環に結合する複数のグリシジルエーテルユニットを有するポリグリシジルエーテル含有脂環式エポキシ樹脂である。 ((Glycidyl ether group-containing alicyclic epoxy resin))
A glycidyl ether group-containing alicyclic epoxy resin has a glycidyl ether unit bonded to an alicyclic ring. Preferably, the glycidyl ether group-containing alicyclic epoxy resin is a polyglycidyl ether-containing alicyclic epoxy resin having a plurality of glycidyl ether units bonded to an alicyclic ring.
　グリシジルエーテル含有脂環式エポキシ樹脂として、例えば、二官能型グリシジルエーテル含有脂環式エポキシ樹脂が挙げられる。二官能型グリシジルエーテル含有脂環式エポキシ樹脂としては、例えば、水添ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＦジグリシジルエーテル、および、ヘキサヒドロフタル酸ジグリシジルエステルが挙げられる。 Examples of glycidyl ether-containing alicyclic epoxy resins include bifunctional glycidyl ether-containing alicyclic epoxy resins. Bifunctional glycidyl ether-containing alicyclic epoxy resins include, for example, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hexahydrophthalic acid diglycidyl ester.
（（エポキシシクロ構造含有エポキシ樹脂））
　エポキシシクロ構造含有エポキシ樹脂は、脂肪族環を形成している隣接する２つの炭素原子と、それら２つの炭素原子に結合する１つの酸素原子とから構成されるエポキシ基を有するエポキシシクロ構造を有する。 ((epoxy cyclostructure-containing epoxy resin))
The epoxy cyclo structure-containing epoxy resin has an epoxy cyclo structure having an epoxy group composed of two adjacent carbon atoms forming an alicyclic ring and one oxygen atom bonded to the two carbon atoms. .
　エポキシシクロ構造含有エポキシ樹脂として、例えば、エポキシシクロヘキサン構造含有エポキシ樹脂（以下、ＥＣＨ構造含有エポキシ樹脂とする。）が挙げられる。 Examples of epoxy cyclo structure-containing epoxy resins include epoxy cyclohexane structure-containing epoxy resins (hereinafter referred to as ECH structure-containing epoxy resins).
　ＥＣＨ構造含有エポキシ樹脂として、例えば、下記化学式（２）に示される１つのＥＣＨ構造を含有するエポキシ樹脂、下記一般式（３）に示される２つのＥＣＨ構造を含有するエポキシ樹脂、および、それらの変性物が挙げられる。 Examples of ECH structure-containing epoxy resins include epoxy resins containing one ECH structure represented by the following chemical formula (2), epoxy resins containing two ECH structures represented by the following general formula (3), and their Modified products are mentioned.
　式（３）中において、Ｘは、連結基（１以上の原子を有する２価の基）を示す。ｍは、０または１を示す。Ｒ２は、水素原子、フッ素原子、アルキル基、フルオロアルキル基、アリール基、フリル基およびチエニル基からなる群から選択される１つの原子または置換基を示す。式（３）中における２つのＲ２は、互いに同一であってもよく互いに異なっていてもよい。 In formula (3), X represents a linking group (a divalent group having one or more atoms). m represents 0 or 1; R2 represents one atom or substituent selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an aryl group, a furyl group and a thienyl group. Two R2's in formula (3) may be the same or different.
　上記一般式（３）に示される２つのＥＣＨ構造を含有するエポキシ樹脂（以下、一般式（３）に示されるＥＣＨ構造含有エポキシ樹脂とする。）は、ＥＣＨ構造（エポキシシクロヘキシル基）を分子の両末端に有し、２つのエポキシシクロヘキシル基が連結基（ｍが０の場合には、炭素－炭素結合）を介して結合する。なお、エポキシシクロヘキシル基は、シクロヘキサン環と、シクロヘキサン環を形成している隣接する２つの炭素原子と、それら２つの炭素原子に結合する１つの酸素原子とにより構成されるエポキシ基とを含む官能基である。 The epoxy resin containing two ECH structures represented by the general formula (3) (hereinafter referred to as the ECH structure-containing epoxy resin represented by the general formula (3)) has an ECH structure (epoxycyclohexyl group) in the molecule It has two epoxycyclohexyl groups at both ends, and two epoxycyclohexyl groups are linked via a linking group (a carbon-carbon bond when m is 0). The epoxycyclohexyl group is a functional group containing a cyclohexane ring, an epoxy group composed of two adjacent carbon atoms forming the cyclohexane ring, and one oxygen atom bonded to the two carbon atoms. is.
　上記一般式（３）においてＲ２で示されるアルキル基として、例えば、炭素数１～６の直鎖または分岐鎖状のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基など）などが挙げられる。 The alkyl group represented by R2 in the general formula (3) includes, for example, a linear or branched alkyl group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.).
　上記一般式（３）においてＲ２で示されるフルオロアルキル基として、例えば、炭素数１～６の直鎖または分岐鎖状のフルオロアルキル基（例えば、パーフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基など）などが挙げられる。 As the fluoroalkyl group represented by R2 in the general formula (3), for example, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms (e.g., perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, etc.).
　上記一般式（３）においてＲ２で示されるアリール基として、例えば、炭素数６～１８のアリール基（例えば、フェニル基、ナフチル基など）などが挙げられる。 Examples of the aryl group represented by R2 in the above general formula (3) include aryl groups having 6 to 18 carbon atoms (eg, phenyl group, naphthyl group, etc.).
　上記一般式（３）においてＸで示される連結基として、例えば、酸素原子、硫黄原子、２価の炭化水素基、ポリオキシアルキレン基、カルボニル基、エーテル基、チオエーテル基、エステル基、カーボネート基、アミド基、および、これらが連結した基などが挙げられる。なお、ｍが０の場合には、２つのＥＣＨ構造が、炭素－炭素結合を介して結合する。 Examples of the linking group represented by X in the general formula (3) include an oxygen atom, a sulfur atom, a divalent hydrocarbon group, a polyoxyalkylene group, a carbonyl group, an ether group, a thioether group, an ester group, a carbonate group, Examples include amide groups and groups in which these groups are linked. Note that when m is 0, two ECH structures are linked via a carbon-carbon bond.
　２価の炭化水素基として、例えば、炭素数１～２０の直鎖または分岐鎖状のアルキレン基（例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基、ブチレン基など）、炭素数１～２０の直鎖または分岐鎖状の不飽和炭化水素基（例えば、プロペニレン基、メチルプロペニレン基、ブテニレン基など）などが挙げられる。 Examples of divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 20 carbon atoms (e.g., methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, butylene group, etc.), linear or branched unsaturated hydrocarbon groups having 1 to 20 carbon atoms (eg, propenylene group, methylpropenylene group, butenylene group, etc.), and the like.
　ポリオキシアルキレン基として、例えば、炭素数１～１２０の直鎖または分岐鎖状のポリオキシアルキレン基（例えば、ポリオキシエチレン基、ポリオキシプロピレン基など）などが挙げられる。 Examples of polyoxyalkylene groups include linear or branched polyoxyalkylene groups having 1 to 120 carbon atoms (eg, polyoxyethylene groups, polyoxypropylene groups, etc.).
　一般式（３）に示されるＥＣＨ構造含有エポキシ樹脂として、具体的には、（３、３’、４、４’－ジエポキシ）ビシクロヘキシル、ビス（３，４－エポキシシクロヘキシルメチル）エーテル、１，２－ビス（３，４－エポキシシクロヘキサン－１－イル）エタン、２，２－ビス（３，４－エポキシシクロヘキサン－１－イル）プロパン、３，４－エポキシシクロヘキシルメチル（３，４－エポキシ）シクロヘキサンカルボキシレート、および、ε－カプロラクトン変性３’，４’－エポキシシクロヘキシルメチル３，４－エポキシシクロヘキサンカルボキリレートが挙げられ、好ましくは、（３、３’、４、４’－ジエポキシ）ビシクロヘキシル（上記式（３）において、ｍが０を示し、Ｒ２が水素原子を示す。）が挙げられる。 Specific examples of ECH structure-containing epoxy resins represented by general formula (3) include (3,3′,4,4′-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1, 2-bis(3,4-epoxycyclohexan-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexan-1-yl)propane, 3,4-epoxycyclohexylmethyl (3,4-epoxy) Cyclohexanecarboxylate and ε-caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, preferably (3,3′,4,4′-diepoxy)bicyclohexyl (In formula (3) above, m represents 0 and R2 represents a hydrogen atom.).
　また、上記一般式（３）に示されるＥＣＨ構造含有エポキシ樹脂は、市販品を用いることもできる。上記一般式（３）に示されるＥＣＨ構造含有エポキシ樹脂の市販品として、例えば、セロキサイド８０００、セロキサイド８０１０、セロキサイド２０２１Ｐ、および、セロキサイド２０８１（以上ダイセル社製）が挙げられる。 A commercially available product can also be used as the ECH structure-containing epoxy resin represented by the general formula (3). Examples of commercially available ECH structure-containing epoxy resins represented by the general formula (3) include Celoxide 8000, Celoxide 8010, Celoxide 2021P, and Celoxide 2081 (manufactured by Daicel Corporation).
　ＥＣＨ構造含有エポキシ樹脂として、好ましくは、上記一般式（３）に示されるＥＣＨ構造含有エポキシ樹脂が挙げられる。 The ECH structure-containing epoxy resin preferably includes the ECH structure-containing epoxy resin represented by the above general formula (3).
　そして、脂環式エポキシ樹脂として、好ましくは、エポキシシクロ構造含有エポキシ樹脂が挙げられる。 And, as the alicyclic epoxy resin, an epoxy cyclo structure-containing epoxy resin is preferably used.
