JPWO2019039587A1 - Sealant for organic electroluminescence device - Google Patents

Abstract

Containing (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 contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group, and a sealing agent for an organic electroluminescence device.

Description

The present invention relates to a sealant for organic electroluminescence elements. For example, the present invention relates to a sealing agent used for sealing an organic electroluminescence element.

In recent years, 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 advanced. Since the organic thin film element can be easily produced by vacuum vapor deposition, solution coating, etc., it has excellent productivity.

The organic electroluminescence 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 into this organic light emitting material layer from one electrode and holes are injected from the other electrode, so that electrons and holes are combined in the organic light emitting material layer to perform self-light emission. The organic electroluminescence display element has advantages that it has good visibility, can be made thinner, and can be driven by a direct current low voltage, as compared with a liquid crystal display element that requires a backlight.

However, such an organic electroluminescence display element has a problem that when the organic light emitting material layer and the electrodes are exposed to the outside air, the light emitting characteristics thereof are rapidly deteriorated and the life is shortened. Therefore, for the purpose of enhancing the stability and durability of the organic electroluminescence display element, in the organic electroluminescence display element, a sealing technique that shields the organic light emitting material layer and electrodes from moisture and oxygen in the atmosphere is essential. Has become.

Patent Document 1 discloses a method of filling a photocurable sealant between organic electroluminescence display element substrates in a top emission organic electroluminescence display element or the like, and irradiating with light to perform sealing. .. However, Patent Document 1 does not describe the encapsulant for organic electroluminescent elements of the present invention.

Patent Document 2 discloses a UV curable resin composition which can secure a sufficient pot life without using a reactivity control 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 merely exemplifies a phosphoric acid ester as a photocationic polymerization initiator, and is not used in Examples, and phosphoric acid ester is not used for suppressing an increase in viscosity after light irradiation.

Patent Document 3 contains an epoxy resin (excluding "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. , A curing reaction is initiated by light irradiation, an organic electroluminescent element sealing adhesive comprising a photo-cationic polymerizable adhesive in which the curing reaction proceeds in a dark reaction even after blocking light is disclosed. 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 sealant for an organic electroluminescence display device, which contains a specific cationically polymerizable compound and a photocationic polymerization initiator. However, there is a problem that the pot life after light irradiation is short. Patent Document 4 merely exemplifies the phosphoric acid ester as a photocationic polymerization initiator, and is not used in the examples, and the phosphoric acid ester is not used for suppressing 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 composed of a compound having an ether bond, and cured. A method for sealing an organic electroluminescence device with a post-curing composition in which a control agent has a compound having an ether bond is disclosed. However, such a sealing method has a problem that outgas may be generated at the time of light irradiation to deteriorate the device.
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 does not use it in Examples, and does not use phosphoric acid ester in order to suppress an increase in viscosity after light irradiation.

Patent Document 6 discloses an adduct (A) of a bisphenol A type epoxy resin and at least one phosphoric acid having active hydrogen, a compound (B) having two or more alicyclic epoxy groups, and a cationic light An ultraviolet curable resin composition containing a polymerization initiator (C) is disclosed. However, such a resin composition using (A) has a problem that the manufacturing method of (A) is complicated and outgas is generated by a by-product to deteriorate the element. Patent Document 6 does not describe a sealant for an organic electroluminescence element.

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, there is no description about a flame-retardant curable composition used for other purposes in the first place, and a usable time after light irradiation and generation of outgas during light irradiation. Patent Document 7 does not describe a sealant for an organic electroluminescence element.

JP, 2001-357973, A Japanese Patent No. 5919574 Japanese Patent No. 4800247 JP, 2016-58273, A Japanese Patent No. 4384509 JP-A-7-247342 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 encapsulant for an organic electroluminescence element, in which the increase in viscosity after light irradiation is small and the organic electroluminescence element is less likely to deteriorate.

［式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６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。

［式中、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６及びＲ^１７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 (A), a cationic photopolymerization initiator (B), and (C) one or more phosphoric acid compounds selected from the group consisting of phosphoric acid esters and phosphorous acid esters. And (A) a cationically polymerizable compound containing (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group, a sealant for an organic electroluminescent device. ..
<2> The encapsulant for organic electroluminescence device according to <1>, wherein the (C) phosphoric acid compound is (C1) phosphoric acid ester.
<3> (C1) phosphate 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). <2> The encapsulant for organic electroluminescence devices according to <2>, which contains at least one selected.

[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 encapsulant for organic electroluminescence device according to <1>, wherein the (C) phosphoric acid compound is (C2) phosphite.
<5> (C2) 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 formula ( <4>, containing at least one selected from the group consisting of a compound represented by C2-4), a compound represented by formula (C2-5) and a compound represented by formula (C2-6). A sealing agent for organic electroluminescence device of.

