WO2019039587A1 - Sealing agent for organic electroluminescent elements - Google Patents

Sealing agent for organic electroluminescent elements 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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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 CN201880053942.2A priority Critical patent/CN110999537B/en
Priority to JP2019537707A priority patent/JP7123943B2/en
Priority to KR1020207002163A priority patent/KR102536932B1/en
Publication of WO2019039587A1 publication Critical patent/WO2019039587A1/en

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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).

Abstract

A sealing agent for organic electroluminescent elements, which contains (A) a cationically polymerizable compound, (B) a cationic photopolymerization initiator, and (C) one or more phosphoric acid compounds selected from the group consisting of phosphate esters and phosphite esters, and wherein the cationically polymerizable compound (A) contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group.

Description

有機エレクトロルミネッセンス素子用封止剤Sealant for organic electroluminescent devices
　本発明は、有機エレクトロルミネッセンス素子用封止剤に関する。例えば、有機エレクトロルミネッセンス素子封止用に用いられる封止剤に関する。 The present invention relates to a sealant for an organic electroluminescent device. For example, the present invention relates to a sealing agent used for sealing an organic electroluminescent element.
　近年、有機エレクトロルミネッセンス（有機ＥＬ）表示素子や有機薄膜太陽電池素子等の有機薄膜素子を用いた有機光デバイスの研究が進められている。有機薄膜素子は真空蒸着や溶液塗布等により簡便に作製できるため、生産性に優れる。 In recent years, research on 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. The organic thin film element can be easily manufactured by vacuum deposition, solution coating or the like, and therefore, is excellent in productivity.
　有機エレクトロルミネッセンス表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された薄膜構造体を有する。この有機発光材料層に一方の電極から電子が注入されると共に他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して自己発光を行う。有機エレクトロルミネッセンス表示素子は、バックライトを必要とする液晶表示素子等と比較して視認性がよく、より薄型化が可能であり、かつ、直流低電圧駆動が可能であるという利点を有する。 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.
　ところが、このような有機エレクトロルミネッセンス表示素子は、有機発光材料層や電極が外気に曝されるとその発光特性が急激に劣化し寿命が短くなるという問題があった。従って、有機エレクトロルミネッセンス表示素子の安定性及び耐久性を高めることを目的として、有機エレクトロルミネッセンス表示素子においては、有機発光材料層や電極を大気中の水分や酸素から遮断する封止技術が不可欠となっている。 However, such an 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.
　特許文献１には、上面発光型有機エレクトロルミネッセンス表示素子等において、有機エレクトロルミネッセンス表示素子基板の間に光硬化性の封止剤を満たし、光を照射して封止する方法が開示されている。しかしながら、特許文献１は、本発明の有機エレクトロルミネッセンス素子用封止剤について記載がない。 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. . However, patent document 1 does not describe the sealing agent for organic electroluminescent elements of this invention.
　特許文献２には、反応性制御剤を遅延硬化剤として使用することなく、十分な可使時間を確保できるＵＶ硬化性樹脂組成物が開示されている。しかしながら、光照射後の可使時間が短い問題があった。特許文献２は、エポキシ基を有する脂環式化合物について記載がない。特許文献２は、リン酸エステルを光カチオン重合開始剤として例示するだけであり、実施例で使用しておらず、リン酸エステルを、光照射後の粘度の上昇を抑えるために使用しない。 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.
　特許文献３には、エポキシ樹脂（「末端にエポキシ基を有するポリアルキレンオキサイド付加ビスフェノール誘導体」を除く）、光カチオン重合開始剤、並びに、末端にエポキシ基を有するポリアルキレンオキサイド付加ビスフェノール誘導体を含有し、光照射により硬化反応が開始し、光を遮断した後にも暗反応で硬化反応が進行する光カチオン重合性接着剤からなることを特徴とする有機エレクトロルミネッセンス素子封止用接着剤が開示されている。特許文献３は、エポキシ基を有する脂環式化合物について記載がない。特許文献３は、光照射時にアウトガスを発生して素子を劣化させるという問題があった。 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. Disclosed is 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.
特許文献４には、特定のカチオン重合性化合物と、光カチオン重合開始剤とを含有する有機エレクトロルミネッセンス表示素子用封止剤が開示されている。しかしながら、光照射後の可使時間が短い問題があった。特許文献４は、リン酸エステルを光カチオン重合開始剤として例示するだけであり、実施例で使用しておらず、リン酸エステルを、光照射後の粘度の上昇を抑えるために使用しない。 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. However, there is a problem that the pot life after light irradiation is short. 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.
　特許文献５には、光カチオン重合性化合物１００質量部、光カチオン重合開始剤０．１～３０質量部、エーテル結合を有する化合物からなる硬化制御剤０．１～３０質量部を含有し、硬化制御剤がエーテル結合を有する化合物を有する後硬化組成物による有機エレクトロルミネッセンス素子の封止方法が開示されている。しかしながら、この様な封止方法では、光照射時にアウトガスを発生して素子を劣化させることがあるという問題があった。
　特許文献５は、エポキシ基を有する脂環式化合物について記載がない。特許文献５は、リン酸エステルを光カチオン重合開始剤として例示するだけであり、実施例で使用しておらず、リン酸エステルを、光照射後の粘度の上昇を抑えるために使用しない。 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. However, such a sealing method has a problem that outgassing may occur at the time of light irradiation to deteriorate the element.
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.
　特許文献６には、ビスフェノールＡ型エポキシ樹脂と少なくとも１個の活性水素を有するリン酸類との付加物（Ａ）と、脂環式エポキシ基を２個以上有する化合物（Ｂ）と、カチオン性光重合開始剤（Ｃ）を含有する紫外線硬化型樹脂組成物が開示されている。しかしながら、この様な（Ａ）を用いた樹脂組成物では、（Ａ）の製造方法が複雑であり、副生成物によりアウトガスを発生して素子を劣化させるという問題点があった。特許文献６は、有機エレクトロルミネッセンス素子用封止剤について記載がない。 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. However, in the resin composition using such (A), 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.
　特許文献７には、放射線硬化性成分を含むと共に、異なる化合物群に属する少なくとも２つの難燃剤を含む放射線硬化性組成物が開示されている。しかしながら、特許文献７では、そもそも他目的に用いられる難燃性の硬化性組成物であり、光照射後の可使時間及び光照射時のアウトガス発生に関する記載はない。特許文献７は、有機エレクトロルミネッセンス素子用封止剤について記載がない。 Patent Document 7 discloses a radiation curable composition containing a radiation curable component and at least two flame retardants belonging to different compound groups. However, 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.
特開２００１－３５７９７３号公報JP 2001-357973 A 特許５９１９５７４号公報Patent 5919574 gazette 特許４８００２４７号公報Patent No. 4800247 特開２０１６－５８２７３号公報JP, 2016-58273, A 特許４３８４５０９号公報Patent 4384509 gazette 特開平７－２４７３４２号公報Japanese Patent Application Laid-Open No. 7-247342 特表２００７－５１３２３４号公報Japanese Patent Application Publication No. 2007-513234
　本発明は上記事情に鑑みてなされたものであり、光照射後の粘度の上昇が少なく、有機エレクトロルミネッセンス素子を劣化させにくい有機エレクトロルミネッセンス素子用封止剤を提供することを目的とする。 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.
　即ち、本発明は、以下の通りである。
＜１＞（Ａ）カチオン重合性化合物と、（Ｂ）光カチオン重合開始剤と、（Ｃ）リン酸エステル及び亜リン酸エステルからなる群より選択される１種以上のリン酸化合物と、を含有し、（Ａ）カチオン重合性化合物が、（Ａ－１）エポキシ基を有する脂環式化合物及び（Ａ－２）エポキシ基を有する芳香族化合物を含有する、有機エレクトロルミネッセンス素子用封止剤。
＜２＞（Ｃ）リン酸化合物が（Ｃ１）リン酸エステルである＜１＞記載の有機エレクトロルミネッセンス素子用封止剤。
＜３＞（Ｃ１）リン酸エステルが、式（Ｃ１－１）で表される化合物、式（Ｃ１－２）で表される化合物及び式（Ｃ１－３）で表される化合物からなる群より選択される少なくとも一種を含有する、＜２＞記載の有機エレクトロルミネッセンス素子用封止剤。
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 ［式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。］
＜４＞（Ｃ）リン酸化合物が（Ｃ２）亜リン酸エステルである＜１＞記載の有機エレクトロルミネッセンス素子用封止剤。
＜５＞（Ｃ２）亜リン酸エステルが、式（Ｃ２－１）で表される化合物、式（Ｃ２－２）で表される化合物、式（Ｃ２－３）で表される化合物、式（Ｃ２－４）で表される化合物、式（Ｃ２－５）で表される化合物及び式（Ｃ２－６）で表される化合物からなる群より選択される少なくとも一種を含有する、＜４＞記載の有機エレクトロルミネッセンス素子用封止剤。
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
 ［式中、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。］
＜６＞（Ａ－２）エポキシ基を有する芳香族化合物が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂からなる群から選択される１種以上である＜１＞～＜５＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。
＜７＞（Ｂ）光カチオン重合開始剤が、オニウム塩である＜１＞～＜６＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。
＜８＞（Ｂ）光カチオン重合開始剤の使用量が、（Ａ）カチオン重合性化合物１００質量部に対して、０．０５～５．０質量部である＜１＞～＜７＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。
＜９＞更に、光増感剤を含有する＜１＞～＜８＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。
＜１０＞更に、シランカップリング剤を含有する＜１＞～＜９＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。
＜１１＞＜１＞～＜１０＞のいずれか一項に記載の有機エレクトロルミネッセンス素子用封止剤の硬化体。
＜１２＞＜１１＞記載の硬化体を含む、有機エレクトロルミネッセンス素子用封止材。
＜１３＞有機エレクトロルミネッセンス素子と、＜１２＞記載の有機エレクトロルミネッセンス素子用封止材と、を含む、有機エレクトロルミネッセンス表示装置。
＜１４＞第一の部材に、＜１＞～＜１０＞のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤を付着させる付着工程と、付着させた前記有機エレクトロルミネッセンス素子用封止剤に光を照射する照射工程と、光照射された前記有機エレクトロルミネッセンス素子用封止剤を介して、前記第一の部材と第二の部材とを貼り合わせる貼合工程と、を有する、有機エレクトロルミネッセンス表示装置の製造方法。
＜１５＞前記第一の部材が基板であり、前記第二の部材が有機エレクトロルミネッセンス素子である、＜１４＞記載の有機エレクトロルミネッセンス表示装置の製造方法。 That is, 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 .
The sealing agent for organic electroluminescent elements of the <1> description whose <2> (C) phosphoric acid compound is a (C1) phosphoric acid ester.
<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.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
 [Wherein, 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.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
 [Wherein, 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. ]
<6> (A-2) Any one of <1> to <5>, wherein the aromatic compound having an epoxy group is one or more selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins The sealing agent for organic electroluminescent elements of 1 item.
The sealing agent for organic electroluminescent elements of any one of <1>-<6> whose <7> (B) photocationic polymerization initiator is onium salt.
Any one of <1> to <7> in which the amount of use of the cationic photopolymerization initiator of <8> (B) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound (A) The sealing agent for organic electroluminescent elements of any one of-.
<9> A sealing agent for an organic electroluminescent device according to any one of <1> to <8>, further containing a photosensitizer.
<10> A sealing agent for an organic electroluminescent device according to any one of <1> to <9>, further containing a silane coupling agent.
Hardened | cured material of sealing agent for organic electroluminescent elements as described in any one of <11><1>-<10>.
The sealing material for organic electroluminescent elements containing the hardened | cured material as described in <12><11>.
The organic electroluminescent display apparatus containing the <13> organic electroluminescent element and the sealing material for organic electroluminescent elements as described in <12>.
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 | substrate, and the said 2nd member is an organic electroluminescent element.
　本発明によれば、光照射後の粘度の上昇が少なく、有機エレクトロルミネッセンス素子を劣化させにくい有機エレクトロルミネッセンス素子用封止剤を提供できる。 According to 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.
　以下、本実施形態を詳細に説明する。 Hereinafter, the present embodiment will be described in detail.
　本実施形態に係る有機エレクトロルミネッセンス素子用封止剤は、
（Ａ）カチオン重合性化合物、
（Ｂ）光カチオン重合開始剤、並びに
（Ｃ）リン酸エステル及び亜リン酸エステルからなる群より選択される少なくとも１種のリン酸化合物
を含有することを特徴とする。
　また、本実施形態に係る有機エレクトロルミネッセンス素子用封止剤は、（Ａ）カチオン重合性化合物が、（Ａ－１）エポキシ基を有する脂環式化合物、及び（Ａ－２）エポキシ基を有する芳香族化合物を含有することを特徴とする。 The sealant for an organic electroluminescent device according to the present embodiment 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.