　脂環式エポキシ樹脂の重量平均分子量は、例えば、２００以上、また、例えば、１０００以下、好ましくは、５００以下である。重量平均分子量（Ｍｗ）は、ポリスチレンを標準物質とするゲルパーミエーションクロマトグラフィー（ＧＰＣ)により求めることができる（以下同様）。 The weight average molecular weight of the alicyclic epoxy resin is, for example, 200 or more and, for example, 1000 or less, preferably 500 or less. The weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC) using polystyrene as a standard (the same applies hereinafter).
　また、脂環式エポキシ樹脂におけるエポキシ当量は、例えば、９０ｇ／ｅｑ．以上、好ましくは、１００ｇ／ｅｑ．以上、例えば、２５０ｇ／ｅｑ．以下、好ましくは、１９０ｇ／ｅｑ．以下である。エポキシ当量は、ＪＩＳ　Ｋ７２３６：２００１に準拠して測定できる（以下同様）。 Also, the epoxy equivalent of the alicyclic epoxy resin is, for example, 90 g/eq. above, preferably 100 g/eq. Above, for example, 250 g/eq. Below, preferably 190 g/eq. It is below. The epoxy equivalent can be measured according to JIS K7236:2001 (the same applies hereinafter).
（脂肪族エポキシ樹脂）
　脂肪族エポキシ樹脂としては、例えば、二官能性脂肪族エポキシ樹脂が挙げられる。二官能性脂肪族エポキシ樹脂としては、例えば、エチレングリコールジグリシジルエーテル、ロピレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、および、ネオペンチルグリコールジグリシジルエーテルが挙げられ、好ましくは、ネオペンチルグリコールジグリシジルエーテルが挙げられる。 (aliphatic epoxy resin)
Aliphatic epoxy resins include, for example, bifunctional aliphatic epoxy resins. Difunctional aliphatic epoxy resins include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether, preferably neo Pentyl glycol diglycidyl ether may be mentioned.
　脂肪族エポキシ樹脂の重量平均分子量は、例えば、１５０以上、また、例えば、４００以下である。 The weight average molecular weight of the aliphatic epoxy resin is, for example, 150 or more and, for example, 400 or less.
　また、脂肪族エポキシ樹脂におけるエポキシ当量は、例えば、６０ｇ／ｅｑ．以上、また、例えば、２５０ｇ／ｅｑ．以下である。 Also, the epoxy equivalent of the aliphatic epoxy resin is, for example, 60 g/eq. above, and for example, 250 g/eq. It is below.
　エポキシ化合物が、脂環式エポキシ樹脂および脂肪族エポキシ樹脂を含む場合には、脂環式エポキシ樹脂の含有量は、脂環式エポキシ樹脂および脂肪族エポキシ樹脂の総量１００質量部に対して、例えば、１０質量部以上、好ましくは、２０質量部以上、また、例えば、５０質量部以下、好ましくは、４０質量部以下である。また、脂環式エポキシ樹脂の含有量は、カチオン重合性化合物に対して、例えば、５質量％以上、好ましくは、１０質量％以上、また、例えば、３０質量％以下、好ましくは、２０質量％以下である。 When the epoxy compound contains an alicyclic epoxy resin and an aliphatic epoxy resin, the content of the alicyclic epoxy resin is, for example, , 10 parts by mass or more, preferably 20 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass or less. In addition, the content of the alicyclic epoxy resin is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 30% by mass or less, preferably 20% by mass, relative to the cationic polymerizable compound. It is below.
　また、エポキシ化合物が、脂環式エポキシ樹脂および脂肪族エポキシ樹脂を含む場合には、脂肪族エポキシ樹脂の含有量は、脂環式エポキシ樹脂および脂肪族エポキシ樹脂の総量１００質量部に対して、例えば、４０質量部以上、好ましくは、５０質量部以上、より好ましくは、６０質量部以上、また、例えば、９０質量部以下、好ましくは、８０質量部以下である。また、脂肪族エポキシ樹脂の含有量は、カチオン重合性化合物に対して、例えば、２０質量％以上、好ましくは、３０質量％以上、また、例えば、５０質量％以下、好ましくは、４０質量％以下である。 When the epoxy compound contains an alicyclic epoxy resin and an aliphatic epoxy resin, the content of the aliphatic epoxy resin is For example, it is 40 parts by mass or more, preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and for example, 90 parts by mass or less, preferably 80 parts by mass or less. Further, the content of the aliphatic epoxy resin is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, 50% by mass or less, preferably 40% by mass or less, relative to the cationic polymerizable compound. is.
　エポキシ化合物は、単独使用または２種類以上併用することができる。 Epoxy compounds can be used alone or in combination of two or more.
　そして、エポキシ化合物の含有量は、カチオン重合性化合物に対して、例えば、３０質量％以上、好ましくは、４０質量％以上、また、例えば、７０質量％以下、好ましくは、６０質量％以下である。 The content of the epoxy compound is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less, relative to the cationic polymerizable compound. .
［オキセタン化合物］
　オキセタン化合物は、例えば、１以上５以下のオキセタン環を含有する。 [Oxetane compound]
The oxetane compound contains, for example, from 1 to 5 oxetane rings.
　オキセタン化合物として、例えば、１つのオキセタン環を有する単官能オキセタン化合物、２つのオキセタン環を有する二官能オキセタン化合物、および、３つ以上のオキセタン環を有する三官能以上のオキセタン化合物が挙げられる。 Examples of oxetane compounds include monofunctional oxetane compounds having one oxetane ring, bifunctional oxetane compounds having two oxetane rings, and trifunctional or higher oxetane compounds having three or more oxetane rings.
　単官能オキセタン化合物として、例えば、３－エチル－３－ヒドロキシメチルオキセタン、３－（メタ）アリルオキシメチル－３－エチルオキセタン、（３－エチル－３－オキセタニルメトキシ）メチルベンゼン、２－エチルヘキシル（３－エチル－３－オキセタニルメチル）エーテル、エチルジエチレングリコール（３－エチル－３－オキセタニルメチル）エーテル、および、３－シクロヘキシルメチルー３－エチル－オキセタンが挙げられる。 Examples of monofunctional oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 3-(meth)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, 2-ethylhexyl (3 -ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl)ether, and 3-cyclohexylmethyl-3-ethyl-oxetane.
　二官能オキセタン化合物として、例えば、１，４－ビス｛〔（３－エチル－３－オキセタニル）メトキシ〕メチル｝ベンゼン、３，３’－（オキシビスメチレン）ビス（３－エチルオキセタン）、１，４－ビス〔（３－エチル－３－オキセタニル）メトキシ〕ベンゼン、１，３－ビス〔（３－エチル－３－オキセタニル）メトキシ〕ベンゼン、３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、１，４－ビス〔（３－エチル－３－オキセタニルメトキシ）メチル〕ベンゼン、１，２－ビス〔（３－エチル－３－オキセタニルメトキシ）メチル〕エタン、１，２－ビス〔（３－エチル－３－オキセタニルメトキシ）メチル〕プロパン、エチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、および、ジシクロペンテニルビス（３－エチル－３－オキセタニルメチル）エーテルが挙げられ、好ましくは、３，３’－（オキシビスメチレン）ビス（３－エチルオキセタン）が挙げられる。 Examples of bifunctional oxetane compounds include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3,3′-(oxybismethylene)bis(3-ethyloxetane), 1, 4-bis[(3-ethyl-3-oxetanyl)methoxy]benzene, 1,3-bis[(3-ethyl-3-oxetanyl)methoxy]benzene, 3,7-bis(3-oxetanyl)-5-oxa -nonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,2-bis[( 3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, and dicyclopentenylbis(3-ethyl-3-oxetanylmethyl)ether are preferred. includes 3,3′-(oxybismethylene)bis(3-ethyloxetane).
　三官能以上のオキセタン化合物として、例えば、トリメチロールプロパントリス（３－エチル－３－オキセタニルメチル）エーテル、ペンタエリスリトールトリス（３－エチル－３－オキセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３－エチル－３－オキセタニルメチル）エーテル、および、ジペンタエリスリトールペンタキス（３－エチル－３－オキセタニルメチル）エーテルが挙げられる。 Examples of trifunctional or higher oxetane compounds include trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3 -oxetanylmethyl) ether, and dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether.
　オキセタン化合物は、市販品を用いることもできる。オキセタン化合物の市販品として、例えば、アロンオキセタン　ＯＸＴ－２２１（３，３’－（オキシビスメチレン）ビス（３－エチルオキセタン））、アロンオキセタン　ＯＸＴ－１２１（以上東亜合成化学社製）が挙げられる。 Commercially available oxetane compounds can also be used. Examples of commercially available oxetane compounds include Aron oxetane OXT-221 (3,3'-(oxybismethylene)bis(3-ethyloxetane)) and Aron oxetane OXT-121 (manufactured by Toagosei Chemical Co., Ltd.). .
　オキセタン化合物として、好ましくは、二官能オキセタン化合物が挙げられる。 The oxetane compound preferably includes a bifunctional oxetane compound.
　オキセタン化合物は、単独使用または２種類以上併用することができる。 The oxetane compound can be used alone or in combination of two or more.
　オキセタン化合物の含有量は、カチオン重合性化合物に対して、例えば、３０質量％以上、好ましくは、４０質量％以上、また、例えば、７０質量％以下、好ましくは、６０質量％以下である。 The content of the oxetane compound is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 70% by mass or less, preferably 60% by mass or less, relative to the cationic polymerizable compound.
　また、カチオン重合性化合物の含有量は、有機ＥＬ用表示素子用封止材に対して、例えば、８０質量％以上、好ましくは、９０質量％以上、また、例えば、９８質量％以下である。 In addition, the content of the cationic polymerizable compound is, for example, 80% by mass or more, preferably 90% by mass or more, and, for example, 98% by mass or less with respect to the sealing material for organic EL display elements.