[In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are carbon atoms which may each independently have a substituent. Indicates a hydrogen group. ]
<6> (A-2) The aromatic compound having an epoxy group is one or more selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and is any one of <1> to <5>. The encapsulant for organic electroluminescence devices according to item 1.
<7> (B) The photocationic polymerization initiator is an onium salt, The sealant for organic electroluminescent elements as described in any one of <1>-<6>.
<8> Any of <1> to <7> in which the amount of the (B) photocationic polymerization initiator used is 0.05 to 5.0 parts by mass relative to 100 parts by mass of the (A) cationically polymerizable compound. The encapsulant for an organic electroluminescence device according to item 1.
<9> The encapsulant for organic electroluminescence devices according to any one of <1> to <8>, which further contains a photosensitizer.
<10> The encapsulant for organic electroluminescence devices according to any one of <1> to <9>, further containing a silane coupling agent.
<11> A cured product of the encapsulant for organic electroluminescence elements according to any one of <1> to <10>.
<12> An encapsulant for an organic electroluminescence device, containing the cured product according to <11>.
<13> An organic electroluminescence display device including the organic electroluminescence element and the organic electroluminescence element sealing material according to <12>.
<14> An attaching step of attaching the organic electroluminescent element sealant according to any one of <1> to <10> to the first member, and the attached organic electroluminescent element sealant. An irradiation step of irradiating the agent with light, and a bonding step of bonding the first member and the second member through the light-irradiated sealant for organic electroluminescence element, and an organic step. Manufacturing method of electroluminescent display device.
<15> The method for manufacturing an organic electroluminescence display device according to <14>, wherein the first member is a substrate and the second member is an organic electroluminescence element.

According to the present invention, it is possible to provide a sealant for an organic electroluminescence element, which is less likely to increase in viscosity after irradiation with light and is less likely to deteriorate the organic electroluminescence element.

Hereinafter, this embodiment will be described in detail.

The organic electroluminescent element sealant according to the present embodiment,
(A) cationically polymerizable compound,
It is characterized by containing (B) a cationic photopolymerization initiator and (C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphorous acid esters.
Moreover, in the organic electroluminescent element sealing agent according to the present embodiment, the (A) cationically polymerizable compound has (A-1) an alicyclic compound having an epoxy group, and (A-2) an epoxy group. It is characterized by containing an aromatic compound.

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

(A) Cationic Polymerizable Compound The encapsulant for organic electroluminescent elements according to the present embodiment contains (A) a cationic polymerizable compound as an essential component. The (A) cationically polymerizable compound is preferably photopolymerizable.

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

(A-1) Epoxy group-containing alicyclic compound As the alicyclic compound having an epoxy group (hereinafter sometimes referred to as alicyclic epoxy compound), at least one cycloalkane ring (for example, cyclohexene) A compound having a ring, a cyclopentene ring, a pinene ring, etc.) with a suitable oxidizing agent such as hydrogen peroxide or peracid, or a derivative thereof, or an aromatic epoxy compound (for example, bisphenol A type) Hydrogenated epoxy compounds and the like obtained by hydrogenating an epoxy resin, a bisphenol F type epoxy resin or the like). One or more of these compounds may be selected and used.

Examples of the alicyclic epoxy compound include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylalkyl (meth)acrylate (for example, 3,4-epoxycyclohexylmethyl (meth ) Acrylate etc.), (3,3′,4,4′-diepoxy)bicyclohexyl, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin and the like.

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

（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）

(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 bond, or an ester bond. , Carbonate groups, amide bonds, or groups in which a plurality of these are linked)

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

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, further preferably less than 300, and further preferably 100 to 280.

When the alicyclic epoxy compound has a molecular weight distribution, the alicyclic epoxy compound preferably has a number average molecular weight within 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
-Deaerator: ERC-3310 manufactured by ERMA
・Pump: PU-980 manufactured by JASCO Corporation
・Flow rate: 1.0 ml/min
-Autosampler: Tosoh AS-8020
・Column oven: L-5030 manufactured by Hitachi, Ltd.
・Set temperature: 40℃
・Column configuration: TSKguardcolumnMP (×L) 6.0 mm ID×4.0 cm 2 manufactured by Tosoh Corporation, and TSK-GELMULTIPORE HXL-M 7.8 mm ID 2 30.0 cm 2 manufactured by Tosoh Corporation, detectors: RI Hitachi L-3350
・Data processing: SIC480 data station

(A-2) Aromatic Compound Having Epoxy Group As the aromatic compound having an epoxy group (hereinafter sometimes referred to as an aromatic epoxy compound), any of a monomer, an oligomer and a polymer can be used, and a 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, novolac phenol type epoxy resin, cresol novolac type epoxy resin, modified products thereof, and the like. .. 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, the compound represented by the following formula (A2-1) is preferable.

（式（Ａ２−１）中、ｎは０．１〜３０の実数を示し、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４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。）

(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 number 1 to Represents the 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.

Among the 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 preferable.

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

When the aromatic epoxy compound has a molecular weight distribution, the number average molecular weight of the aromatic epoxy compound is preferably within the above range. In addition, in this specification, a number average molecular weight shows the value of polystyrene conversion measured by gel permeation chromatography (GPC) on the above-mentioned measurement conditions.