In addition, in the sealing agent for an organic electroluminescent element according to the present embodiment, (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.
　次に、本実施形態に係る有機エレクトロルミネッセンス素子用封止剤の成分について説明する。 Next, components of the sealing agent for an organic electroluminescent element according to the present embodiment will be described.
（Ａ）カチオン重合性化合物
　本実施形態に係る有機エレクトロルミネッセンス素子用封止剤は、（Ａ）カチオン重合性化合物を必須成分とする。（Ａ）カチオン重合性化合物は、光重合性であることが好ましい。 (A) Cationic Polymerizable 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.
　（Ａ）カチオン重合性化合物は、（Ａ－１）エポキシ基を有する脂環式化合物及び（Ａ－２）エポキシ基を有する芳香族化合物を含有する。これにより、良好な接着性及び低透湿性が得られる。 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.
（Ａ－１）エポキシ基を有する脂環式化合物
　エポキシ基を有する脂環式化合物（以下、脂環式エポキシ化合物ということもある）としては、少なくとも１個のシクロアルカン環（例えば、シクロへキセン環、シクロペンテン環、ピネン環等）を有する化合物を、過酸化水素、過酸等の適当な酸化剤でエポキシ化することによって得られる化合物又はその誘導体や、芳香族エポキシ化合物（例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等）を水素化して得られる水素化エポキシ化合物等が挙げられる。これらの化合物は、１種以上を選択して使用してもよい。 (A-1) 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) 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.
　脂環式エポキシ化合物としては、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、３，４－エポキシシクロヘキシルアルキル（メタ）アクリレート（例えば、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート等）、（３、３’、４、４’－ジエポキシ）ビシクロヘキシル、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂等が挙げられる。 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.
　脂環式エポキシ化合物の中では、１，２－エポキシシクロヘキサン構造を有する脂環式エポキシ化合物が好ましい。１，２－エポキシシクロヘキサン構造を有する脂環式エポキシ化合物の中では、下記式（Ａ１－１）で表される化合物が好ましい。 Among the cycloaliphatic epoxy compounds, cycloaliphatic epoxy compounds having a 1,2-epoxycyclohexane structure are preferred. Among the alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, a compound represented by the following formula (A1-1) is preferable.
Figure JPOXMLDOC01-appb-C000019
 （式（Ａ１－１）中、Ｘは単結合又は連結基（１以上の原子を有する２価の基）を示し、連結基は、２価の炭化水素基、カルボニル基、エーテル結合、エステル結合、カーボネート基、アミド結合、又は、これらが複数個連結した基である）
Figure JPOXMLDOC01-appb-C000019
 (In the formula (A1-1), 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は連結基が好ましい。連結基の中では、エステル結合を有する官能基が好ましい。これらの中では、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が好ましい。 X is preferably a linking group. Among the linking groups, functional groups having an ester bond are preferred. Among these, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.
　脂環式エポキシ化合物の分子量は、透湿性や保存安定性の点で、４５０以下が好ましく、４００以下がより好ましく、３００未満が更に好ましく、１００～２８０が一層好ましい。 From the viewpoint of moisture permeability and storage stability, 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.
　脂環式エポキシ化合物が分子量分布を有する場合は、脂環式エポキシ化合物の数平均分子量が上記範囲であることが好ましい。なお、本明細書中、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により下記測定条件で測定される、ポリスチレン換算の値を示す。
・溶媒（移動相）：ＴＨＦ
・脱気装置：ＥＲＭＡ社製ＥＲＣ－３３１０
・ポンプ：日本分光社製ＰＵ－９８０
・流速：１．０ｍｌ／ｍｉｎ
・オートサンプラ：東ソー社製ＡＳ－８０２０
・カラムオーブン：日立製作所製Ｌ－５０３０
・設定温度：４０℃
・カラム構成：東ソー社製ＴＳＫｇｕａｒｄｃｏｌｕｍｎＭＰ（×Ｌ）６．０ｍｍＩＤ×４．０ｃｍ　２本、及び東ソー社製ＴＳＫ－ＧＥＬＭＵＬＴＩＰＯＲＥ　ＨＸＬ－Ｍ　７．８ｍｍＩＤ×３０．０ｃｍ　２本、計４本
・検出器：ＲＩ　日立製作所製Ｌ－３３５０
・データ処理：ＳＩＣ４８０データステーション When the alicyclic epoxy compound has a molecular weight distribution, the number average molecular weight of the alicyclic epoxy compound is preferably in the above range. In addition, in this specification, a number average molecular weight shows the value of polystyrene conversion measured by the following measurement conditions by gel permeation chromatography (GPC).
-Solvent (mobile phase): THF
Degassing device: ERC-3310 manufactured by ERMA
Pump: PU-980 manufactured by JASCO Corporation
・ Flow rate: 1.0 ml / min
・ Auto sampler: AS-8020 manufactured by Tosoh Corporation
・ Column oven: Hitachi L-5030
・ Setting temperature: 40 ° C
-Column configuration: TSKguardcolumnMP (× L) 6.0 mm ID × 4.0 cm 2 manufactured by Tosoh Corp., TSK-GELMULTIPORE HXL-M manufactured by Tosoh Corp. 7.8 mm ID × 30.0 cm 2 units, total of 4 detectors: RI Hitachi L-3350
Data processing: SIC 480 data station
（Ａ－２）エポキシ基を有する芳香族化合物
　エポキシ基を有する芳香族化合物（以下、芳香族エポキシ化合物ということもある）としては、モノマー、オリゴマー又はポリマーのいずれも使用可能であり、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、ノボラックフェノール型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、これらの変性物等が挙げられる。これらのエポキシ樹脂は、１種以上を選択して使用してもよい。
　これらの中では、ビスフェノール構造を有する芳香族エポキシ化合物が好ましい。ビスフェノール構造を有する芳香族エポキシ化合物の中では、下記式（Ａ２－１）で表される化合物が好ましい。 (A-2) 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.
Figure JPOXMLDOC01-appb-C000020
 （式（Ａ２－１）中、ｎは０．１～３０の実数を示し、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４は、それぞれ独立に水素原子又は置換若しくは非置換の炭素原子数１～５のアルキル基を表す。）
Figure JPOXMLDOC01-appb-C000020
 (In the formula (A2-1), 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)
　Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４は、水素原子又はメチル基が好ましい。Ｒ２１、Ｒ２２、Ｒ２３、Ｒ２４は、同一が好ましい。 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.
　ビスフェノール構造を有する芳香族エポキシ化合物の中では、ビスフェノールＡ型エポキシ樹脂及びビスフェノールＦ型エポキシ樹脂からなる群より選択される１種以上が好ましい。 Among the 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.
　芳香族エポキシ化合物の分子量は、透湿性等の点で、１００～５０００が好ましく、１５０～１０００がより好ましく、２００～４５０が最も好ましい。 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.
　芳香族エポキシ化合物が分子量分布を有する場合は、芳香族エポキシ化合物の数平均分子量が上記範囲であることが好ましい。なお、本明細書中、数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により上述した測定条件で測定される、ポリスチレン換算の値を示す。 When the aromatic epoxy compound has a molecular weight distribution, the number average molecular weight of the aromatic epoxy compound is preferably in the above range. In addition, in this specification, a number average molecular weight shows the value of polystyrene conversion measured on the measurement conditions mentioned above by gel permeation chromatography (GPC).
　本実施形態の（Ａ）カチオン重合性化合物は、モノマー、オリゴマー又はポリマーの何れも使用できる。 As the (A) cationically polymerizable compound of the present embodiment, any of monomers, oligomers or polymers can be used.
　本実施形態の（Ａ）カチオン重合性化合物は、エポキシ化合物であることが好ましい。 The (A) cationically polymerizable compound of the present embodiment is preferably an epoxy compound.
　本実施形態の（Ａ）カチオン重合性化合物は、環状エーテル基、カチオン重合性ビニル基等のカチオン重合性基を２個以上有することが好ましく、２個有することがより好ましい。 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.
　本実施形態では、（Ａ－１）及び（Ａ－２）以外の他のカチオン重合性化合物を更に使用できる。（Ａ－１）及び（Ａ－２）以外の他のカチオン重合性化合物としては、環状エーテル類、カチオン重合性ビニル化合物等が挙げられる。環状エーテル類としては、エポキシ、オキセタン等の化合物が挙げられる。 In the present embodiment, cationically polymerizable compounds other than (A-1) and (A-2) can be further used. Examples of cationically polymerizable compounds other than (A-1) and (A-2) include cyclic ethers and cationically polymerizable vinyl compounds. Examples of cyclic ethers include compounds such as epoxy and oxetane.
　（Ａ）カチオン重合性化合物１００質量部中、（Ａ－１）及び（Ａ－２）以外の他のカチオン重合性化合物の含有量は、４０質量部以下が好ましく、２０質量部以下がより好ましく、１０質量部以下が最も好ましい。（Ａ）カチオン重合性化合物１００質量部中、（Ａ－１）及び（Ａ－２）以外の他のカチオン重合性化合物の含有量は、例えば１質量部以上であってよく、５質量部以上であってもよく、０質量部であってもよい。 (A) In 100 parts by mass of the cationically polymerizable compound, 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. (A) In 100 parts by mass of the cationically polymerizable compound, 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.
　カチオン重合性ビニル化合物としては、ビニルエーテル、ビニルアミン、スチレン等が挙げられる。これらの化合物若しくは誘導体は、１種以上を選択して使用してもよい。 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.
　（Ａ－１）及び（Ａ－２）以外の他のカチオン重合性化合物の中では、ジグリシジルエーテル化合物、オキセタン化合物、ビニルエーテル化合物からなる１種以上が好ましい。 Among the cationically polymerizable compounds other than (A-1) and (A-2), one or more kinds of diglycidyl ether compounds, oxetane compounds and vinyl ether compounds are preferable.
　ジグリシジルエーテル化合物としては、アルキレングリコールのジグリシジルエーテル（例えば、エチレングリコールのジグリシジルエーテル、プロピレングリコールのジグリシジルエーテル、１，６－ヘキサンジオールのジグリシジルエーテル等）、多価アルコールのポリグリシジルエーテル（例えば、グリセリン又はそのアルキレンオキサイド付加体のジ又はトリグリシジルエーテル等）、ポリアルキレングリコールのジグリシジルエーテル（例えば、ポリエチレングリコール又はそのアルキレンオキサイド付加体のジグリシジルエーテル、ポリプロピレングリコール又はそのアルキレンオキサイド付加体のジグリシジルエーテル等）が挙げられる。ここで、アルキレンオキサイドとしては、エチレンオキサイド及びプロピレンオキサイド等の脂肪族系が挙げられる。 Examples of 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.). Here, as the alkylene oxide, aliphatics such as ethylene oxide and propylene oxide may be mentioned.
　オキセタン化合物としては、特に限定されないが、３－エチル－３－ヒドロキシメチルオキセタン（東亜合成（株）製商品名アロンオキセタンＯＸＴ－１０１等）、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（同ＯＸＴ－１２１等）、３－エチル－３－（フェノキシメチル）オキセタン（同ＯＸＴ－２１１等）、ジ（１－エチル－（３－オキセタニル））メチルエーテル（同ＯＸＴ－２２１等）、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン（同ＯＸＴ－２１２等）等が挙げられる。オキセタン化合物とは、分子内に１個以上のオキセタン環を有する化合物をいう。 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 molecule.
　ビニルエーテル化合物としては、特に限定されないが、エチレングリコールジビニルエーテル、エチレングリコールモノビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールモノビニルエーテル、トリエチレングリコールジビニルエーテル、プロピレングリコールジビニルエーテル、ジプロピレングリコールジビニルエーテル、ブタンジオールジビニルエーテル、ヘキサンジオールジビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ヒドロキシエチルモノビニルエーテル、ヒドロキシノニルモノビニルエーテル、トリメチロールプロパントリビニルエーテル等のジ又はトリビニルエーテル化合物、エチルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、オクタデシルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシブチルビニルエーテル、２－エチルヘキシルビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、ｎ－プロピルビニルエーテル、イソプロピルビニルエーテル、イソプロペニルエーテルｏ－プロピレンカーボネート、ドデシルビニルエーテル、ジエチレングリコールモノビニルエーテル、オクタデシルビニルエーテル等のモノビニルエーテル化合物等が挙げられる。 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-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether Etc.
　（Ａ－１）エポキシ基を有する脂環式化合物の使用量は、（Ａ）カチオン重合性化合物１００質量部中、３０～９５質量部が好ましく、５０～９０質量部がより好ましく、６０～８０質量部が最も好ましく、６５～７５質量部が尚更好ましい。３０質量部以上であれば耐久性が得られ、９５質量部以下であれば耐久性が得られる。 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.