＜カチオン重合開始剤＞
　カチオン重合開始剤は、例えば、光照射により酸を発生する光酸発生剤である。 <Cationic polymerization initiator>
A cationic polymerization initiator is, for example, a photoacid generator that generates an acid upon irradiation with light.
　カチオン重合開始剤は、特に制限されず、公知のカチオン重合開始剤を用いることができる。 The cationic polymerization initiator is not particularly limited, and known cationic polymerization initiators can be used.
　カチオン重合開始剤は、単独使用または２種類以上併用することができる。 The cationic polymerization initiator can be used alone or in combination of two or more.
　カチオン重合開始剤の含有量は、カチオン重合性化合物１００質量部に対して、例えば、０．５質量部以上、好ましくは、０．８質量部以上、より好ましくは、１．３質量部以上、また、例えば、５質量部以下、好ましくは、２．５質量部以下である。 The content of the cationic polymerization initiator is, for 100 parts by mass of the cationic polymerizable compound, for example, 0.5 parts by mass or more, preferably 0.8 parts by mass or more, more preferably 1.3 parts by mass or more, Also, for example, it is 5 parts by mass or less, preferably 2.5 parts by mass or less.
　また、カチオン重合開始剤の含有量は、有機ＥＬ用表示素子用封止材に対して、例えば、０．５質量％以上、好ましくは、１質量％以上、また、例えば、１０質量％以下、好ましくは、５質量％以下である。 The content of the cationic polymerization initiator is, for example, 0.5% by mass or more, preferably 1% by mass or more, and, for example, 10% by mass or less, relative to the sealing material for organic EL display elements. Preferably, it is 5% by mass or less.
＜紫外線吸収剤＞
　紫外線吸収剤は、白色光を吸収し、カチオン重合開始剤から、酸が発生することを抑制する成分である。 <Ultraviolet absorber>
The ultraviolet absorber is a component that absorbs white light and suppresses the generation of acid from the cationic polymerization initiator.
　紫外線吸収剤としては、例えば、ベンゾトリアゾール化合物、ベンゾフェノン化合物、トリアジン化合物、および、シアノアクリレート化合物が挙げられる。 Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, and cyanoacrylate compounds.
　ベンゾトリアゾール化合物としては、例えば、２－（５－メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２，２－ヒドロキシ－３，５－ビス（α，α－ジメチルベンジル）フェニル、２－（２´－ヒドロキシ－５´－メチル－フェニル）ベンゾトリアゾール、２－（２´－ヒドロキシ－３´，５´－ジ－ｔ－ブチル－フェニル）ベンゾトリアゾール、２－（２´－ヒドロキシ－３´－ｔ－ブチル－５´－メチル－フェニル）－５－クロロ・ベンゾトリアゾール、２－（２´－ヒドロキシ－３´，５´－ジ－ｔ－ブチル－フェニル）－５－クロロ・ベンゾトリアゾール、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）－フェノール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、および、２－（２´－ヒドロキシ－４´－ｎ－オクトキシ・フェニル）ベンゾトリアゾールが挙げられる。好ましくは、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）－フェノール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、および、２－［２－ヒドロキシ－５－［２－（メタクリロイルオキシ）エチル］フェニル］－２Ｈ－ベンゾトリアゾールが挙げられる。より好ましくは、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）－フェノール、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、さらに好ましくは、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾールが挙げられる。 Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2,2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl, 2-(2′- hydroxy-5′-methyl-phenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-butyl-phenyl)benzotriazole, 2-(2′-hydroxy-3′-t- Butyl-5′-methyl-phenyl)-5-chloro benzotriazole, 2-(2′-hydroxy-3′,5′-di-t-butyl-phenyl)-5-chloro benzotriazole, 2-( 2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, and 2-(2' -hydroxy-4'-n-octoxyphenyl)benzotriazole. preferably 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, and , 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole. more preferably 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, More preferred is 2-(2-hydroxy-5-methylphenyl)benzotriazole.
　ベンゾトリアゾール化合物としては、市販品を用いることもできる。ベンゾトリアゾール化合物の市販品として、例えば、チヌビン２３４（２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）－フェノール、ＢＡＳＦジャパン株式会社製）、ＫＥＭＩＳＯＲＢ７１（２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、ケミプロ化成社製）、および、ＲＵＶＡ－９３（２－［２－ヒドロキシ－５－［２－（メタクリロイルオキシ）エチル］フェニル］－２Ｈ－ベンゾトリアゾール、大塚化学社製）が挙げられる。 A commercially available product can also be used as the benzotriazole compound. Examples of commercially available benzotriazole compounds include Tinuvin 234 (2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)-phenol, manufactured by BASF Japan Ltd.). , KEMISORB71 (2-(2-hydroxy-5-methylphenyl)benzotriazole, manufactured by Chemipro Kasei Co., Ltd.), and RUVA-93 (2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl] -2H-benzotriazole, manufactured by Otsuka Chemical Co., Ltd.).
　ベンゾフェノン化合物としては、例えば、[２－ヒドロキシ－４－（オクチルオキシ）フェニル]（フェニル）メタノン、２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノン、２，４－ジヒドロキシ・ベンゾフェノン、２－ヒドロキシ－４－メトキシ・ベンゾフェノン、２，２´－ジヒドロキシ－４－メトキシ・ベンゾフェノン、２，２´－ジヒドロキシ－４，４´－ジメトキシ・ベンゾフェノン、２，２´－ジヒドロキシ－４，４´－ジメトキシ－５－スルフォベンゾフェノン、２－ヒドロキシ－４－メトキシ－２´－カルボキシ・ベンゾフェノン、２－ヒドロキシ－４－メトキシ－５－スルフォベンゾフェノン・トリヒドレート、２－ヒドロキシ－４－ｎ－ドデシロキシ・ベンゾフェノン、２－ヒドロキシ－４－ベンジロキシベンゾフェノン、２，２´，４，４´－テトラヒドロキシ・ベンゾフェノン、２－ヒドロキシ－４－ドデシロキシ－ベンゾフェノン、および、２－ヒドロキシ－４－（２－ヒドロキシ－３－メタクリロキシ）プロポキシベンゾフェノンが挙げられる。好ましくは、[２－ヒドロキシ－４－（オクチルオキシ）フェニル]（フェニル）メタノン、および、２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノンが挙げられる。より好ましくは、２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノンが挙げられる。 Examples of benzophenone compounds include [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone, 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -methoxy benzophenone, 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5- Sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-dodecyloxy benzophenone, 2-hydroxy -4-benzyloxybenzophenone, 2,2',4,4'-tetrahydroxy benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, and 2-hydroxy-4-(2-hydroxy-3-methacryloxy)propoxy Benzophenone is mentioned. Preferred are [2-hydroxy-4-(octyloxy)phenyl](phenyl)methanone and 2-hydroxy-4-n-octyloxybenzophenone. More preferred is 2-hydroxy-4-n-octyloxybenzophenone.
　ベンゾフェノン化合物としては、市販品を用いることもできる。ベンゾフェノン化合物の市販品として、例えば、ＫＥＭＩＳＯＲＢ１２（２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノン、ケミプロ化成社製）、および、アデカスタブ１４１３（［２－ヒドロキシ－４－（オクチルオキシ）フェニル］（フェニル）メタノン、ＡＤＥＫＡ社製）が挙げられる。 A commercially available product can also be used as the benzophenone compound. Commercially available benzophenone compounds include, for example, KEMIISORB12 (2-hydroxy-4-n-octyloxybenzophenone, manufactured by Chemipro Kasei Co., Ltd.) and Adekastab 1413 ([2-hydroxy-4-(octyloxy)phenyl](phenyl) Methanone, manufactured by ADEKA).
　トリアジン化合物としては、例えば、２－［４，６－ジ（２，４－キシリル）－１，３，５－トリアジン－２－イル］－５－オクチルオキシフェノール、および、２，４－ジフェニル－６－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－１，３，５－トリアジンが挙げられ、好ましくは、２，４－ジフェニル－６－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－１，３，５－トリアジンが挙げられる。 Examples of triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol and 2,4-diphenyl- 6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazines, preferably 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1, 3,5-triazines are mentioned.
　トリアジン化合物としては、市販品を用いることもできる。トリアジン化合物の市販品として、例えば、ＫＥＭＩＳＯＲＢ１０２（２，４－ジフェニル－６－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－１，３，５－トリアジン、ケミプロ化成社製）が挙げられる。 A commercially available product can also be used as the triazine compound. Examples of commercially available triazine compounds include KEMISORB102 (2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, manufactured by Chemipro Kasei).
　シアノアクリレート化合物としては、例えば、エチル－２－シアノ－３－（３´，４´－メチレンジオキシフェニル）－アクリレートが挙げられる。 Examples of cyanoacrylate compounds include ethyl-2-cyano-3-(3',4'-methylenedioxyphenyl)-acrylate.
　紫外線吸収剤としては、好ましくは、ベンゾトリアゾール化合物、ベンゾフェノン化合物、および、トリアジン化合物、より好ましくは、ベンゾトリアゾール化合物、および、ベンゾフェノン化合物、さらに好ましくは、紫外線吸収剤として、ベンゾトリアゾール化合物、または、ベンゾフェノン化合物が選択される。 As the UV absorber, preferably a benzotriazole compound, a benzophenone compound, and a triazine compound, more preferably a benzotriazole compound and a benzophenone compound, more preferably as a UV absorber, a benzotriazole compound or benzophenone. A compound is selected.
　紫外線吸収剤が、ベンゾトリアゾール化合物、または、ベンゾフェノン化合物であれば、白色光に対する安定性に、より一層優れる。 If the UV absorber is a benzotriazole compound or a benzophenone compound, the stability against white light is even better.