As the cationically polymerizable compound (A) of this embodiment, any of a monomer, an oligomer and a polymer 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 cationically polymerizable groups such as a cyclic ether group and a cationically polymerizable vinyl group, and more preferably has two.

In this embodiment, a cationically polymerizable compound 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 cyclic ethers include compounds such as epoxy and oxetane.

In 100 parts by mass of the (A) cationically polymerizable compound, the content of the other cationically polymerizable compound other than (A-1) and (A-2) is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less. Most preferably, it is 10 parts by mass or less. In 100 parts by mass of the (A) 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, and 5 parts by mass or more. Or 0 parts by mass.

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

Among the other 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.

Examples of the diglycidyl ether compound include diglycidyl ether of alkylene glycol (for example, 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), diglycidyl ether of polyalkylene glycol (for example, diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or its alkylene oxide adduct) Diglycidyl ether, etc.). Here, examples of the alkylene oxide include aliphatic compounds such as ethylene oxide and propylene oxide.

The oxetane compound is not particularly limited, but 3-ethyl-3-hydroxymethyl oxetane (trade name Aron oxetane OXT-101 manufactured by Toagosei Co., Ltd.), 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 etc.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (the same OXT-212 etc.) and the like. The oxetane compound means a compound having one or more oxetane rings in the molecule.

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 divinyl ether. Di- or trivinyl ether compounds such as vinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, Monovinyl ether compounds such as 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. Can be mentioned.

The amount of the (A-1) epoxy group-containing alicyclic compound used is preferably 30 to 95 parts by mass, more preferably 50 to 90 parts by mass, and 60 to 80 parts by mass of 100 parts by mass of the (A) cationically polymerizable compound. Most preferred is parts by weight, and even more preferred is 65 to 75 parts by weight. When it is 30 parts by mass or more, durability is obtained, and when it is 95 parts by mass or less, durability is obtained.

As for the usage-amount of the aromatic compound which has (A-2) an epoxy group, 5-70 mass parts is preferable in 100 mass parts of (A) cationically polymerizable compounds, 10-50 mass parts is more preferable, 20-40 mass parts. Parts are most preferred, and 25 to 35 parts by mass are even more preferred. If it is 5 parts by mass or more, durability will be obtained, and if it is 70 parts by mass or less, durability will be obtained.

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

(B) Photocationic Polymerization Initiator The encapsulant for organic electroluminescent elements according to the present embodiment contains (B) a photocationic polymerization initiator as an essential component. When the photocationic polymerization initiator is used, the encapsulant of this embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

(B) The cationic photopolymerization initiator is not particularly limited, but aryl sulfonium salt derivatives (for example, Syracure UVI-6990, Syracure UVI-6974 manufactured by Dow Chemical Co., and ADEKA OPTOMER SP-150 manufactured by Asahi Denka Co., Ltd.). , Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1, manufactured by Double Bond Co., Ltd. Ciba Cure 1190, etc.), aryl iodonium salt derivatives (for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan), allene-ion complex derivatives, diazonium salt derivatives, triazine initiators and others. Acid generators such as halides and the like. The cation species of the photocationic polymerization initiator is preferably an onium salt represented by the formula (B-1).

The cationic photopolymerization initiator (B) is not particularly limited, and examples thereof include onium salts represented by the formula (B-1).

（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）：

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−、−ＳＯ_２−、−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。）

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

Represents a divalent group represented by. Wherein (B-1-1), E represents a divalent group, G is -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO- , -COO-, -CONH-, an alkylene or phenylene group having 1 to 3 carbon atoms (R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a shows 0-5. a+1 E and A G may be the same or different. a is preferably an integer. X ⁻ is a counter ion of onium, and the number thereof is p+1 per molecule. )

Although the onium ion of the formula (B-1-1) is not particularly limited, 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-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthrenium, diphenylphenacylsulfonium , 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium and the like.

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. And these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl. It may be substituted with at least one selected from the group consisting of arylsulfonyl, alkyleneoxy, amino, cyano and nitro groups and halogen. The number of Rs is m+p(m-1)+1 and may be the same or different. Further, two or more Rs are mutually directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR′—, —CO—, —COO—, —CONH—, carbon number. It may be bonded via the alkylene or phenylene groups of 1 to 3 to form a ring structure containing the element A. Here, R'is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

