WO2019039587A1 - 有機エレクトロルミネッセンス素子用封止剤 - Google Patents

有機エレクトロルミネッセンス素子用封止剤 Download PDF

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Publication number
WO2019039587A1
WO2019039587A1 PCT/JP2018/031335 JP2018031335W WO2019039587A1 WO 2019039587 A1 WO2019039587 A1 WO 2019039587A1 JP 2018031335 W JP2018031335 W JP 2018031335W WO 2019039587 A1 WO2019039587 A1 WO 2019039587A1
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Prior art keywords
organic electroluminescent
group
compound
formula
compound represented
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PCT/JP2018/031335
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English (en)
French (fr)
Japanese (ja)
Inventor
泰則 石田
貴子 星野
慶次 後藤
山下　幸彦
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デンカ株式会社
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Priority to JP2019537707A priority Critical patent/JP7123943B2/ja
Priority to KR1020207002163A priority patent/KR102536932B1/ko
Priority to CN201880053942.2A priority patent/CN110999537B/zh
Publication of WO2019039587A1 publication Critical patent/WO2019039587A1/ja

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    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • 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
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • 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
    • C08K5/54—Silicon-containing compounds
    • 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
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • H01L23/293—Organic, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a sealant for an organic electroluminescent device.
  • the present invention relates to a sealing agent used for sealing an organic electroluminescent element.
  • organic light devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been advanced.
  • organic thin film element can be easily manufactured by vacuum deposition, solution coating or the like, and therefore, is excellent in productivity.
  • the organic electroluminescent display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected from one of the electrodes into the organic light emitting material layer and holes are injected from the other electrode, whereby electrons and holes are combined in the organic light emitting material layer to cause self-emission.
  • the organic electroluminescent display device has the advantages of being more visible, being able to be thinner, and being capable of direct current low voltage driving, as compared with a liquid crystal display device or the like requiring a backlight.
  • organic electroluminescent display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outside air, the light emission characteristics thereof are rapidly deteriorated and the life becomes short. Therefore, for the purpose of enhancing the stability and durability of the organic electroluminescent display device, in the organic electroluminescent display device, it is essential to use a sealing technique for shielding the organic light emitting material layer and the electrodes from moisture and oxygen in the atmosphere. It has become.
  • Patent Document 1 discloses a method of filling a photocurable sealant between organic electroluminescence display element substrates in a top emission type organic electroluminescence display element or the like and irradiating light for sealing. .
  • patent document 1 does not describe the sealing agent for organic electroluminescent elements of this invention.
  • Patent Document 2 discloses a UV curable resin composition capable of securing a sufficient pot life without using a reactivity controlling agent as a delayed curing agent. However, there is a problem that the pot life after light irradiation is short. Patent Document 2 does not describe an alicyclic compound having an epoxy group. Patent Document 2 exemplifies only a phosphoric acid ester as a photocationic polymerization initiator, and is not used in the examples, and a phosphoric acid ester is not used to suppress an increase in viscosity after light irradiation.
  • Patent Document 3 contains an epoxy resin (except for "a polyalkylene oxide-added bisphenol derivative having an epoxy group at the end"), a cationic photopolymerization initiator, and a polyalkylene oxide-added bisphenol derivative having an epoxy group at an end.
  • an adhesive for sealing an organic electroluminescent element characterized in that the curing reaction is initiated by light irradiation and the curing reaction proceeds in the dark reaction even after blocking the light. There is.
  • Patent Document 3 does not describe an alicyclic compound having an epoxy group.
  • Patent Document 3 has a problem that outgas is generated at the time of light irradiation to deteriorate the element.
  • Patent Document 4 discloses a sealing agent for an organic electroluminescent display element, which comprises a specific cationically polymerizable compound and a cationic light polymerization initiator.
  • Patent Document 4 merely exemplifies a phosphoric acid ester as a photocationic polymerization initiator, and is not used in the examples, and a phosphoric acid ester is not used to suppress an increase in viscosity after light irradiation.
  • Patent Document 5 contains 100 parts by mass of a cationic photopolymerizable compound, 0.1 to 30 parts by mass of a cationic photopolymerization initiator, and 0.1 to 30 parts by mass of a curing control agent comprising a compound having an ether bond, and is cured Disclosed is a method of sealing an organic electroluminescent device with a post-curing composition having a compound in which the control agent has an ether bond.
  • Patent Document 5 does not describe an alicyclic compound having an epoxy group.
  • Patent Document 5 merely exemplifies a phosphoric acid ester as a photocationic polymerization initiator, and is not used in the examples, and a phosphoric acid ester is not used to suppress an increase in viscosity after light irradiation.
  • Patent Document 6 discloses an adduct (A) of a bisphenol A type epoxy resin and a phosphoric acid having at least one active hydrogen, a compound (B) having two or more alicyclic epoxy groups, and cationic light.
  • An ultraviolet curable resin composition containing a polymerization initiator (C) is disclosed.
  • the method of producing (A) is complicated, and there is a problem that outgas is generated by a by-product to deteriorate the element.
  • Patent Document 6 does not describe a sealant for an organic electroluminescent device.
  • Patent Document 7 discloses a radiation curable composition containing a radiation curable component and at least two flame retardants belonging to different compound groups.
  • Patent Document 7 is a flame retardant curable composition that is originally used for other purposes, and there is no description about the pot life after light irradiation and the outgas generation at the time of light irradiation.
