KR102536932B1 - Encapsulant for organic electroluminescent elements - Google Patents

Abstract

(A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) one or more phosphoric acid compounds selected from the group consisting of phosphoric acid esters and phosphorous acid esters, (A) a cationically polymerizable compound ( A-1) Encapsulant for organic electroluminescent elements containing the alicyclic compound which has an epoxy group, and (A-2) the aromatic compound which has an epoxy group.

Description

Encapsulant for organic electroluminescent elements

The present invention relates to an encapsulant for organic electroluminescent devices. For example, it relates to the encapsulant used for encapsulation of an organic electroluminescent element.

Recently, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been conducted. Organic thin-film elements are excellent in productivity because they can be simply manufactured by vacuum deposition or solution application.

An organic electroluminescent display device has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. When electrons are injected from one electrode into the organic light emitting material layer and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to perform self-luminescence. An organic electroluminescent display element has advantages in that it has good visibility, can be made thinner, and can be driven at a low DC voltage compared to a liquid crystal display element requiring a backlight.

However, such an organic electroluminescent display device has a problem in that, when an organic light emitting material layer or an electrode is exposed to the outside air, its light emitting characteristics are rapidly deteriorated and its lifetime is shortened. Therefore, for the purpose of enhancing the stability and durability of the organic electroluminescent display element, an organic light emitting material layer or electrode is shielded from moisture or oxygen in the air.

Patent Document 1 discloses a method of filling a photocurable encapsulant between substrates of an organic electroluminescent display element in a top emission type organic electroluminescent display element and the like, and then irradiating light to seal the element. However, Patent Document 1 has no description about the encapsulant for organic electroluminescent elements of the present invention.

Patent Document 2 discloses a UV curable resin composition capable of securing a sufficient pot life without using a reactivity control agent as a delayed curing agent. However, there was a problem that the pot life after light irradiation was short. Patent Document 2 does not describe an alicyclic compound having an epoxy group. Patent Document 2 only exemplifies phosphoric acid ester as a photocationic polymerization initiator, but does not use it in Examples, and does not use phosphoric acid ester to suppress the 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 terminal"), a photocationic polymerization initiator, and a polyalkylene oxide added bisphenol derivative having an epoxy group at the terminal. An adhesive for sealing an organic electroluminescent device is disclosed, which is characterized in that it consists of a photocationically polymerizable adhesive in which a curing reaction is initiated by, and a curing reaction proceeds as a dark reaction even after blocking light. Patent Document 3 does not describe an alicyclic compound having an epoxy group. Patent Literature 3 had a problem of deteriorating the element by generating outgas during light irradiation.

Patent Document 4 discloses an encapsulant for organic electroluminescent display elements containing a specific cationically polymerizable compound and a photocationic polymerization initiator. However, there was a problem that the pot life after light irradiation was short. Patent Document 4 only exemplifies phosphoric acid ester as a photocationic polymerization initiator, but does not use it in Examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

Patent Document 5 contains 100 parts by mass of a photocationically polymerizable compound, 0.1 to 30 parts by mass of a photocationic polymerization initiator, and 0.1 to 30 parts by mass of a curing control agent composed of a compound having an ether bond, wherein the curing control agent contains a compound having an ether bond. A method of encapsulating an organic electroluminescent device using a post-curing composition having a composition is disclosed. However, this sealing method has a problem that outgas may be generated during light irradiation to deteriorate the element.

Patent Document 5 does not describe an alicyclic compound having an epoxy group. Patent Document 5 only exemplifies phosphoric acid ester as a photocationic polymerization initiator, but does not use it in Examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

In Patent Document 6, 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 a cationic photopolymerization initiator (C) An ultraviolet curable resin composition containing is disclosed. However, in the resin composition using such (A), there was a problem that the manufacturing method of (A) was complicated, and outgas was generated by by-products to deteriorate the device. Patent Document 6 has no description about the encapsulant for organic electroluminescent elements.

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, in Patent Document 7, it is a flame retardant curable composition originally used for other purposes, and there is no description about the pot life after light irradiation and outgas generation during light irradiation. Patent Document 7 has no description about the encapsulant for organic electroluminescent elements.

Patent Document 1: Japanese Unexamined Patent Publication No. 2001-357973 Patent Document 2: Japanese Patent No. 5919574 Patent Document 3: Japanese Patent No. 4800247 Patent Document 4: Japanese Unexamined Patent Publication No. 2016-58273 Patent Document 5: Japanese Patent No. 4384509 Patent Document 6: Japanese Unexamined Patent Publication No. 7-247342 Patent Document 7: Japanese Patent Publication No. 2007-513234

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic electroluminescent element encapsulant that hardly deteriorates the organic electroluminescent element with little increase in viscosity after light irradiation.

That is, this invention is as follows.

<1> contains (A) a cationic polymerizable compound, (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) cationic polymerizable The encapsulant for organic electroluminescent elements in which the compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group.

<2> The sealing agent for organic electroluminescent elements as described in <1> whose phosphoric acid compound (C) is (C1) phosphoric acid ester.

<3> (C1) Phosphoric acid ester contains at least one 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) <2>, the sealing agent for organic electroluminescent elements.

[In the formula, 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> The sealing agent for organic electroluminescent elements as described in <1> whose phosphoric acid compound (C) is (C2) phosphite ester.

<5> (C2) Phosphorous acid ester is a compound represented by formula (C2-1), a compound represented by formula (C2-2), a compound represented by formula (C2-3), a compound represented by formula (C2-4), a formula The sealing agent for organic electroluminescent elements as described in <4> containing at least 1 sort(s) selected from the group which consists of a compound represented by (C2-5) and a compound represented by formula (C2-6).

[Wherein, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrocarbon group which may have a substituent.]

<6> (A-2) The organic electroporation according to any one of <1> to <5>, wherein the aromatic compound having an epoxy group is at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin. Encapsulant for luminescence elements.

<7> (B) The sealing agent for organic electroluminescent elements in any one of <1>-<6> whose photocationic polymerization initiator is an onium salt.

<8> The organic electroluminescent device according to any one of <1> to <7>, wherein the amount of the photocationic polymerization initiator (B) is 0.05 to 5.0 parts by mass based on 100 parts by mass of the cationic polymerizable compound (A). sealant for use.