　（Ａ－２）エポキシ基を有する芳香族化合物の使用量は、（Ａ）カチオン重合性化合物１００質量部中、５～７０質量部が好ましく、１０～５０質量部がより好ましく、２０～４０質量部が最も好ましく、２５～３５質量部が尚更好ましい。５質量部以上であれば耐久性が得られ、７０質量部以下であれば耐久性が得られる。 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.
　（Ａ）カチオン重合性化合物１００質量部中、（Ａ－１）エポキシ基を有する脂環式化合物と（Ａ－２）エポキシ基を有する芳香族化合物の合計の含有量は、６０質量部以上が好ましく、８０質量部以上がより好ましく、９０質量部以上が最も好ましく、１００質量部が尚更好ましい。 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.
（Ｂ）光カチオン重合開始剤
　本実施形態に係る有機エレクトロルミネッセンス素子用封止剤は、（Ｂ）光カチオン重合開始剤を必須成分とする。光カチオン重合開始剤を用いる場合、本実施形態の封止剤は、紫外線等のエネルギー線照射により硬化可能となる。 (B) Photocationic polymerization initiator The sealing agent for organic electroluminescent elements which concerns on this embodiment has (B) photocationic polymerization initiator as an essential component. When using a photocationic polymerization initiator, the sealing agent of the present embodiment can be cured by irradiation with energy rays such as ultraviolet rays.
　（Ｂ）光カチオン重合開始剤としては、特に限定されないが、アリールスルホニウム塩誘導体（例えば、ダウケミカル社製のサイラキュアＵＶＩ－６９９０、サイラキュアＵＶＩ－６９７４、旭電化工業社製のアデカオプトマーＳＰ－１５０、アデカオプトマーＳＰ－１５２、アデカオプトマーＳＰ－１７０、アデカオプトマーＳＰ－１７２、サンアプロ社製のＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ、ＬＷ－Ｓ１、ダブルボンド社製のチバキュアー１１９０等）、アリールヨードニウム塩誘導体（例えば、チバスペシャリティーケミカルズ社製のイルガキュア２５０、ローディア・ジャパン社製のＲＰ－２０７４）、アレン－イオン錯体誘導体、ジアゾニウム塩誘導体、トリアジン系開始剤及びその他のハロゲン化物等の酸発生剤等が挙げられる。光カチオン重合開始剤のカチオン種としては、式（Ｂ－１）で表されるオニウム塩が好ましい。 (B) 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 photopolymerization initiator, onium salts represented by the formula (B-1) are preferable.
（Ｂ）光カチオン重合開始剤としては、特に限定されないが、式（Ｂ－１）で表されるオニウム塩が挙げられる。 The cationic photopolymerization initiator (B) is not particularly limited, and examples include onium salts represented by the formula (B-1).
Figure JPOXMLDOC01-appb-C000021
 （ＡはＶＩＡ族～ＶＩＩＡ族の原子価ｍの元素を示す。ｍは１～２を示す。ｐは０～３を示す。ｍ、ｐは整数が好ましい。ＲはＡに結合している有機基を示す。Ｄは下記式（Ｂ－１－１）：
Figure JPOXMLDOC01-appb-C000022
 で表される２価の基を示す。式（Ｂ－１－１）中、Ｅは２価の基を表し、Ｇは－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＮＨ－、－ＮＲ’－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、炭素数１～３のアルキレン又はフェニレン基（Ｒ’は炭素数１～５のアルキル基又は炭素数６～１０のアリール基）を示す。ａは０～５を示す。ａ＋１個のＥ及びＡ個のＧはそれぞれ同一であっても異なっていてもよい。ａは整数が好ましい。Ｘ－はオニウムの対イオンであり、その個数は１分子当りｐ＋１である。）
Figure JPOXMLDOC01-appb-C000021
 (A represents an element having a valence m of group VIA to group VIIA. M represents 1 to 2. p represents 0 to 3. m and p are preferably integers. R is an organic group bonded to A D represents a group represented by the following formula (B-1-1):
Figure JPOXMLDOC01-appb-C000022
 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 represents 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. )
　式（Ｂ－１－１）のオニウムイオンは特に限定されないが、４－（フェニルチオ）フェニルジフェニルスルホニウム、ビス［４－（ジフェニルスルホニオ）フェニル］スルフィド、ビス〔４－｛ビス［４－（２－ヒドロキシエトキシ）フェニル］スルホニオ｝フェニル〕スルフィド、ビス｛４－［ビス（４－フルオロフェニル）スルホニオ］フェニル｝スルフィド、４－（４－ベンゾイル－２－クロロフェニルチオ）フェニルビス（４－フルオロフェニル）スルホニウム、４－（４－ベンゾイルフェニルチオ）フェニルジフェニルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジ－ｐ－トリルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジフェニルスルホニウム、２－［（ジ－ｐ－トリル）スルホニオ］チオキサントン、２－［（ジフェニル）スルホニオ］チオキサントン、４－［４－（４－ｔｅｒｔ－ブチルベンゾイル）フェニルチオ］フェニルジ－ｐ－トリルスルホニウム、４－（４－ベンゾイルフェニルチオ）フェニルジフェニルスルホニウム、５－（４－メトキシフェニル）チアアンスレニウム、５－フェニルチアアンスレニウム、ジフェニルフェナシルスルホニウム、４－ヒドロキシフェニルメチルベンジルスルホニウム、２－ナフチルメチル（１－エトキシカルボニル）エチルスルホニウム、４－ヒドロキシフェニルメチルフェナシルスルホニウム、オクタデシルメチルフェナシルスルホニウム等が挙げられる。 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-tolylsulfonium, 7-isopropyl-9-oxo -10-thia-9,10-dihydroan Racen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyl di-p -Tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthraenium, 5-phenylthiaanthraenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2 And -naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium and the like.
　ＲはＡに結合している有機基である。Ｒは、例えば、炭素数６～３０のアリール基、炭素数４～３０の複素環基、炭素数１～３０のアルキル基、炭素数２～３０のアルケニル基又は炭素数２～３０のアルキニル基を表し、これらはアルキル、ヒドロキシ、アルコキシ、アルキルカルボニル、アリールカルボニル、アルコキシカルボニル、アリールオキシカルボニル、アリールチオカルボニル、アシロキシ、アリールチオ、アルキルチオ、アリール、複素環、アリールオキシ、アルキルスルフィニル、アリールスルフィニル、アルキルスルホニル、アリールスルホニル、アルキレンオキシ、アミノ、シアノ、ニトロの各基及びハロゲンからなる群より選ばれる少なくとも１種で置換されていてもよい。Ｒの個数はｍ＋ｐ（ｍ－１）＋１であり、それぞれ互いに同一であっても異なっていてもよい。又２個以上のＲが互いに直接又は－Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ２－、－ＮＨ－、－ＮＲ’－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、炭素数１～３のアルキレン若しくはフェニレン基を介して結合して元素Ａを含む環構造を形成してもよい。ここで、Ｒ’は炭素数１～５のアルキル基又は炭素数６～１０のアリール基である。 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. Here, R ′ is an alkyl group of 1 to 5 carbon atoms or an aryl group of 6 to 10 carbon atoms.
　上記において炭素数６～３０のアリール基としては、フェニル基等の単環式アリール基及びナフチル、アントラセニル、フェナンスレニル、ピレニル、クリセニル、ナフタセニル、ベンズアントラセニル、アントラキノリル、フルオレニル、ナフトキノン、アントラキノン等の縮合多環式アリール基が挙げられる。 In the above, 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.
　上記の炭素数６～３０のアリール基、炭素数４～３０の複素環基、炭素数１～３０のアルキル基、炭素数２～３０のアルケニル基又は炭素数２～３０のアルキニル基は少なくとも１種の置換基を有してもよく、置換基の例としては、メチル、エチル、プロピル、ブチル、ペンチル、オクチル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクダデシル等の炭素数１～１８の直鎖アルキル基；イソプロピル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、イソペンチル、ネオペンチル、ｔｅｒｔ－ペンチル、イソヘキシル等の炭素数１～１８の分岐アルキル基；シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等の炭素数３～１８のシクロアルキル基；ヒドロキシ基；メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、ｓｅｃ－ブトキシ、ｔｅｒｔ－ブトキシ、ヘキシルオキシ、デシルオキシ、ドデシルオキシ等の炭素数１～１８の直鎖又は分岐のアルコキシ基；アセチル、プロピオニル、ブタノイル、２－メチルプロピオニル、ヘプタノイル、２－メチルブタノイル、３－メチルブタノイル、オクタノイル、デカノイル、ドデカノイル、オクタデカノイル等の炭素数２～１８の直鎖又は分岐のアルキルカルボニル基；ベンゾイル、ナフトイル等の炭素数７～１１のアリールカルボニル基；メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、ｓｅｃ－ブトキシカルボニル、ｔｅｒｔ－ブトキシカルボニル、オクチロキシカルボニル、テトラデシルオキシカルボニル、オクタデシロキシカルボニル等の炭素数２～１９の直鎖又は分岐のアルコキシカルボニル基；フェノキシカルボニル、ナフトキシカルボニル等の炭素数７～１１のアリールオキシカルボニル基；フェニルチオカルボニル、ナフトキシチオカルボニル等の炭素数７～１１のアリールチオカルボニル基；アセトキシ、エチルカルボニルオキシ、プロピルカルボニルオキシ、イソプロピルカルボニルオキシ、ブチルカルボニルオキシ、イソブチルカルボニルオキシ、ｓｅｃ－ブチルカルボニルオキシ、ｔｅｒｔ－ブチルカルボニルオキシ、オクチルカルボニルオキシ、テトラデシルカルボニルオキシ、オクタデシルカルボニルオキシ等の炭素数２～１９の直鎖又は分岐のアシロキシ基；フェニルチオ、２－メチルフェニルチオ、３－メチルフェニルチオ、４－メチルフェニルチオ、２－クロロフェニルチオ、３－クロロフェニルチオ、４－クロロフェニルチオ、２－ブロモフェニルチオ、３－ブロモフェニルチオ、４－ブロモフェニルチオ、２－フルオロフェニルチオ、３－フルオロフェニルチオ、４－フルオロフェニルチオ、２－ヒドロキシフェニルチオ、４－ヒドロキシフェニルチオ、２－メトキシフェニルチオ、４－メトキシフェニルチオ、１－ナフチルチオ、２－ナフチルチオ、４－［４－（フェニルチオ）ベンゾイル］フェニルチオ、４－［４－（フェニルチオ）フェノキシ］フェニルチオ、４－［４－（フェニルチオ）フェニル］フェニルチオ、４－（フェニルチオ）フェニルチオ、４－ベンゾイルフェニルチオ、４－ベンゾイル－２－クロロフェニルチオ、４－ベンゾイル－３－クロロフェニルチオ、４－ベンゾイル－３－メチルチオフェニルチオ、４－ベンゾイル－２－メチルチオフェニルチオ、４－（４－メチルチオベンゾイル）フェニルチオ、４－（２－メチルチオベンゾイル）フェニルチオ、４－（ｐ－メチルベンゾイル）フェニルチオ、４－（ｐ－エチルベンゾイル）フェニルチオ４－（ｐ－イソプロピルベンゾイル）フェニルチオ、４－（ｐ－ｔｅｒｔ－ブチルベンゾイル）フェニルチオ等の炭素数６～２０のアリールチオ基；メチルチオ、エチルチオ、プロピルチオ、イソプロピルチオ、ブチルチオ、イソブチルチオ、ｓｅｃ－ブチルチオ、ｔｅｒｔ－ブチルチオ、ペンチルチオ、イソペンチルチオ、ネオペンチルチオ、ｔｅｒｔ－ペンチルチオ、オクチルチオ、デシルチオ、ドデシルチオ等の炭素数１～１８の直鎖又は分岐のアルキルチオ基；フェニル、トリル、ジメチルフェニル、ナフチル等の炭素数６～１０のアリール基；チエニル、フラニル、ピラニル、ピロリル、オキサゾリル、チアゾリル、ピリジル、ピリミジル、ピラジニル、インドリル、ベンゾフラニル、ベンゾチエニル、キノリル、イソキノリル、キノキサリニル、キナゾリニル、カルバゾリル、アクリジニル、フェノチアジニル、フェナジニル、キサンテニル、チアントレニル、フェノキサジニル、フェノキサチイニル、クロマニル、イソクロマニル、ジベンゾチエニル、キサントニル、チオキサントニル、ジベンゾフラニル等の炭素数４～２０の複素環基；フェノキシ、ナフチルオキシ等の炭素数６～１０のアリールオキシ基；メチルスルフィニル、エチルスルフィニル、プロピルスルフィニル、イソプロピルスルフィニル、ブチルスルフィニル、イソブチルスルフィニル、ｓｅｃ－ブチルスルフィニル、ｔｅｒｔ－ブチルスルフィニル、ペンチルスルフィニル、イソペンチルスルフィニル、ネオペンチルスルフィニル、ｔｅｒｔ－ペンチルスルフィニル、オクチルスルフィニル等の炭素数１～１８の直鎖又は分岐のアルキルスルフィニル基；フェニルスルフィニル、トリルスルフィニル、ナフチルスルフィニル等の炭素数６～１０のアリールスルフィニル基；メチルスルホニル、エチルスルホニル、プロピルスルホニル、イソプロピルスルホニル、ブチルスルホニル、イソブチルスルホニル、ｓｅｃ－ブチルスルホニル、ｔｅｒｔ－ブチルスルホニル、ペンチルスルホニル、イソペンチルスルホニル、ネオペンチルスルホニル、ｔｅｒｔ－ペンチルスルホニル、オクチルスルホニル等の炭素数１～１８の直鎖又は分岐のアルキルスルホニル基；フェニルスルホニル、トリルスルホニル（トシル基）、ナフチルスルホニル等の炭素数の６～１０のアリールスルホニル基；式（Ｂ－１－２）
Figure JPOXMLDOC01-appb-C000023
 で表されるアルキレンオキシ基（Ｑは水素原子又はメチル基を表し、ｋは１～５の整数を表す）；非置換のアミノ基；炭素数１～５のアルキル及び／又は炭素数６～１０のアリールでモノ置換若しくはジ置換されているアミノ基；シアノ基；ニトロ基；フッ素、塩素、臭素、ヨウ素等のハロゲン等が挙げられる。 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 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl Cycloalkyl group; hydroxy group; methoxy, ethoxy, propoxy, isopropyl Linear or branched alkoxy group having 1 to 18 carbon atoms such as s, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, A linear or branched alkylcarbonyl group having 2 to 18 carbon atoms such as 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc .; an aryl having 7 to 11 carbon atoms such as benzoyl or naphthoyl Carbonyl group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl A linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as tetradecyloxycarbonyl or octadecyloxycarbonyl; an aryloxycarbonyl group having 7 to 11 carbons such as phenoxycarbonyl or naphthoxycarbonyl; phenylthiocarbonyl or naphtho Arylthio carbonyl group having 7 to 11 carbon atoms such as xythio carbonyl; acetoxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, A linear or branched acyloxy group having 2 to 19 carbon atoms such as octyl carbonyloxy, tetradecyl carbonyloxy, octadecyl carbonyloxy, etc .; phenylthio, 2-methyl Henylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluoro Phenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [ 4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl- 2-Black Phenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio Arylthio having 6 to 20 carbon atoms, such as 4- (p-methylbenzoyl) phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, A linear or branched alkylthio group having 1 to 18 carbon atoms such as silthio and dodecylthio; an aryl group having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl and naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, Pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, phenantazinyl, phenoxazinyl, chromanyl, isochromanyl, dibenzothinyl, Heterocyclic groups having 4 to 20 carbon atoms such as thioxanthonyl and dibenzofuranyl; aryloxy groups having 6 to 10 carbons such as phenoxy and naphthyloxy; Rusulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl etc. 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, octylsulfonyl and the like; a carbon number such as phenylsulfonyl, tolylsulfonyl (tosyl group) and naphthylsulfonyl 6 to 10 arylsulfonyl group; Formula (B-1-2)
Figure JPOXMLDOC01-appb-C000023
 An alkyleneoxy group represented by (Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5); unsubstituted amino group; alkyl having 1 to 5 carbon atoms and / or 6 to 10 carbon atoms Amino groups mono- or di-substituted with aryls of the following: cyano group; nitro group; halogen such as fluorine, chlorine, bromine, iodine and the like.
