JP7397151B2 - Composition - Google Patents

Description

The present invention relates to a composition, a sealant for an organic electroluminescent device, a cured product, a sealant for an organic electroluminescent device, an organic electroluminescent display device, and a method for manufacturing an organic electroluminescent display device.

In recent years, research has been progressing on organic optical devices using organic thin film elements such as organic electroluminescent (organic EL) display elements and organic thin film solar cell elements. Organic thin film elements can be easily manufactured by vacuum evaporation, solution coating, etc., and therefore have excellent productivity.

An organic electroluminescent display element has a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into this organic light emitting material layer from one electrode and holes are injected from the other electrode, so that the electrons and holes combine within the organic light emitting material layer to cause self-luminescence. Organic electroluminescent display elements have the advantage that they have better visibility than liquid crystal display elements that require a backlight, can be made thinner, and can be driven at a low DC voltage.

However, such an organic electroluminescent display element has a problem in that when the organic light emitting material layer or electrode is exposed to the outside air, its light emitting characteristics deteriorate rapidly and its lifespan is shortened. Therefore, in order to improve the stability and durability of organic electroluminescent display elements, sealing technology that shields the organic light emitting material layer and electrodes from moisture and oxygen in the atmosphere is essential for organic electroluminescent display elements. It has become.

Patent Document 1 discloses a method of filling a photocurable sealant between organic electroluminescent display element substrates and irradiating light for sealing in a top-emitting type organic electroluminescent display element or the like. . However, Patent Document 1 does not describe the sealant for organic electroluminescent elements of the present invention.

Patent Document 2 discloses a UV curable resin composition that can ensure 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 irradiation with light 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, and does not use it in the examples, and does not use phosphoric acid ester to suppress the 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 end"), a photocationic polymerization initiator, and a polyalkylene oxide-added bisphenol derivative having an epoxy group at the end. discloses an adhesive for sealing an organic electroluminescent device, which is comprised of a photo-cationic polymerizable adhesive that initiates a curing reaction upon irradiation with light and progresses through a dark reaction even after the light is shut off. There is. Patent Document 3 does not describe an alicyclic compound having an epoxy group. Patent Document 3 has a problem in that outgas is generated during light irradiation and the element is deteriorated.

Patent Document 4 discloses a sealing agent 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 irradiation with light was short. Patent Document 4 only exemplifies phosphoric acid ester as a photocationic polymerization initiator, and does not use it in the examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

Patent Document 5 discloses that the composition contains 100 parts by mass of a photocationic 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 consisting of a compound having an ether bond. A method for sealing an organic electroluminescent device using a post-curing composition in which the control agent has a compound having an ether bond is disclosed. However, such a sealing method has a problem in that outgas may be generated during light irradiation and the element may deteriorate.
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 and does not use it in the examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

Patent Document 6 describes an adduct (A) of a bisphenol A 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 photoresist. An ultraviolet curable resin composition containing a polymerization initiator (C) is disclosed. However, such a resin composition using (A) has the problem that the manufacturing method of (A) is complicated, and that by-products generate outgas and deteriorate the device. Patent Document 6 does not describe a sealant 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, the composition is originally a flame-retardant curable composition used for other purposes, and there is no description regarding the pot life after irradiation with light and the generation of outgas during irradiation with light. Patent Document 7 does not describe a sealant for organic electroluminescent elements.

Patent Document 8 discloses a sealant for an organic electroluminescent display element containing a cationically polymerizable compound and a photocationic polymerization initiator, wherein the cationically polymerizable compound is a compound represented by a specific structure. An encapsulant for organic electroluminescent display elements is disclosed.
Patent Document 8 only exemplifies phosphoric acid ester as a photocationic polymerization initiator, and does not use it in the examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

Patent Document 9 discloses a sealing agent for sealing the light extraction direction of a top emission type organic electroluminescent device containing a photopolymerizable compound and a photocationic polymerization initiator, The compound consists of 20 to 80 parts by weight of an epoxy compound having an aliphatic cyclic skeleton and 80 to 20 parts by weight of a bisphenol F type epoxy resin, based on 100 parts by weight of the photopolymerizable compound, and the wavelength of the cured product is A sealing agent for an organic electroluminescent device is disclosed that has a total light transmittance of 80% or more in the wavelength range of 380 to 800 nm.
Patent Document 9 only exemplifies phosphoric acid ester as a photocationic polymerization initiator and does not use it in the examples, and does not use phosphoric acid ester to suppress the increase in viscosity after light irradiation.

Patent Document 10 describes an alicyclic epoxy compound (A) having a cycloaliphatic skeleton and two or more epoxy groups in the molecule, silica (B), and a phosphite (C). A liquid curable epoxy resin composition is disclosed.
Patent Document 10 only exemplifies an aromatic epoxy compound having a bisphenol structure as a reactive diluent, and does not use it in the examples. Do not use it to suppress the rise in temperature or to prevent organic electroluminescent elements from deteriorating.