　とりわけ好ましくは、紫外線吸収剤は、白色光に対する安定性を、さらに向上させる観点から、ベンゾトリアゾール化合物である。 Particularly preferably, the ultraviolet absorber is a benzotriazole compound from the viewpoint of further improving the stability against white light.
　紫外線吸収剤は、単独使用または２種類以上併用することができる。 The ultraviolet absorbers can be used alone or in combination of two or more.
　紫外線吸収剤の含有量は、カチオン重合性化合物１００質量部に対して、例えば、０．０５質量部以上、好ましくは、０．４質量部以上、より好ましくは、０．８質量部以上、また、例えば、２質量部以下、好ましくは、１．５質量部以下である。 The content of the ultraviolet absorber is, for example, 0.05 parts by mass or more, preferably 0.4 parts by mass or more, more preferably 0.8 parts by mass or more with respect to 100 parts by mass of the cationic polymerizable compound, and , for example, 2 parts by mass or less, preferably 1.5 parts by mass or less.
　また、紫外線吸収剤の含有量は、有機ＥＬ用表示素子用封止材に対して、例えば、０．１質量％以上、好ましくは、０．５質量％以上、より好ましくは、０．８質量％以上、また、例えば、２質量％以下、好ましくは、有機ＥＬ用表示素子用封止材の、硬化後の信頼性を向上する観点から、１．５質量％以下、さらに好ましくは、１．２質量％以下である。 Further, the content of the ultraviolet absorber is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.8% by mass, relative to the sealing material for organic EL display elements. % or more, and for example, 2% by mass or less, preferably 1.5% by mass or less, more preferably 1.5% by mass or less, from the viewpoint of improving the reliability of the sealing material for organic EL display elements after curing. It is 2% by mass or less.
　紫外線吸収剤の含有量が、上記下限以上であれば、白色光に対する安定性を向上できる。 If the content of the ultraviolet absorber is equal to or higher than the above lower limit, the stability against white light can be improved.
　また、紫外線吸収剤の含有量が、上記上限以下であれば、紫外線を照射して硬化した際の硬化性が保持される。 Also, if the content of the ultraviolet absorber is equal to or less than the above upper limit, the curability when cured by irradiation with ultraviolet rays is maintained.
＜フェノール性の水酸基を有する化合物＞
　フェノール性の水酸基を有する化合物は、光照射によりカチオン重合開始剤から生じた酸を捕捉する成分である。 <Compound having a phenolic hydroxyl group>
A compound having a phenolic hydroxyl group is a component that scavenges an acid generated from a cationic polymerization initiator upon irradiation with light.
　フェノール性の水酸基を有する化合物は、分子内に、１以上のフェノール性の水酸基を有する化合物である。また、フェノール性の水酸基を有する化合物には、上記したベンゾトリアゾール化合物、上記したベンゾフェノン化合物、上記したトリアジン化合物、および、上記したシアノアクリレート化合物は含まれない。 A compound having a phenolic hydroxyl group is a compound having one or more phenolic hydroxyl groups in the molecule. Further, the compounds having a phenolic hydroxyl group do not include the above benzotriazole compounds, the above benzophenone compounds, the above triazine compounds, and the above cyanoacrylate compounds.
　このようなフェノール性の水酸基を有する化合物として、好ましくは、１つのベンゼン環を有し、そのベンゼン環が１つのフェノール性の水酸基を有する一官能のフェノール性の水酸基を有する化合物、１つのベンゼン環を有し、そのベンゼン環が２つのフェノール性の水酸基を有する二官能のフェノール性の水酸基を有する化合物、および、１つのベンゼン環を有し、そのベンゼン環が３つ以上のフェノール性の水酸基を有する三官能以上のフェノール性の水酸基を有する化合物が挙げられる。つまり、フェノール性の水酸基を有する化合物は、好ましくは、１つのベンゼン環を有する。これにより、安定性に優れる。 As such a compound having a phenolic hydroxyl group, preferably a compound having a monofunctional phenolic hydroxyl group having one benzene ring, the benzene ring having one phenolic hydroxyl group, one benzene ring and a compound having a bifunctional phenolic hydroxyl group in which the benzene ring has two phenolic hydroxyl groups, and a compound having one benzene ring, in which the benzene ring has three or more phenolic hydroxyl groups compounds having a trifunctional or higher phenolic hydroxyl group. That is, a compound having a phenolic hydroxyl group preferably has one benzene ring. This ensures excellent stability.
　一官能のフェノール性の水酸基を有する化合物としては、例えば、下記式（４）で示す化合物が挙げられる。

　上記式（４）において、Ｒ３は、水素原子、炭素数１～１０のアルキル基、および、アルキルエステル基を示す。 Examples of compounds having a monofunctional phenolic hydroxyl group include compounds represented by the following formula (4).

In formula (4) above, R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl ester group.
　炭素数１～１０のアルキル基を示す。炭素数１～１０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、および、デシル基が挙げられる。 Indicates an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
　アルキルエステル基は、下記式（５）で示される。
－Ｒ４－Ｃ（＝Ｏ）－Ｏ－Ｒ５　　（５） An alkyl ester group is represented by the following formula (5).
—R 4 —C(=O) —OR 5 (5)
　上記式（５）において、Ｒ４は、炭素数１～６のアルキレン基を示す。炭素数１～６のアルキレン基としては、例えば、メチレン基、メチルメチレン基、ジメチルメチレン基、エチレン基、プロピレン基、トリメチレン基、および、ブチレン基が挙げられる。 In the above formula (5), R4 represents an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group and butylene group.
　上記式（５）において、Ｒ５は、炭素数１～１０のアルキル基を示す。炭素数１～１０のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、および、デシル基が挙げられる。 In the above formula (5), R5 represents an alkyl group having 1 to 10 carbon atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.
　このような一官能のフェノール性の水酸基を有する化合物として、好ましくは、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール（上記式（４）において、Ｒ３がメチル基を示す化合物）、および、ベンゼンプロパン酸　３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ－Ｃ７－Ｃ９側鎖アルキルエステル（上記式（４）において、Ｒ３が、アルキルエステル基を示し、上記式（５）において、Ｒ４がエチレン基を示し、Ｒ５がヘプチル基を示す化合物と、Ｒ４がエチレン基を示し、Ｒ５がオクチル基を示す化合物と、Ｒ４がエチレン基を示し、Ｒ５がノニル基を示す化合物との混合物）が挙げられ、好ましくは、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾールが挙げられる。 As such a compound having a monofunctional phenolic hydroxyl group, preferably 2,6-di-tert-butyl-p-cresol (a compound in which R3 represents a methyl group in the above formula (4)), and Benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester (in the above formula (4), R3 represents an alkyl ester group, the above formula (5) , a compound in which R4 represents an ethylene group and R5 represents a heptyl group, a compound in which R4 represents an ethylene group and R5 represents an octyl group, and a compound in which R4 represents an ethylene group and R5 represents a nonyl group. mixture), preferably 2,6-di-tert-butyl-p-cresol.
　つまり、上記式（４）で示す化合物は、好ましくは、アルキルエステル基を含まない。そのため、白色光の安定性に対する添加量の寄与が高いため、白色光の安定性と硬化性の両立の観点で見るとより一層優れる。 That is, the compound represented by formula (4) above preferably does not contain an alkyl ester group. Therefore, since the contribution of the addition amount to the stability of white light is high, it is even more excellent from the viewpoint of compatibility between the stability of white light and curability.
　二官能のフェノール性の水酸基を有する化合物としては、例えば、ヒドロキノン、レゾルシノール、ｔｅｒｔ－ブチルカテコール、および、ｔｅｒｔ－ブチルヒドロキノンが挙げられる。 Examples of compounds having a bifunctional phenolic hydroxyl group include hydroquinone, resorcinol, tert-butylcatechol, and tert-butylhydroquinone.
　三官能以上のフェノール性の水酸基を有する化合物としては、例えば、ピロガロールが挙げられる。 Examples of compounds having trifunctional or higher phenolic hydroxyl groups include pyrogallol.
　フェノール性の水酸基を有する化合物として、好ましくは、一官能のフェノール性の水酸基を有する化合物、および、二官能のフェノール性の水酸基を有する化合物、より好ましくは、白色光に対する安定性および硬化性の両立の観点から、一官能のフェノール性の水酸基を有する化合物が挙げられる。 As the compound having a phenolic hydroxyl group, preferably a compound having a monofunctional phenolic hydroxyl group and a compound having a bifunctional phenolic hydroxyl group, more preferably a compound having both stability and curability to white light From the viewpoint of, a compound having a monofunctional phenolic hydroxyl group can be mentioned.
　また、フェノール性の水酸基を有する化合物の分子量は、例えば、９４以上、好ましくは、１００以上、より好ましくは、２００以上、また、例えば、１０００以下、好ましくは、５００以下、白色光に対する安定性および硬化性の両立の観点から、より好ましくは、３００以下である。分子量が少ないと白色光の安定性に対する添加量の寄与が高いため、白色光の安定性および硬化性の両立の観点で見るとより一層優れる。 In addition, the molecular weight of the compound having a phenolic hydroxyl group is, for example, 94 or more, preferably 100 or more, more preferably 200 or more, and for example, 1000 or less, preferably 500 or less, stability against white light and From the viewpoint of compatibility with curability, it is more preferably 300 or less. When the molecular weight is low, the contribution of the amount added to the stability of white light is high, so it is even more excellent from the viewpoint of compatibility between the stability of white light and curability.
　フェノール性の水酸基を有する化合物は、単独使用または２種類以上併用することができる。 A compound having a phenolic hydroxyl group can be used alone or in combination of two or more.