  • Patent Document 7 does not describe a sealing agent for an organic electroluminescent device.
  • Patent 5919574 gazette Patent No. 4800247 JP, 2016-58273, A Patent 4384509 gazette Japanese Patent Application Laid-Open No. 7-247342 Japanese Patent Application Publication No. 2007-513234
  • the present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a sealing agent for an organic electroluminescent device, in which the increase in viscosity after light irradiation is small and the organic electroluminescent device is hardly deteriorated.
  • the present invention is as follows. ⁇ 1> (A) cationically polymerizable compound, (B) photocationic polymerization initiator, and (C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid ester and phosphorous acid ester
  • a sealing agent for an organic electroluminescent device comprising (A) a cationically polymerizable compound, and (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group .
  • ⁇ 3> (C1) from the group consisting of a compound represented by Formula (C1-1), a compound represented by Formula (C1-2), and a compound represented by Formula (C1-3)
  • the sealing agent for organic electroluminescent elements as described in ⁇ 2> containing at least 1 type selected.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrocarbon group which may have a substituent.
  • the sealing agent for organic electroluminescent elements of the ⁇ 1> description whose ⁇ 4> (C) phosphoric acid compound is a (C2) phosphite.
  • the compound represented by ⁇ 5> (C2) phosphite ester is a compound represented by Formula (C2-1), the compound represented by Formula (C2-2), the compound represented by Formula (C2-3), Formula (C2)
  • the compound according to ⁇ 4> which contains at least one selected from the group consisting of a compound represented by C2-4), a compound represented by the formula (C2-5) and a compound represented by the formula (C2-6) Sealant for organic electroluminescent devices.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently carbonized optionally having a substituent] Indicates a hydrogen group.
  • ⁇ 9> A sealing agent for an organic electroluminescent device according to any one of ⁇ 1> to ⁇ 8>, further containing a photosensitizer.
  • the adhesion process which makes the sealing agent for organic electroluminescent elements of any one of ⁇ 1>- ⁇ 10> adhere to the ⁇ 14> 1st member,
  • the said sealing for organic electroluminescent elements made to adhere Organic compound comprising: an irradiation step of irradiating a light with a light and a bonding step of bonding the first member and the second member through the light irradiated sealing agent for an organic electroluminescent element
  • Method of manufacturing an electroluminescent display device The manufacturing method of the organic electroluminescent display apparatus as described in ⁇ 14> the ⁇ 15> said 1st member is a board
  • the present invention it is possible to provide a sealing agent for an organic electroluminescent device, in which the increase in viscosity after light irradiation is small and the organic electroluminescent device is hardly deteriorated.
  • the sealant for an organic electroluminescent device is (A) cationically polymerizable compounds, It is characterized by containing (B) a photocationic polymerization initiator, and (C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphorous acid esters.
  • (A) the cationically polymerizable compound includes (A-1) an alicyclic compound having an epoxy group, and (A-2) an epoxy group. It is characterized by containing an aromatic compound.
  • the sealant for an organic electroluminescent element according to the present embodiment contains (A) a cationic polymerizable compound as an essential component.
  • the (A) cationically polymerizable compound is preferably photopolymerizable.
  • the cationic polymerizable compound (A) contains an alicyclic compound having an epoxy group (A-1) and an aromatic compound having an epoxy group (A-2). Thereby, good adhesion and low moisture permeability can be obtained.
  • Alicyclic compound having an epoxy group As an alicyclic compound having an epoxy group (hereinafter sometimes referred to as an alicyclic epoxy compound), at least one cycloalkane ring (for example, cyclohexene) Compounds obtained by epoxidizing a compound having a ring, cyclopentene ring, pinene ring etc.) with a suitable oxidizing agent such as hydrogen peroxide or peracid, or a derivative thereof, or an aromatic epoxy compound (eg bisphenol A type)
  • a suitable oxidizing agent such as hydrogen peroxide or peracid, or a derivative thereof, or an aromatic epoxy compound (eg bisphenol A type)
  • the hydrogenated epoxy compound etc. which are obtained by hydrogenating an epoxy resin, a bisphenol F-type epoxy resin etc. are mentioned.
  • One or more of these compounds may be selected and used.
  • Examples of alicyclic epoxy compounds include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl (meth) acrylate (eg, 3,4-epoxycyclohexylmethyl (meth) Acrylate, etc.), (3,3 ′, 4,4′-diepoxy) bicyclohexyl, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, etc. may be mentioned.
  • cycloaliphatic epoxy compounds having a 1,2-epoxycyclohexane structure are preferred.
  • alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure a compound represented by the following formula (A1-1) is preferable.
  • X represents a single bond or a linking group (divalent group having one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond A carbonate group, an amide bond, or a group in which a plurality of these are linked)
  • X is preferably a linking group.
  • the linking groups functional groups having an ester bond are preferred.
  • 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.
  • the molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, still more preferably less than 300, and still more preferably 100 to 280.
  • the number average molecular weight of the alicyclic epoxy compound is preferably in the above range.
  • a number average molecular weight shows the value of polystyrene conversion measured by the following measurement conditions by gel permeation chromatography (GPC).