<9> The sealing agent for organic electroluminescent elements as described in any one of <1>-<8> containing a photosensitizer further.

<10> The encapsulant for organic electroluminescent elements according to any one of <1> to <9>, further containing a silane coupling agent.

<11> The hardened|cured material of the sealing agent for organic electroluminescent elements in any one of <1>-<10>.

<12> The sealing material for organic electroluminescent elements containing the cured body as described in <11>.

<13> An organic electroluminescent display device comprising an organic electroluminescent element and the sealing material for an organic electroluminescent element according to <12>.

<14> affixing step of adhering the organic electroluminescent element encapsulant according to any one of <1> to <10> to the first member, and a light applied to the organic electroluminescent element encapsulant A manufacturing method of an organic electroluminescent display device having an irradiation step of irradiating and a bonding step of bonding the first member and the second member together through the light-irradiated encapsulant for organic electroluminescent elements.

<15> The manufacturing method of the organic electroluminescent display device according to <14>, wherein the first member is a substrate and the second member is an organic electroluminescent element.

ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element encapsulation|sealing agent for which the viscosity rise after light irradiation is small and the organic electroluminescent element is hard to deteriorate can be provided.

Hereinafter, this embodiment is described in detail.

The encapsulant for organic electroluminescent elements according to the present embodiment

(A) a cationically polymerizable compound;

(B) a photocationic polymerization initiator;

(C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphorous acid esters

Characterized in that it contains.

Further, the encapsulant for organic electroluminescent devices according to this embodiment (A) cationically polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group. characterized by

Next, components of the encapsulant for organic electroluminescent elements according to the present embodiment will be described.

(A) cationically polymerizable compound

The sealing agent for organic electroluminescent elements concerning this embodiment has (A) cationically polymerizable compound as an essential component. (A) It is preferable that a cationically polymerizable compound is photopolymerizable.

(A) The cationically polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group. Thereby, favorable adhesiveness and low moisture permeability can be obtained.

(A-1) an alicyclic compound having an epoxy group

As the alicyclic compound having an epoxy group (hereinafter also referred to as an alicyclic epoxy compound), a compound having at least one cycloalkane ring (for example, a cyclohexene ring, a cyclopentene ring, a pinene ring, etc.) A hydrogenated epoxy compound obtained by hydrogenating a compound obtained by epoxidizing with an oxidizing agent or a derivative thereof, or an aromatic epoxy compound (eg, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.), and the like. These compounds may select and use 1 or more types.

As the alicyclic epoxy compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylalkyl (meth)acrylate (for example, 3,4-epoxycyclo Hexylmethyl (meth)acrylate, etc.), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc. are mentioned.

Among the alicyclic epoxy compounds, an alicyclic epoxy compound having a 1,2-epoxycyclohexane structure is preferable. Among the alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, compounds represented by the following formula (A1-1) are preferred.

(In formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether linkage, an ester linkage, a carbonate group, an amide linkage or any of these multiple connected groups)

X is preferably a linking group. Among the linking groups, a functional group having an ester bond is preferable. Among these, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferable.

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, from the viewpoint of moisture permeability and storage stability.

When an alicyclic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of an alicyclic epoxy compound is the said range. In this specification, the number average molecular weight represents a value in terms of polystyrene measured by gel permeation chromatography (GPC) under the following measurement conditions.

・Solvent (mobile phase): THF

Degassing device: ERC-3310 manufactured by ERMA

・Pump: PU-980 manufactured by Nippon Bunko Co., Ltd.

·Flow rate: 1.0ml/min

Autosampler: AS-8020 manufactured by Tosoh Corporation

・Column oven: Hitachi L-5030

・Setting temperature: 40℃

Column configuration: 2 TSKguardcolumnMP(×L) 6.0mmID×4.0cm from Tosoh and 2 TSK-GELMULTIPORE HXL-M 7.8mmID×30.0cm from Tosoh, 4 in total

・Detector: RI Hitachi L-3350

Data Processing: SIC480 Data Station

(A-2) Aromatic compound having an epoxy group

As the aromatic compound having an epoxy group (hereinafter also referred to as an aromatic epoxy compound), any monomer, oligomer or polymer 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 resins, fluorene-type epoxy resins, novolac phenol-type epoxy resins, cresol novolac-type epoxy resins, and modified products thereof. These epoxy resins may select and use 1 or more types.

Among these, an aromatic epoxy compound having a bisphenol structure is preferable. Among aromatic epoxy compounds having a bisphenol structure, compounds represented by the following formula (A2-1) are preferred.

(In formula (A2-1), n represents a real number of 0.1 to 30, and R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms) indicates.)

R ²¹ , R ²² , R ²³ and R ²⁴ are preferably hydrogen atoms or methyl groups. R ²¹ , R ²² , R ²³ and R ²⁴ are preferably the same.

Among aromatic epoxy compounds having a bisphenol structure, at least one selected from the group consisting of bisphenol A-type epoxy resins and bisphenol F-type epoxy resins is preferred.

The molecular weight of the aromatic epoxy compound is preferably from 100 to 5000, more preferably from 150 to 1000, and most preferably from 200 to 450 from the viewpoint of moisture permeability and the like.

When an aromatic epoxy compound has molecular weight distribution, it is preferable that the number average molecular weight of an aromatic epoxy compound is the said range. In the present specification, the number average molecular weight represents a value in terms of polystyrene measured by gel permeation chromatography (GPC) under the above-described measurement conditions.

As the (A) cationically polymerizable compound of the present embodiment, any monomer, oligomer or polymer can be used.

It is preferable that (A) cationically polymerizable compound of this embodiment is an epoxy compound.

The (A) cationically polymerizable compound of the present embodiment preferably has two or more cationically polymerizable groups such as a cyclic ether group and a cationically polymerizable vinyl group, and more preferably has two.

In this embodiment, other cationically polymerizable compounds other than (A-1) and (A-2) can be further used. Examples of other cationically polymerizable compounds other than (A-1) and (A-2) include cyclic ethers and cationically polymerizable vinyl compounds. Examples of the cyclic ethers include compounds such as epoxy and oxetane.