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

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 various kinds of substituents, and examples of the substituents include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl. Group; branched alkyl group having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like having 3 to 18 carbon atoms A cycloalkyl group; a hydroxy group; a linear or branched alkoxy group having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy. Group: Acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc., having a linear or branched alkyl group having 2 to 18 carbon atoms. Carbonyl group; arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl and naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxy. Carbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc., linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms; phenoxycarbonyl, naphthoxycarbonyl, etc., aryloxycarbonyl group having 7 to 11 carbon atoms; phenylthiocarbonyl An arylthiocarbonyl group having 7 to 11 carbon atoms such as naphthoxythiocarbonyl; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyl. A linear or branched acyloxy group having 2 to 19 carbon atoms such as oxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy; phenylthio, 2-methylphenyl Phenylthio, 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-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthio Benzyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio 4-(p-isopropylbenzoyl)phenylthio, 4-(p-tert-butylbenzoyl)phenylthio and the like having 6 to 6 carbon atoms. 20 arylthio groups; carbon number such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio. 1-18 linear or branched alkylthio group; aryl group having 6-10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl , Benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thiofuranthyl, dibenzothionyl, thiofurantonyl, etc. Heterocyclic group having 4 to 20 carbon atoms; aryloxy group having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; Rusulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, etc. 1-18 linear or branched alkylsulfinyl group; arylsulfinyl group having 6-10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl , Sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl and the like, linear or branched alkylsulfonyl group having 1 to 18 carbon atoms; phenylsulfonyl, tolyl Arylsulfonyl group having 6 to 10 carbon atoms such as sulfonyl (tosyl group) and naphthylsulfonyl; Formula (B-1-2)

An alkyleneoxy group represented by (Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5); an unsubstituted amino group; alkyl having 1 to 5 carbons and/or 6 to 10 carbons. Amino group mono- or di-substituted with aryl; a cyano group; a nitro group; halogens such as fluorine, chlorine, bromine and iodine.

P in the formula (B-1) represents the number of repeating units of [DA ⁺ Rm _-1 ] bond, and is preferably an integer of 0 to 3.

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

Examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl). ) 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)phenylbis(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-benzoylphenylthio)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-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio) ] Phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5 Triarylsulfonium such as -(4-ethoxyphenyl)thiaanthrhenium and 5-(2,4,6-trimethylphenyl)thiaanthrhenium; diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenyl Diarylsulfonium such as methylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl( 1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium , 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium and other monoarylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacyl Examples thereof include trialkylsulfonium such as sulfonium.

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-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert) -Butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaanthrenium, diphenylphenacyl One or more kinds of sulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium are preferable.

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 alkyl sulfonic acid compounds, and methide compounds. Examples of X ⁻ include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ ; 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 such as PO ₄ ³⁻ ; PF ₆ ⁻ , PF ₅ OH ⁻ , fluorophosphate ions such as fluorinated alkylfluorophosphate 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 fluoroarsenate ions such as AsF ₆ ⁻ and AsF ₅ OH ⁻ .

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

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

In the formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is 1 to 5, and preferably an integer. The b Rf's may be the same or different. 2-4 are more preferable and, as for the number b of Rf, 2-3 are the most preferable.
In the fluorinated alkylfluorophosphate 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. 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; further cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. And the like. Specific _{examples, 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 preferable fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , and [((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 cationic photopolymerization initiator may be dissolved in a solvent in advance in order to facilitate 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 and diethyl carbonate.

One or more of these photocationic polymerization initiators may be selected and used.

Examples of the anionic species of the photocationic polymerization initiator (B) include boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, and the like. One or more of these anionic species may be selected and used. Among these, fluorides are preferable because they are excellent in photocurability and have improved adhesiveness and adhesive durability. Of the fluorides, hexafluoroantimonate is preferred.

Among the cationic photopolymerization initiators (B), a triarylsulfonium salt hexafluoroantimonate represented by the formula (B-2) and diphenyl 4-thiophenoxyphenylsulfonium tris( represented by the formula (B-3) One or more of pentafluoroethyl)trifluorophosphate is preferable, and a triarylsulfonium salt hexafluoroantimonate is more preferable.

The amount of the (B) cationic photopolymerization initiator used is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the (A) cationically polymerizable compound. When the amount of the photocationic polymerization initiator used is 0.05 parts by mass or more, the photocurability does not deteriorate, and when it is 5 parts by mass or less, the adhesion durability does not decrease.

(C) Phosphoric Acid Compound The encapsulant for organic electroluminescence elements according to the present embodiment contains (C) a phosphoric acid compound as an essential component. The phosphoric acid compound is one or more selected from the group consisting of (C1) phosphoric acid ester and (C2) phosphorous acid ester. The phosphoric acid compound is preferably an organic phosphoric acid compound. Among the phosphoric acid compounds, (C1) phosphoric acid ester is preferable.

Examples of the (C1) phosphoric acid ester include diethylbenzyl 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, triphenylphosphate, butylpyrophosphate, tricresylphosphate, trixylenylphosphate, octyldiphenyl Examples thereof include phosphate, cresyl diphenyl phosphate, xylenyl diphosphate, monobutyl phosphate, dibutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, ammonium ethyl acid phosphate, and 2-ethylhexyl acid phosphate salt.

The (C1) 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). It is preferable to contain at least one kind, and it is more preferable to contain the compound represented by the formula (C1-2).

In formula (C1-1), formula (C1-2) and formula (C1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently have a substituent. Represents a good hydrocarbon group.