　式（Ｂ－１）中のｐは［Ｄ－Ａ＋Ｒｍ－１］結合の繰り返し単位数を表し、０～３の整数であることが好ましい。 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.
　式（Ｂ－１）中のオニウムイオン［Ａ＋］として好ましいものはスルホニウム、ヨードニウム、セレニウムであるが、代表例としては以下のものが挙げられる。 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.
　スルホニウムイオンとしては、トリフェニルスルホニウム、トリ－ｐ－トリルスルホニウム、トリ－ｏ－トリルスルホニウム、トリス（４－メトキシフェニル）スルホニウム、１－ナフチルジフェニルスルホニウム、２－ナフチルジフェニルスルホニウム、トリス（４－フルオロフェニル）スルホニウム、トリ－１－ナフチルスルホニウム、トリ－２－ナフチルスルホニウム、トリス（４－ヒドロキシフェニル）スルホニウム、４－（フェニルチオ）フェニルジフェニルスルホニウム、４－（ｐ－トリルチオ）フェニルジ－ｐ－トリルスルホニウム、４－（４－メトキシフェニルチオ）フェニルビス（４－メトキシフェニル）スルホニウム、４－（フェニルチオ）フェニルビス（４－フルオロフェニル）スルホニウム、４－（フェニルチオ）フェニルビス（４－メトキシフェニル）スルホニウム、４－（フェニルチオ）フェニルジ－ｐ－トリルスルホニウム、ビス［４－（ジフェニルスルホニオ）フェニル］スルフィド、ビス〔４－｛ビス［４－（２－ヒドロキシエトキシ）フェニル］スルホニオ｝フェニル〕スルフィド、ビス｛４－［ビス（４－フルオロフェニル）スルホニオ］フェニル｝スルフィド、ビス｛４－［ビス（４－メチルフェニル）スルホニオ］フェニル｝スルフィド、ビス｛４－［ビス（４－メトキシフェニル）スルホニオ］フェニル｝スルフィド、４－（４－ベンゾイル－２－クロロフェニルチオ）フェニルビス（４－フルオロフェニル）スルホニウム、４－（４－ベンゾイル－２－クロロフェニルチオ）フェニルジフェニルスルホニウム、４－（４－ベンゾイルフェニルチオ）フェニルビス（４－フルオロフェニル）スルホニウム、４－（４－ベンゾイルフェニルチオ）フェニルジフェニルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジ－ｐ－トリルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジフェニルスルホニウム、２－［（ジ－ｐ－トリル）スルホニオ］チオキサントン、２－［（ジフェニル）スルホニオ］チオキサントン、４－［４－（４－ｔｅｒｔ－ブチルベンゾイル）フェニルチオ］フェニルジ－ｐ－トリルスルホニウム、４－［４－（４－ｔｅｒｔ－ブチルベンゾイル）フェニルチオ］フェニルジフェニルスルホニウム、４－［４－（ベンゾイルフェニルチオ）］フェニルジ－ｐ－トリルスルホニウム、４－［４－（ベンゾイルフェニルチオ）］フェニルジフェニルスルホニウム、５－（４－メトキシフェニル）チアアンスレニウム、５－フェニルチアアンスレニウム、５－トリルチアアンスレニウム、５－（４－エトキシフェニル）チアアンスレニウム、５－（２，４，６－トリメチルフェニル）チアアンスレニウム等のトリアリールスルホニウム；ジフェニルフェナシルスルホニウム、ジフェニル４－ニトロフェナシルスルホニウム、ジフェニルベンジルスルホニウム、ジフェニルメチルスルホニウム等のジアリールスルホニウム；フェニルメチルベンジルスルホニウム、４－ヒドロキシフェニルメチルベンジルスルホニウム、４－メトキシフェニルメチルベンジルスルホニウム、４－アセトカルボニルオキシフェニルメチルベンジルスルホニウム、２－ナフチルメチルベンジルスルホニウム、２－ナフチルメチル（１－エトキシカルボニル）エチルスルホニウム、フェニルメチルフェナシルスルホニウム、４－ヒドロキシフェニルメチルフェナシルスルホニウム、４－メトキシフェニルメチルフェナシルスルホニウム、４－アセトカルボニルオキシフェニルメチルフェナシルスルホニウム、２－ナフチルメチルフェナシルスルホニウム、２－ナフチルオクタデシルフェナシルスルホニウム、９－アントラセニルメチルフェナシルスルホニウム等のモノアリールスルホニウム；ジメチルフェナシルスルホニウム、フェナシルテトラヒドロチオフェニウム、ジメチルベンジルスルホニウム、ベンジルテトラヒドロチオフェニウム、オクタデシルメチルフェナシルスルホニウム等のトリアルキルスルホニウム等が挙げられる。 As the sulfonium ion, triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluorophenyl) 4) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio) phenyldi-p-tolylsulfonium, 4 -(4-Methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) Phenyl bis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy)] Phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-Methoxyphenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzo Phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p- Tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] Thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyl di-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoyl) Phenylthio )] Phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, 5-tolylianthrenium, Triarylsulfoniums such as 5- (4-ethoxyphenyl) thiaansurenium, 5- (2,4,6-trimethylphenyl) thiaansurenium, etc .; diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, Diarylsulfonium such as diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetoca Bonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium Monoarylsulfonium such as 4-acetonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium, etc .; dimethylphenacylsulfonium, phenacyl Tetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octa Trialkyl sulfonium such as sill methyl phenacyl sulfonium and the like.
　これらのオニウムイオンの中では、スルホニウムイオンとヨードニウムイオンからなる１種以上が好ましく、スルホニウムイオンがより好ましい。スルホニウムイオンとしては、トリフェニルスルホニウム、トリ－ｐ－トリルスルホニウム、４－（フェニルチオ）フェニルジフェニルスルホニウム、ビス［４－（ジフェニルスルホニオ）フェニル］スルフィド、ビス〔４－｛ビス［４－（２－ヒドロキシエトキシ）フェニル］スルホニオ｝フェニル〕スルフィド、ビス｛４－［ビス（４－フルオロフェニル）スルホニオ］フェニル｝スルフィド、４－（４－ベンゾイル－２－クロロフェニルチオ）フェニルビス（４－フルオロフェニル）スルホニウム、４－（４－ベンゾイルフェニルチオ）フェニルジフェニルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジ－ｐ－トリルスルホニウム、７－イソプロピル－９－オキソ－１０－チア－９，１０－ジヒドロアントラセン－２－イルジフェニルスルホニウム、２－［（ジ－ｐ－トリル）スルホニオ］チオキサントン、２－［（ジフェニル）スルホニオ］チオキサントン、４－［４－（４－ｔｅｒｔ－ブチルベンゾイル）フェニルチオ］フェニルジ－ｐ－トリルスルホニウム、４－［４－（ベンゾイルフェニルチオ）］フェニルジフェニルスルホニウム、５－（４－メトキシフェニル）チアアンスレニウム、５－フェニルチアアンスレニウム、ジフェニルフェナシルスルホニウム、４－ヒドロキシフェニルメチルベンジルスルホニウム、２－ナフチルメチル（１－エトキシカルボニル）エチルスルホニウム、４－ヒドロキシフェニルメチルフェナシルスルホニウム及びオクタデシルメチルフェナシルスルホニウムからなる１種以上が好ましい。 Among these onium ions, one or more kinds of sulfonium ions and iodonium ions are preferable, and sulfonium ions are more preferable. As the 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-Benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo- 10- A-9,10-Dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butyl] Benzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium 1 Or more.
　　式（Ｂ－１）においてＸ－は対イオンである。その個数は１分子当りｐ＋１である。対イオンは、特に限定されないが、ホウ素化合物、リン化合物、アンチモン化合物、ヒ素化合物、アルキルスルホン酸化合物等のハロゲン化物、メチド化合物等が挙げられる。Ｘ－としては、例えば、Ｆ－、Ｃｌ－、Ｂｒ－、Ｉ－等のハロゲンイオン；ＯＨ－；ＣｌＯ４ －；ＦＳＯ３ －、ＣｌＳＯ３ －、ＣＨ３ＳＯ３ －、Ｃ６Ｈ５ＳＯ３ －、ＣＦ３ＳＯ３ －等のスルホン酸イオン類；ＨＳＯ４ －、ＳＯ４ ２－等の硫酸イオン類；ＨＣＯ３ －、ＣＯ３ ２－等の炭酸イオン類；Ｈ２ＰＯ４ －、ＨＰＯ４ ２－、ＰＯ４ ３－等のリン酸イオン類；ＰＦ６ －、ＰＦ５ＯＨ－、フッ素化アルキルフルオロリン酸イオン等のフルオロリン酸イオン類；ＢＦ４ －、Ｂ（Ｃ６Ｆ５）４ －、Ｂ（Ｃ６Ｈ４ＣＦ３）４ －等のホウ酸イオン類；ＡｌＣｌ４ －；ＢｉＦ６ －等が挙げられる。その他にはＳｂＦ６ －、ＳｂＦ５ＯＨ－等のフルオロアンチモン酸イオン類、或いはＡｓＦ６ －、ＡｓＦ５ＯＨ－等のフルオロヒ素酸イオン類等が挙げられる。 In formula (B-1), 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. Other examples include fluoroantimonate ions such as SbF 6 − and SbF 5 OH − , and fluoroarsenic acid ions such as AsF 6 − and AsF 5 OH − .
　フッ素化アルキルフルオロリン酸イオンとしては、式（Ｂ－１－３）等で表されるフッ素化アルキルフルオロリン酸イオン等が挙げられる。 Examples of the fluorinated alkyl fluorophosphate ion include fluorinated alkyl fluorophosphate ions represented by the formula (B-1-3) and the like.