  • Aromatic Compound Having an Epoxy Group As an aromatic compound having an epoxy group (hereinafter sometimes referred to as an aromatic epoxy compound), any of monomers, oligomers or polymers can be used, and bisphenol A type Epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolak phenol type epoxy resin, cresol novolac type epoxy resin, modified products thereof, etc. may be mentioned. . One or more of these epoxy resins may be selected and used. Among these, aromatic epoxy compounds having a bisphenol structure are preferable. Among the aromatic epoxy compounds having a bisphenol structure, a compound represented by the following formula (A2-1) is preferable.
  • n represents a real number of 0.1 to 30, and R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 6 carbon atoms) Represents an alkyl group of 5)
  • R 21 , R 22 , R 23 and R 24 are preferably a hydrogen atom or a methyl group.
  • R 21 , R 22 , R 23 and R 24 are preferably the same.
  • aromatic epoxy compounds having a bisphenol structure at least one selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins is preferable.
  • the molecular weight of the aromatic epoxy compound is preferably 100 to 5000, more preferably 150 to 1000, and most preferably 200 to 450, from the viewpoint of moisture permeability and the like.
  • the number average molecular weight of the aromatic epoxy compound is preferably in the above range.
  • a number average molecular weight shows the value of polystyrene conversion measured on the measurement conditions mentioned above by gel permeation chromatography (GPC).
  • any of monomers, oligomers or polymers can be used.
  • the (A) cationically polymerizable compound of the present embodiment is preferably an epoxy compound.
  • the (A) cationically polymerizable compound of the present embodiment preferably has two or more cationic polymerizable groups such as a cyclic ether group and a cationically polymerizable vinyl group, and more preferably has two.
  • cationically polymerizable compounds other than (A-1) and (A-2) can be further used.
  • cationically polymerizable compounds other than (A-1) and (A-2) include cyclic ethers and cationically polymerizable vinyl compounds.
  • cyclic ethers include compounds such as epoxy and oxetane.
  • the content of other cationically polymerizable compounds other than (A-1) and (A-2) is preferably 40 parts by mass or less, more preferably 20 parts by mass or less And 10 parts by mass or less are most preferable.
  • the content of the other cationically polymerizable compound other than (A-1) and (A-2) may be, for example, 1 part by mass or more, 5 parts by mass or more Or 0 parts by mass.
  • Examples of cationically polymerizable vinyl compounds include vinyl ethers, vinyl amines, styrene and the like. One or more of these compounds or derivatives may be selected and used.
  • one or more kinds of diglycidyl ether compounds, oxetane compounds and vinyl ether compounds are preferable.
  • diglycidyl ether compounds include diglycidyl ethers of alkylene glycol (eg, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,6-hexanediol, etc.), polyglycidyl ether of polyhydric alcohol (Eg, di- or tri-glycidyl ether of glycerin or alkylene oxide adduct thereof), diglycidyl ether of polyalkylene glycol (eg, diglycidyl ether of polyethylene glycol or alkylene oxide adduct thereof, polypropylene glycol or alkylene oxide adduct thereof Diglycidyl ether etc.).
  • alkylene oxide aliphatics such as ethylene oxide and propylene oxide may be mentioned.
  • the oxetane compound is not particularly limited, but 3-ethyl-3-hydroxymethyl oxetane (manufactured by Toagosei Co., Ltd., trade name Aron oxetane OXT-101, etc.), 1,4-bis [(3-ethyl-3-oxetanyl) ) Methoxymethyl] benzene (the same OXT-121 etc.), 3-ethyl-3- (phenoxymethyl) oxetane (the same OXT-211 etc.), di (1-ethyl- (3-oxetanyl)) methyl ether (the same OXT-) 221 and the like), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (the same as OXT-212 and the like) and the like.
  • An oxetane compound refers to a compound having one or more oxetane rings in the
  • the vinyl ether compound is not particularly limited, but ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol di Di- or trivinyl ether compounds such as vinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadeci Monovinyl ether compounds such as vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhex
  • the amount of the alicyclic compound having an epoxy group (A-1) is preferably 30 to 95 parts by mass, more preferably 50 to 90 parts by mass, and more preferably 60 to 80 parts by mass per 100 parts by mass of the cationically polymerizable compound (A). Parts by weight are most preferred, and 65 to 75 parts by weight are even more preferred. If it is 30 mass parts or more, durability will be acquired, and if 95 mass parts or less, durability will be acquired.
  • the amount of the aromatic compound having an epoxy group (A-2) is preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 20 to 40 parts by mass in 100 parts by mass of the cationically polymerizable compound (A). Parts are most preferred, and 25 to 35 parts by weight are even more preferred. If it is 5 parts by mass or more, the durability is obtained, and if it is 70 parts by mass or less, the durability is obtained.
  • the total content of (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group is at least 60 parts by mass in 100 parts by mass of the cationically polymerizable compound (A) Preferably, it is 80 parts by mass or more, more preferably 90 parts by mass or more, and still more preferably 100 parts by mass.
  • the sealing agent for organic electroluminescent elements which concerns on this embodiment has (B) photocationic polymerization initiator as an essential component.
  • the sealing agent of the present embodiment can be cured by irradiation with energy rays such as ultraviolet rays.