(A) In 100 parts by mass of the cationically polymerizable compound, the content of the 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 Part by mass or less is most preferred. (A) In 100 parts by mass of the cationically polymerizable compound, the content of cationically polymerizable compounds other than (A-1) and (A-2) may be, for example, 1 part by mass or more, or 5 parts by mass or more, and 0 It may be a mass part.

Examples of the cationically polymerizable vinyl compound include vinyl ether, vinylamine, and styrene. One or more of these compounds or derivatives may be selected and used.

Among other cationically polymerizable compounds other than (A-1) and (A-2), at least one of a diglycidyl ether compound, an oxetane compound, and a vinyl ether compound is preferable.

As the diglycidyl ether compound, diglycidyl ether 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 (for example, di- or triglycidyl ether of glycerin or its alkylene oxide adduct, etc.), diglycidyl ether of polyalkylene glycol (for example, polyethylene glycol or diglycidyl ether of the alkylene oxide adduct, polypropylene glycol, or diglycidyl ether of the alkylene oxide adduct, etc.). Here, examples of the alkylene oxide include aliphatic types such as ethylene oxide and propylene oxide.

The oxetane compound is not particularly limited, but 3-ethyl-3-hydroxymethyloxetane (trade name Aronoxetane OXT-101 manufactured by Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3- Oxetanyl) methoxymethyl] benzene (Copper OXT-121 etc.), 3-ethyl-3-(phenoxymethyl) oxetane (Copper OXT-211 etc.), di(1-ethyl-(3-oxetanyl) )) methyl ether (Copper OXT-221 etc.), 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane (Copper OXT-212 etc.), etc. are mentioned. An oxetane compound refers to a compound having one or more oxetane rings in a molecule.

Although it does not specifically limit as a vinyl ether compound, 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 Di or trivinyl, such as glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimethylolpropane trivinyl ether Ether compounds, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n - Monovinyl ether compounds, such as propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether, etc. are mentioned.

(A-1) The amount of the alicyclic compound having an epoxy group is preferably 30 to 95 parts by mass, more preferably 50 to 90 parts by mass, most preferably 60 to 80 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (A). , 65 to 75 parts by mass is more preferable. Durability can be obtained when it is 30 parts by mass or more, and durability can be obtained when it is 95 parts by mass or less.

(A-2) The amount of aromatic compound having an epoxy group is preferably 5 to 70 parts by mass, more preferably 10 to 50 parts by mass, most preferably 20 to 40 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (A). 25-35 mass parts is more preferable. Durability can be obtained when it is 5 parts by mass or more, and durability can be obtained when it is 70 parts by mass or less.

(A) In 100 parts by mass of the cationically polymerizable compound, the total content of the alicyclic compound having an epoxy group (A-1) and the aromatic compound having an epoxy group (A-2) is preferably 60 parts by mass or more, and 80 parts by mass or more It is more preferable, 90 parts by mass or more is most preferable, and 100 parts by mass is even more preferable.

(B) photocationic polymerization initiator

The sealing agent for organic electroluminescent elements concerning this embodiment uses (B) photocationic polymerization initiator as an essential component. When using a photocationic polymerization initiator, the sealing agent of this embodiment becomes hardenable by irradiation of energy rays, such as an ultraviolet-ray.

(B) The photocationic polymerization initiator is not particularly limited, but arylsulfonium salt derivatives (e.g. Cyracure UVI-6990, Cyracure UVI-6974 manufactured by Dow Chemical Co., Ltd., Adeka Optomer manufactured by Asahi Denka Kogyo) SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, San Afro's CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW -S1, Cibacur 1190 manufactured by Double Bond, etc.), aryliodonium salt derivatives (eg, Irgacure 250 manufactured by Chiba Specialty Chemicals, RP-2074 manufactured by Rhodia-Japan), allene-ion complex derivatives acid generators such as diazonium salt derivatives, triazine-based initiators, and other halides; and the like. As a cationic species of a photocationic polymerization initiator, an onium salt represented by formula (B-1) is preferable.

(B) Although it does not specifically limit as a photocationic polymerization initiator, Onium salt represented by Formula (B-1) is mentioned.

(A represents an element with a valence m of groups VIA to VIIA. m represents 1 to 2. p represents 0 to 3. m and p are preferably integers. R represents an organic group bonded to A D is the following formula (B-1-1):

represents a divalent group represented by In formula (B-1-1), E represents a divalent group, and G represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, - COO-, -CONH-, a C1-C3 alkylene or phenylene group (R' represents a C1-C5 alkyl group or a C6-C10 aryl group). a represents 0 to 5; a+1 piece of E and A piece of G may be the same or different, respectively. a is preferably an integer. X ^- is a counterion of onium, and the number is p+1 per molecule.)

The onium ion of 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) 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-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di- p-Tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonyl Phonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthrenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzyl Sulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium, etc. are mentioned.

R is an organic group bonded to A. R represents, 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, and these are alkyl, hydroxyl Roxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl , alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro, and at least one member selected from the group consisting of halogen. The number of R's is m+p(m-1)+1, which may be the same or different. In addition, two or more R's are directly connected to each other or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, carbon number 1 They may be bonded through an alkylene or phenylene group of ~3 to form a ring structure containing element A. Here, R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, chrysenyl groups, naphthacenyl groups, benzanthracenyl groups, anthraquinolyl groups, fluorenyl groups, and naphthyl groups. and condensed polycyclic aryl groups such as toquinone and anthraquinone.

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 may have at least one substituent, Examples of the substituent include straight-chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy group; Straight chain or branched chain having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, etc. an alkoxy group of; Straight chain of 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc. or a branched alkylcarbonyl group; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as tetradecyloxycarbonyl and octadecyloxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl; Acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetra straight-chain or branched acyloxy groups having 2 to 19 carbon atoms, such as decylcarbonyloxy and octadecylcarbonyloxy; Phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 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-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl- 3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl) arylthio groups having 6 to 20 carbon atoms such as phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio; Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decyl straight-chain or branched alkylthio groups having 1 to 18 carbon atoms such as thio and dodecylthio; aryl groups 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, quina zolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thi heterocyclic groups having 4 to 20 carbon atoms such as oxanthonyl and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; Methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl straight-chain or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as pinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; Methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsul straight-chain or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as phonyl, tert-pentylsulfonyl, and octylsulfonyl; arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl; Formula (B-1-2)

Alkyleneoxy group represented by (Q represents a hydrogen atom or a methyl group, k represents an integer of 1 to 5); unsubstituted amino group; an amino group monosubstituted or disubstituted with an alkyl having 1 to 5 carbon atoms and/or an aryl having 6 to 10 carbon atoms; cyano group; nitro group; Halogens, such as fluorine, chlorine, bromine, and iodine, etc. are mentioned.