［（Ｒｆ）ｂＰＦ６－ｂ］－　　　　　（Ｂ－１－３） [(Rf) b PF 6-b ] - (B-1-3)
　式（Ｂ－１－３）において、Ｒｆはフッ素原子で置換されたアルキル基を表す。Ｒｆの個数ｂは、１～５であり、整数であることが好ましい。ｂ個のＲｆはそれぞれ同一であっても異なっていてもよい。Ｒｆの個数ｂは、２～４がより好ましく、２～３が最も好ましい。
　式（Ｂ－１－３）で表されるフッ素化アルキルフルオロリン酸イオンにおいて、Ｒｆはフッ素原子で置換されたアルキル基を表し、好ましい炭素数は１～８、更に好ましい炭素数は１～４である。アルキル基としては、メチル、エチル、プロピル、ブチル、ペンチル、オクチル等の直鎖アルキル基；イソプロピル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル等の分岐アルキル基；更にシクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等のシクロアルキル基等が挙げられる。具体例としては、ＣＦ３、ＣＦ３ＣＦ２、（ＣＦ３）２ＣＦ、ＣＦ３ＣＦ２ＣＦ２、ＣＦ３ＣＦ２ＣＦ２ＣＦ２、（ＣＦ３）２ＣＦＣＦ２、ＣＦ３ＣＦ２（ＣＦ３）ＣＦ、（ＣＦ３）３Ｃ等が挙げられる。 In formula (B-1-3), 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.
In the fluorinated alkyl fluorophosphate ion represented by the formula (B-1-3), 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. Examples of the alkyl group 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. Specific examples thereof include 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.
　好ましいフッ素化アルキルフルオロリン酸アニオンの具体例としては、［（ＣＦ３ＣＦ２）２ＰＦ４］－、［（ＣＦ３ＣＦ２）３ＰＦ３］－、［（（ＣＦ３）２ＣＦ）２ＰＦ４］－、［（（ＣＦ３）２ＣＦ）３ＰＦ３］－、［（ＣＦ３ＣＦ２ＣＦ２）２ＰＦ４］－、［（ＣＦ３ＣＦ２ＣＦ２）３ＰＦ３］－、［（（ＣＦ３）２ＣＦＣＦ２）２ＰＦ４］－、［（（ＣＦ３）２ＣＦＣＦ２）３ＰＦ３］－、［（ＣＦ３ＣＦ２ＣＦ２ＣＦ２）２ＰＦ４］－及び［（ＣＦ３ＣＦ２ＣＦ２ＣＦ２）３ＰＦ３］－等が挙げられる。 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.
光カチオン重合開始剤は、エポキシ化合物、エポキシ樹脂への溶解を容易にするため、あらかじめ溶剤類に溶解したものを用いてもよい。溶剤類としては、例えば、プロピレンカーボネート、エチレンカーボネート、１，２－ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート等のカーボネート類等が挙げられる。 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. Examples of the solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate and the like.
　これらの光カチオン重合開始剤は、１種以上を選択して使用してもよい。 One or more of these photocationic polymerization initiators may be selected and used.
　（Ｂ）光カチオン重合開始剤のアニオン種としては、ホウ素化合物、リン化合物、アンチモン化合物、ヒ素化合物、アルキルスルホン酸化合物等のハロゲン化物等が挙げられる。これらのアニオン種は、１種以上を選択して使用してもよい。これらの中では、光硬化性に優れ、接着性、接着耐久性が向上する点で、フッ化物が好ましい。フッ化物の中では、ヘキサフルオロアンチモネートが好ましい。 Examples of the 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. One or more of these anion species may be selected and used. Among these, fluoride is preferable in terms of excellent photocurability, and improved adhesion and adhesion durability. Among the fluorides, hexafluoroantimonate is preferred.
　（Ｂ）光カチオン重合開始剤の中では、式（Ｂ－２）で表されるトリアリールスルホニウム塩ヘキサフルオロアンチモネート、式（Ｂ－３）で表されるジフェニル４－チオフェノキシフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェートからなる１種以上が好ましく、トリアリールスルホニウム塩ヘキサフルオロアンチモネートがより好ましい。 (B) Among the cationic photopolymerization initiators, triarylsulfonium salt hexafluoroantimonate represented by the formula (B-2), diphenyl 4-thiophenoxyphenylsulfonium tris represented by the formula (B-3) One or more kinds of pentafluoroethyl) trifluorophosphate are preferable, and triarylsulfonium salt hexafluoroantimonate is more preferable.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　（Ｂ）光カチオン重合開始剤の使用量は、（Ａ）カチオン重合性化合物１００質量部に対して、０．０５～５質量部が好ましく、０．１～３質量部がより好ましい。光カチオン重合開始剤の使用量が０．０５質量部以上であれば光硬化性が悪くなることもないし、５質量部以下であれば接着耐久性を低下させることもない。 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.
（Ｃ）リン酸化合物
　本実施形態に係る有機エレクトロルミネッセンス素子用封止剤は、（Ｃ）リン酸化合物を必須成分とする。リン酸化合物は、（Ｃ１）リン酸エステルと（Ｃ２）亜リン酸エステルからなる群から選択される１種以上である。リン酸化合物としては、有機リン酸化合物が好ましい。リン酸化合物の中では、（Ｃ１）リン酸エステルが好ましい。 (C) Phosphoric acid compound 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. Among the phosphoric acid compounds, (C1) phosphoric acid esters are preferred.
　（Ｃ１）リン酸エステルとしては、ジエチルベンジルホスフェート、トリメチルホスフェート、トリエチルホスフェート、トリｎ－ブチルホスフェート、トリス（ブトキシエチル）ホスフェート、トリス（２－エチルヘキシル）ホスフェート、（ＲＯ）３Ｐ＝Ｏ［Ｒ＝ラウリル基、セチル基、ステアリル基又はオレイル基］、トリス（２－クロロエチル）ホスフェート、トリス（２－ジクロロプロピル）ホスフェート、トリフェニルホスフェート、ブチルピロホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、オクチルジフェニルホスフェート、クレジルジフェニルホスフェート、キシレニルジホスフェート、モノブチルホスフェート、ジブチルホスフェート、ジ－２－エチルヘキシルホスフェート、モノイソデシルホスフェート、アンモニウムエチルアシッドホスフェート、及び、２－エチルヘキシルアシッドホスフェート塩等が挙げられる。 As the (C1) phosphoric acid ester, diethyl benzyl phosphate, trimethyl phosphate, triethyl phosphate, tri n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) 3 P = O [R = Lauryl group, cetyl group, stearyl group or oleyl group], tris (2-chloroethyl) phosphate, tris (2-dichloropropyl) phosphate, triphenyl phosphate, butyl pyrophosphate, tricresyl phosphate, trixylenyl phosphate, octyl diphenyl Phosphate, cresyl diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodec Phosphate, ammonium ethyl acid phosphate, and 2-ethylhexyl acid phosphate salt.
　（Ｃ１）リン酸エステルは、式（Ｃ１－１）で表される化合物、式（Ｃ１－２）で表される化合物及び式（Ｃ１－３）で表される化合物からなる群から選択される少なくとも一種を含有することが好ましく、式（Ｃ１－２）で表される化合物を含有することがより好ましい。 (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).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（Ｃ１－１）、式（Ｃ１－２）及び式（Ｃ１－３）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。 In formulas (C1-1), (C1-2) and (C1-3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently have a substituent It also shows good hydrocarbon groups.
　式（Ｃ１－２）中のＲ２、Ｒ３及びＲ４、並びに、式（Ｃ１－３）中のＲ５及びＲ６は、各式中で同一の基であることが好ましい。 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.
　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６における炭化水素基が有していてもよい置換基としては、例えば、オキシアルキル基等が挙げられる。Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６における炭化水素基は、非置換の炭化水素基であることが好ましい。 As a substituent which the hydrocarbon group in 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.
　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６における炭化水素基は、アルキル基又はアリール基であることが好ましく、アルキル基又はフェニル基であることがより好ましく、アルキル基であることが更に好ましい。アルキル基の炭素原子数は、例えば１～１８であってよく、４～１３であることが好ましい。 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.
　式（Ｃ１－１）で表される化合物としては、例えば、モノアルキルホスフェート（すなわち、Ｒ１がアルキル基である化合物）等であってよく、具体例としては、モノエチルホスフェート、モノｎ－ブチルホスフェート、モノ（ブトキシエチル）ホスフェート、モノ（２－エチルヘキシル）ホスフェート等が挙げられる。 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.
　式（Ｃ１－２）で表される化合物としては、トリアルキルホスフェート（すなわち、Ｒ２、Ｒ３及びＲ４がアルキル基である化合物）が好ましい。このとき、Ｒ２、Ｒ３及びＲ４のアルキル基の炭素原子数は、１～１８であることが好ましく、４～１２であることがより好ましく、８であることが更に好ましい。 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). At this time, 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.
　トリアルキルホスフェートの具体例としては、トリエチルホスフェート、トリｎ－ブチルホスフェート、トリス（ブトキシエチル）ホスフェート、トリス（２－エチルヘキシル）ホスフェート、（ＲＯ）３Ｐ＝Ｏ（Ｒは、ラウリル基、セチル基、ステアリル基又はオレイル基）等が挙げられる。 Specific examples of trialkyl phosphates include triethyl phosphate, tri n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) 3 P = O (R is a lauryl group, cetyl group, Stearyl group or oleyl group) and the like can be mentioned.
　式（Ｃ１－３）で表される化合物としては、例えば、ジアルキルホスフェート（すなわち、Ｒ５及びＲ６がアルキル基である化合物）等が挙げられる。ジアルキルホスフェートの具体例としては、ジブチルホスフェート、ビス（２－エチルヘキシル）ホスフェート等が挙げられる。 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.
　式（Ｃ１－１）、式（Ｃ１－２）及び式（Ｃ１－３）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、アルキル基を含む炭化水素基、芳香族環を含む炭化水素基、脂肪族環を含む炭化水素基の１種以上であってもよい。炭化水素基は、一部不飽和基を有するものであってもよく、任意の原子や置換基を有しても良い。このとき、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、アルキル基を含む炭化水素基が好ましい。また、炭化水素基は、非置換の飽和基が好ましい。Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、同一が好ましい。 In Formula (C1-1), Formula (C1-2) and Formula (C1-3), 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. At this time, 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. Preferably, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are identical.
　（Ｃ２）亜リン酸エステルとしては、トリメチルホスファイト、トリエチルホスファイト、トリｎ－ブチルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリイソオクチルホスファイト、トリデシルホスファイト、トリイソデシルホスファイト、トリス（トリデシル）ホスファイト、トリオレイルホスファイト、トリステアリルホスファイト、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、トリス（２，４－ジ－ｔ－ブチルフェニル）ホスファイト、フェニルジイソオクチルホスファイト、フェニルジイソデシルホスファイト、ジフェニルモノ（２－エチルヘキシル）ホスファイト、ジフェニルイソオクチルホスファイト、ジフェニルモノデシルホスファイト、ジフェニルモノイソデシルホスファイト、ジフェニルモノ（トリデシル）ホスファイト、ビス（ノニルフェニル）ジノニルフェニルホスファイト、テトラフェニルジプロピレングリコールジホスファイト、ポリ（ジプロピレングリコール）フェニルホスファイト、ジイソデシルペンタエリスリトールジホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、テトラフェニルテトラ（トリデシル）ペンタエリスリトールテトラホスファイト、テトラ（トリデシル）－４，４’－イソプロピリデンジフェニルホスファイト、トリラウリルトリチオホスファイト、ジメチルハイドロジエンホスファイト、ジブチルハイドロジエンホスファイト、ジ（２－エチルヘキシル）ハイドロジエンホスファイト、ジラウリルハイドロジエンホスファイト、ジオレイルハイドロジエンホスファイト、ジフェニルハイドロジエンホスファイト、ジフェニルモノ（２－エチルヘキシル）ホスファイト、ジフェニルモノデシルホスファイト、及びジフェニルモノ（トリデシル）ホスファイト等が挙げられる。 (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) phosphite, diphenyl isooctyl phosphite, diphenyl monodecyl phosphite, diphenyl mono isodecyl phosphite , Diphenyl mono (tridecyl) phosphite, bis (nonylphenyl) dinonylphenyl phosphite, tetraphenyl dipropylene glycol diphosphite, poly (dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite, bis (tridecyl) Pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidenediphenyl Phosphite, trilauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di ( -Ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono (2-ethyl hexyl) phosphite, diphenyl mono decyl phosphite, and diphenyl mono (tridecyl) A phosphite etc. are mentioned.