　フェノール性の水酸基を有する化合物の含有量は、カチオン重合性化合物１００質量部に対して、例えば、０．０１質量部以上、好ましくは、０．０５質量部以上、より好ましくは、０．０８質量部以上、さらに好ましくは、０．１質量部以上、また、例えば、０．５質量部以下、好ましくは、０．３質量部以下、より好ましくは、０．１５質量部以下である。 The content of the compound having a phenolic hydroxyl group is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound. parts or more, more preferably 0.1 parts by mass or more, and for example, 0.5 parts by mass or less, preferably 0.3 parts by mass or less, more preferably 0.15 parts by mass or less.
　また、フェノール性の水酸基を有する化合物の含有量は、有機ＥＬ用表示素子用封止材に対して、例えば、０．０１質量％以上、好ましくは、０．０５質量％以上、より好ましくは、０．０８質量％以上、さらに好ましくは、０．１質量％以上、また、例えば、０．５質量％以下、好ましくは、０．３質量％以下、より好ましくは、０．１５質量％以下である。 The content of the compound having a phenolic hydroxyl group is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.08% by mass or more, more preferably 0.1% by mass or more, and for example, 0.5% by mass or less, preferably 0.3% by mass or less, more preferably 0.15% by mass or less be.
　フェノール性の水酸基を有する化合物の含有量が、上記下限以上であれば、白色光に対する安定性を向上できる。 If the content of the compound having a phenolic hydroxyl group is at least the above lower limit, the stability against white light can be improved.
　また、フェノール性の水酸基を有する化合物の含有量が、上記上限以下であれば、硬化性に優れる。 Also, if the content of the compound having a phenolic hydroxyl group is equal to or less than the above upper limit, the curability is excellent.
　そして、紫外線吸収剤に対するフェノール性の水酸基を有する化合物の質量比（フェノール性の水酸基を有する化合物／紫外線吸収剤）は、０．０１以上、好ましくは、０．０３以上、より好ましくは、０．０７以上、さらに好ましくは、０．０９以上、とりわけ好ましくは、０．１以上、また、１．００未満、好ましくは、０．５以下、より好ましくは、０．３以下、さらに好ましくは、０．２以下である。 The mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber (compound having a phenolic hydroxyl group/ultraviolet absorber) is 0.01 or more, preferably 0.03 or more, more preferably 0.03 or more. 07 or more, more preferably 0.09 or more, particularly preferably 0.1 or more, and less than 1.00, preferably 0.5 or less, more preferably 0.3 or less, further preferably 0 .2 or less.
　上記質量比が、上記下限以上であれば、白色光に対する安定性を向上できる。 If the mass ratio is equal to or higher than the lower limit, the stability against white light can be improved.
　一方、上記質量比が、上記下限未満であれば、白色光に対する安定性が低下する。 On the other hand, if the mass ratio is less than the lower limit, the stability against white light is lowered.
　また、上記質量比が、上記上限以下であれば、有機ＥＬ用表示素子用封止材の信頼性に優れる。 Further, when the mass ratio is equal to or less than the upper limit, the reliability of the sealing material for organic EL display elements is excellent.
　一方、上記質量比が、上記上限を超過すると、有機ＥＬ用表示素子用封止材の信頼性が低下する。 On the other hand, when the above mass ratio exceeds the above upper limit, the reliability of the sealing material for organic EL display elements is lowered.
＜有機ＥＬ用表示素子用封止材の調製＞
　有機ＥＬ用表示素子用封止材を調製するには、まず、カチオン重合性化合物カチオン重合性化合物と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とを混合し、混合物を調製する。次いで、この混合物に、カチオン重合開始剤を配合し、混合する。これにより、有機ＥＬ用表示素子用封止材を調製する。 <Preparation of sealing material for display element for organic EL>
To prepare a sealant for an organic EL display element, first, a cationically polymerizable compound, a cationically polymerizable compound, an ultraviolet absorber, and a compound having a phenolic hydroxyl group are mixed to prepare a mixture. Next, a cationic polymerization initiator is added to this mixture and mixed. This prepares the sealing material for organic EL display elements.
　上記調製において、必要により、添加剤を配合することもできる。つまり、有機ＥＬ用表示素子用封止材は、添加剤を含むこともできる。 In the above preparation, additives can be added as necessary. That is, the sealing material for organic EL display elements can also contain an additive.
　添加剤としては、例えば、増感剤、粘着付与剤、酸化防止剤、重合開始助剤、老化防止剤、濡れ性改良剤、界面活性剤、可塑剤、紫外線吸収剤、防腐剤、および、抗菌剤が挙げられる。 Additives include, for example, sensitizers, tackifiers, antioxidants, polymerization initiation aids, anti-aging agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, preservatives, and antibacterial agents.
　添加剤の配合割合は、用途および目的に応じて、適宜設定される。 The blending ratio of additives is appropriately set according to the application and purpose.
　添加剤は、単独使用または２種類以上併用することができる。 Additives can be used singly or in combination of two or more.
　また、有機ＥＬ用表示素子用封止材は、溶剤を含むこともできるが、好ましくは、有機ＥＬ用表示素子用封止材は、実質的に、溶剤を含まない。具体的には、溶剤含有量は、例えば、０．０５質量％以下、好ましくは、０．０１質量％以下、さらに好ましくは、０．００１質量％以下である。 The organic EL display element sealing material may contain a solvent, but preferably the organic EL display element sealing material does not substantially contain a solvent. Specifically, the solvent content is, for example, 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably 0.001% by mass or less.
＜有機ＥＬ用表示素子用封止材の物性＞
　有機ＥＬ用表示素子用封止材は、好ましくは、２５℃で液状である。２５℃で液状であるとは、２５℃での粘度が、５ｍＰａ・ｓ以上、また、５０ｍＰａ・ｓ以下である性状と定義される。有機ＥＬ用表示素子用封止材が、２５℃で液状であれば、インクジェットによる吐出性に優れる。 <Physical properties of sealing material for display element for organic EL>
The organic EL display element sealing material is preferably liquid at 25°C. Being liquid at 25°C is defined as having a viscosity of 5 mPa·s or more and 50 mPa·s or less at 25°C. If the sealing material for organic EL display elements is liquid at 25° C., it is excellent in jettability by inkjet.
　また、２５℃での粘度（後述する初期粘度）は、例えば、１ｍＰａ・ｓ以上、好ましくは、５ｍＰａ・ｓ以上、より好ましくは、１０ｍＰａ・ｓ以上、また、例えば、５０ｍＰａ・ｓ以下、好ましくは、３０ｍＰａ・ｓ以下、より好ましくは、２５ｍＰａ・ｓ以下である。 Further, the viscosity at 25° C. (initial viscosity described later) is, for example, 1 mPa s or more, preferably 5 mPa s or more, more preferably 10 mPa s or more, and for example, 50 mPa s or less, preferably , 30 mPa·s or less, more preferably 25 mPa·s or less.
　上記粘度の測定方法は、後述する実施例で詳述する。 The method for measuring the viscosity will be described in detail in the examples below.
　また、有機ＥＬ用表示素子用封止材の硬化物は、好ましくは、透明性を有する。具体的には、有機ＥＬ用表示素子用封止材の硬化物の全光線透過率（ＪＩＳ　Ｋ　７３６１－１に準拠）は、例えば、８０％以上、好ましくは、８５％以上、より好ましくは、９０％以上、また、例えば、１００％以下である。 In addition, the cured product of the sealing material for organic EL display elements preferably has transparency. Specifically, the total light transmittance (in accordance with JIS K 7361-1) of the cured product of the sealing material for organic EL display elements is, for example, 80% or more, preferably 85% or more, and more preferably 90% or more and, for example, 100% or less.
＜作用効果＞
　この有機ＥＬ用表示素子用封止材において、紫外線吸収剤に対するフェノール性の水酸基を有する化合物の質量比（フェノール性の水酸基を有する化合物／紫外線吸収剤）が、０．０１以上１．００未満である。この有機ＥＬ用表示素子用封止材において、上記質量比が、０．０１以上であるため、白色光に対する安定性を向上できる。また、この有機ＥＬ用表示素子用封止材において、上記質量比が、１．００未満であるため、硬化性の観点から、硬化後の有機ＥＬ素子の信頼性を向上できる。 <Effect>
In the sealing material for an organic EL display element, the mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber (compound having a phenolic hydroxyl group/ultraviolet absorber) is 0.01 or more and less than 1.00. be. In this sealing material for an organic EL display element, since the mass ratio is 0.01 or more, the stability against white light can be improved. Moreover, in this sealing material for organic EL display elements, since the mass ratio is less than 1.00, the reliability of the cured organic EL element can be improved from the viewpoint of curability.
　そして、このような有機ＥＬ用表示素子用封止材は、白色光に対する安定性、および、硬化後の信頼性に優れるため、有機ＥＬ用表示素子の封止材として、好適に用いることができる。とりわけ、この有機ＥＬ用表示素子用封止材は、白色光に対する安定性を有するため、増粘が抑制されている。そのため、インクジェット法において、好適に用いることができる。 Since such a sealing material for organic EL display elements has excellent stability against white light and excellent reliability after curing, it can be suitably used as a sealing material for organic EL display elements. . In particular, since this organic EL display element sealing material has stability against white light, thickening is suppressed. Therefore, it can be suitably used in the inkjet method.
＜変形例＞
　上記した説明では、有機ＥＬ用表示素子用封止材を調製するには、まず、カチオン重合性化合物カチオン重合性化合物と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とを混合し、混合物を調製した後に、この混合物に、カチオン重合開始剤を配合するが、カチオン重合性化合物と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とともに、カチオン重合開始剤を一括で配合することもできる。 <Modification>
In the above description, in order to prepare the sealing material for an organic EL display element, first, a cationically polymerizable compound, a cationically polymerizable compound, an ultraviolet absorber, and a compound having a phenolic hydroxyl group are mixed, and the mixture is After preparing this mixture, a cationic polymerization initiator is blended, but the cationic polymerization initiator can be blended together with the cationic polymerizable compound, the ultraviolet absorber, and the compound having a phenolic hydroxyl group. .