In Formula (B-1), p represents the number of repeating units of the [DA ⁺ R _{m -1} ] bond, and is preferably an integer of 0 to 3.

Preferable examples of the onium ion [A ⁺ ] in the formula (B-1) are sulfonium, iodonium and selenium, but typical examples include the following.

As the sulfonium ion, triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium Phonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulphonium Phonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis( 4-Fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, bis[4-(diphenylsulfonium) phonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sul phonio]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-benzoyl 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) alcohol Fonio] thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[ 4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)] Phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaantrenium, 5-tolylthiaantrenium, 5-(4-ethoxyphenyl)thiaantrenium, 5-(2 , 4,6-trimethylphenyl) triarylsulfoniums such as thiaanthrenium; diarylsulfoniums such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium; Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naph Tylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium monoarylsulfoniums such as phonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium; and trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

Among these onium ions, one or more of sulfonium ions and iodonium ions are preferred, and sulfonium ions are more preferred. 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-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di- p-Tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonyl Phonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaantrenium, diphenylphenacylsulfonium, 4-hydroxyphenyl At least one of methylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium is preferred.

In Formula (B-1), X ^- is a counterion. Their number is p+1 per molecule. The counterion is not particularly limited, but examples thereof include boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, and methide compounds. Examples of X ⁻ include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ ; OH ^- ; ClO ₄ ^- ; sulfonic acid ions such as FSO ₃ ^- , ClSO ₃ ^- , CH ₃ SO ₃ ^- , C ₆ H ₅ SO ₃ ^- , CF ₃ SO ₃ ^- ; sulfuric acid ions such as HSO ₄ ^- and SO ₄ ^2- ; carbonic acid ions such as HCO ₃ ^- and CO ₃ ^2- ; phosphoric acid ions such as H ₂ PO ₄ ^- , HPO ₄ ^{2 -} , PO ₄ ^3- ; PF ₆ ^- , PF ₅ OH ^- , fluorophosphate ions such as fluorinated alkylfluorophosphate ions; boric acid ions such as BF ₄ ^- , B(C ₆ F ₅ ) ₄ ^- , B(C ₆ H ₄ CF ₃ ) ₄ ^- ; AlCl ₄ ^- ; BiF ₆ ^- and the like. Other examples include fluoroantimonic acid ions such as SbF ₆ ^- and SbF ₅ OH ^- , and fluoroarsenic acid ions such as AsF ₆ ^- and AsF ₅ OH ^- .

Examples of the fluorinated alkylfluorophosphate ion include fluorinated alkylfluorophosphate ions represented by formula (B-1-3) and the like.

[(Rf) _b PF _6-b ] ^- (B-1-3)

In formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is 1 to 5, preferably an integer. The b pieces of Rf may be the same or different. As for the number b of Rf, 2-4 are more preferable, and 2-3 are the most preferable.

In the fluorinated alkylfluorophosphate ion represented by formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom, and preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; Furthermore, cycloalkyl groups, such as a cyclopropyl, a cyclobutyl, a cyclopentyl, and a cyclohexyl, etc. are mentioned. _Specific examples 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, and the like.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(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 photocationic polymerization initiator may use what was previously dissolved in solvents in order to facilitate dissolution in an epoxy compound or an epoxy resin. Examples of solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

These photocationic polymerization initiators may select and use 1 or more types.

(B) Halides, such as a boron compound, a phosphorus compound, an antimony compound, an arsenic compound, and an alkyl sulfonic acid compound, etc. are mentioned as anionic species of a photocationic polymerization initiator. These anion species may select and use 1 or more types. Among them, fluorides are preferred because of their excellent photocurability and improved adhesiveness and adhesive durability. Among the fluorides, hexafluoroantimonate is preferred.

(B) Among photocationic polymerization initiators, triarylsulfonium salt hexafluoroantimonate represented by formula (B-2), diphenyl 4-thiophenoxyphenylsulfonium tris represented by formula (B-3) (penta At least one of fluoroethyl)trifluorophosphate is preferable, and a triarylsulfonium salt hexafluoroantimonate is more preferable.

(B) As for the usage-amount of a photocationic polymerization initiator, 0.05-5 mass parts is preferable with respect to 100 mass parts of (A) cationically polymerizable compounds, and 0.1-3 mass parts is more preferable. When the usage-amount of the photocationic polymerization initiator is 0.05 parts by mass or more, photocurability is not deteriorated, and when it is 5 parts by mass or less, adhesive durability is not lowered.

(C) phosphoric acid compound

The sealing agent for organic electroluminescent elements concerning this embodiment has (C) a phosphoric acid compound as an essential component. The phosphoric acid compound is at least one selected from the group consisting of (C1) phosphoric acid esters and (C2) phosphorous acid esters. As the phosphoric acid compound, an organic phosphoric acid compound is preferable. Among phosphoric acid compounds, (C1) phosphoric acid esters are preferable.

(C1) phosphoric acid esters include diethylbenzyl phosphate, trimethyl phosphate, triethyl phosphate, trin-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, trixyl Nylphosphate, octyldiphenylphosphate, cresyldiphenylphosphate, xylenyldiphosphate, monobutylphosphate, dibutylphosphate, di-2-ethylhexylphosphate, monoisodecylphosphate, ammoniumethylacidphosphate and 2-ethylhexylacidphosphate A salt etc. are mentioned.

(C1) The phosphoric acid ester preferably contains at least one 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 more preferable to contain a compound represented by the formula (C1-2).

In formulas (C1-1), (C1-2), and (C1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrocarbon group which may have a substituent. indicate

It is preferable that R ² , R ³ and R ⁴ in formula (C1-2) and R ⁵ and R ⁶ in formula (C1-3) are the same group in each formula.