^R 2 in the formula (C1-2), ^{R 3} and ^{R 4,} and, ^{R 5} and ^{R 6} in the formula (C1-3), it is preferable in the formula are the same groups.

Examples of the substituent that the hydrocarbon group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have include an oxyalkyl group and the like. The hydrocarbon group for R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an unsubstituted hydrocarbon group.

The hydrocarbon group for 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. More preferably. The number of carbon atoms in the alkyl group may be, for example, 1 to 18, preferably 4 to 13.

The compound represented by the formula (C1-1) may be, for example, a monoalkyl phosphate (that is, a compound in which R ¹ is an alkyl group), and specific examples include monoethyl phosphate and mono n-butyl. Examples thereof 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 alkyl groups). 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 even more preferably 8.

Specific examples of the trialkyl phosphate, 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.

Examples of the compound represented by the formula (C1-3) include dialkyl phosphate (that is, a compound in which R ⁵ and R ⁶ are alkyl groups) and the like. Specific examples of the dialkyl phosphate include dibutyl phosphate and bis(2-ethylhexyl) phosphate.

In formula (C1-1), formula (C1-2) and formula (C1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are 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 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. Further, 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.

Examples of (C2) phosphite include trimethylphosphite, triethylphosphite, tri-n-butylphosphite, tris(2-ethylhexyl)phosphite, triisooctylphosphite, tridecylphosphite, triisodecylphosphite. , Tris(tridecyl)phosphite, trioleylphosphite, tristearylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, phenyldiiso 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) ) 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, tetraphenyl tetra(tridecyl) pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenylphosphite, trilauryl trithiophosphite, dimethylhydrodienephosphite Fight, dibutylhydrogen phosphite, di(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl Examples include monodecyl phosphite and diphenyl mono(tridecyl)phosphite.

The (C2) 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), or a formula (C2-4). ), a compound represented by the formula (C2-5), and a compound represented by the formula (C2-6).

In formula (C2-1) to 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 independent. Shows 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: An oxyalkyl group and the like can be 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 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. A group or a phenyl group is more preferable, and an alkyl group is further preferable. The alkyl group may have, for example, 1 to 30 carbon atoms, and preferably 1 to 18 carbon atoms.

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 the same as 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 phosphite (that is, a compound in which R ⁸ and R ⁹ are alkyl groups) and the like.

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 alkyl groups) and the like. In addition, specific examples of the compound represented by the formula (C2-3) include triethylphosphite, tris(2-ethylhexyl)phosphite, tridecylphosphite, trilaurylphosphite, tris(tridecyl)phosphite, trio. Examples thereof include rail phosphite and diphenyl monodecyl phosphite.

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 alkyl groups). Further, specific examples of the compound represented by the formula (C2-4) include bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, and distearyl pentaerythritol diphosphite. ..

Examples of the compound represented by the formula (C2-5) include dialkyl hydrogen phosphite (that is, a compound in which R ¹⁵ and R ¹⁶ are alkyl groups). In addition, specific examples of the compound represented by the formula (C2-5) include diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, and dioleyl hydrogen phosphite.

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). Further, specific examples of the compound represented by the formula (C2-6) include monoethylhydrogenphosphite, mono(2-ethylhexyl)hydrogenphosphite, monolaurylhydrogenphosphite, monooleylhydrogenphosphite, and the like. ..

In formula (C2-1) to 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, 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 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. Further, 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, trimethylphosphite, triethylphosphite, tri-n-butylphosphite, tris(2-ethylhexyl)phosphite, triisooctylphosphite, tridecylphosphite, triisodecylphosphite, trisphosphite. A compound represented by the compound represented by the formula (C2-3) such as (tridecyl)phosphite, trioleylphosphite, tristearylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, and diphenylmonodecylphosphite. , Diisodecyl pentaerythritol diphosphite, bis(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, dimethylhydrogen phosphite, dibutylhydrodiene phosphite, di One or more selected from the group consisting of (2-ethylhexyl) hydrogenene phosphite, dilauryl hydrogenene phosphite and dioleyl hydrogenene phosphite are preferable, and the compound represented by formula (C2-3) is more preferable. .. Among the compounds represented by the formula (C2-3), trimethylphosphite, triethylphosphite, tri-n-butylphosphite, tris(2-ethylhexyl)phosphite, triisooctylphosphite, tridecylphosphite, Trialkyl phosphites such as triisodecyl phosphite, tris(tridecyl)phosphite, trioleyl phosphite and tristearyl phosphite are preferable. Among the trialkyl phosphites, tridecyl phosphite is preferred.

The amount of the (C) phosphoric acid compound used is preferably 0.1 to 5 parts by mass, and more preferably 0.02 to 3 parts by mass, relative to 100 parts by mass of the (A) cationically polymerizable compound. When the amount of the (C) phosphoric acid compound used is 0.1 parts by mass or more, an 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 encapsulant for organic electroluminescent elements of the present embodiment may contain a photosensitizer. The photosensitizer is a compound that absorbs energy rays and efficiently generates cations from the photocationic polymerization initiator.