　（Ｃ２）亜リン酸エステルは、式（Ｃ２－１）で表される化合物、式（Ｃ２－２）で表される化合物、式（Ｃ２－３）で表される化合物、式（Ｃ２－４）で表される化合物、式（Ｃ２－５）で表される化合物及び式（Ｃ２－６）で表される化合物からなる群から選択される少なくとも一種を含有することが好ましい。 (C2) 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).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（Ｃ２－１）～式（Ｃ２－６）中、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。 In formulas (C2-1) to (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.
　Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７における炭化水素基が有していてもよい置換基としては、例えば、オキシアルキル基等が挙げられる。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７における炭化水素基は、非置換の炭化水素基であることが好ましい。 As a substituent which 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 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.
　Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７における炭化水素基は、アルキル基又はアリール基であることが好ましく、アルキル基又はフェニル基であることがより好ましく、アルキル基であることが更に好ましい。アルキル基の炭素原子数は、例えば１～３０であってよく、１～１８であることが好ましい。 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.
　式（Ｃ２－２）中のＲ８及びＲ９、式（Ｃ２－３）中のＲ１０、Ｒ１１及びＲ１２、式（Ｃ２－４）中のＲ１３及びＲ１４、並びに、式（Ｃ２－５）中のＲ１５及びＲ１６は、各式中で互いに同一であることが好ましい。 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.
　式（Ｃ２－１）で表される化合物としては、例えば、モノアルキルホスファイト（すなわち、Ｒ７がアルキル基である化合物）等が挙げられる。 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.
　式（Ｃ２－２）で表される化合物としては、例えば、ジアルキルホスファイト（すなわち、Ｒ８及びＲ９がアルキル基である化合物）等が挙げられる。 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).
　式（Ｃ２－３）で表される化合物としては、例えば、トリアルキルホスファイト（すなわち、Ｒ１０、Ｒ１１及びＲ１２がアルキル基である化合物）等が挙げられる。また、式（Ｃ２－３）で表される化合物の具体例としては、トリエチルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリデシルホスファイト、トリラウリルホスファイト、トリス（トリデシル）ホスファイト、トリオレイルホスファイト、ジフェニルモノデシルホスファイト等が挙げられる。 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.
　式（Ｃ２－４）で表される化合物としては、例えば、ビス（アルキル）ペンタエリスリトールジホスファイト（すなわち、Ｒ１３及びＲ１４がアルキル基である化合物）等が挙げられる。また、式（Ｃ２－４）で表される化合物の具体例としては、ビス（デシル）ペンタエリスリトールジホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト等が挙げられる。 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. .
　式（Ｃ２－５）で表される化合物としては、例えば、ジアルキルハイドロゲンホスファイト（すなわち、Ｒ１５及びＲ１６がアルキル基である化合物）等が挙げられる。また、式（Ｃ２－５）で表される化合物の具体例としては、ジエチルハイドロゲンホスファイト、ビス（２－エチルヘキシル）ハイドロゲンホスファイト、ジラウリルハイドロゲンホスファイト、ジオレイルハイドロゲンホスファイト等が挙げられる。 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.
　式（Ｃ２－６）で表される化合物としては、例えば、モノアルキルハイドロゲンホスファイト（すなわち、Ｒ１７がアルキル基である化合物）等が挙げられる。また、式（Ｃ２－６）で表される化合物の具体例としては、モノエチルハイドロゲンホスファイト、モノ（２－エチルヘキシル）ハイドロゲンホスファイト、モノラウリルハイドロゲンホスファイト、モノオレイルハイドロゲンホスファイト等が挙げられる。 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. .
　式（Ｃ２－１）～式（Ｃ２－６）中、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７は、それぞれ独立に、アルキル基を含む炭化水素基、芳香族環を含む炭化水素基、脂肪族環を含む炭化水素基の１種以上であってもよい。炭化水素基は、一部不飽和基を有するものであってもよく、任意の原子や置換基を有しても良い。このとき、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７は、アルキル基を含む炭化水素基が好ましい。また、炭化水素基は、非置換の飽和基が好ましい。Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７は、同一が好ましい。 In the formulas (C2-1) to (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 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. At this time, 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.
　亜リン酸エステルの中では、トリメチルホスファイト、トリエチルホスファイト、トリｎ－ブチルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリイソオクチルホスファイト、トリデシルホスファイト、トリイソデシルホスファイト、トリス（トリデシル）ホスファイト、トリオレイルホスファイト、トリステアリルホスファイト、トリフェニルホスファイト、トリス（ノニルフェニル）ホスファイト、ジフェニルモノデシルホスファイト等の式（Ｃ２－３）で表される化合物で表す化合物、ジイソデシルペンタエリスリトールジホスファイト、ビス（トリデシル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ジメチルハイドロジエンホスファイト、ジブチルハイドロジエンホスファイト、ジ（２－エチルヘキシル）ハイドロジエンホスファイト、ジラウリルハイドロジエンホスファイト、ジオレイルハイドロジエンホスファイトからなる群から選択される１種以上が好ましく、式（Ｃ２－３）で表される化合物がより好ましい。式（Ｃ２－３）で表される化合物の中では、トリメチルホスファイト、トリエチルホスファイト、トリｎ－ブチルホスファイト、トリス（２－エチルヘキシル）ホスファイト、トリイソオクチルホスファイト、トリデシルホスファイト、トリイソデシルホスファイト、トリス（トリデシル）ホスファイト、トリオレイルホスファイト、トリステアリルホスファイト等のトリアルキルホスファイトが好ましい。トリアルキルホスファイトの中では、トリデシルホスファイトが好ましい。 Among the 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, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite At least one member selected from the group consisting of dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite and dioleyl hydrogen phosphite is preferable, and The compound represented by (C2-3) is more preferable. Among the compounds represented by the formula (C2-3), trimethyl phosphite, triethyl phosphite, tri n-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, Preferred are trialkyl phosphites such as triisodecyl phosphite, tris (tridecyl) phosphite, trioleyl phosphite and tristearyl phosphite. Among the trialkyl phosphites, tridecyl phosphite is preferred.
　（Ｃ）リン酸化合物の使用量は、（Ａ）カチオン重合性化合物１００質量部に対して、０．１～５質量部が好ましく、０．０２～３質量部がより好ましい。（Ｃ）リン酸化合物の使用量が０．１質量部以上であれば、光照射後の粘度の上昇を抑えることができ、５質量部以下であれば光硬化性が悪くなることもない。 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). When 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、光増感剤を含有してもよい。光増感剤とは、エネルギー線を吸収して、光カチオン重合開始剤からカチオンを効率よく発生させる化合物をいう。 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.
　光増感剤としては、特に限定されないが、ベンゾフェノン誘導体、フェノチアジン誘導体、フェニルケトン誘導体、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、ナフタセン誘導体、クリセン誘導体、ペリレン誘導体、ペンタセン誘導体、アクリジン誘導体、ベンゾチアゾール誘導体、ベンゾイン誘導体、フルオレン誘導体、ナフトキノン誘導体、アントラキノン誘導体、キサンテン誘導体、キサントン誘導体、チオキサンテン誘導体、チオキサントン誘導体、クマリン誘導体、ケトクマリン誘導体、シアニン誘導体、アジン誘導体、チアジン誘導体、オキサジン誘導体、インドリン誘導体、アズレン誘導体、トリアリルメタン誘導体、フタロシアニン誘導体、スピロピラン誘導体、スピロオキサジン誘導体、チオスピロピラン誘導体、有機ルテニウム錯体等が挙げられる。これらの中では、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン等のフェニルケトン誘導体及び／又は９，１０－ジブトキシアントラセン等のアントラセン誘導体が好ましく、アントラセン誘導体がより好ましい。アントラセン誘導体の中では、９，１０－ジブトキシアントラセンが好ましい。 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, thiospi Pyran derivatives, organic ruthenium complexes. Among these, 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. Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferred.
　光増感剤の使用量は、光硬化性が悪くならず、貯蔵安定性が低下しない点で、（Ａ）カチオン重合性化合物１００質量部に対して、０．０１～１０質量部が好ましく、０．０２～５質量部がより好ましい。 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、シランカップリング剤を含有してもよい。シランカップリング剤を含有することにより、本実施形態の光カチオン重合組成物は、優れた接着性や接着耐久性を示す。 The sealing agent for organic electroluminescent elements of this embodiment may contain a silane coupling agent. By containing a silane coupling agent, the photocationic polymerization composition of the present embodiment exhibits excellent adhesion and adhesion durability.
　シランカップリング剤としては、特に限定されないが、γ－クロロプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリクロルシラン、ビニルトリエトキシシラン、ビニル－トリス（β－メトキシエトキシ）シラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－メルカプトプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリメトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルメチルジメトキシシラン及びγ－ユレイドプロピルトリエトキシシラン等が挙げられる。これらのシランカップリング剤は、１種以上を選択して使用してもよい。これらの中では、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－（メタ）アクリロキシプロピルトリメトキシシランからなる群から選択される１種以上が好ましく、γ－グリシドキシプロピルトリメトキシシランがより好ましい。 The silane coupling agent is not particularly limited, and γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ- (meth) Acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-ureidopropyltriethoxysilane Etc. It is. One or more of these silane coupling agents may be selected and used. Among these, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy One or more selected from the group consisting of silanes is preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.
シランカップリング剤の使用量は、接着性や接着耐久性が得られる点で、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、０．１～１０質量部が好ましく、０．２～５質量部がより好ましい。 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤の硬化や接着に用いられる光源としては、特に限定されないが、ハロゲンランプ、メタルハライドランプ、ハイパワーメタルハライドランプ（インジウム等を含有する）、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、キセノンランプ、キセノンエキシマランプ、キセノンフラッシュランプ、ライトエミッティングダイオード（以下、ＬＥＤという）等が挙げられる。これらの光源は、それぞれの光カチオン重合開始剤の反応波長に対応するエネルギー線の照射を効率よく行える点で、好ましい。 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.
　上記光源は、各々放射波長やエネルギー分布が異なる。そのため、上記光源は光カチオン重合開始剤の反応波長等により適宜選択される。又、自然光（太陽光）も反応開始光源になり得る。 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. In addition, natural light (sunlight) can also be a reaction initiation light source.
　上記光源の照射としては、直接照射、反射鏡やファイバー等による集光照射を行ってもよい。低波長カットフィルター、熱線カットフィルター、コールドミラー等も用いることもできる。 As 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、光照射後の硬化速度を促進するために、後加熱処理をしてもよい。後加熱の温度は、有機エレクトロルミネッセンス素子の封止に用いる場合には、有機エレクトロルミネッセンス素子にダメージを与えない点で、１５０℃以下が好ましく、８０℃以下がより好ましい。また、後加熱の温度は、６０℃以上が好ましい。 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. Moreover, as for the temperature of post-heating, 60 degreeC or more is preferable.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、接着剤として用いてもよい。本実施形態の接着剤は、有機エレクトロルミネッセンス素子等のパッケージ等の接着に、好適に用いることができる。 You may use the sealing agent for organic electroluminescent elements of this embodiment as an adhesive agent. The adhesive of the present embodiment can be suitably used for adhesion of packages such as organic electroluminescent elements.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤の製造方法については、上記の成分を十分に混合できれば特に制限されない。各成分の混合方法としては、特に限定されないが、プロペラの回転に伴う撹拌力を利用する撹拌方法、自転公転による遊星式撹拌機等の通常の分散機を利用する方法等が挙げられる。これらの混合方法は、低コストで、安定した混合を行える点で、好ましい。 About 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 | limited in particular. Although it does not specifically limit as a mixing method of each component, 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤を用いる基材の接着方法としては、例えば、有機エレクトロルミネッセンス素子用封止剤を一方の基材の全面又は一部に塗布する工程と、前記有機エレクトロルミネッセンス素子用封止剤が塗布された基材の有機エレクトロルミネッセンス素子用封止剤に光を照射する工程と、前記光を照射された有機エレクトロルミネッセンス素子用封止剤が硬化するまでの間に、前記一方の基材に他方の基材を貼合する工程と、前記有機エレクトロルミネッセンス素子用封止剤により貼合された基材を硬化させる工程と、を有することにより、基材を光や熱に晒すことなく接着できる。 As a method of adhering a substrate using the sealant for an organic electroluminescent device of the present embodiment, for example, a step of applying a sealant for an organic electroluminescent device to the entire surface or a part of one substrate, and the organic Between the process of irradiating light to the sealing agent for organic electroluminescent elements of the base material to which the sealing agent for electroluminescent elements was applied, and until the sealing agent for organic electroluminescent elements irradiated with the light is cured And a step of bonding the other base to the one base, and a step of curing the base bonded by the sealing agent for an organic electroluminescent device, whereby the base is lightened. It can bond without being exposed to heat and heat.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤を用いて有機エレクトロルミネッセンス表示装置を製造する方法としては、例えば、一方の基板上（背面板）に本実施形態の有機エレクトロルミネッセンス素子用封止剤を塗布し、該有機エレクトロルミネッセンス素子用封止剤に光を照射して活性化させた後に、光を遮断し、該組成物を介して背面板とエレクトロルミネッセンス素子を形成した基板を貼り合せる方法等が挙げられる。この方法により、有機エレクトロルミネッセンス素子を光や熱に晒すことなく封止できる。 As a method of manufacturing 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. By this method, the organic electroluminescent element can be sealed without being exposed to light or heat.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤を用いて、一方の基板に本実施形態の有機エレクトロルミネッセンス素子用封止剤を塗布し、有機エレクトロルミネッセンス素子用封止剤を介して、他方の基板を貼り合せ、本実施形態の有機エレクトロルミネッセンス素子用封止剤に光を照射する方法を用いて有機エレクトロルミネッセンス表示装置を製造できる。 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 | substrate and irradiating light to the sealing agent for organic electroluminescent elements of this embodiment.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、光を照射してから１０分後の粘度が、光照射前の粘度と比較して５倍未満であることが好ましい。光としては、ＵＶが好ましい。例えば、高圧水銀灯にてＵＶを１００ｍＷ／ｃｍ２で３０秒間照射してから１０分後の粘度が、ＵＶ照射前の粘度と比較して５倍未満であることが、より好ましい。 It is preferable that 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. As light, UV is preferred. For example, it is more preferable that 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.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、（Ｂ）光カチオン重合開始剤が、照射した光を吸収して励起し、その励起種が分解して酸を発生することが好ましい。 In the sealant for an organic electroluminescent element of the present embodiment, it is preferable that the (B) photocationic polymerization initiator absorb and excite the irradiated light, and the excited species be decomposed to generate an acid.