Japanese Patent Application Publication No. 2001-357973 Patent No. 5919574 Patent No. 4800247 JP 2016-58273 Publication Patent No. 4384509 Japanese Patent Application Publication No. 7-247342 Special Publication No. 2007-513234 JP 2016-58273 Publication JP2009-79230A Japanese Patent Application Publication No. 2012-116935

The present invention has been made in view of the above circumstances, and provides a composition that exhibits little increase in viscosity after irradiation with light, can be suitably used as a sealant for organic electroluminescent devices, and is resistant to deterioration of organic electroluminescent devices. The purpose is to

［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＞記載の組成物。
＜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＞記載の組成物。

［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＞（Ｃ）リン酸化合物の使用量が、（Ａ）カチオン重合性化合物１００質量部に対して、０．１～５質量部である＜１＞～＜５＞のいずれか１項に記載の組成物。
＜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項に記載の組成物。
＜８＞（Ｂ）光カチオン重合開始剤の含有量が、（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項に記載の組成物。
＜９＞光増感剤を更に含有する、＜１＞～＜８＞のいずれか１項に記載の組成物。
＜１０＞シランカップリング剤を更に含有する、＜１＞～＜９＞のいずれか１項に記載の組成物。
＜１１＞＜１＞～＜１０＞のいずれか一項に記載の組成物を含む、有機エレクトロルミネッセンス素子用封止剤。
＜１２＞＜１＞～＜１０＞のいずれか一項に記載の組成物の硬化体。
＜１３＞＜１２＞に記載の硬化体を含む、有機エレクトロルミネッセンス素子用封止材。
＜１４＞有機エレクトロルミネッセンス素子と、＜１３＞に記載の有機エレクトロルミネッセンス素子用封止材と、を含む、有機エレクトロルミネッセンス表示装置。
＜１５＞第一の部材に、＜１＞～＜１０＞のいずれか１項に記載の組成物を付着させる付着工程と、付着させた前記組成物に光を照射する照射工程と、光照射された前記組成物を介して、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。
＜１６＞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、＜１５＞に記載の有機エレクトロルミネッセンス表示装置の製造方法。
＜１７＞（Ａ）カチオン重合性化合物と、（Ｂ）光カチオン重合開始剤と、（Ｃ）リン酸エステル及び亜リン酸エステルからなる群より選択される１種以上のリン酸化合物と、を含有し、
（Ａ）カチオン重合性化合物が、（Ａ－１）エポキシ基を有する脂環式化合物及び（Ａ－２）エポキシ基を有する芳香族化合物を含有し、
（Ａ－２）エポキシ基を有する芳香族化合物が、ビスフェノール構造を有する芳香族エポキシ化合物を含有し、
光照射前の粘度をＶ０、波長３６５ｎｍ、１００ｍＷ／ｃｍ^２の紫外線を３０秒間照射した後の粘度をＶνとしたとき、式：Ｖν／Ｖ０にしたがって求めた光照射後の粘度変化率が１０以下であり、
温度８５℃、相対湿度８５質量％の条件下にて１０００時間暴露した後、６Ｖの電圧を１０秒間印加した後における、高温高湿度条件下のダークスポットの直径が、１５０μｍ以下である、組成物。 That is, the present invention is as follows.
<1> (A) a cationic 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 phosphite esters; Contains
(A) the cationic polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group,
(A-2) the aromatic compound having an epoxy group contains (A-2-1) bisphenol A type epoxy resin and (A-2-2) bisphenol F type epoxy resin,
The ratio A ₁ /A 2 (mass ratio) between the content A ₁ of (A-2-1) bisphenol A type epoxy resin and the content _{A 2} of (A-2-2) bisphenol F type epoxy resin is 0. .2 to 5.
<2> The composition according to <1>, wherein the phosphoric acid compound (C) is a phosphoric ester (C1).
<3> (C1) Phosphoric ester is from the group consisting of a compound represented by formula (C1-1), a compound represented by formula (C1-2), and a compound represented by formula (C1-3) The composition according to <2>, containing at least one selected one.