The photosensitizer is not particularly limited, 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 Examples thereof include an allylmethane derivative, a phthalocyanine derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, and an organic ruthenium complex. 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 preferable, and anthracene derivatives are more preferable. Among the 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 (A) cationically polymerizable compound, in that the photocurability does not deteriorate and the storage stability does not decrease. 0.02 to 5 parts by mass is more preferable.

The encapsulant for organic electroluminescent elements of the present embodiment may contain a silane coupling agent. By containing the silane coupling agent, the cationic photopolymerization composition of the present embodiment exhibits excellent adhesiveness and adhesive durability.

The silane coupling agent is not particularly limited, but is 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. 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)acryloxypropyltrimethoxysilane. One or more selected from the group consisting of silanes are preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable.

The amount of the silane coupling agent used is preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the components (A) and (B), from the viewpoint of obtaining adhesiveness and adhesive durability. .2 to 5 parts by mass is more preferable.

The light source used for curing or adhering the organic electroluminescent element sealing agent of the present embodiment is not particularly limited, but a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, Examples thereof include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and a light emitting diode (hereinafter referred to as LED). These light sources are preferable because they can efficiently irradiate energy rays corresponding to the reaction wavelength of each photocationic polymerization initiator.

The light sources have different emission wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the photocationic polymerization initiator. In addition, natural light (sunlight) can also be a reaction initiation light source.

As the irradiation of the light source, direct irradiation or converging irradiation using a reflecting mirror, a fiber or the like may be performed. A low wavelength cut filter, a heat ray cut filter, a cold mirror, etc. can also be used.

The organic electroluminescent element sealant of the present embodiment may be subjected to post-heat treatment in order to accelerate the curing rate after light irradiation. When used for sealing the organic electroluminescence element, the post-heating temperature is preferably 150° C. or lower, more preferably 80° C. or lower, from the viewpoint of not damaging the organic electroluminescence element. Further, the post-heating temperature is preferably 60° C. or higher.

The encapsulant for organic electroluminescent elements of this embodiment may be used as an adhesive. The adhesive of this embodiment can be suitably used for adhesion of packages such as organic electroluminescence elements.

The method for producing the encapsulant for organic electroluminescent elements of the present embodiment is not particularly limited as long as the above components can be sufficiently mixed. The mixing method of each component is not particularly limited, and examples thereof include a stirring method using a stirring force accompanying rotation of a propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable in that low-cost and stable mixing can be performed.

As a method for adhering a base material using the encapsulant for organic electroluminescence element of the present embodiment, for example, a step of applying the encapsulant for an organic electroluminescence element to the whole surface or a part of one base material, and the organic material. A step of irradiating light to the organic electroluminescent element sealing agent of the base material coated with the electroluminescent element sealing agent, and until the organic electroluminescent element sealing agent irradiated with the light is cured. In addition, the step of bonding the other base material to the one base material, and the step of curing the base material bonded by the organic electroluminescent element sealing agent, the Can be bonded without being exposed to heat.

As a method of manufacturing an organic electroluminescence display device using the organic electroluminescent element sealing agent of the present embodiment, for example, on one substrate (back plate) on the organic electroluminescent element sealing agent of the present embodiment And irradiating the organic electroluminescent element sealant with light to activate it, and then blocking the light, and bonding the back plate and the substrate on which the electroluminescent element is formed through the composition. Etc. By this method, the organic electroluminescence element can be sealed without exposing it to light or heat.

Using the organic electroluminescent element sealing agent of the present embodiment, one substrate is coated with the organic electroluminescent element sealing agent of the present embodiment, through the organic electroluminescent element sealing agent, the other An organic electroluminescence display device can be manufactured by using a method in which substrates are bonded and the encapsulant for organic electroluminescence elements of the present embodiment is irradiated with light.

The organic electroluminescent element sealant of the present embodiment preferably has a viscosity of 10 minutes after light irradiation, which is less than 5 times the viscosity before light irradiation. As the light, UV is preferable. For example, it is more preferable that the viscosity 10 minutes after irradiation of UV with a high pressure mercury lamp at 100 mW/cm ² for 30 seconds is less than 5 times the viscosity before UV irradiation.

In the encapsulant for organic electroluminescent elements of the present embodiment, it is preferable that (B) the photocationic polymerization initiator absorbs and irradiates the irradiated light, and the excited species are decomposed to generate an acid.

The encapsulant for organic electroluminescent elements of the present embodiment has a small increase in viscosity after light irradiation, can suppress the generation of outgas, and is less likely to deteriorate the organic electroluminescent element.

Although the preferred embodiment of the present invention has been described above, the present invention is not limited to the above embodiment.

For example, one aspect of the present invention may be a cured product obtained by curing the above-mentioned encapsulant for organic electroluminescence elements.