As a substituent which the hydrocarbon group in ^R1 , ^R2 , ^R3 , ^R4 , ^R5 and ^R6 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 an unsubstituted 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 still more preferably an alkyl group. The number of carbon atoms in the alkyl group may be, for example, 1 to 18, preferably 4 to 13.

The compound represented by formula (C1-1) may be, for example, a monoalkyl phosphate (ie, a compound in which R ¹ is an alkyl group), etc. Specific examples include monoethyl phosphate, mono-n-butyl phosphate, mono(butoxyethyl) phosphate, Mono (2-ethylhexyl) phosphate etc. are mentioned.

As the compound represented by formula (C1-2), trialkyl phosphate (ie, a compound in which R ² , R ³ and R ⁴ are alkyl groups) is preferable. At this time, the number of carbon atoms in 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.

Specific examples of the trialkyl phosphate include triethyl phosphate, trin-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) ₃ P=O (R is a lauryl group, a cetyl group, a stearyl group or an oleyl group); and the like.

As a compound represented by Formula (C1-3), dialkyl phosphate (namely, the compound whose ^R5 and ^R6 are an alkyl group) etc. are mentioned, for example. Specific examples of the dialkyl phosphate include dibutyl phosphate and bis(2-ethylhexyl) phosphate.

In formulas (C1-1), (C1-2) and (C1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrocarbon group containing an alkyl group; At least one of a hydrocarbon group containing an aromatic ring and a hydrocarbon group containing an aliphatic ring may be used. The hydrocarbon group may have a partially unsaturated group and may have an arbitrary 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. Also, the hydrocarbon group is preferably an unsubstituted saturated group. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably the same.

(C2) Phosphite esters include trimethyl phosphite, triethyl phosphite, trin-butyl phosphite, tris (2-ethylhexyl) 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, phenyldi Soo-octyl phosphite, phenyl diisodecyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isooctyl phosphite, diphenyl monodecyl phosphite, diphenyl monoisodecyl phosphite, diphenyl mono ( Tridecyl)phosphite, bis(nonylphenyl)dinonylphenylphosphite, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol)phenyl phosphite, diisodecylpentaerythritol diphosphite, bis(tridecyl)penta Erythritol diphosphite, distearylpentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'- Isopropylidenediphenylphosphite, trilauryl trithiophosphite, dimethylhydrodiene phosphite, dibutylhydrodiene phosphite, di(2-ethylhexyl)hydrodiene phosphite, dilauryl hydrodiene phosphite, dioleyl hydrodiene phosphite, diphenylhydrodiene phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, and diphenyl mono(tridecyl) phosphite; and the like.

(C2) The phosphorous acid ester is a compound represented by formula (C2-1), a compound represented by formula (C2-2), a compound represented by formula (C2-3), a compound represented by formula (C2-4), a formula (C2- It is preferable to contain at least 1 sort(s) selected from the group which consists of a compound represented by 5) and a compound represented by Formula (C2-6).

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.

Examples of the substituent that 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 include an oxyalkyl group. there is. 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 unsubstituted 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, and more preferably an alkyl group or a phenyl group. It is preferable, and it is more preferable that it is an alkyl group. The number of carbon atoms in the alkyl group may be, for example, 1 to 30, 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), R in formula (C2-5) ¹⁵ and R ¹⁶ are preferably identical to each other in each formula.

As a compound represented by Formula (C2-1), monoalkyl phosphite (ie, the compound whose ^R7 is an alkyl group) etc. are mentioned, for example.

As a compound represented by Formula (C2-2), dialkyl phosphite (ie, the compound in which ^R8 and ^R9 are an alkyl group) etc. are mentioned, for example.

Examples of the compound represented by formula (C2-3) include trialkyl phosphites (ie, compounds in which R ¹⁰ , R ¹¹ and R ¹² are alkyl groups) and the like. In addition, as a specific example of the compound represented by Formula (C2-3), triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris (tridecyl) phosphite, trioleate Il phosphite, diphenyl monodecyl phosphite, etc. are mentioned.

Examples of the compound represented by formula (C2-4) include bis(alkyl)pentaerythritol diphosphite (ie, a compound in which R ¹³ and R ¹⁴ are alkyl groups) and the like. Moreover, as a specific example of the compound represented by Formula (C2-4), bis (decyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, etc. are mentioned.

As a compound represented by Formula (C2-5), dialkyl hydrogen phosphite (ie, the compound in which ^R15 and ^R16 are an alkyl group) etc. are mentioned, for example. Further, specific examples of the compound represented by formula (C2-5) include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, and dioleyl hydrogen phosphite. there is.

As a compound represented by Formula (C2-6), monoalkyl hydrogen phosphite (ie, the compound whose ^R17 is an alkyl group) etc. are mentioned, for example. In addition, specific examples of the compound represented by formula (C2-6) include monoethyl hydrogen phosphite, mono(2-ethylhexyl) hydrogen phosphite, monolauryl hydrogen phosphite, monooleyl hydrogen phosphite, and the like. can be heard

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 At least one of a hydrocarbon group containing an alkyl group, a hydrocarbon group containing an aromatic ring, and a hydrocarbon group containing an aliphatic ring may be used. The hydrocarbon group may have a partially unsaturated group and may have an arbitrary 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. Also, the hydrocarbon group is preferably an unsubstituted 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.

Among the phosphorous acid esters, trimethyl phosphite, triethyl phosphite, trin-butyl phosphite, tris (2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris (tris Decyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, diphenyl monodecyl phosphite, etc. Compounds represented by compounds represented by formula (C2-3) , Diisodecylpentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dimethylhydrodiene phosphite, dibutylhydro At least one selected from the group consisting of diene phosphite, di(2-ethylhexyl)hydrodiene phosphite, dilauryl hydrodiene phosphite, and dioleyl hydrodiene phosphite is preferred, and represented by formula (C2-3) compounds are more preferred. Among the compounds represented by formula (C2-3), trimethyl phosphite, triethyl phosphite, trin-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triiso Trialkyl phosphites, such as decyl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, and tristearyl phosphite, are preferable. Among trialkyl phosphites, tridecyl phosphite is preferred.