  • the cationic photopolymerization initiator is not particularly limited, but arylsulfonium salt derivatives (for example, CYRACURE UVI-6990, CYRACURE UVI-6974 manufactured by Dow Chemical Co., Adeka Optomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd.) , Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1, Double Bond, manufactured by San-Apro Corporation 1190, etc.), aryliodonium salt derivatives (eg Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan), allene-ion complex derivatives, diazonium salt derivatives, triazine initiators and the like It includes acid generators such as halides of. As the cationic species of the cationic photo
  • the cationic photopolymerization initiator (B) is not particularly limited, and examples include onium salts represented by the formula (B-1).
  • R is an organic group bonded to A D represents a group represented by the following formula (B-1-1): And a divalent group represented by In formula (B-1-1), E represents a divalent group, and G is -O-, -S-, -SO-, -SO 2- , -NH-, -NR'-, -CO- And —COO—, —CONH—, an alkylene having 1 to 3 carbon atoms or a phenylene group (R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms).
  • a 0 to 5; a + 1 pieces of E and A pieces of G may be identical to or different from each other. a is preferably an integer.
  • X - is a counter ion of onium, and the number is p + 1 per molecule.
  • the onium ion of the formula (B-1-1) is not particularly limited, but 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- ⁇ bis [4- (2) -Hydroxyethoxy) phenyl] sulfonio ⁇ phenyl] sulfide, bis ⁇ 4- [bis (4-fluorophenyl) sulfonio] phenyl ⁇ sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenyl bis (4-fluorophenyl) Sulfonium, 4- (4-Benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-toly
  • R is an organic group bonded to A.
  • R is, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms Which represent alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl And may be substituted with at least one selected from the group consisting of arylsulfonyl, alkyleneoxy, amino, cyano and nitro, and halogen.
  • the number of R's is m + p (m-1) +1, and they may be identical to or different from one another.
  • the two or more R may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH-, carbon atoms
  • the ring structure containing the element A may be formed by bonding through 1 to 3 alkylene or phenylene groups.
  • R ′ is an alkyl group of 1 to 5 carbon atoms or an aryl group of 6 to 10 carbon atoms.
  • examples of the aryl group having 6 to 30 carbon atoms include a monocyclic aryl group such as a phenyl group, and condensation of naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone etc.
  • Polycyclic aryl groups are mentioned.
  • the aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms or the alkynyl group having 2 to 30 carbon atoms is at least 1 It may have a substituent of a species, and examples of the substituent include linear alkyl having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, ocdadecyl and the like
  • a branched alkyl group having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; and
  • alkylsulfinyl groups 1 to 18 linear or branched alkylsulfinyl groups; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl , Sec-butyl sulfonyl, tert-butyl sulfonyl, pentyl sulfone , A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl
  • P in the formula (B-1) represents the number of repeating units of [D-A + R m-1 ] bond, and is preferably an integer of 0 to 3.
  • Preferred examples of the onium ion [A + ] in the formula (B-1) include sulfonium, iodonium and selenium, and the following may be mentioned as representative examples.
  • sulfonium ions and iodonium ions are preferable, and sulfonium ions are more preferable.
  • sulfonium ion triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- ⁇ bis [4- (2-)] Hydroxyethoxy) phenyl] sulfonio ⁇ phenyl] sulfide, bis ⁇ 4- [bis (4-fluorophenyl) sulfonio] phenyl ⁇ sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium , 4- (4-Benzoyl-2-chlorophenylthio)
  • X - is a counter ion.
  • the number is p + 1 per molecule.
  • the counter ion is not particularly limited, and examples thereof include boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, and methide compounds.
  • X - include, for example, F -, Cl -, Br -, I - halogen, such as ion; OH -; ClO 4 -; FSO 3 -, ClSO 3 -, CH 3 SO 3 -, C 6 H 5 SO 3 -, CF 3 SO 3 - sulfonate ion such as; HSO 4 -, sulfate ions of SO 4 2- and the like; HCO 3 -, CO 3 carbonate ions of 2-like; H 2 PO 4 -, HPO 4 2, phosphate ions of PO 4 3- and the like; PF 6 -, PF 5 OH -, fluorophosphate ions such as fluorinated alkyl fluorophosphate ion; BF 4 -, B (C 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such as; AlCl 4 -; BiF 6 -, and the like.
  • fluoroantimonate
  • fluorinated alkyl fluorophosphate ion examples include fluorinated alkyl fluorophosphate ions represented by the formula (B-1-3) and the like.
  • Rf represents an alkyl group substituted with a fluorine atom.
  • the number b of Rf is 1 to 5 and is preferably an integer.
  • the b R f s may be the same or different.
  • the number b of Rf is more preferably 2 to 4, and most preferably 2 to 3.
  • Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. It is.
  • alkyl group examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl And cycloalkyl groups of the following.
  • CF 3 , CF 3 CF 2 , (CF 3 ) 2 CF, CF 3 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 , (CF 3 ) 2 CFCF 2 , CF 3 CF 2 (CF 3 ) CF, (CF 3 ) 3 C, etc. may be mentioned.
  • Examples of preferred fluorinated alkyl fluorophosphate anion [(CF 3 CF 2) 2 PF 4] -, [(CF 3 CF 2) 3 PF 3] -, [((CF 3) 2 CF) 2 PF 4 ] ⁇ , [(CF 3 ) 2 CF) 3 PF 3 ] ⁇ , [(CF 3 CF 2 CF 2 ) 2 PF 4 ] ⁇ , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3) 2 CFCF 2) 2 PF 4] -, [((CF 3) 2 CFCF 2) 3 PF 3] -, [(CF 3 CF 2 CF 2 CF 2) 2 PF 4] - and [ (CF 3 CF 2 CF 2 CF 2) 3 PF 3] - , and the like.