　本実施形態の有機エレクトロルミネッセンス素子用封止剤は、光照射後の粘度の上昇が少なく、アウトガスの発生を抑制でき、有機エレクトロルミネッセンス素子を劣化させにくい。 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.
　以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されない。 As mentioned above, although the suitable embodiment of the present invention was described, the present invention is not limited to the above-mentioned embodiment.
　例えば、本発明の一側面は、上述の有機エレクトロルミネッセンス素子用封止剤を硬化してなる硬化体であってよい。 For example, one aspect of the present invention may be a cured product obtained by curing the above-mentioned sealing agent for an organic electroluminescent device.
　また、本発明の他の一側面は、上述の硬化体を含む、有機エレクトロルミネッセンス素子用封止材であってよい。この封止材は、硬化体であってよく、封止剤の硬化体と他の構成材料とを含むものであってもよい。他の構成材料としては、例えば、窒化珪素膜、酸化珪素膜、窒化酸化珪素等の無機物層、シリカ、マイカ、カオリン、タルク、酸化アルミニウム等の無機フィラー等が挙げられる。 Moreover, the other one side of this invention may be the sealing material for organic electroluminescent elements containing the above-mentioned hardened | cured material. 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.
　また、本発明の更に他の一側面は、有機エレクトロルミネッセンス素子と、上述の有機エレクトロルミネッセンス素子用封止材と、を含む、有機エレクトロルミネッセンス表示装置であってよい。 Further, 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.
　また、本発明において、有機エレクトロルミネッセンス表示装置の製造方法は、第一の部材に、上述の有機エレクトロルミネッセンス素子用封止剤を付着させる付着工程と、付着させた有機エレクトロルミネッセンス素子用封止剤に光を照射する照射工程と、光照射された前記有機エレクトロルミネッセンス素子用封止剤を介して、第一の部材と第二の部材とを貼り合わせる貼合工程と、を有するものであってよい。この製造方法において、例えば、第一の部材は基板であってよく、第二の部材は有機エレクトロルミネッセンス素子であってよい。この製造方法における各工程の条件等は、上述の実施形態の記載に基づいて適宜選択してよい。 Further, in the present invention, 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. Good. In this manufacturing method, for example, the first member may be a substrate, and 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.
　以下、実験例を挙げて、本実施形態を更に詳細に説明する。本実施形態はこれらに限定されるものではない。特記しない限り、２３℃、相対湿度５０質量％で試験した。 Hereinafter, the present embodiment will be described in more detail by way of experimental examples. The present embodiment is not limited to these. Unless otherwise stated, it was tested at 23 ° C. and 50% by mass relative humidity.
　実験例では、以下の化合物を使用した。 The following compounds were used in the experimental examples.
（Ａ－１）エポキシ基を有する脂環式化合物として下記を用いた。
（ａ－１－１）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（ダイセル化学社製「セロキサイド２０２１Ｐ」）
（ａ－１－２）水添ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ＹＸ８０００」、分子量３８０～４３０）
（ａ－１－３）３，４－エポキシシクロヘキシルメチルメタクリレート（ダイセル社製「サイクロマーＭ１００」） (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）エポキシ基を有する芳香族化合物として下記を用いた。
（ａ－２－１）ビスフェノールＡ型エポキシ樹脂（三菱化学社製「ｊＥＲ８２８」、分子量３６０～３９０）
（ａ－２－２）ビスフェノールＦ型エポキシ樹脂（三菱化学社製「ｊＥＲ８０６」、分子量３２０～３４０）
（ａ－２－３）ビスフェノールＦ型エポキシ樹脂（三井化学社製「ＹＬ９８３Ｕ」、分子量３６０～３８０）
（ａ－２－４）ビスフェノールＦ型エポキシ樹脂（ＡＤＥＫＡ社製「ＫＲＭ－２４９０」、分子量３４０～３８０） (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)
　その他のカチオン重合性化合物として下記を用いた。
（ａ－３）トリプロピレングリコールジグリシジルエーテル（共栄社化学社製「エポライト２００Ｐ」）
（ａ－４）ジ（１－エチル－（３－オキセタニル））メチルエーテル（東亞合成社製「アロンオキセタンＯＸＴ－２２１」）
（ａ－５）シクロヘキサンジメタノールジビニルエーテル（日本カーバイド社製「ＣＨＤＶＥ」） The following was used as another cationically polymerizable compound.
(A-3) Tripropylene glycol diglycidyl ether ("Epolight 200P" manufactured by Kyoeisha Chemical Co., Ltd.)
(A-4) Di (1-ethyl- (3-oxetanyl)) methyl ether ("Aron oxetane OXT-221" manufactured by Toagosei Co., Ltd.)
(A-5) Cyclohexane dimethanol divinyl ether ("CHDVE" manufactured by Nippon Carbide Corporation)
（Ｂ）成分の光カチオン重合開始剤として下記を用いた。
（ｂ－１）トリアリールスルホニウム塩ヘキサフルオロアンチモネート（ＡＤＥＫＡ社製「アデカオプトマーＳＰ－１７０」、アニオン種はヘキサフルオロアンチモネート）
（ｂ－２）トリアリールスルホニウム塩（ジフェニル４－チオフェノキシフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、サンアプロ社製「ＣＰＩ－２００Ｋ」、アニオン種はリン化合物） The following was used as a photocationic polymerization initiator of (B) component.
(B-1) Triarylsulfonium salt hexafluoroantimonate ("ADEKA 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）成分のリン酸エステル及び／又は亜リン酸エステルとして下記を用いた。
（ｃ－１）トリス（２－エチルヘキシル）ホスフェート（大八化学工業社製「ＴＯＰ」）
（ｃ－２）トリデシルホスファイト（城北化学工業社製「ＪＰ－３１０」）
（ｃ－３）ビス（デシル）ペンタエリスリトールジホスファイト（城北化学工業社製「ＪＰＥ－１０」）
（ｃ－４）ビス（２－エチルヘキシル）ハイドロゲンホスファイト（城北化学工業社製「ＪＰＥ－２０８」）
（ｃ－５）ジフェニルモノデシルホスファイト（城北化学工業社製「ＪＰＭ－３１１」）
（ｃ－６　比較例）トリ－ｎ－オクチルホスフィンオキサイド（北興化学工業社製「Ｔ．Ｏ．Ｐ．Ｏ（登録商標）」）
（ｃ－７　比較例）トリ－ｎ－オクチルホスフィン（城北化学工業社製「ＴＯＣＰ」）
（ｃ－８　比較例）１８－クラウン－６－エーテル（日本曹達社製「クラウンエーテル　Ｏ－１８」） The following was used as phosphate ester and / or phosphite ester of (C) component.
(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.)
　光増感剤として下記を用いた。
（ｇ－１）９，１０－ジブトキシアントラセン（川崎化成工業社製「ＡＮＴＨＲＡＣＵＲＥ　ＵＶＳ－１３３１」） The following was used as a photosensitizer.
(G-1) 9, 10-dibutoxyanthracene ("KARA CHEMICAL INDUSTRY""ANTHRACUREUVS-1331")
　シランカップリング剤として下記を用いた。
（ｆ－１）γ－グリシドキシプロピルトリメトキシシラン（信越シリコーン社製「ＫＢＭ－４０３」） The following was used as a silane coupling agent.
(F-1) γ-Glycidoxypropyltrimethoxysilane (Shin-Etsu Silicone "KBM-403")
　表１～２に示す種類の原材料を、表１～２に示す組成割合で混合し、実施例及び比較例の有機エレクトロルミネッセンス素子用封止剤を調製した。組成割合の単位は質量部である。 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.
　実施例及び比較例の有機エレクトロルミネッセンス素子用封止剤について、下記の各測定を行った。その結果を表１～２に示した。 The following measurement was performed about the sealing agent for organic electroluminescent elements of an Example and a comparative example. The results are shown in Tables 1 and 2.
〔粘度〕
　封止剤の粘度（せん断粘度）はＥ型粘度計（１°３４’×Ｒ２４のコーンローター）を用い、温度２５℃、回転数１０ｒｐｍの条件下で測定した。 〔viscosity〕
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.
〔光照射後の粘度変化〕
　実施例及び比較例で得られた各有機エレクトロルミネッセンス素子用封止剤をガラス基板の上に塗布し、その基板に紫外線照射装置（ＨＯＹＡ社製超高圧水銀ランプ照射装置、「ＵＬ－７５０」）を用いて波長３６５ｎｍ、１００ｍＷ／ｃｍ２の紫外線を３０秒間照射した。紫外線を照射し終えてから１０分後において、Ｅ型粘度計（１°３４’×Ｒ２４のコーンローター）を用い、温度２５℃、回転数１０ｒｐｍの条件下で測定した。そして、光照射前の粘度をＶ０、光照射後の粘度をＶνとしたとき、式：Ｖν／Ｖ０にしたがって粘度変化率を求めた。粘度変化率は、遅硬化性が良好な点で、５以下が好ましい。 [Viscosity change after light irradiation]
Each sealing agent for organic electroluminescent elements obtained by the Example and the comparative example is apply | coated on a glass substrate, 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. Then, when the viscosity before light irradiation is V0 and the viscosity after light irradiation is VV, the viscosity change rate was determined according to the formula: Vν / V0. The viscosity change rate is preferably 5 or less from the viewpoint of good late curing property.
〔光硬化条件〕
　封止剤の硬化物性及び接着性の評価に際し、下記光照射条件により、封止剤を硬化させた。無電極放電メタルハライドランプ搭載ＵＶ硬化装置（フュージョン社製）により、３６５ｎｍの波長の積算光量４，０００ｍＪ／ｃｍ２の条件にて、封止剤を光硬化させた後、８０℃のオーブン中で、３０分間の後加熱処理を実施し、硬化体を得た。 [Light curing conditions]
When evaluating the curing physical properties and adhesiveness of the sealing agent, 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.
〔透湿度〕
　厚さ０．１ｍｍのシート状の硬化体を前記光硬化条件にて作製し、ＪＩＳ　Ｚ０２０８「防湿包装材料の透湿度試験方法（カップ法）」に準じ、吸湿剤として塩化カルシウム（無水）を用い、雰囲気温度６０℃、相対湿度９０％の条件で測定した。透湿度は１２０ｇ／（ｍ２・２４ｈｒ）以下が好ましい。 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.
〔引張せん断接着強さ〕
　ホウ珪酸ガラス試験片（縦２５ｍｍ×横２５ｍｍ×厚２．０ｍｍ、テンパックス（登録商標）ガラス）を２枚用い、接着面積０．５ｃｍ２、接着厚み８０μｍで、上記の光硬化条件にて封止剤を硬化させた。硬化後、封止剤で接合した試験片を用い、引張剪断接着強さ（単位：ＭＰＡ）を、温度２３℃、相対湿度５０％の環境下で、引張速度１０ｍｍ／分で測定した。引張せん断接着強さは１５ＭＰａ以上が好ましい。 [Tensile shear bond strength]
Using two borosilicate glass test pieces (25 mm long x 25 mm wide x 2.0 mm thick, Tempax (registered trademark) glass), with a bonding area of 0.5 cm 2 and a bonding thickness of 80 μm, sealed under the above-mentioned photo-curing conditions The curing agent was allowed to cure. After curing, tensile shear adhesive strength (unit: MPA) was measured at a tensile speed of 10 mm / min under an environment of a temperature of 23 ° C. and a relative humidity of 50% using a test piece joined with a sealant. The tensile shear adhesive strength is preferably 15 MPa or more.