(C) The phosphoric acid compound used is preferably 0.1 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, based on 100 parts by mass of the cationically polymerizable compound (A). (C) If the usage-amount of a phosphoric acid compound is 0.1 mass part or more, the viscosity raise after light irradiation can be suppressed, and photocurability will not deteriorate if it is 5 mass parts or less.

The sealing agent for organic electroluminescent elements of this embodiment may contain a photosensitizer. A photosensitizer refers to a compound that absorbs energy rays and efficiently generates cations from a photocationic polymerization initiator.

The photosensitizer is not particularly limited, but benzophenone derivatives, phenothiazine derivatives, phenylketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine Derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, organic ruthenium complexes, etc. can Among these, phenylketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and/or anthracene derivatives such as 9,10-dibutoxyanthracene are preferred, and anthracene derivatives are more preferred. . Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferred.

The amount of use of the photosensitizer is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 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.

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 this embodiment shows excellent adhesiveness and adhesive durability.

The silane coupling agent is not particularly limited, but γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-( meta) acryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyl dimethoxysilane and γ-ureidopropyltriethoxysilane; and the like. These silane coupling agents may select and use 1 or more types. Among these, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(meth)acryloxypropyl At least one selected from the group consisting of trimethoxysilane is preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

The amount of the silane coupling agent used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on 100 parts by mass of the total of component (A) and component (B), from the viewpoint of obtaining adhesiveness and adhesive durability.

Although not particularly limited as a light source used for curing or bonding the encapsulant for an organic electroluminescent element of the present embodiment, a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium, etc.), a low-pressure mercury lamp, High-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like. These light sources are preferable in terms of being able to efficiently irradiate energy rays corresponding to the reaction wavelength of each photocationic polymerization initiator.

Each of the light sources has a different radiation wavelength or energy distribution. Therefore, the said light source is suitably selected according to the reaction wavelength of a photocationic polymerization initiator, etc. In addition, natural light (sunlight) can also be a reaction initiating light source.

As the irradiation of the light source, direct irradiation or condensed irradiation using a reflector, fiber, or the like may be performed. A low wavelength cut filter, a hot wire cut filter, a cold mirror, or the like can also be used.

In order to promote the curing rate after light irradiation, the sealing agent for organic electroluminescent elements of this embodiment may be subjected to post-heating treatment. The post-heating temperature is preferably 150°C or lower, and more preferably 80°C or lower, from the viewpoint of not damaging the organic electroluminescent element when used for encapsulation of the organic electroluminescent element. Further, the post-heating temperature is preferably 60°C or higher.

You may use the sealing agent for organic electroluminescent elements of this embodiment as an adhesive agent. The adhesive of this embodiment can be used suitably for bonding packages, such as an organic electroluminescent element.

The manufacturing method of the encapsulant for organic electroluminescent elements of this embodiment is not particularly limited as long as the above components can be sufficiently mixed. The method of mixing each component is not particularly limited, but examples thereof include a method of using a stirring method using a stirring force according to rotation of a propeller and a method using a conventional disperser such as a planetary stirrer by rotation and revolution. These mixing methods are preferable in terms of being able to perform stable mixing at low cost.

As a method of bonding a base material using the organic electroluminescent element encapsulant of the present embodiment, for example, a step of applying an organic electroluminescent element encapsulant to the entire surface or part of one base material; The process of irradiating light to the organic electroluminescent element encapsulant of the base material to which the organic electroluminescent element encapsulant is applied, and until the organic electroluminescent element encapsulant to which the light is irradiated is cured In the meantime, the base material is not exposed to light or heat by having a step of bonding the base material on the other side to the base material on the one hand, and a step of curing the base material bonded by the encapsulant for the organic electroluminescent element. can be glued.

As a method of manufacturing an organic electroluminescent display device using the organic electroluminescent element encapsulant of the present embodiment, for example, on one substrate (rear plate), the organic electroluminescent element of the present embodiment A method of applying an encapsulant for an organic electroluminescent element, irradiating light to the encapsulant for an organic electroluminescent element to activate it, blocking light, and attaching a back plate and a substrate on which an electroluminescent element is formed through the composition etc. can be mentioned. By this method, the organic electroluminescent element can be sealed without exposing it to light or heat.

Using the organic electroluminescent element encapsulant of the present embodiment, the organic electroluminescent element encapsulant of the present embodiment is applied to one substrate, and the organic electroluminescent element encapsulant is applied to the other substrate. An organic electroluminescent display device can be manufactured using the method of attaching the substrates together and irradiating light to the organic electroluminescent element encapsulant of the present embodiment.

It is preferable that the viscosity of the sealing agent for organic electroluminescent elements of this embodiment 10 minutes after light irradiation is less than 5 times compared with the viscosity before light irradiation. As light, UV is preferable. For example, it is more preferable that the viscosity 10 minutes after UV irradiation at 100 mW/cm 2 for 30 seconds by a high-pressure mercury lamp is less than 5 times compared to the viscosity before UV irradiation.

It is preferable that the sealing agent for organic electroluminescent elements of this embodiment absorbs and excites the light irradiated by the (B) photocationic polymerization initiator, and the excited species are decomposed to generate an acid.

The encapsulant for organic electroluminescent elements of this embodiment has little increase in viscosity after light irradiation, can suppress generation|occurrence|production of outgas, and it is hard to deteriorate an organic electroluminescent element.

Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

For example, one aspect of the present invention may be a cured product formed by curing the above-described encapsulant for organic electroluminescent devices.

In addition, another aspect of the present invention may be an encapsulant for an organic electroluminescent element comprising the cured body described above. This sealing material may be a hardened body or may contain a constituent material different from the hardened body of the sealing agent. Examples of other constituent materials include an inorganic material layer such as a silicon nitride film, a silicon oxide film, and a silicon nitride oxide film, and an inorganic filler such as silica, mica, kaolin, talc, and aluminum oxide.

Further, another aspect of the present invention may be an organic electroluminescent display device including an organic electroluminescent element and the above-described encapsulant for the organic electroluminescent element.