＜有機ＥＬ表示装置＞
　図１を参照して、本発明の有機ＥＬ表示装置の一実施形態を説明する。 <Organic EL display device>
One embodiment of the organic EL display device of the present invention will be described with reference to FIG.
　有機ＥＬ表示装置１０は、基板１と、基板１の厚み方向一方面に実装される有機ＥＬ素子２と、有機ＥＬ素子２を被覆する封止層３とを備える。 The organic EL display device 10 includes a substrate 1 , an organic EL element 2 mounted on one surface of the substrate 1 in the thickness direction, and a sealing layer 3 covering the organic EL element 2 .
［基板］
　基板１は、有機ＥＬ素子２を支持している。 [substrate]
A substrate 1 supports an organic EL element 2 .
　基板１としては、例えば、ガラス基板、および、プラスチック基板が挙げられ、好ましくは、ガラス基板が挙げられる。 Examples of the substrate 1 include glass substrates and plastic substrates, preferably glass substrates.
　基板１の厚みは、例えば、０．１ｍｍ以上、また、例えば、２０ｍｍ以下である。 The thickness of the substrate 1 is, for example, 0.1 mm or more and, for example, 20 mm or less.
［有機ＥＬ素子］
　有機ＥＬ素子２は、公知の有機ＥＬ素子であり、基板１に搭載されている。有機ＥＬ素子２は、図示しないが、カソード反射電極と、有機ＥＬ層と、アノード透明電極とを備えている。 [Organic EL element]
The organic EL element 2 is a known organic EL element and mounted on the substrate 1 . The organic EL element 2 includes a cathode reflective electrode, an organic EL layer, and an anode transparent electrode (not shown).
　封止層３は、有機ＥＬ素子２が大気中の水分などにより劣化することを抑制するための層である。 The sealing layer 3 is a layer for suppressing deterioration of the organic EL element 2 due to moisture in the atmosphere.
　封止層３は、上記した有機ＥＬ用表示素子用封止材の硬化物からなる。 The sealing layer 3 is made of a cured product of the above-described organic EL display element sealing material.
　封止層３の厚みは、例えば、１μｍ以上、また、例えば、１００μｍ以下である。 The thickness of the sealing layer 3 is, for example, 1 μm or more and, for example, 100 μm or less.
＜有機ＥＬ表示装置の製造方法＞
　図２Ａ～図２Ｃを参照して、本発明の有機ＥＬ表示装置の製造方法の一実施形態を説明する。 <Method for manufacturing organic EL display device>
An embodiment of the method for manufacturing an organic EL display device of the present invention will be described with reference to FIGS. 2A to 2C.
　有機ＥＬ表示装置の製造方法は、基板１を準備する第１工程と、基板１の厚み方向一方面に、有機ＥＬ素子２を実装する第２工程と、インクジェット法によって、有機ＥＬ素子２を被覆する封止層３を形成する第３工程とを備える。 The method for manufacturing an organic EL display device includes a first step of preparing a substrate 1, a second step of mounting an organic EL element 2 on one side in the thickness direction of the substrate 1, and coating the organic EL element 2 by an inkjet method. and a third step of forming the sealing layer 3 to be formed.
［第１工程］
　第１工程では、図２Ａに示すように、基板１を準備する。 [First step]
In the first step, a substrate 1 is prepared as shown in FIG. 2A.
［第２工程］
　第２工程では、図２Ｂに示すように、基板１の厚み方向一方面に、例えば、公知の方法（例えば、真空蒸着法）により、有機ＥＬ素子２を実装する。 [Second step]
In the second step, as shown in FIG. 2B, the organic EL element 2 is mounted on one surface of the substrate 1 in the thickness direction by, for example, a known method (eg, vacuum deposition method).
［第３工程］
　第３工程では、図２Ｃに示すように、インクジェット法によって、有機ＥＬ素子２を被覆する封止層３を形成する。インクジェット法によれば、有機ＥＬ素子２を確実に封止できる。 [Third step]
In the third step, as shown in FIG. 2C, the sealing layer 3 that covers the organic EL element 2 is formed by the inkjet method. According to the inkjet method, the organic EL element 2 can be reliably sealed.
　具体的には、まず、インクジェット法によって、有機ＥＬ用表示素子用封止材を、有機ＥＬ素子２を被覆するように、配置する。その後、有機ＥＬ用表示素子用封止材に、光を照射して、有機ＥＬ用表示素子用封止材を硬化させる。これにより、有機ＥＬ表示装置１０を製造する。 Specifically, first, the organic EL display element sealing material is arranged so as to cover the organic EL element 2 by an inkjet method. Thereafter, the organic EL display element sealing material is irradiated with light to cure the organic EL display element sealing material. Thus, the organic EL display device 10 is manufactured.
　有機ＥＬ表示装置１０は、信頼性に優れる有機ＥＬ用表示素子用封止材の硬化物からなる封止層３によって、有機ＥＬ素子２が被覆されている。そのため、信頼性に優れる。 In the organic EL display device 10, the organic EL elements 2 are covered with a sealing layer 3 made of a cured product of a highly reliable organic EL display element sealing material. Therefore, it is highly reliable.
　また、有機ＥＬ表示装置の製造方法は、インクジェット法によって、有機ＥＬ素子２を被覆し、かつ、信頼性に優れる有機ＥＬ用表示素子用封止材の硬化物からなる封止層３を形成する。そのため、信頼性に優れる有機ＥＬ表示装置１０を製造できる。 In addition, the manufacturing method of the organic EL display device includes forming the sealing layer 3 which covers the organic EL element 2 and is made of a cured product of a highly reliable sealing material for an organic EL display element by an inkjet method. . Therefore, the organic EL display device 10 having excellent reliability can be manufactured.
　また、図示しないが、有機ＥＬ表示装置１０は、厚み方向一方面および／または厚み方向他方面に、別の封止層（例えば、無機封止層）を備えることもできる。 Also, although not shown, the organic EL display device 10 can be provided with another sealing layer (for example, an inorganic sealing layer) on one side in the thickness direction and/or the other side in the thickness direction.
　次に、本発明を、実施例および比較例に基づいて説明するが、本発明は、下記の実施例によって限定されるものではない。なお、「部」および「％」は、特に言及がない限り、質量基準である。また、以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限値（「以下」、「未満」として定義されている数値）または下限値（「以上」、「超過」として定義されている数値）に代替することができる。 Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited by the following examples. "Parts" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.
＜成分の詳細＞
　各実施例、および、各比較例で用いた成分の、商品名および略語について、詳述する。ＣＥＬ８０１０：（３、３’、４、４’－ジエポキシ）ビシクロヘキシル、商品名「セロキサイド８０１０」、ダイセル社製
ＮＰＧ（Ｇ）：ネオペンチルグリコールジグリシジルエーテル、阪本薬品工業社製
ＯＸＴ２２１：３，３’－（オキシビスメチレン）ビス（３－エチルオキセタン）、商品名「アロンオキセタン　ＯＸＴ－２２１」、東亜合成化学社製
Ｔｉｎｕｖｉｎ２３４：２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ビス（１－メチル－１－フェニルエチル）－フェノール、ＢＡＳＦジャパン株式会社製
ＫＥＭＩＳＯＲＢ７１：２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、ケミプロ化成社製
ＲＵＶＡ－９３：２－［２－ヒドロキシ－５－［２－（メタクリロイルオキシ）エチル］フェニル］－２Ｈ－ベンゾトリアゾール、大塚化学社製
ＫＥＭＩＳＯＲＢ１２：２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノン、ケミプロ化成社製
アデカスタブ１４１３：［２－ヒドロキシ－４－（オクチルオキシ）フェニル］（フェニル）メタノン、ＡＤＥＫＡ社製
ＫＥＭＩＳＯＲＢ１０２：２，４－ジフェニル－６－（２－ヒドロキシ－４－ヘキシルオキシフェニル）－１，３，５－トリアジン、ケミプロ化成社製
ＢＨＴ：２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、分子量２２０
Ｉｒｇａｎоｘ１１３５：ベンゼンプロパン酸　３，５－ビス（１，１－ジメチルエチル）－４－ヒドロキシ－Ｃ７－Ｃ９側鎖アルキルエステル、分子量３９０ <Details of ingredients>
The trade names and abbreviations of the components used in each example and each comparative example are described in detail. CEL8010: (3,3′,4,4′-diepoxy)bicyclohexyl, trade name “Celoxide 8010”, Daicel NPG (G): neopentyl glycol diglycidyl ether, Sakamoto Yakuhin Kogyo OXT221: 3,3 '-(Oxybismethylene)bis(3-ethyloxetane), trade name "Aronoxetane OXT-221", Tinuvin234 manufactured by Toagosei Chemical Co., Ltd.: 2-(2H-benzotriazol-2-yl)-4,6-bis (1-methyl-1-phenylethyl)-phenol, BASF Japan Ltd. KEMIISORB71: 2-(2-hydroxy-5-methylphenyl) benzotriazole, Chemipro Kasei Co., Ltd. RUVA-93: 2-[2-hydroxy- 5-[2-(Methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, KEMIISORB12 manufactured by Otsuka Chemical Co., Ltd.: 2-hydroxy-4-n-octyloxybenzophenone, Adekastab 1413 manufactured by Chemipro Kasei Co., Ltd.: [2-Hydroxy-4 -(Octyloxy)phenyl](phenyl)methanone, ADEKA KEMIISORB102: 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, Chemipro Kasei BHT : 2,6-di-tert-butyl-p-cresol, molecular weight 220
Irganox 1135: Benzenepropanoic acid 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester, molecular weight 390
＜有機ＥＬ用表示素子用封止材の調製＞
　　実施例１～実施例１１、および、比較例１～比較例６
　表１に記載の配合処方に基づいて、まず、カチオン重合性化合物カチオン重合性化合物と、紫外線吸収剤と、フェノール性の水酸基を有する化合物とを混合し、混合物を調製した。次いで、この混合物に、カチオン重合開始剤を配合し、混合した。これにより、有機ＥＬ用表示素子用封止材を調製した。 <Preparation of sealing material for display element for organic EL>
Examples 1 to 11 and Comparative Examples 1 to 6
Based on the formulation shown in Table 1, first, a cationic polymerizable compound, an ultraviolet absorber, and a compound having a phenolic hydroxyl group were mixed to prepare a mixture. Then, a cationic polymerization initiator was added to this mixture and mixed. This prepared the sealing material for display elements for organic EL.