  • the photo cationic polymerization initiator may be previously dissolved in solvents in order to facilitate the dissolution in the epoxy compound and the epoxy resin.
  • solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate and the like.
  • One or more of these photocationic polymerization initiators may be selected and used.
  • anionic species of the photo cationic polymerization initiator (B) include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds and alkylsulfonic acid compounds.
  • halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds and alkylsulfonic acid compounds.
  • fluoride is preferable in terms of excellent photocurability, and improved adhesion and adhesion durability.
  • fluorides hexafluoroantimonate is preferred.
  • pentafluoroethyl) trifluorophosphate are preferable, and triarylsulfonium salt hexafluoroantimonate is more preferable.
  • the amount of the cationic photopolymerization initiator (B) used is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound (A). If the amount of the photo cationic polymerization initiator used is 0.05 parts by mass or more, the photocurability does not deteriorate, and if 5 parts by mass or less, the adhesion durability does not decrease.
  • the sealing agent for organic electroluminescent elements which concerns on this embodiment has (C) phosphoric acid compound as an essential component.
  • the phosphoric acid compound is one or more selected from the group consisting of (C1) phosphoric ester and (C2) phosphorous ester.
  • As a phosphoric acid compound an organic phosphoric acid compound is preferable.
  • (C1) phosphoric acid esters are preferred.
  • (C1) phosphate ester is selected from the group consisting of a compound represented by Formula (C1-1), a compound represented by Formula (C1-2) and a compound represented by Formula (C1-3) It is preferable to contain at least one, and it is more preferable to contain the compound represented by Formula (C1-2).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently have a substituent It also shows good hydrocarbon groups.
  • R 2 , R 3 and R 4 in the formula (C1-2) and R 5 and R 6 in the formula (C 1-3) are preferably the same group in each formula.
  • R ⁇ 1 >, R ⁇ 2 >, R ⁇ 3 >, R ⁇ 4 >, R ⁇ 5 > and R ⁇ 6 > may have, an oxyalkyl group etc. are mentioned, for example.
  • the hydrocarbon group in R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is preferably a non-substituted hydrocarbon group.
  • the hydrocarbon group in R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and an alkyl group Is more preferred.
  • the carbon atom number of the alkyl group may be, for example, 1 to 18, and preferably 4 to 13.
  • the compound represented by the formula (C1-1) may be, for example, monoalkyl phosphate (that is, a compound in which R 1 is an alkyl group), and specific examples thereof include monoethyl phosphate and mono n-butyl. Examples include phosphate, mono (butoxyethyl) phosphate, mono (2-ethylhexyl) phosphate and the like.
  • the compound represented by the formula (C1-2) is preferably a trialkyl phosphate (that is, a compound in which R 2 , R 3 and R 4 are an alkyl group).
  • the number of carbon atoms of the alkyl group of R 2 , R 3 and R 4 is preferably 1 to 18, more preferably 4 to 12, and still more preferably 8.
  • Examples of the compound represented by the formula (C1-3) include dialkyl phosphates (that is, compounds in which R 5 and R 6 are an alkyl group).
  • Specific examples of dialkyl phosphates include dibutyl phosphate, bis (2-ethylhexyl) phosphate and the like.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently carbonized containing an alkyl group It may be one or more of a hydrogen group, a hydrocarbon group containing an aromatic ring, and a hydrocarbon group containing an aliphatic ring.
  • the hydrocarbon group may have a partially unsaturated group, and may have any atom or substituent.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are preferably hydrocarbon groups containing an alkyl group.
  • the hydrocarbon group is preferably a non-substituted saturated group.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical.
  • C2 As a phosphite ester, trimethyl phosphite, triethyl phosphite, tri n-butyl phosphite, tris (2-ethyl hexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite Tris (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, phenyl diiso Octyl phosphite, phenyldiisodecyl phosphite, diphenyl mono (2-ethylhexyl) pho
  • the phosphite is a compound represented by the formula (C2-1), a compound represented by the formula (C2-2), a compound represented by the formula (C2-3), a compound represented by the formula (C2-4) And at least one selected from the group consisting of compounds represented by formula (C2-5) and compounds represented by formula (C2-6).
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are each independently Represents a hydrocarbon group which may have a substituent.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 may have, for example, An oxyalkyl group etc. are mentioned.
  • the hydrocarbon group in R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is preferably a non-substituted hydrocarbon group.
  • the hydrocarbon group in R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 is preferably an alkyl group or an aryl group, It is more preferably a group or a phenyl group, and still more preferably an alkyl group.
  • the carbon atom number of the alkyl group may be, for example, 1 to 30, and preferably 1 to 18.
  • R 8 and R 9 in Formula (C2-2), R 10 , R 11 and R 12 in Formula (C2-3), R 13 and R 14 in Formula (C2-4), and Formula (C2) R 15 and R 16 in -5) are preferably identical to each other in each formula.
  • Examples of the compound represented by the formula (C2-1) include monoalkyl phosphite (that is, a compound in which R 7 is an alkyl group) and the like.