In addition, in the present invention, the manufacturing method of the organic electroluminescent display device includes the attaching step of attaching the above-described organic electroluminescent element encapsulant to the first member, and the adhered organic electroluminescent element encapsulant It may have an irradiation process of irradiating light to, and a bonding process of bonding the first member and the second member together through the light-irradiated sealing agent for organic electroluminescent elements. In this manufacturing method, for example, the first member may be a substrate, and the second member may be an organic electroluminescent element. Conditions and the like of each step in this manufacturing method may be appropriately selected based on the description of the above-described embodiment.

Example

Hereinafter, the present embodiment will be described in more detail by way of an experimental example. This embodiment is not limited to these. Unless otherwise specified, the test was performed at 23°C and a relative humidity of 50% by mass.

In the experimental example, the following compounds were used.

(A-1) The following was used as an alicyclic compound having an epoxy group.

(a-1-1) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxide 2021P" by Daicel Chemical Co., Ltd.)

(a-1-2) Hydrogenated bisphenol A type epoxy resin ("YX8000" manufactured by Mitsubishi Chemical Corporation, molecular weight 380 to 430)

(a-1-3) 3,4-epoxycyclohexylmethyl methacrylate ("Cyclomer M100" manufactured by Daicel)

(A-2) The following was used as an aromatic compound having an epoxy group.

(a-2-1) bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, molecular weight 360 to 390)

(a-2-2) bisphenol F type epoxy resin ("jER806" manufactured by Mitsubishi Chemical Corporation, molecular weight 320 to 340)

(a-2-3) bisphenol F-type epoxy resin (Mitsui Chemical Co., Ltd. "YL983U", molecular weight 360 to 380)

(a-2-4) Bisphenol F type epoxy resin ("KRM-2490" manufactured by ADEKA, molecular weight 340 to 380)

As other cationically polymerizable compounds, the following was used.

(a-3) Tripropylene glycol diglycidyl ether ("Epolite 200P" by Kyoeisha Chemical Co., Ltd.)

(a-4) di(1-ethyl-(3-oxetanyl))methyl ether (“Aronoxetane OXT-221” manufactured by Toagosei Co., Ltd.)

(a-5) cyclohexanedimethanol divinyl ether ("CHDVE" manufactured by Nippon Carbide)

(B) The following was used as a photocationic polymerization initiator of component.

(b-1) triarylsulfonium salt hexafluoroantimonate ("Adeka Optomer SP-170" manufactured by ADEKA, the anion species is hexafluoroantimonate)

(b-2) triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, "CPI-200K" manufactured by San Afro Co., Ltd., the anion species is a phosphorus compound)

As the phosphoric acid ester and/or phosphorous acid ester of component (C), the following was used.

(c-1) Tris (2-ethylhexyl) phosphate ("TOP" manufactured by Daihachi Chemical Industry Co., Ltd.)

(c-2) tridecyl phosphite ("JP-310" manufactured by Johoku Chemical Industry Co., Ltd.)

(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-octylphosphine oxide (“T.O.P.O (registered trademark)” manufactured by Hokko Chemical Industry Co., Ltd.)

(c-7 Comparative Example) Tri-n-octylphosphine (“TOCP” manufactured by Chohoku Chemical Industry Co., Ltd.)

(c-8 comparative example) 18-crown-6-ether ("Crown Ether O-18" manufactured by Nippon Soda Co., Ltd.)

As the photosensitizer, the following was used.

(g-1) 9,10-dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Chemical Industry Co., Ltd.)

The following was used as a silane coupling agent.

(f-1) γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone Co., Ltd.)

Raw materials of the types shown in Tables 1 and 2 were mixed in the composition ratios shown in Tables 1 and 2 to prepare encapsulants for organic electroluminescent elements of Examples and Comparative Examples. The unit of the composition ratio is the mass part.

Each of the following measurements was performed about the sealing agent for organic electroluminescent devices of Examples and Comparative Examples. The results are shown in Tables 1 and 2.

〔viscosity〕

The viscosity (shear viscosity) of the encapsulant was measured using an E-type viscometer (1 ° 34' × R24 cone rotor) under conditions of a temperature of 25 ° C. and a rotation speed of 10 rpm.

[Viscosity change after light irradiation]

Each organic electroluminescent element encapsulant obtained in Examples and Comparative Examples was applied onto a glass substrate, and the substrate was irradiated with an ultraviolet ray irradiation device (ultra-high pressure mercury lamp irradiation device manufactured by HOYA, "UL-750"). An ultraviolet ray with a wavelength of 365 nm and 100 mW/cm 2 was irradiated for 30 seconds. Ten minutes after completion of the ultraviolet irradiation, the viscosity was measured using an E-type viscometer (1°34'×R24 cone rotor) under conditions of a temperature of 25°C and a rotation speed of 10 rpm. Then, when the viscosity before light irradiation was V0 and the viscosity after light irradiation was Vν, the viscosity change rate was obtained according to the formula: Vν/V0. The rate of change in viscosity is preferably 5 or less from the viewpoint of good self-curing property.

[Photocuring conditions]

The encapsulant was cured under the following light irradiation conditions at the time of evaluating the cured physical properties and adhesiveness of the encapsulant. After photo-curing the encapsulant under conditions of a cumulative light intensity of 4,000 mJ/cm 2 with a wavelength of 365 nm by a UV curing device (manufactured by Fusion Co.) equipped with an electrodeless discharge metal halide lamp, a post-heat treatment was performed in an oven at 80 ° C. for 30 minutes. Thus, a cured product was obtained.

[Permeability]

A sheet-like cured body with a thickness of 0.1 mm was produced under the above photocuring conditions, and calcium chloride (anhydrous) was used as a moisture absorbent in accordance with JIS Z0208 “Test method for moisture permeability of moisture-proof packaging materials (cup method)” at an ambient temperature of 60 ° C. and relative humidity. It was measured under the condition of 90%. As for moisture permeability, 120 g/(m<2>*24hr) or less is preferable.

[Tensile shear adhesive strength]

Using two borosilicate glass test pieces (length 25 mm × width 25 mm × thickness 2.0 mm, Tempax (registered trademark) glass), the sealing agent was cured under the photocuring conditions with an adhesive area of 0.5 cm 2 and an adhesive thickness of 80 μm. After curing, the tensile shear adhesive strength (unit: MPA) was measured at a tensile speed of 10 mm/min in an environment of a temperature of 23° C. and a relative humidity of 50% using the test piece bonded with the sealant. The tensile shear adhesive strength is preferably 15 MPa or more.