＜評価＞
[白色光に対する安定性]
　各実施例および各比較例の有機ＥＬ用表示素子用封止材の粘度を測定した。具体的には、Ｅ型粘度計（ＬＶ－ＤＶ－ＩＩ＋　Ｐｒｏ、ＢＲＯＯＫＦＩＥＬＤ社製、ローター角度：１°、ローター半径：２４ｍｍ）を用いて、ＪＩＳ　Ｋ５６００－２－３（２０１４年）のコーンプレート粘度計法に準拠して、また、調製直後（調製後６０分以内）２５℃の粘度（初期粘度）を測定した。測定時のコーンプレートの回転数は、２０ｒｐｍとした。 <Evaluation>
[Stability against white light]
The viscosity of the sealing material for organic EL display elements of each example and each comparative example was measured. Specifically, using an E-type viscometer (LV-DV-II+ Pro, manufactured by BROOKFIELD, rotor angle: 1 °, rotor radius: 24 mm), JIS K5600-2-3 (2014) cone plate viscosity The viscosity (initial viscosity) at 25° C. was measured immediately after preparation (within 60 minutes after preparation) according to the measurement method. The rotational speed of the cone plate during measurement was 20 rpm.
　その後、この有機ＥＬ用表示素子用封止材を、無色透明の２０ｍｌのバイアル瓶に、１０ｍｌ計量し、蛍光灯の明かりが６００ルクスになるような場所に設置したミックスローターの上で６時間回転させた。その粘度（６時間後粘度）を、上記と同様の条件で、Ｅ型粘度計を用いて測定した。 After that, 10 ml of this sealing material for an organic EL display element is weighed into a colorless and transparent 20 ml vial bottle, and rotated for 6 hours on a mix rotor installed in a place where the light of a fluorescent lamp is 600 lux. let me The viscosity (viscosity after 6 hours) was measured using an E-type viscometer under the same conditions as above.
　そして、増粘率を、下記式（６）に基づいて算出した。その結果を表１に示す。
増粘率＝（６時間後粘度／初期粘度）－１　　　（６） Then, the viscosity increase rate was calculated based on the following formula (6). Table 1 shows the results.
Thickening rate = (viscosity after 6 hours/initial viscosity) -1 (6)
　また、白色光に対する安定性について、下記の基準に基づいて評価した。その結果を表１に示す。
○：増粘率が２０%未満であった。
△：増粘率が２０%以上５０%未満であった。
×：増粘率が５０%以上であった。 Also, the stability to white light was evaluated based on the following criteria. Table 1 shows the results.
Good: The viscosity increase rate was less than 20%.
Δ: The viscosity increase rate was 20% or more and less than 50%.
x: The viscosity increase rate was 50% or more.
[塗布安定性]
　各実施例および各比較例の有機ＥＬ用表示素子用封止材を、インクジェットカートリッジＤＭＣ－１１６１０（富士フイルムＤｉｍａｔｉｘ社製）に導入した。そのインクジェットカートリッジを、蛍光灯下に設置したインクジェット装置ＤＭＰ－２８３１（富士フイルムＤｉｍａｔｉｘ社製）にセットし、塗布状態の調整を行った後、５０ｍｍ×５０ｍｍの無アルカリガラス上に５００μｍピッチで１０００滴塗布した。その後、この有機ＥＬ用表示素子用封止材を、蛍光灯下で３時間放置し、再度、インクジェットカートリッジを用いて、無アルカリガラス上に５００μｍピッチで１０００滴塗布し、その際の塗布できなかった個数を確認した。塗布安定性について、下記の基準に基づいて評価した。その結果を表１に示す。
○：３時間放置後、塗布できなかった液滴の個数が、放置前に対して、９８%以上であった。
△：３時間放置後、塗布できなかった液滴の個数が、放置前に対して、９０％以上９８%未満であった。
×：３時間放置後、塗布できなかった液滴の個数が、放置前に対して、９０％未満であった。 [Coating stability]
The organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). The inkjet cartridge was set in an inkjet device DMP-2831 (manufactured by Fuji Film Dimatix) installed under a fluorescent light, and after adjusting the coating state, 1000 droplets were placed on a non-alkali glass of 50 mm × 50 mm at a pitch of 500 μm. applied. After that, the sealing material for an organic EL display element was left under a fluorescent lamp for 3 hours, and again, using an inkjet cartridge, 1000 droplets were applied on non-alkali glass at a pitch of 500 μm. I confirmed the number of The coating stability was evaluated based on the following criteria. Table 1 shows the results.
Good: The number of droplets that could not be applied after standing for 3 hours was 98% or more of the number before standing.
Δ: After standing for 3 hours, the number of droplets that could not be applied was 90% or more and less than 98% of the number before standing.
x: After standing for 3 hours, the number of droplets that could not be applied was less than 90% of the number before standing.
[硬化率]
（評価用基板の作製）
　各実施例および各比較例の有機ＥＬ用表示素子用封止材を、インクジェットカートリッジＤＭＣ－１１６１０（富士フイルムＤｉｍａｔｉｘ社製）に導入した。そのインクジェットカートリッジをインクジェット装置ＤＭＰ－２８３１（富士フイルムＤｉｍａｔｉｘ社製）にセットし、塗布状態の調整を行った後、５０ｍｍ×５０ｍｍの無アルカリガラス上に４０ｍｍ×４０ｍｍのサイズで硬化後の厚みが１０μｍになるように塗布した。これにより、塗膜を得た。次いで、塗膜を１分間、温度２５℃、湿度５０％の環境で放置した後、塗膜に、波長３９５ｎｍのＵＶ－ＬＥＤで照度１００ｍＷ／ｃｍ２、１５００ｍＪ／ｃｍ２の光を照射し、硬化させた。これにより、評価用基板を製造した。 [Curing rate]
(Preparation of substrate for evaluation)
The organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). After setting the inkjet cartridge in an inkjet device DMP-2831 (manufactured by Fujifilm Dimatix) and adjusting the coating state, a 40 mm × 40 mm size was placed on a 50 mm × 50 mm alkali-free glass with a thickness of 10 μm after curing. was applied so as to be Thus, a coating film was obtained. Next, the coating film is left for 1 minute in an environment with a temperature of 25° C. and a humidity of 50%, and then the coating film is irradiated with light from a UV-LED with a wavelength of 395 nm at an illuminance of 100 mW/cm 2 and 1500 mJ/cm 2 to cure. let me Thus, an evaluation board was manufactured.
（硬化率の測定）
　各実施例および各比較例の有機ＥＬ用表示素子用封止材と、評価用基板とについて、ＦＴ－ＩＲ測定を実施した。 (Measurement of curing rate)
FT-IR measurement was performed on the organic EL display element sealing material of each example and each comparative example and the substrate for evaluation.
　そして、１３７１ｃｍ－１の波数のピーク（ＣＨ－伸縮振動に帰属されるピーク）の高さ（Ｐ１）をリファレンスとして、８３１ｃｍ－１の波数のピーク（エポキシ基に帰属されるピーク）の高さ（Ｐ２）の比率を求め、下記式（７）に基づき、硬化率を算出した。
その結果を表１に示す。
｛（Ｐ２ｂ／Ｐ１ｂ）－（Ｐ２ａ／Ｐ１ａ）｝／（Ｐ２ｂ／Ｐ１ｂ）×１００　　（７） Then, using the height (P1) of the 1371 cm -1 wavenumber peak (CH-stretching vibration peak) as a reference, the 831 cm -1 wavenumber peak (the peak attributed to the epoxy group) height ( The ratio of P2) was obtained, and the curing rate was calculated based on the following formula (7).
Table 1 shows the results.
{(P2b/P1b)-(P2a/P1a)}/(P2b/P1b)×100 (7)
　上記式（７）において、Ｐ１ａは硬化後の１３７１ｃｍ－１の波数のピーク高さを示し、Ｐ１ｂは硬化前の１３７１ｃｍ－１の波数のピーク高さを示し、Ｐ２ａは硬化後の８３１ｃｍ－１の波数のピーク高さを示し、Ｐ２ｂは、硬化前の８３１ｃｍ－１波数のピーク高さを示す。 In the above formula (7), P1a indicates the peak height of the wave number of 1371 cm after curing, P1b indicates the peak height of the wave number of 1371 cm -1 before curing, and P2a indicates the peak height of the wave number of 831 cm -1 after curing . Wavenumber peak height is indicated, and P2b indicates the peak height of 831 cm −1 wavenumber before curing.