[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 composition according to <1>, wherein the phosphoric acid compound (C) is a phosphite (C2).
<5> (C2) Phosphite 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 ( Description <4>, containing at least one selected from the group consisting of the compound represented by C2-4), the compound represented by formula (C2-5), and the compound represented by formula (C2-6) Composition 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 each independently may have a substituent. Indicates a hydrogen group. ]
<6> In any one of <1> to <5>, the amount of the phosphoric acid compound (C) used is 0.1 to 5 parts by mass based on 100 parts by mass of the cationically polymerizable compound (A). Compositions as described.
<7> The composition according to any one of <1> to <6>, wherein the photocationic polymerization initiator (B) is an onium salt.
<8> Any of <1> to <7>, wherein the content of the cationic photopolymerization initiator (B) is 0.05 to 5.0 parts by mass based on 100 parts by mass of the cationically polymerizable compound (A). The composition according to item 1.
<9> The composition according to any one of <1> to <8>, further containing a photosensitizer.
<10> The composition according to any one of <1> to <9>, further containing a silane coupling agent.
<11> A sealant for an organic electroluminescent device, comprising the composition according to any one of <1> to <10>.
<12> A cured product of the composition according to any one of <1> to <10>.
<13> A sealing material for an organic electroluminescent element, comprising the cured product according to <12>.
<14> An organic electroluminescent display device comprising an organic electroluminescent element and the sealing material for an organic electroluminescent element according to <13>.
<15> An adhesion step of adhering the composition according to any one of <1> to <10> to a first member, an irradiation step of irradiating the adhered composition with light, and a light irradiation step. a bonding step of bonding the first member and the second member together via the composition prepared above.
<16> The method for manufacturing an organic electroluminescent display device according to <15>, wherein the first member is a substrate and the second member is an organic electroluminescent element.
<17> (A) a cationic 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 phosphite esters; Contains
(A) the cationic polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group,
(A-2) the aromatic compound having an epoxy group contains an aromatic epoxy compound having a bisphenol structure,
When the viscosity before light irradiation is V0 and the viscosity after irradiation with ultraviolet rays of wavelength 365 nm and 100 mW/ ^cm2 for 30 seconds is Vν, the viscosity change rate after light irradiation calculated according to the formula: Vν/V0 is 10 or less and
A composition in which the diameter of a dark spot under high temperature and high humidity conditions is 150 μm or less after being exposed for 1000 hours at a temperature of 85° C. and a relative humidity of 85% by mass, and after applying a voltage of 6 V for 10 seconds. .

According to the present invention, it is possible to provide a composition that exhibits little increase in viscosity after irradiation with light, can be suitably used as a sealant for organic electroluminescent devices, and is resistant to deterioration of organic electroluminescent devices.

This embodiment will be described in detail below.

The composition according to this embodiment is
(A) cationic polymerizable compound,
It is characterized by containing (B) a photocationic polymerization initiator and (C) at least one phosphoric acid compound selected from the group consisting of phosphoric acid esters and phosphite esters.
Further, in the composition according to the present embodiment, (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. It is characterized by
The composition according to this embodiment can be suitably used as a sealant for organic electroluminescent devices.

Next, the components of the composition (hereinafter also referred to as "sealant for organic electroluminescent elements") according to this embodiment will be explained.

(A) Cationically polymerizable compound The composition according to this embodiment includes (A) a cationically polymerizable compound as an essential component. (A) The cationically polymerizable compound is preferably photopolymerizable.

(A) The cationic polymerizable compound contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group. This provides good adhesion and low moisture permeability.

(A-1) Alicyclic compound having an epoxy group The alicyclic compound having an epoxy group (hereinafter also referred to as an alicyclic epoxy compound) includes at least one cycloalkane ring (for example, cyclohexene). Aromatic epoxy compounds (e.g., bisphenol A type Examples include hydrogenated epoxy compounds obtained by hydrogenating epoxy resins, bisphenol F type epoxy resins, etc.). One or more types of these compounds may be selected and used.

Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl (meth)acrylate (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, etc.

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

（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, carbonyl group, ether bond, or ester bond. , carbonate group, amide bond, or a group in which multiple of these are connected)

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

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, even more preferably less than 300, and even more preferably 100 to 280.

When the alicyclic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of the alicyclic epoxy compound is within the above range. Note that in this specification, the number average molecular weight indicates a value in terms of polystyrene, which is measured by gel permeation chromatography (GPC) under the following measurement conditions.
・Solvent (mobile phase): THF
・Deaerator: ERC-3310 manufactured by ERMA
・Pump: JASCO Corporation PU-980
・Flow rate: 1.0ml/min
・Auto sampler: Tosoh AS-8020
・Column oven: Hitachi L-5030
・Set temperature: 40℃
・Column configuration: 2 TSKguardcolumn MP (xL) 6.0 mm ID x 4.0 cm manufactured by Tosoh, and 2 TSK-GELMULTIPORE HXL-M 7.8 mm ID x 30.0 cm manufactured by 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 of monomers, oligomers, or polymers can be used, and bisphenol A type Examples include 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, and modified products thereof. . One or more types of these epoxy resins may be selected and used.
Among these, aromatic epoxy compounds having a bisphenol structure are preferred. Among the aromatic epoxy compounds having a bisphenol structure, a compound represented by the following formula (A2-1) is preferred.

（式（Ａ２－１）中、ｎは０～３０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 formula (A2-1), n represents a real number from 0 to 30, and R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 5 carbon atoms. (represents an alkyl group)

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. n is preferably a real number from 0.1 to 30.

Among the aromatic epoxy compounds having a bisphenol structure, one or more selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins are preferred.
(A-2) The aromatic compound having an epoxy group preferably contains (A-2-1) a bisphenol A type epoxy resin and (A-2-2) a bisphenol F type epoxy resin.
The ratio A 1 /A 2 (mass ratio) between the content A ₁ of the component (A-2-1) and the content _{A 2} of the component (A- _2-2 ) is preferably 0.2 to 5. preferable. That is, the mass ratio of the (A-2-1) component and the (A-2-2) component is (A-2-1):(A-2-2)=1:5 to 5:1. is preferred.