  • Examples of the compound represented by the formula (C2-2) include dialkyl phosphites (that is, compounds in which R 8 and R 9 are an alkyl group).
  • Examples of the compound represented by the formula (C2-3) include trialkyl phosphites (that is, compounds in which R 10 , R 11 and R 12 are an alkyl group) and the like. Further, specific examples of the compound represented by the formula (C2-3) include triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trio Rail phosphite, diphenyl monodecyl phosphite and the like can be mentioned.
  • Examples of the compound represented by the formula (C2-4) include bis (alkyl) pentaerythritol diphosphite (that is, a compound in which R 13 and R 14 are an alkyl group). Further, specific examples of the compound represented by the formula (C2-4) include bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like. .
  • Examples of the compound represented by the formula (C2-5) include dialkyl hydrogen phosphites (that is, compounds in which R 15 and R 16 are an alkyl group) and the like. Further, specific examples of the compound represented by the formula (C2-5) include diethyl hydrogen phosphite, bis (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite and the like.
  • Examples of the compound represented by the formula (C2-6) include monoalkyl hydrogen phosphite (that is, a compound in which R 17 is an alkyl group) and the like. Further, specific examples of the compound represented by the formula (C2-6) include monoethyl hydrogen phosphite, mono (2-ethyl hexyl) hydrogen phosphite, mono lauryl hydrogen phosphite, monooleyl hydrogen phosphite and the like. .
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 each represent Independently, it may be one or more of a hydrocarbon group containing an alkyl group, a hydrocarbon group containing an aromatic ring, and a hydrocarbon group containing an aliphatic ring.
  • the hydrocarbon group may have a partially unsaturated group, and may have any atom or substituent.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are preferably hydrocarbon groups containing an alkyl group.
  • the hydrocarbon group is preferably a non-substituted saturated group.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are preferably the same.
  • phosphites trimethyl phosphite, triethyl phosphite, tri n-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris Compounds represented by a compound represented by the formula (C2-3) such as (tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl monodecyl phosphite and the like , Diisodecyl pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, diste
  • trimethyl phosphite triethyl phosphite, tri n-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite
  • trialkyl phosphites such as triisodecyl phosphite, tris (tridecyl) phosphite, trioleyl phosphite and tristearyl phosphite.
  • trialkyl phosphites tridecyl phosphite is preferred.
  • the amount of the phosphoric acid compound (C) used is preferably 0.1 to 5 parts by mass, and more preferably 0.02 to 3 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound (A).
  • the amount of the phosphoric acid compound used is 0.1 parts by mass or more, the increase in viscosity after light irradiation can be suppressed, and when it is 5 parts by mass or less, the photocurability does not deteriorate.
  • the sealing agent for organic electroluminescent elements of this embodiment may contain a photosensitizer.
  • the photosensitizer refers to a compound that absorbs energy rays and efficiently generates a cation from the photocationic polymerization initiator.
  • the photosensitizer is not particularly limited, and is, for example, benzophenone derivative, phenothiazine derivative, phenyl ketone derivative, naphthalene derivative, anthracene derivative, phenanthrene derivative, naphthacene derivative, chrysene derivative, perylene derivative, pentacene derivative, acridine derivative, benzothiazole derivative, Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, xanthone derivative, thioxanthene derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, tri Allylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives,
  • phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and / or anthracene derivatives such as 9,10-dibutoxyanthracene are preferable, and anthracene derivatives are more preferable.
  • anthracene derivatives 9,10-dibutoxyanthracene is preferred.
  • the amount of the photosensitizer used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound (A), from the viewpoint that photocurability does not deteriorate and storage stability does not decrease. 0.02 to 5 parts by mass is more preferable.
  • the sealing agent for organic electroluminescent elements of this embodiment may contain a silane coupling agent.
  • a silane coupling agent By containing a silane coupling agent, the photocationic polymerization composition of the present embodiment exhibits excellent adhesion and adhesion durability.
  • the silane coupling agent is not particularly limited, and ⁇ -chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, ⁇ - (meth) Acryloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxys
  • silane coupling agents may be selected and used.
  • ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ - (meth) acryloxypropyltrimethoxy One or more selected from the group consisting of silanes is preferred, and ⁇ -glycidoxypropyltrimethoxysilane is more preferred.
  • the amount of the silane coupling agent used is preferably 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B) in terms of obtaining adhesiveness and adhesion durability. 2 to 5 parts by mass is more preferable.
  • the light source used for curing and adhesion of the sealant for an organic electroluminescent element of the present embodiment is not particularly limited, and halogen lamps, metal halide lamps, high power metal halide lamps (containing indium etc.), low pressure mercury lamps, A high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, a light emitting diode (hereinafter referred to as an LED) and the like can be mentioned.
  • These light sources are preferable in that they can efficiently irradiate energy beams corresponding to the reaction wavelengths of the respective cationic photopolymerization initiators.
  • the light sources have different emission wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the cationic photopolymerization initiator and the like.
  • natural light can also be a reaction initiation light source.
  • irradiation of the said light source you may perform direct irradiation, condensing irradiation by a reflective mirror, a fiber, etc.
  • a low wavelength cut filter, a heat ray cut filter, a cold mirror or the like can also be used.
  • the sealant for an organic electroluminescent element of the present embodiment may be subjected to a post heat treatment in order to accelerate the curing rate after light irradiation.