[有機ＥＬ素子の信頼性]
　各実施例および各比較例の有機ＥＬ用表示素子用封止材を、インクジェットカートリッジＤＭＣ－１１６１０（富士フイルムＤｉｍａｔｉｘ社製）に導入した。そのインクジェットカートリッジをインクジェット装置ＤＭＰ－２８３１（富士フイルムＤｉｍａｔｉｘ社製）にセットし、吐出状態の調整を行った後、ガラス基板に、硬化後の厚みが１０μｍとなるように、１５ｍｍ×１５ｍｍのサイズで塗布し、塗膜を得た。 [Reliability of organic EL elements]
The organic EL display element sealing material of each example and each comparative example was introduced into an inkjet cartridge DMC-11610 (manufactured by Fuji Film Dimatix). After setting the inkjet cartridge in an inkjet device DMP-2831 (manufactured by Fuji Film Dimatix) and adjusting the ejection state, a 15 mm × 15 mm size ink was applied to a glass substrate so that the thickness after curing was 10 μm. It was applied to obtain a coating film.
　次いで、塗膜を、１分間、温度２５℃、湿度５０％の環境で放置した後、塗膜に、波長３９５ｎｍのＵＶ－ＬＥＤで、照度１００ｍＷ／ｃｍ２、１５００ｍＪ／ｃｍ２の光を照射し、硬化させ、硬化膜を得た Next, the coating film was left for 1 minute in an environment with a temperature of 25° C. and a humidity of 50%, and then irradiated with light from a UV-LED with a wavelength of 395 nm at an illuminance of 100 mW/cm 2 and 1500 mJ/cm 2 . , cured to obtain a cured film
　次いで、硬化膜に対して、２５００Ｗ（ＩＣＰ電源）、３００Ｗ（ＲＦ電源）、ＤＣバイアス２００Ｖ、アルゴン（Ａｒ）流量５０ｓｃｃｍ、１０ｍｔｏｒｒの圧力条件で１分間プラズマ処理した。 Next, the cured film was plasma-treated for 1 minute under the conditions of 2500 W (ICP power supply), 300 W (RF power supply), DC bias of 200 V, argon (Ar) flow rate of 50 sccm, and pressure of 10 mtorr.
　その後、ＳｉＮｘターゲットを用いてＲＦスパッタリング法により、硬化膜側に、膜厚１００ｎｍの無機封止層（ＳｉＮｘ膜）を形成した。これにより、第１評価用基板を製造した。 After that, an inorganic sealing layer (SiNx film) with a thickness of 100 nm was formed on the cured film side by RF sputtering using a SiNx target. Thus, a first evaluation substrate was manufactured.
　別途、他のガラス基板に、有機ＥＬ素子を実装し、第２評価用基板を製造した。次いで、第１評価用基板と第２評価用基板とを張り合わせた。これにより、評価用有機ＥＬ表示装置を製造した。 Separately, an organic EL element was mounted on another glass substrate to manufacture a second evaluation substrate. Next, the first evaluation substrate and the second evaluation substrate were bonded together. Thus, an evaluation organic EL display device was manufactured.
　次いで、評価用有機ＥＬ表示装置について、信頼性試験を８５℃の条件で実施した。具体的には、各評価用有機ＥＬ表示装置を８５℃にて１００時間保存した後の発光面積率（％）を以下の方法で求めた。すなわち、Ｍｏｔｉｃ　Ｉｍａｇｅｓ　Ｐｌｕｓソフト（島津理化社製）を用いて、初期状態の発光面積と、１００時間保存後の発光面積とを算出し、下記式（８）に基づき、発光面積率を算出した。
発光面積率（％）＝１００時間保存後の発光面積/初期状態の発光面積×１００　　（８） Next, the organic EL display device for evaluation was subjected to a reliability test at 85°C. Specifically, the emission area ratio (%) after each organic EL display device for evaluation was stored at 85° C. for 100 hours was determined by the following method. That is, using Motic Images Plus software (manufactured by Shimadzu Rika Co., Ltd.), the luminescent area in the initial state and the luminescent area after storage for 100 hours were calculated, and the luminescent area ratio was calculated based on the following formula (8).
Luminescent area ratio (%) = Luminous area after storage for 100 hours/Luminous area in initial state x 100 (8)
　有機ＥＬ素子の信頼性について、下記の基準に基づいて評価した。その結果を表１に示す。
○：発光面積率が、８０％以上であった。
△：発光面積率が、５０％以上８０%未満であった。
×：発光面積率が、５０%未満であった。 The reliability of the organic EL device was evaluated based on the following criteria. Table 1 shows the results.
○: The emission area ratio was 80% or more.
Δ: The emission area ratio was 50% or more and less than 80%.
x: Emission area ratio was less than 50%.
　なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示にすぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれるものである。 Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as limiting. Variations of the invention that are obvious to those skilled in the art are intended to be included in the following claims.
　本発明の有機ＥＬ用表示素子用封止材、有機ＥＬ表示装置および有機ＥＬ表示装置の製造方法は、画像表示装置の製造において、好適に用いられる。 The sealing material for an organic EL display device, the organic EL display device, and the method for manufacturing an organic EL display device of the present invention are suitably used in the manufacture of an image display device.
１　　　基板
２　　　有機ＥＬ素子
３　　　封止層
１０　　有機ＥＬ表示装置 Reference Signs List 1 substrate 2 organic EL element 3 sealing layer 10 organic EL display device

Claims (9)

  1. 　カチオン重合性化合物と、
    　カチオン重合開始剤と、
    　紫外線吸収剤と、
    　フェノール性の水酸基を有する化合物とを含み、
    　前記紫外線吸収剤に対する前記フェノール性の水酸基を有する化合物の質量比（フェノール性の水酸基を有する化合物／紫外線吸収剤）が、０．０１以上１．００未満である、有機ＥＬ用表示素子用封止材。     a cationic polymerizable compound;
    a cationic polymerization initiator;
    a UV absorber;
    and a compound having a phenolic hydroxyl group,
    The mass ratio of the compound having a phenolic hydroxyl group to the ultraviolet absorber (compound having a phenolic hydroxyl group/ultraviolet absorber) is 0.01 or more and less than 1.00. material.
  2. 　前記カチオン重合性化合物は、エポキシ化合物および／またはオキセタン化合物である、請求項１に記載の有機ＥＬ用表示素子用封止材。 The encapsulant for organic EL display elements according to claim 1, wherein the cationic polymerizable compound is an epoxy compound and/or an oxetane compound.
  3. 　前記紫外線吸収剤は、ベンゾトリアゾール化合物、または、ベンゾフェノン化合物である、請求項１に記載の有機ＥＬ用表示素子用封止材。 The encapsulant for an organic EL display element according to claim 1, wherein the ultraviolet absorber is a benzotriazole compound or a benzophenone compound.
  4. 　前記紫外線吸収剤の含有量が、０．１質量％以上２質量％以下である、請求項１に記載の有機ＥＬ用表示素子用封止材。 The encapsulant for an organic EL display element according to claim 1, wherein the content of the ultraviolet absorber is 0.1% by mass or more and 2% by mass or less.
  5. 　前記フェノール性の水酸基を有する化合物の含有量が、０．０１質量％以上０．５質量％以下である、請求項１に記載の有機ＥＬ用表示素子用封止材。 The encapsulant for an organic EL display element according to claim 1, wherein the content of the compound having a phenolic hydroxyl group is 0.01% by mass or more and 0.5% by mass or less.
  6. 　２５℃で液状であり、
    　溶剤含有量が、０．０５質量％以下である、請求項１に記載の有機ＥＬ用表示素子用封止材。     liquid at 25°C,
    The sealing material for an organic EL display element according to claim 1, wherein the solvent content is 0.05% by mass or less.
  7. 　２５℃での粘度が、５ｍＰａ・ｓ以上５０ｍＰａ・ｓ以下である、請求項１に記載の有機ＥＬ用表示素子用封止材。 The encapsulant for an organic EL display element according to claim 1, wherein the viscosity at 25°C is 5 mPa·s or more and 50 mPa·s or less.
  8. 　基板と、
    　前記基板の厚み方向一方面に実装される有機ＥＬ素子と、
    　前記有機ＥＬ素子を被覆する封止層とを備え、
    　前記封止層は、請求項１に記載の有機ＥＬ用表示素子用封止材の硬化物からなる、有機ＥＬ表示装置。     a substrate;
    an organic EL element mounted on one surface in the thickness direction of the substrate;
    A sealing layer covering the organic EL element,
    An organic EL display device, wherein the sealing layer is made of a cured product of the organic EL display element sealing material according to claim 1 .
  9. 　基板を準備する第１工程と、
    　前記基板の厚み方向一方面に、有機ＥＬ素子を実装する第２工程と、
    　インクジェット法によって、前記有機ＥＬ素子を被覆する封止層を形成する第３工程とを備え、
    　前記封止層は、請求項１に記載の有機ＥＬ用表示素子用封止材の硬化物からなる、有機ＥＬ表示装置の製造方法。     a first step of preparing a substrate;
    a second step of mounting an organic EL element on one surface in the thickness direction of the substrate;
    A third step of forming a sealing layer covering the organic EL element by an inkjet method,
    A method for manufacturing an organic EL display device, wherein the sealing layer comprises a cured product of the organic EL display element sealing material according to claim 1 .
PCT/JP2023/006769 2022-02-28 2023-02-24 Encapsulant for organic el display element, organic el display device, and method for producing organic el display device WO2023163113A1 (en)

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JP2005306952A (en) * 2004-04-20 2005-11-04 Japan Epoxy Resin Kk Epoxy resin composition as sealing material for light-emitting element
JP2009249569A (en) * 2008-04-09 2009-10-29 Japan Epoxy Resin Kk Epoxy resin composition for optical element sealing material
JP2012132028A (en) * 2012-04-09 2012-07-12 Mitsubishi Chemicals Corp Epoxy resin composition for optical element sealing material
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