(A-2-1) Bisphenol A type epoxy resin Bisphenol A type epoxy resin is, for example, an epoxy resin in which R ²¹ , R ²² , R ²³ and R ²⁴ in formula (A2-1) are methyl groups. good. Bisphenol A type epoxy resin refers to one obtained by condensing bisphenol A and epichlorohydrin in the presence of an alkali catalyst, for example. Furthermore, a modified epoxy resin or the like may be used in which the epoxy group or hydroxyl group of the bisphenol A type epoxy resin is reacted with a vegetable oil or fat fatty acid or a modifier. Note that hydrogenated epoxy compounds obtained by hydrogenating bisphenol A epoxy resins (for example, hydrogenated bisphenol A epoxy resins corresponding to the above-mentioned alicyclic epoxy compounds) are not included in bisphenol A epoxy resins.

(A-2-2) Bisphenol F-type epoxy resin Bisphenol F-type epoxy resin is, for example, an epoxy resin in which R ²¹ , R ²² , R ²³ and R ²⁴ in formula (A2-1) are hydrogen atoms. good. Bisphenol F type epoxy resin refers to one obtained by condensing bisphenol F and epichlorohydrin in the presence of an alkali catalyst, for example. Furthermore, a modified epoxy resin or the like may be used in which the epoxy group or hydroxyl group of the bisphenol F type epoxy resin is reacted with a vegetable oil or fat fatty acid or a modifier. Note that hydrogenated epoxy compounds obtained by hydrogenating bisphenol F-type epoxy resins (for example, hydrogenated bisphenol F-type epoxy resins corresponding to the above-mentioned alicyclic epoxy compounds) are not included in bisphenol F-type epoxy resins.

The molecular weight of the aromatic epoxy compound, especially the molecular weight of (A-2-1) bisphenol A type epoxy resin and (A-2-2) bisphenol F type epoxy resin, is preferably 100 to 5000 from the viewpoint of moisture permeability, etc. More preferably 150 to 1000, most preferably 200 to 450.

When the aromatic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of the aromatic epoxy compound is within the above range. In this specification, the number average molecular weight indicates a polystyrene equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.

As the cationic polymerizable compound (A) of this embodiment, any of monomers, oligomers, and polymers can be used.

The cationically polymerizable compound (A) of this embodiment is preferably an epoxy compound.

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

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

(A) The content of other cationically polymerizable compounds other than (A-1) and (A-2) in 100 parts by mass of the cationically polymerizable compound is preferably 40 parts by mass or less, more preferably 20 parts by mass or less. , most preferably 10 parts by mass or less. (A) The content of other cationically polymerizable compounds other than (A-1) and (A-2) in 100 parts by mass of the cationic polymerizable compound may be, for example, 1 part by mass or more, and 5 parts by mass or more. It may be 0 parts by mass.

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 the cationic polymerizable compounds other than (A-1) and (A-2), one or more of diglycidyl ether compounds, oxetane compounds, and vinyl ether compounds are preferred.

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. (e.g., di- or triglycidyl ether of glycerin or its alkylene oxide adduct), diglycidyl ether of polyalkylene glycol (e.g., 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 alkylene oxides such as ethylene oxide and propylene oxide.

Examples of oxetane compounds include, but are not limited to, 3-ethyl-3-hydroxymethyloxetane (trade name: Aronoxetane OXT-101, manufactured by Toagosei Co., Ltd., etc.), 1,4-bis[(3-ethyl-3-oxetanyl) ) methoxymethyl]benzene (OXT-121, etc.), 3-ethyl-3-(phenoxymethyl)oxetane (OXT-211, etc.), di(1-ethyl-(3-oxetanyl))methyl ether (OXT- 221, etc.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (OXT-212, etc.), and the like. The oxetane compound refers to a compound having one or more oxetane rings in the molecule.

Vinyl ether compounds include, but are not limited to, 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, butane 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, cyclohexanedimethanol 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.

(A-1) The amount of the alicyclic compound having an epoxy group to be used is preferably 30 to 95 parts by weight, more preferably 50 to 90 parts by weight, and more preferably 60 to 80 parts by weight based on 100 parts by weight of the cationic polymerizable compound (A). Parts by weight are most preferred, and 65 to 75 parts by weight are even more preferred. This tends to further improve the durability of the cured product.

(A-2) The amount of the aromatic compound having an epoxy group used is preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight, and 20 to 40 parts by weight based on 100 parts by weight of the cationic polymerizable compound (A). parts by weight is most preferred, and 25 to 35 parts by weight is even more preferred. This tends to further improve the durability of the cured product.

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

(B) Photocationic polymerization initiator The composition according to this embodiment includes (B) a photocationic polymerization initiator as an essential component. When using a photocationic polymerization initiator, the composition of this embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

(B) Examples of the photocationic polymerization initiator include, but are not limited to, arylsulfonium salt derivatives (for example, Cylacure UVI-6990, Cylacure UVI-6974 manufactured by Dow Chemical Co., Ltd., and Adeka Optomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd.). , ADEKA OPTOMER SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP-172, CPI-100P manufactured by Sun-Apro, CPI-101A, CPI-200K, CPI-210S, LW-S1, manufactured by Double Bond Cibacure 1190, etc.), aryliodonium 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. Examples include acid generators such as halides. The cationic species of the photocationic polymerization initiator is preferably an onium salt represented by formula (B-1).