Further, another aspect of the present invention may be a sealing material for an organic electroluminescence element, which includes the above-mentioned cured body. The encapsulant may be a cured product, or may include a cured product of the encapsulant and other constituent materials. Examples of other constituent materials include an inorganic layer such as a silicon nitride film, a silicon oxide film, and silicon nitride oxide, and an inorganic filler such as silica, mica, kaolin, talc, and aluminum oxide.

Still another aspect of the present invention may be an organic electroluminescence display device including the organic electroluminescence element and the above-mentioned sealing material for organic electroluminescence element.

Further, in the present invention, the method for manufacturing an organic electroluminescence display device comprises a first member, an attaching step of attaching the above-mentioned organic electroluminescent element sealant, and the attached organic electroluminescent element sealant. An irradiation step of irradiating light to the substrate, and a bonding step of bonding the first member and the second member through the light-irradiated sealant for organic electroluminescence element. Good. In this manufacturing method, for example, the first member may be a substrate and the second member may be an organic electroluminescent element. The conditions and the like of each step in this manufacturing method may be appropriately selected based on the description of the above embodiment.

Hereinafter, the present embodiment will be described in more detail with reference to experimental examples. The present embodiment is not limited to these. Unless otherwise specified, the tests were carried out at 23° C. and 50% by weight relative humidity.

The following compounds were used in the experimental examples.

(A-1) The following was used as the alicyclic compound having an epoxy group.
(A-1-1) 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (“Celoxide 2021P” manufactured by Daicel Chemical Industries, 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-epoxycyclohexyl methyl methacrylate ("Cyclomer M100" manufactured by Daicel)

(A-2) The following were used as the 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 ("YL983U" manufactured by Mitsui Chemicals, Inc., molecular weight 360 to 380)
(A-2-4) Bisphenol F type epoxy resin ("KRM-2490" manufactured by ADEKA, molecular weight 340 to 380)

The following were used as other cationically polymerizable compounds.
(A-3) Tripropylene glycol diglycidyl ether ("Epolite 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) Cyclohexanedimethanol divinyl ether (“CHDVE” manufactured by Nippon Carbide Co.)

The following was used as the photocationic polymerization initiator of the component (B).
(B-1) Triarylsulfonium salt hexafluoroantimonate ("ADEKA PTOMER SP-170" manufactured by ADEKA, anion species being hexafluoroantimonate)
(B-2) Triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, "CPI-200K" manufactured by San-Apro Ltd., anion species being phosphorus compounds)

The following were used as the phosphoric acid ester and/or the phosphorous acid ester as the component (C).
(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 Co., Ltd.)
(C-6 Comparative Example) Tri-n-octylphosphine oxide ("TOPO (registered trademark)" manufactured by Hokuko Kagaku Kogyo 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.)

The following were used as photosensitizers.
(G-1) 9,10-dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Kasei Co., Ltd.)

The following were used as the 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 at the composition ratios shown in Tables 1 and 2 to prepare the encapsulants for organic electroluminescent elements of Examples and Comparative Examples. The unit of composition ratio is parts by mass.

The following respective measurements were carried out on the encapsulants for organic electroluminescence elements of Examples and Comparative Examples. The results are shown in Tables 1-2.

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

[Viscosity change after light irradiation]
The sealing agent for each organic electroluminescence element obtained in Examples and Comparative Examples was applied onto a glass substrate, and the substrate was irradiated with an ultraviolet ray irradiation device (a super high pressure mercury lamp irradiation device manufactured by HOYA, "UL-750"). Was used to irradiate ultraviolet rays having a wavelength of 365 nm and 100 mW/cm ² for 30 seconds. Ten minutes after the irradiation with ultraviolet rays was completed, measurement was performed 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, assuming that the viscosity before light irradiation is V0 and the viscosity after light irradiation is Vν, the rate of change in viscosity was determined according to the formula: Vν/V0. The viscosity change rate is preferably 5 or less in terms of good slow curing property.

[Light curing conditions]
Upon evaluation of the cured material properties and adhesiveness of the sealant, the sealant was cured under the following light irradiation conditions. After photocuring the encapsulant with a UV curing device equipped with an electrodeless discharge metal halide lamp (manufactured by Fusion Co., Ltd.) under the condition of an integrated light quantity of 4,000 mJ/cm ² at a wavelength of 365 nm, in an oven at 80° C., Post-heat treatment was carried out for 30 minutes to obtain a cured product.

(Water vapor transmission rate)
A sheet-like cured body having a thickness of 0.1 mm was prepared under the above-mentioned photo-curing conditions, and calcium chloride (anhydrous) was used as a moisture absorbent in accordance with JIS Z0208 "Moisture permeability test method for moisture-proof packaging materials (cup method)". The ambient temperature was 60° C. and the relative humidity was 90%. The water vapor permeability is preferably 120 g/(m ² ·24 hr) or less.

[Tensile shear bond strength]
Two pieces of borosilicate glass test pieces (length 25 mm × width 25 mm × thickness 2.0 mm, Tempax (registered trademark) glass) were used, and the adhesive area was 0.5 cm ² , the adhesive thickness was 80 μm, and sealed under the above photocuring conditions. The stopper was cured. 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 a test piece bonded with a sealant. The tensile shear adhesive strength is preferably 15 MPa or more.