［アウトガス量］
　封止剤をガラス基板の上に単位面積当たりの塗布量が１０ｍｇ／ｃｍ２となるように塗布し、その基板に紫外線照射装置（ＨＯＹＡ社製、超高圧水銀ランプ照射装置「ＵＬ－７５０」）を用いて波長３６５ｎｍ、１００ｍＷ／ｃｍ２の紫外線を１０秒間照射した。その後、８０℃で６０分間加熱し、発生したガス成分を捕集・濃縮して、ＧＣ／ＭＳ（Ａｇｉｌｅｎｔ　Ｔｅｃｈｎｏｌｏｇｙ社製、「ＧＣ／ＭＳ　７８９０Ｂ／５９７７Ｂ」）でアウトガス量を測定した。アウトガス量は６０ｐｐｍ以下が好ましい。 [Outgas amount]
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.
〔有機ＥＬの評価〕
〔有機ＥＬ素子基板の作製〕
　ＩＴＯ電極付きガラス基板をアセトン、イソプロパノールそれぞれを用いて洗浄した。その後、真空蒸着法にて以下の化合物を薄膜となるように順次蒸着し、陽極／正孔注入層／正孔輸送層／発光層／電子注入層／陰極からなる有機ＥＬ素子基板を得た。各層の構成は以下の通りである。
・陽極　ＩＴＯ、陽極の膜厚２５０ｎｍ
・正孔注入層　銅フタロシアニン　厚さ３０ｎｍ
・正孔輸送層　Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ジナフチルベンジジン（α－ＮＰＤ）　厚さ２０ｎｍ
・発光層　トリス（８－ヒドロキシキノリナト）アルミニウム（金属錯体系材料）、発光層の膜厚１０００Å
・電子注入層　フッ化リチウム　厚さ１ｎｍ
・陰極　アルミニウム、陽極の膜厚２５０ｎｍ [Evaluation of organic EL]
[Preparation of Organic EL Element Substrate]
The ITO electrode-attached glass substrate was washed with acetone and isopropanol respectively. Thereafter, the following compounds were sequentially vapor-deposited into a thin film by a vacuum vapor deposition method to obtain an organic EL element substrate comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode. The composition of each layer is as follows.
・ 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 (α-NPD) thickness 20 nm
-Light emitting layer Tris (8-hydroxyquinolinato) aluminum (metal complex material), 1000 Å of light emitting layer
・ Electron injection layer Lithium fluoride 1 nm thick
・ Cathode aluminum, film thickness 250 nm of anode
〔有機ＥＬ素子の作製〕
　実施例及び比較例で得られた封止剤を、窒素雰囲気下にて塗工装置にてガラスに塗布し、有機ＥＬ素子基板と貼り合わせ、接着厚み１０μｍで前記光硬化条件にて、この封止剤を硬化させ、有機ＥＬ素子を作製した。 [Fabrication of Organic EL Element]
The sealing agent obtained in Examples and Comparative Examples is applied to glass in a nitrogen atmosphere by a coating apparatus with a coating apparatus, bonded to an organic EL element substrate, and this sealing with an adhesive thickness of 10 μm under the above-mentioned light curing conditions The curing agent was cured to produce an organic EL device.
〔有機ＥＬ評価〕
〔初期〕
　作製した直後の有機ＥＬ素子を、８５℃、相対湿度８５質量％の条件下にて１０００時間暴露した後、６Ｖの電圧を印加し、有機ＥＬ素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。 [Organic EL evaluation]
〔initial〕
The organic EL device immediately after production is exposed for 1000 hours under the condition of 85 ° C. and relative humidity 85 mass%, a voltage of 6 V is applied, and the light emission state of the organic EL device is observed visually and with a microscope. The diameter of the spot was measured.
〔高温高湿度〕
　作製した直後の有機ＥＬ素子を、８５℃、相対湿度８５質量％の条件下にて１０００時間暴露した後、６Ｖの電圧を印加し、有機ＥＬ素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。 [High temperature high humidity]
The organic EL device immediately after production is exposed for 1000 hours under the condition of 85 ° C. and relative humidity 85 mass%, a voltage of 6 V is applied, and the light emission state of the organic EL device is observed visually and with a microscope. The diameter of the spot was measured.
　ダークスポットの直径は、３００μｍ以下が好ましく、５０μｍ以下がより好ましく、ダークスポットはないことが最も好ましい。 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.
［保存安定性評価］
　封止剤の初期粘度（Ｖ０、封止剤調製直後の粘度）を測定した後、容器に入れて蓋をした状態（密閉系）で約４０℃の高温環境下における促進試験で４週間後の封止剤の粘度（Ｖ４）を測定した。そして、式：Ｖ４／Ｖ０にしたがって粘度変化率を求めた。粘度変化率は、保存安定性が良好な点で、１．５以下が好ましい。 [Storage stability evaluation]
The initial viscosity (V0, viscosity immediately after preparation of the sealant) of the sealant is measured, and after 4 weeks in an accelerated test in a high temperature environment of about 40 ° C. in a container-covered state (closed system) The viscosity (V4) of the sealant was measured. And the viscosity change rate was calculated | required according to Formula: V4 / V0. The viscosity change rate is preferably 1.5 or less from the viewpoint of good storage stability.
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　本実施形態の封止剤は、光照射時にアウトガスを発生しにくいので、耐久性が良好であり、素子を劣化させない。本実施形態以外の封止剤は、効果を有しない。（Ｃ）成分を使用しない場合、光照射後の粘度変化が大きい（実験例１５）。ホスフィンオキサイドを使用した場合、封止剤が硬化しない（実験例１６）。ホスフィンを使用した場合、封止剤がゲル化し、本実施形態の効果を有しない（実験例１７）。クラウンエーテルを使用した場合、高温高湿度における耐久性が得られない（実験例１８）。（Ｂ）成分を使用しない場合、封止剤が硬化しない（実験例１９）。（Ａ－２）成分を使用しない場合、耐久性が得られない（実験例２０）。（Ａ－１）成分を使用しない場合、高温高湿度における耐久性が得られない（実験例２１）。
  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. When the component (C) is not used, the viscosity change after light irradiation is large (Experimental Example 15). When phosphine oxide is used, the sealant does not cure (Example 16). When phosphine is used, the sealant gels and does not have the effect of this embodiment (Experimental Example 17). When crown ether is used, durability at high temperature and high humidity can not be obtained (Example 18). When the component (B) is not used, the sealant does not cure (Example 19). When the component (A-2) is not used, durability can not be obtained (Experimental Example 20). When the component (A-1) is not used, durability at high temperature and high humidity can not be obtained (Experimental Example 21).

Claims (15)

  1. 　（Ａ）カチオン重合性化合物と、（Ｂ）光カチオン重合開始剤と、（Ｃ）リン酸エステル及び亜リン酸エステルからなる群より選択される１種以上のリン酸化合物と、を含有し、
    　（Ａ）カチオン重合性化合物が、（Ａ－１）エポキシ基を有する脂環式化合物及び（Ａ－２）エポキシ基を有する芳香族化合物を含有する、有機エレクトロルミネッセンス素子用封止剤。     (A) a cationically polymerizable compound, (B) a cationic light polymerization initiator, and (C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphorous acid esters,
    A sealing agent for an organic electroluminescent element, wherein the (A) cationically polymerizable compound comprises (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group.
  2. 　（Ｃ）リン酸化合物が（Ｃ１）リン酸エステルである請求項１に記載の有機エレクトロルミネッセンス素子用封止剤。 The sealing agent for an organic electroluminescent element according to claim 1, wherein the (C) phosphoric acid compound is a (C1) phosphoric acid ester.
  3. 　（Ｃ１）リン酸エステルが、式（Ｃ１－１）で表される化合物、式（Ｃ１－２）で表される化合物及び式（Ｃ１－３）で表される化合物からなる群より選択される少なくとも一種を含有する、請求項２に記載の有機エレクトロルミネッセンス素子用封止剤。
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     ［式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。］     (C1) The phosphate ester is selected from the group consisting of a compound represented by the formula (C1-1), a compound represented by the formula (C1-2) and a compound represented by the formula (C1-3) The sealing agent for organic electroluminescent elements of Claim 2 which contains at least 1 type.
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
     [Wherein, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrocarbon group which may have a substituent. ]
  4. 　（Ｃ）リン酸化合物が（Ｃ２）亜リン酸エステルである請求項１に記載の有機エレクトロルミネッセンス素子用封止剤。 The sealing agent for an organic electroluminescent element according to claim 1, wherein the phosphoric acid compound (C) is a (C2) phosphite.
  5. 　（Ｃ２）亜リン酸エステルが、式（Ｃ２－１）で表される化合物、式（Ｃ２－２）で表される化合物、式（Ｃ２－３）で表される化合物、式（Ｃ２－４）で表される化合物、式（Ｃ２－５）で表される化合物及び式（Ｃ２－６）で表される化合物からなる群より選択される少なくとも一種を含有する、請求項４に記載の有機エレクトロルミネッセンス素子用封止剤。
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
     ［式中、Ｒ７、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６及びＲ１７はそれぞれ独立に置換基を有していてもよい炭化水素基を示す。］     (C2) 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) The organic compound according to claim 4, which contains at least one selected from the group consisting of a compound represented by (), a compound represented by (C2-5) and a compound represented by (C2-6) Sealant for electroluminescent devices.
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
    Figure JPOXMLDOC01-appb-C000009
     [Wherein, 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. ]
  6. 　（Ａ－２）エポキシ基を有する芳香族化合物が、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂からなる群から選択される１種以上である請求項１～５のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。 The aromatic compound having an epoxy group (A-2) is at least one selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins, according to any one of claims 1 to 5. Sealant for organic electroluminescent devices.
  7. 　（Ｂ）光カチオン重合開始剤が、オニウム塩である請求項１～６のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。 The encapsulant for an organic electroluminescent device according to any one of claims 1 to 6, wherein the cationic photopolymerization initiator (B) is an onium salt.
  8. 　（Ｂ）光カチオン重合開始剤の使用量が、（Ａ）カチオン重合性化合物１００質量部に対して、０．０５～５．０質量部である請求項１～７のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。 The use amount of the photo cationic polymerization initiator (B) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the cationic polymerizable compound (A) according to any one of claims 1 to 7. Sealant for organic electroluminescent devices.
  9. 　更に、光増感剤を含有する請求項１～８のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。 The sealant for an organic electroluminescent device according to any one of claims 1 to 8, further comprising a photosensitizer.
  10. 　更に、シランカップリング剤を含有する請求項１～９のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤。 The sealant for an organic electroluminescent device according to any one of claims 1 to 9, further comprising a silane coupling agent.
  11. 　請求項１～１０のいずれか一項に記載の有機エレクトロルミネッセンス素子用封止剤の硬化体。 A cured product of the sealant for an organic electroluminescent device according to any one of claims 1 to 10.
  12. 　請求項１１に記載の硬化体を含む、有機エレクトロルミネッセンス素子用封止材。 The sealing material for organic electroluminescent elements containing the hardened | cured material of Claim 11.
  13. 　有機エレクトロルミネッセンス素子と、
    　請求項１２に記載の有機エレクトロルミネッセンス素子用封止材と、を含む、有機エレクトロルミネッセンス表示装置。     An organic electroluminescent device,
    An organic electroluminescent display device comprising the sealing material for an organic electroluminescent device according to claim 12.
  14. 　第一の部材に、請求項１～１０のいずれか１項に記載の有機エレクトロルミネッセンス素子用封止剤を付着させる付着工程と、
    　付着させた前記有機エレクトロルミネッセンス素子用封止剤に光を照射する照射工程と、
    　光照射された前記有機エレクトロルミネッセンス素子用封止剤を介して、前記第一の部材と第二の部材とを貼り合わせる貼合工程と、
    を有する、有機エレクトロルミネッセンス表示装置の製造方法。     An adhesion step of adhering the sealant for an organic electroluminescent device according to any one of claims 1 to 10 to a first member;
    An irradiation step of irradiating light to the attached sealing agent for an organic electroluminescent element;
    Bonding step of bonding the first member and the second member via the light-irradiated sealing agent for an organic electroluminescent element;
    A method of manufacturing an organic electroluminescent display device, comprising:
  15. 　前記第一の部材が基板であり、
    　前記第二の部材が有機エレクトロルミネッセンス素子である、請求項１４に記載の有機エレクトロルミネッセンス表示装置の製造方法。     The first member is a substrate,
    The manufacturing method of the organic electroluminescent display apparatus of Claim 14 whose said 2nd member is an organic electroluminescent element.
PCT/JP2018/031335 2017-08-24 2018-08-24 Sealing agent for organic electroluminescent elements WO2019039587A1 (en)

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