  • the temperature of the post-heating is preferably 150 ° C. or less, and more preferably 80 ° C. or less, from the viewpoint of not damaging the organic electroluminescent device when used for sealing the organic electroluminescent device.
  • 60 degreeC or more is preferable.
  • the adhesive of the present embodiment can be suitably used for adhesion of packages such as organic electroluminescent elements.
  • the manufacturing method of the sealing agent for organic electroluminescent elements of this embodiment if said component can be mixed sufficiently, it will not be restrict
  • the stirring method using the stirring force accompanying rotation of a propeller The method of utilizing normal dispersers, such as a planetary stirrer by rotation revolution, etc. are mentioned. These mixing methods are preferable in that stable mixing can be performed at low cost.
  • an organic electroluminescent display device using the sealing agent for organic electroluminescent devices of this embodiment, for example, the sealing agent for organic electroluminescent devices of this embodiment on one substrate (rear plate) After applying the light to the sealing agent for organic electroluminescent element to activate it, then blocking the light and bonding the back plate and the substrate on which the electroluminescent element is formed via the composition Etc.
  • the organic electroluminescent element can be sealed without being exposed to light or heat.
  • the sealant for an organic electroluminescent device of the present embodiment is applied to one of the substrates using the sealant for an organic electroluminescent device of the present embodiment, and the other substrate is coated with the sealant for an organic electroluminescent device.
  • An organic electroluminescent display device can be manufactured using the method of bonding a board
  • the viscosity after 10 minutes of light irradiation is less than 5 times compared with the viscosity before light irradiation in the sealing agent for organic electroluminescent elements of this embodiment.
  • UV is preferred.
  • the viscosity 10 minutes after irradiating UV with 100 mW / cm 2 with a high pressure mercury lamp for 30 seconds is less than 5 times compared with the viscosity before UV irradiation.
  • the (B) photocationic polymerization initiator absorb and excite the irradiated light, and the excited species be decomposed to generate an acid.
  • the sealant for an organic electroluminescent device of the present embodiment has a small increase in viscosity after light irradiation, can suppress the generation of outgassing, and is less likely to deteriorate the organic electroluminescent device.
  • one aspect of the present invention may be a cured product obtained by curing the above-mentioned sealing agent for an organic electroluminescent device.
  • the other one side of this invention may be the sealing material for organic electroluminescent elements containing the above-mentioned hardened
  • the sealing material may be a cured body, and may include the cured body of the sealing agent and other constituent materials.
  • Other constituent materials include, for example, inorganic layers such as silicon nitride films, silicon oxide films and silicon nitride oxides, and inorganic fillers such as silica, mica, kaolin, talc and aluminum oxide.
  • Still another aspect of the present invention may be an organic electroluminescent display device including an organic electroluminescent device and the above-described sealing material for an organic electroluminescent device.
  • the method of manufacturing an organic electroluminescent display device includes an attaching step of attaching the above-mentioned encapsulant for an organic electroluminescent device to the first member, and the encapsulant for an organic electroluminescent device attached thereto. And a bonding step of bonding the first member and the second member through the light-irradiated sealing agent for an organic electroluminescent element.
  • the first member may be a substrate
  • the second member may be an organic electroluminescent device.
  • the conditions and the like of each step in this manufacturing method may be appropriately selected based on the description of the above-described embodiment.
  • A-1 The following was used as an alicyclic compound having an epoxy group.
  • A-1-1) 3 ', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Ceroxide 2021P” manufactured by Daicel Chemical Industries, Ltd.)
  • A-1-2 Hydrogenated bisphenol A type epoxy resin ("YX 8000” manufactured by Mitsubishi Chemical Corporation, molecular weight 380 to 430)
  • A-1-3 3,4-epoxycyclohexylmethyl methacrylate
  • Cyclomer M100 manufactured by Daicel Corporation
  • A-2) The following was used as an aromatic compound having an epoxy group.
  • A-2-1 Bisphenol A type epoxy resin ("jER 828” manufactured by Mitsubishi Chemical Corporation, molecular weight 360 to 390)
  • A-2-2 Bisphenol F type epoxy resin ("jER 806” manufactured by Mitsubishi Chemical Corporation, molecular weight 320 to 340)
  • A-2-3 Bisphenol F type epoxy resin (Mitsui Chemical Co., Ltd. "YL 983 U", molecular weight 360-380)
  • A-2-4 Bisphenol F type epoxy resin ("KRM-2490” manufactured by ADEKA Corporation, molecular weight 340 to 380)
  • B-1 Triarylsulfonium salt hexafluoroantimonate
  • ADKA OPTOMER SP-170 manufactured by Adeka, anion species is hexafluoroantimonate
  • B-2 Triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, "CPI-200K” manufactured by San-Apro, anion species is phosphorus compound)
  • C-1 Tris (2-ethylhexyl) phosphate ("TOP" manufactured by Daihachi Chemical Industry Co., Ltd.)
  • C-2) Tridecyl phosphite (manufactured by Johoku Chemical Industry Co., Ltd.