(B) The photocationic polymerization initiator is not particularly limited, but includes onium salts represented by 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 of group VIA to group VIIA with a valence m. m represents 1 to 2. p represents 0 to 3. m and p are preferably integers. R is an organic compound bonded to A. represents a group.D is the following formula (B-1-1):

It shows 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-, an alkylene group having 1 to 3 carbon atoms or a phenylene group (R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a represents 0 to 5. a+1 E's and a G's may be the same or different. a is preferably an integer. X ⁻ is a counter ion of onium, and its number is p+1 per molecule. )

The onium ion of formula (B-1) is not particularly limited, but includes 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxy) ethoxy)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)thianthrenium, 5-phenylthianthrenium, 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. These are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl , arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen. The number of R's is m+p(m-1)+1, and they may be the same or different from each other. Also, two or more R's are directly connected to each other or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, carbon number A ring structure containing element A may be formed by bonding via 1 to 3 alkylene or phenylene groups. 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, the aryl group having 6 to 30 carbon atoms includes a monocyclic aryl group such as a phenyl group, and a condensation group such as 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 above aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms has at least one Examples of substituents include straight chain alkyl having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, ocdadecyl, etc. Group; Branched alkyl group having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl; 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. cycloalkyl group; hydroxy group; linear or branched alkoxy having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy, etc. Group: Straight chain or branched alkyl having 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc. 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 Straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as carbonyl, tetradecyloxycarbonyl, and octadecyloxycarbonyl; Aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; phenylthiocarbonyl , naphthoxythiocarbonyl and other arylthiocarbonyl groups having 7 to 11 carbon atoms; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyl Straight chain or branched acyloxy groups having 2 to 19 carbon atoms such as oxy, octylcarbonyloxy, tetradecylcarbonyloxy, 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)phenylthio, Arylthio groups having 6 to 20 carbon atoms such as 4-(p-ethylbenzoyl)phenylthio 4-(p-isopropylbenzoyl)phenylthio, 4-(p-tert-butylbenzoyl)phenylthio; methylthio, ethylthio, propylthio, isopropylthio, Straight chain or branched alkylthio groups having 1 to 18 carbon atoms such as butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio; phenyl, Aryl groups having 6 to 10 carbon atoms such as tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, Heterocyclic groups having 4 to 20 carbon atoms such as carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl; phenoxy, naphthyloxy Aryloxy groups having 6 to 10 carbon atoms such as; methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl , tert-pentylsulfinyl, octylsulfinyl, and other linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms; C6 to 10 arylsulfinyl groups such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; methylsulfonyl, ethylsulfonyl , propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl, etc. Chain or branched alkylsulfonyl group; arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group), 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; alkyl having 1 to 5 carbon atoms and/or 6 to 10 carbon atoms Amino groups mono- or di-substituted with aryl; cyano groups; nitro groups; halogens such as fluorine, chlorine, bromine, and iodine.

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

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

Sulfonium ions 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)thianthrenium, 5-phenylthianthrenium, 5-tolylthianthrenium, 5-( Triarylsulfoniums such as 4-ethoxyphenyl)thianthrenium, 5-(2,4,6-trimethylphenyl)thianthrenium; diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium Diarylsulfoniums such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1- ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2 - Monoarylsulfoniums such as naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacylsulfonium, etc. trialkylsulfonium and the like.

Among these onium ions, one or more of sulfonium ions and iodonium ions are preferred, and sulfonium ions are more preferred. Sulfonium ions include 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)thianthrenium, 5-phenylthianthrenium, diphenylphenacyl One or more of sulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, and octadecylmethylphenacylsulfonium is preferred.

In formula (B-1), X ⁻ is a counter ion. The number is p+1 per molecule. Counter ions include, but are not particularly limited to, boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, halides such as alkylsulfonic acid compounds, methide compounds, and the like. 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 Sulfonic acid ions such as ^- , CF ₃ SO ₃ ^- ; Sulfuric acid ions such as HSO ₄ ^- , SO ₄ ^2- ; Carbonate ions such as HCO ₃ ^- , CO ₃ ^2- ; H ₂ PO ₄ ^- , HPO ₄ Phosphate ions such as ^2- , PO ₄ ^3- ; Fluorophosphate ions such as PF ₆ ^- , PF ₅ OH ^- , and fluorinated alkylfluorophosphate ions; BF ₄ ^- , B(C ₆ F ₅ ) ₄ ^- , B(C ₆ H ₄ CF ₃ ) ₄ ^- , and other boric acid ions; 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 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, and is preferably an integer. The b Rfs may be the same or different. The number b of Rf is more preferably 2 to 4, most preferably 2 to 3.
In the fluorinated alkylfluorophosphate ion represented by formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. It is. Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. cycloalkyl groups and the like. 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 cationic photopolymerization initiator may be dissolved in a solvent in advance to facilitate dissolution into the epoxy compound or epoxy resin. Examples of the solvent 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.