[out gas amount]

An encapsulant is applied on a glass substrate so that the coating amount per unit area is 10 mg/cm2, and the substrate is irradiated with a wavelength of 365 nm and 100 mW/cm 2 using an ultraviolet irradiation device (manufactured by HOYA, ultra-high pressure mercury lamp irradiation device “UL-750”). of UV was irradiated for 10 seconds. Thereafter, the gas components generated by heating at 80 ° C. for 60 minutes were collected and concentrated, and the amount of outgas was measured by GC/MS (“GC/MS 7890B/5977B” manufactured by Agilent Technology). As for the amount of outgas, 60 ppm or less is preferable.

[Evaluation of Organic EL]

[Production of organic EL device substrate]

A glass substrate with an ITO electrode was cleaned using acetone and isopropanol, respectively. Thereafter, the following compounds were sequentially deposited into thin films by vacuum deposition to obtain an organic EL element substrate composed of anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode. The configuration of each layer is as follows.

・Anode ITO, anode film thickness 250nm

Hole injection layer copper phthalocyanine thickness 30nm

Hole transport layer N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD) thickness 20nm

Light emitting layer Tris(8-hydroxyquinolinato)aluminum (metal complex material), thickness of light emitting layer 1000 Å

･Thickness of electron injection layer lithium fluoride 1nm

Cathode aluminum, anode film thickness 250nm

[Production of organic EL element]

The sealing agent obtained in Examples and Comparative Examples was applied to glass with a coating device under a nitrogen atmosphere, bonded to the organic EL element substrate, and cured under the above photocuring conditions to an adhesive thickness of 10 μm to produce an organic EL device.

[Evaluation of organic EL]

〔Early〕

After exposing the organic EL element immediately after production for 1000 hours under conditions of 85 ° C. and 85% by mass relative humidity, a voltage of 6 V was applied, and the light emission state of the organic EL element was observed with the naked eye and a microscope to measure the diameter of the dark spot. .

[High Temperature, High Humidity]

After exposing the organic EL element immediately after production for 1000 hours under conditions of 85 ° C. and 85% by mass relative humidity, a voltage of 6 V was applied, and the light emission state of the organic EL element was observed with the naked eye and a microscope to measure the diameter of the dark spot. .

The diameter of the dark spot is preferably 300 μm or less, more preferably 50 μm or less, and most preferably no dark spot.

[Storage stability evaluation]

After measuring the initial viscosity of the sealing agent (V0, viscosity immediately after preparation of the sealing agent), put it in a container and cover the lid (closed system), in an accelerated test in a high temperature environment of about 40 ° C., the viscosity of the sealing agent after 4 weeks ( V4) was measured. Then, the viscosity change rate was obtained according to the formula: V4/V0. The viscosity change rate is preferably 1.5 or less from the viewpoint of good storage stability.

Since the sealing agent of this embodiment hardly generates outgas at the time of light irradiation, durability is good and an element is not deteriorated. Sealing agents other than this embodiment do not have an effect. When component (C) is not used, the change in viscosity after light irradiation is large (Experimental Example 15). When using phosphine oxide, the encapsulant is not cured (Experimental Example 16). When phosphine is used, the encapsulant gels and does not have the effect of the present embodiment (Experimental Example 17). When crown ether is used, durability at high temperature and high humidity cannot be obtained (Experimental Example 18). (B) When the component is not used, the encapsulant is not cured (Experimental Example 19). (A-2) When the component is not used, durability cannot be obtained (Experimental Example 20). When the component (A-1) is not used, durability at high temperature and high humidity cannot be obtained (Experimental Example 21).

Claims (15)

(A) a cationically polymerizable compound, (B) a photocationic polymerization initiator, and (C) containing at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphorous acid esters,
(A) The cationically polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group,
(C) The phosphoric acid compound is selected from the group consisting of a compound represented by formula (C1-2), a compound represented by formula (C2-3), a compound represented by formula (C2-4), and a compound represented by formula (C2-5) Encapsulant for organic electroluminescent elements containing at least 1 sort(s) which becomes.

[In the formula, R ² , R ³ and R ⁴ each independently represent a hydrocarbon group which may have a substituent.]

[In the formula, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrocarbon group which may have a substituent.] The method of claim 1,
(C) Encapsulant for organic electroluminescent elements which is a compound in which a phosphoric acid compound is represented by formula (C1-2). The method of claim 1,
(C) An organic electroluminescent element in which the phosphoric acid compound is at least one selected from the group consisting of a compound represented by formula (C2-3), a compound represented by formula (C2-4), and a compound represented by formula (C2-5) sealant for use. The method of claim 1,
(A-2) The sealing agent for organic electroluminescent elements whose aromatic compound which has an epoxy group is 1 or more types chosen from the group which consists of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. The method of claim 1,
(B) The sealing agent for organic electroluminescent elements whose photocationic polymerization initiator is an onium salt. The method of claim 1,
(B) The sealing agent for organic electroluminescent elements whose usage-amount of a photocationic polymerization initiator is 0.05-5.0 mass parts with respect to 100 mass parts of (A) cationically polymerizable compounds. The method of claim 1,
The encapsulant for organic electroluminescent elements further containing a photosensitizer. The method of claim 1,
An encapsulant for organic electroluminescent elements further containing a silane coupling agent. The hardened|cured material of the sealing agent for organic electroluminescent elements in any one of Claims 1-8. An encapsulant for an organic electroluminescent element comprising the cured product according to claim 9. An organic electroluminescent element;
An organic electroluminescent display device comprising the encapsulant for an organic electroluminescent element according to claim 10. An adhesion step of adhering the encapsulant for an organic electroluminescent element according to any one of claims 1 to 8 to a first member;
An irradiation step of irradiating light to the attached encapsulant for organic electroluminescent elements;
The manufacturing method of the organic electroluminescent display device which has the bonding process of bonding the said 1st member and the 2nd member together through the said sealing agent for organic electroluminescent elements irradiated with light. The method of claim 12,
The first member is a substrate,
A method of manufacturing an organic electroluminescent display device in which the second member is an organic electroluminescent element. delete delete