[Amount of outgas]
The sealant was applied onto a glass substrate so that the amount applied per unit area was 10 mg/cm ^2, and the substrate was irradiated with an ultraviolet ray irradiation device (manufactured by HOYA, ultra-high pressure mercury lamp irradiation device “UL-750”). Was used to irradiate ultraviolet rays having a wavelength of 365 nm and 100 mW/cm ² for 10 seconds. Then, the mixture was heated at 80° C. for 60 minutes, the generated gas component was collected and concentrated, and the amount of outgas was measured by GC/MS (manufactured by Agilent Technology, “GC/MS 7890B/5977B”). The amount of outgas is preferably 60 ppm or less.

[Evaluation of organic EL]
[Fabrication of Organic EL Element Substrate]
The glass substrate with the ITO electrode was washed with each of acetone and isopropanol. Then, the following compounds were sequentially deposited by a vacuum deposition method so as to form a thin film to obtain an organic EL device substrate composed of anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode. The structure 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 20 nm
Light emitting layer Tris(8-hydroxyquinolinato) aluminum (metal complex material), thickness of light emitting layer 1000Å
・Electron injection layer Lithium fluoride Thickness 1nm
・Cathode aluminum, anode film thickness 250nm

[Production of organic EL device]
The encapsulant obtained in each of the examples and comparative examples was applied to glass with a coating device in a nitrogen atmosphere, and was bonded to an organic EL element substrate, and the sealing was performed under the above-mentioned photocuring conditions with an adhesive thickness of 10 μm. The curing agent was cured to produce an organic EL device.

[Organic EL evaluation]
〔initial〕
The organic EL device immediately after being produced was exposed for 1000 hours under the conditions of 85° C. and a relative humidity of 85% by mass, a voltage of 6 V was applied, and the light emitting state of the organic EL device was observed visually and with a microscope. The diameter of the spot was measured.

[High temperature and high humidity]
The organic EL device immediately after being produced was exposed for 1000 hours under the conditions of 85° C. and a relative humidity of 85% by mass, a voltage of 6 V was applied, and the light emitting state of the organic EL device was observed visually and with a microscope. The diameter of the spot was measured.

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

The encapsulant of the present embodiment is less likely to generate outgas when irradiated with light, and therefore has good durability and does not deteriorate the element. 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 was used, the sealant did not cure (Experimental Example 16). When phosphine is used, the encapsulant gels and the effect of this embodiment is not obtained (Experimental Example 17). When crown ether is used, durability at high temperature and high humidity cannot be obtained (Experimental Example 18). When the component (B) is not used, the sealant does not cure (Experimental Example 19). When the component (A-2) 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)

Containing (A) a cationically polymerizable compound, (B) a cationic photopolymerization 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 contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group, and a sealing agent for an organic electroluminescence device. The encapsulant for organic electroluminescence devices according to claim 1, wherein the (C) phosphoric acid compound is (C1) phosphoric acid ester. The (C1) 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 encapsulant for organic electroluminescent elements according to claim 2, containing at least one kind.

[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. ] The encapsulant for organic electroluminescence devices according to claim 1, wherein the (C) phosphoric acid compound is (C2) phosphite. The (C2) 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 formula (C2-4). ), the compound represented by Formula (C2-5), and the compound represented by Formula (C2-6) at least 1 type selected from the group consisting of the organic of Claim 4. Sealant for electroluminescent elements.

[In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are carbon atoms which may each independently have a substituent. Indicates a hydrogen group. ] (A-2) The aromatic compound having an epoxy group is one or more selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin. Sealant for organic electroluminescence element. The (B) photocationic polymerization initiator is an onium salt, The sealing agent for organic electroluminescent elements of any one of Claims 1-6. The amount of the (B) cationic photopolymerization initiator used is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the (A) cationically polymerizable compound. A sealing agent for organic electroluminescence device of. Furthermore, the encapsulant for organic electroluminescent elements of any one of Claims 1-8 which contains a photosensitizer. Furthermore, the sealing agent for organic electroluminescent elements of any one of Claims 1-9 containing a silane coupling agent. A cured product of the encapsulant for organic electroluminescence elements according to claim 1. An encapsulant for organic electroluminescence devices, comprising the cured product according to claim 11. An organic electroluminescence device,
An organic electroluminescent display device comprising the organic electroluminescent element sealing material according to claim 12. An attaching step of attaching the organic electroluminescent element sealant according to any one of claims 1 to 10 to the first member;
An irradiation step of irradiating the attached organic electroluminescent element sealing agent with light,
Through a sealing agent for the organic electroluminescence element which is irradiated with light, a bonding step of bonding the first member and the second member,
A method for manufacturing an organic electroluminescence display device, comprising: The first member is a substrate,
The method for manufacturing an organic electroluminescent display device according to claim 14, wherein the second member is an organic electroluminescent element.