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

(B) Among the photocationic polymerization initiators, triarylsulfonium salt hexafluoroantimonate represented by formula (B-2), diphenyl 4-thiophenoxyphenylsulfonium tris( One or more types consisting of (pentafluoroethyl) trifluorophosphate are preferred, and triarylsulfonium salt hexafluoroantimonate is more preferred.

The amount of the photocationic polymerization initiator (B) used is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the cationically polymerizable compound (A). When the amount of the photocationic polymerization initiator used is 0.05 parts by mass or more, the photocurability tends to be further improved, and when it is 5 parts by mass or less, the adhesive durability tends to be further improved.

(C) Phosphoric acid compound The composition according to this embodiment includes (C) a phosphoric acid compound as an essential component. The phosphoric acid compound is one or more selected from the group consisting of (C1) phosphate ester and (C2) phosphite ester. As the phosphoric acid compound, an organic phosphoric acid compound is preferable. Among the phosphoric acid compounds, (C1) phosphoric ester is preferred.

(C1) Phosphate esters 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, triphenyl phosphate, butyl pyrophosphate, tricresyl phosphate, tricylenyl phosphate, octyldiphenyl Examples 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.

(C1) The phosphoric acid ester is selected from the group consisting of a compound represented by formula (C1-1), a compound represented by formula (C1-2), and a compound represented by formula (C1-3). It is preferable to contain at least one type of compound, and more preferably to contain a compound represented by 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; Indicates a good hydrocarbon group.

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

Examples of substituents that the hydrocarbon groups in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have include oxyalkyl groups. The hydrocarbon groups in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably unsubstituted hydrocarbon groups.

The hydrocarbon group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and an alkyl group. 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 formula (C1-1) may be, for example, monoalkyl phosphate (that is, a compound in which R ¹ is an alkyl group), and specific examples include monoethyl phosphate, mono n-butyl Examples include mono(butoxyethyl) phosphate, mono(2-ethylhexyl) phosphate, and the like.

The compound represented by formula (C1-2) is preferably a trialkyl phosphate (ie, a compound in which R ² , R ³ and R ⁴ are alkyl groups). At this time, the number of carbon atoms in the alkyl groups 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 trialkyl phosphates include triethyl phosphate, tri-n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-ethylhexyl) phosphate, (RO) ₃ P=O (R is a lauryl group, a cetyl group, stearyl group or oleyl group).

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

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 each independently a carbonized group 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, or may have any atoms or substituents. 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.

(C2) Phosphite esters include trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, and triisodecyl phosphite. , 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, tetraphenyldipropylene glycol diphosphite, poly(dipropylene glycol) phenyl phosphite, diisodecyl pentaerythritol diphosphite, bis(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite , bis(nonylphenyl)pentaerythritol diphosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, tetra(tridecyl)-4,4'-isopropylidene diphenylphosphite, trilauryl trithiophosphite, dimethylhydrodiene phosphite phyto, dibutylhydrodiene phosphite, di(2-ethylhexyl)hydrodiene phosphite, dilaurylhydrodiene phosphite, dioleylhydrodiene phosphite, diphenylhydrodiene phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl Examples include monodecyl phosphite and diphenyl mono(tridecyl) phosphite.

(C2) Phosphite 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 compound represented by formula (C2-5), 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 independent represents a hydrocarbon group which may have a substituent.

Examples of substituents that the hydrocarbon groups 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: Examples include oxyalkyl groups. The hydrocarbon groups in 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 unsubstituted hydrocarbon groups.

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; or a phenyl group, and even more preferably 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), 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 formula (C2-1) include monoalkyl phosphite (ie, a compound in which R ⁷ is an alkyl group).

Examples of the compound represented by formula (C2-2) include dialkyl phosphites (ie, compounds in which R ⁸ and R ⁹ are alkyl groups).

Examples of the compound represented by formula (C2-3) include trialkylphosphite (ie, a compound in which R ¹⁰ , R ¹¹ and R ¹² are alkyl groups). Further, specific examples of the compound represented by formula (C2-3) include triethyl phosphite, tris(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, trio Examples include rail phosphite and diphenylmonodecyl phosphite.

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). Further, specific examples of the compound represented by formula (C2-4) include bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, etc. .

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

Examples of the compound represented by formula (C2-6) include monoalkyl hydrogen phosphite (ie, a compound in which R ¹⁷ is an alkyl group). Further, 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, etc. .

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 It may be independently 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, or may have any atoms or substituents. 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 phosphite esters, trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tris Compounds represented by formula (C2-3) such as (tridecyl) phosphite, trioleylphosphite, tristearylphosphite, triphenyl phosphite, tris(nonylphenyl) phosphite, diphenylmonodecyl phosphite, etc. , 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)hydrodiene phosphite, dilaurylhydrodiene phosphite, and dioleylhydrodiene phosphite is preferred, and the compound represented by formula (C2-3) is more preferred . Among the compounds represented by formula (C2-3), trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tris(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, Trialkyl phosphites such as triisodecyl phosphite, tris(tridecyl) phosphite, trioleylphosphite, tristearylphosphite and the like are preferred. Among the trialkyl phosphites, tridecyl phosphite is preferred.