  • JP-310 C-3) Bis (decyl) pentaerythritol diphosphite (“JPE-10” manufactured by Johoku Chemical Industry Co., Ltd.) (C-4) Bis (2-ethylhexyl) hydrogen phosphite ("JPE-208” manufactured by Johoku Chemical Industry Co., Ltd.) (C-5) Diphenyl monodecyl phosphite ("JPM-311” manufactured by Johoku Chemical Industry Co., Ltd.) (C-6 Comparative Example) Tri-n-octyl phosphine oxide (“TOO (registered trademark)” manufactured by Hokuko Chemical Co., Ltd.) (C-7 Comparative Example) Tri-n-octylphosphine ("TOCP” manufactured by Johoku Chemical Industry Co., Ltd.) (C-8 Comparative Example) 18-crown-6-ether ("Crown Ether O-18" manufactured by Nippon Soda Co., Ltd.)
  • Raw materials of the types shown in Tables 1 and 2 were mixed at the composition ratio shown in Tables 1 and 2 to prepare encapsulants for organic electroluminescent devices of Examples and Comparative Examples.
  • the unit of the composition ratio is parts by mass.
  • the viscosity (shear viscosity) of the sealant was measured using an E-type viscometer (1 ° 34 ′ ⁇ R24 cone rotor) under conditions of a temperature of 25 ° C. and a rotational speed of 10 rpm.
  • Each sealing agent for organic electroluminescent elements obtained by the Example and the comparative example is apply
  • An ultraviolet irradiation device (The ultra-high pressure mercury lamp irradiation apparatus by HOYA, "UL-750") is applied to the substrate.
  • the ultraviolet rays of 100 mW / cm 2 wavelength were applied for 30 seconds using Ten minutes after the completion of irradiation with ultraviolet light, measurement was carried out using an E-type viscometer (cone rotor with 1 ° 34 ′ ⁇ R24) at a temperature of 25 ° C. and a rotation speed of 10 rpm.
  • the viscosity change rate was determined according to the formula: V ⁇ / V0.
  • the viscosity change rate is preferably 5 or less from the viewpoint of good late curing property.
  • the sealing agent was cured under the following light irradiation conditions. After photocuring the sealing agent with an electrodeless discharge metal halide lamp mounted UV curing device (manufactured by Fusion) under the condition of integrated light quantity of 4,000 mJ / cm 2 of wavelength of 365 nm, in an oven at 80 ° C. After heat treatment for 30 minutes, a cured product was obtained.
  • an electrodeless discharge metal halide lamp mounted UV curing device manufactured by Fusion
  • Moisture permeability A sheet-like cured product having a thickness of 0.1 mm is produced under the above-mentioned photo-curing conditions, and calcium chloride (anhydrous) is used as a moisture absorbent according to JIS Z 0208 "Moisture Moisture Test Method for Moisture-proof Packaging Material (Cup Method)".
  • the ambient temperature was 60.degree. C., and the relative humidity was 90%.
  • the moisture permeability is preferably 120 g / (m 2 ⁇ 24 hr) or less.
  • the sealing agent is applied on a glass substrate so that the coating amount per unit area is 10 mg / cm 2, and an ultraviolet irradiation device (manufactured by HOYA, ultra-high pressure mercury lamp irradiation device “UL-750”) is applied to the substrate. It irradiated for 10 seconds the ultraviolet-ray of 100 mW / cm ⁇ 2 > of wavelength 365nm, using. Thereafter, the mixture was heated at 80 ° C. for 60 minutes, the generated gas component was collected and concentrated, and the outgas amount was measured by GC / MS (manufactured by Agilent Technology, “GC / MS 7890 B / 5977 B”). The amount of outgas is preferably 60 ppm or less.
  • Anode ITO film thickness 250 nm of anode
  • Hole injection layer Copper phthalocyanine 30 nm thick
  • Hole transport layer N, N'-diphenyl-N, N'-dinaphthylbenzidine ( ⁇ -NPD) thickness 20 nm -Light emitting layer
  • Tris (8-hydroxyquinolinato) aluminum (metal complex material) 1000 ⁇ of light emitting layer
  • 300 micrometers or less are preferable, as for the diameter of a dark spot, 50 micrometers or less are more preferable, and it is most preferable that there is no dark spot.
  • the sealant of the present embodiment is less likely to generate outgassing at the time of light irradiation, so the durability is good and the element is not deteriorated. Sealants other than this embodiment have no effect.
  • the component (C) is not used, the viscosity change after light irradiation is large (Experimental Example 15).
  • phosphine oxide is used, the sealant does not cure (Example 16).
  • phosphine When phosphine is used, the sealant gels and does not have the effect of this embodiment (Experimental Example 17).
  • crown ether durability at high temperature and high humidity can not be obtained (Example 18).
  • the component (B) is not used, the sealant does not cure (Example 19).
  • the component (A-2) is not used, durability can not be obtained (Experimental Example 20).
  • the component (A-1) is not used, durability at high temperature and high humidity can not be obtained (Experimental Example 21).

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Theoretical Computer Science (AREA)
  • Epoxy Resins (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Sealing Material Composition (AREA)
  • Optics & Photonics (AREA)
PCT/JP2018/031335 2017-08-24 2018-08-24 有機エレクトロルミネッセンス素子用封止剤 WO2019039587A1 (ja)

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WO2020129792A1 (ja) * 2018-12-18 2020-06-25 積水化学工業株式会社 硬化性樹脂組成物、硬化物、及び、有機ｅｌ表示素子
JPWO2020196669A1 (zh) * 2019-03-27 2020-10-01
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KR102536932B1 (ko) 2023-05-30
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