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

The composition of this embodiment may contain a photosensitizer. A photosensitizer is a compound that absorbs energy rays and efficiently generates cations from a photocationic polymerization initiator.

Examples of photosensitizers include, but are not limited to, 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, Examples include allylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, and organic ruthenium complexes. 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 the photosensitizer used is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the cationic polymerizable compound (A) in that the photocurability does not deteriorate and the storage stability does not deteriorate. More preferably 0.02 to 5 parts by mass.

The composition of this embodiment may contain a silane coupling agent. By containing the silane coupling agent, the composition of this embodiment exhibits excellent adhesiveness and adhesive durability.

Examples of the silane coupling agent include, but are not limited to, 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 types 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 types selected from the group consisting of silanes are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

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

Light sources used for curing and adhesion of the composition of the present embodiment are not particularly limited, but include halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high pressure Examples include 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 that 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, etc. Natural light (sunlight) can also be a light source for starting the reaction.

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

The composition of this embodiment may be subjected to a post-heat treatment in order to accelerate the curing speed after irradiation with light. The temperature of the post-heating is preferably 150° C. or lower, more preferably 80° C. or lower, from the viewpoint of not damaging the organic electroluminescent device when used for sealing the organic electroluminescent device. Moreover, the temperature of post-heating is preferably 60° C. or higher.

The composition of this embodiment may be used as an adhesive. The adhesive of this embodiment can be suitably used for bonding packages of organic electroluminescent devices and the like.

The method for producing the composition of this embodiment is not particularly limited as long as the above components can be sufficiently mixed. Methods for mixing each component include, but are not particularly limited to, a stirring method that utilizes the stirring force accompanying the rotation of a propeller, a method that utilizes a normal dispersion machine such as a planetary stirrer that rotates around its axis, and the like. These mixing methods are preferable because stable mixing can be performed at low cost.

The method of adhering substrates using the composition of this embodiment includes, for example, a step of applying the composition to the entire surface or a part of one of the substrates, and an organic electroluminescent element of the substrate coated with the composition. By having a step of irradiating the sealing agent with light, and a step of laminating the other base material to the one base material until the composition irradiated with light is cured, Can be bonded without exposing the base material to light or heat.

As a method for manufacturing an organic electroluminescent display device using the composition of this embodiment, for example, the composition of this embodiment is applied onto one substrate (back plate), and the composition is irradiated with light. Examples include a method of activating the composition, blocking light, and bonding the back plate and the substrate on which the electroluminescent element is formed via the composition. This method allows the organic electroluminescent device to be sealed without being exposed to light or heat.

An organic electroluminescent display device can also be manufactured by applying the composition of this embodiment to one substrate, bonding the other substrate via the composition, and then irradiating the composition with light.

The composition of this embodiment preferably has a viscosity 10 minutes after irradiation with light that is less than 5 times the viscosity before irradiation with light. As the 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 using a high-pressure mercury lamp is less than 5 times the viscosity before UV irradiation.

In the composition of the present embodiment, it is preferable that the (B) photocationic polymerization initiator absorbs irradiated light and is excited, and the excited species decomposes to generate acid.

The composition of this embodiment has a small increase in viscosity after irradiation with light, can suppress the generation of outgas, and does not easily deteriorate the organic electroluminescent device.

Although the 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 obtained by curing the above-mentioned composition.

Another aspect of the present invention may be a sealing material for an organic electroluminescent device, which includes the above-mentioned cured product. This sealing material may be a cured product, or may include a cured product of the composition and other constituent materials. Examples of other constituent materials include silicon nitride films, silicon oxide films, inorganic layers such as silicon nitride oxide, and inorganic fillers 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-mentioned sealing material for the organic electroluminescent element.

Further, in the present invention, the method for manufacturing an organic electroluminescent display device includes an adhesion step of adhering the above-described composition to the first member, an irradiation step of irradiating the adhered composition with light, and a step of irradiating the composition with light. The method may include a bonding step of bonding the first member and the second member together via the composition. In this manufacturing method, for example, the first member may be a substrate, and the second member may be an organic electroluminescent device. Conditions for each step in this manufacturing method may be appropriately selected based on the description of the above-mentioned embodiments.

Hereinafter, this embodiment will be described in further detail by giving an experimental example. This embodiment is not limited to these. Unless otherwise specified, tests were conducted at 23° C. and 50% relative humidity by weight.

In the experimental example, the following compounds were used.

(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 Co., Ltd.)
(a-1-2) Hydrogenated bisphenol A epoxy resin (“YX8000” manufactured by Mitsubishi Chemical Corporation, molecular weight 380-430)
(a-1-3) 3,4-epoxycyclohexylmethyl methacrylate (“Cyclomer M100” manufactured by Daicel)

(A-2) The following aromatic compound having an epoxy group was used.
(a-2-1-1) Bisphenol A type epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, molecular weight 360-390)
(a-2-1-2) Bisphenol A epoxy resin (“YL980” manufactured by Mitsui Chemicals, molecular weight 240)
(a-2-2-1) Bisphenol F type epoxy resin (“jER806” manufactured by Mitsubishi Chemical Corporation, molecular weight 320-340)
(a-2-2-2) Bisphenol F type epoxy resin (“YL983U” manufactured by Mitsui Chemicals, molecular weight 360-380)
(a-2-2-3) Bisphenol F type epoxy resin (“KRM-2490” manufactured by ADEKA, molecular weight 340-380)

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 (“Aronoxetane OXT-221” manufactured by Toagosei Co., Ltd.)
(a-5) Cyclohexane dimethanol divinyl ether (“CHDVE” manufactured by Nippon Carbide Co., Ltd.)

The following was used as the photocationic polymerization initiator of component (B).
(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-Apro, the anion species is a phosphorus compound)

The following was used as the phosphoric acid ester and/or phosphorous acid ester of 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 Kagaku Kogyo Co., Ltd.)
(c-3) Bis(decyl)pentaerythritol diphosphite (JPE-10 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
(c-4) Bis(2-ethylhexyl)hydrogen phosphite (JPE-208 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
(c-5) Diphenylmonodecyl phosphite (JPM-311 manufactured by Johoku Kagaku Kogyo Co., Ltd.)
(c-6 Comparative Example) Tri-n-octylphosphine oxide (“T.O.P.O (registered trademark)” manufactured by Hokuko Chemical Industry Co., Ltd.)
(c-7 Comparative example) Tri-n-octylphosphine (“TOCP” manufactured by Johoku Kagaku Kogyo Co., Ltd.)
(c-8 Comparative example) 18-crown-6-ether (“Crown Ether O-18” manufactured by Nippon Soda Co., Ltd.)

The following was used as a photosensitizer.
(g-1) 9,10-dibutoxyanthracene (“ANTHRACURE UVS-1331” manufactured by Kawasaki Chemical Industries, Ltd.)

The following was used as the silane coupling agent.
(f-1) γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shin-Etsu Silicone)

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 composition ratio is parts by mass.

The following measurements were performed on the sealants for organic electroluminescent elements of Examples and Comparative Examples. The results are shown in Tables 1 and 2.

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

[Viscosity change after light irradiation]
The sealants for organic electroluminescent elements obtained in the Examples and Comparative Examples were applied onto a glass substrate, and the substrate was exposed to an ultraviolet irradiation device (an ultra-high pressure mercury lamp irradiation device manufactured by HOYA, "UL-750"). Ultraviolet light with a wavelength of 365 nm and a power of 100 mW/cm ² was irradiated for 30 seconds. Ten minutes after the UV irradiation was completed, measurement was performed using an E-type viscometer (1° 34' x R24 cone rotor) at a temperature of 25° C. and a rotation speed of 10 rpm. Then, when the viscosity before light irradiation is V0 and the viscosity after light irradiation is Vν, the viscosity change rate was determined according to the formula: Vν/V0. The viscosity change rate is preferably 10 or less, more preferably 9 or less, most preferably 8 or less, even more preferably 6 or less, and even more preferably 5 or less, in terms of good slow curing properties.

[Light curing conditions]
When evaluating the cured physical properties and adhesive properties of the sealant, the sealant was cured under the following light irradiation conditions. After photo-curing the sealant using a UV curing device equipped with an electrodeless discharge metal halide lamp (manufactured by Fusion) at a cumulative light intensity of 4,000 mJ/ ^cm2 at a wavelength of 365 nm, the sealant was cured in an oven at 80°C. A post-heat treatment was performed for 30 minutes to obtain a cured product.

[Moisture permeability]
A sheet-like cured product with a thickness of 0.1 mm was produced under the above photocuring conditions, and calcium chloride (anhydrous) was used as a moisture absorbent according to JIS Z0208 "Moisture permeability test method for moisture-proof packaging materials (cup method)". The measurement was carried out under conditions of an ambient temperature of 60° C. and a relative humidity of 90%. The moisture permeability is preferably 120 g/(m ² ·24 hr) or less.

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

[Outgas amount]
A sealant is applied onto a glass substrate at a coating amount of 10 mg/cm ² per unit area, and the substrate is exposed to an ultraviolet irradiation device (manufactured by HOYA, ultra-high pressure mercury lamp irradiation device “UL-750”). Ultraviolet light with a wavelength of 365 nm and a power of 100 mW/cm ² was irradiated for 10 seconds. Thereafter, it was heated at 80° C. for 60 minutes, the generated gas components were 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]
[Preparation of organic EL element substrate]
The glass substrate with an ITO electrode was cleaned using acetone and isopropanol, respectively. Thereafter, the following compounds were sequentially deposited to form a thin film using a vacuum evaporation method to obtain an organic EL element substrate consisting of an 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 1000 Å
・Electron injection layer: Lithium fluoride, thickness: 1 nm
・Cathode aluminum, anode film thickness 250nm

[Production of organic EL device]
The sealants obtained in Examples and Comparative Examples were applied to glass using a coating device under a nitrogen atmosphere, bonded to an organic EL element substrate, and the sealant was cured under the photocuring conditions described above with an adhesive thickness of 10 μm. The adhesive was cured to produce an organic EL device. The cathode side of the organic EL element substrate was bonded to glass via a sealant.

[Organic EL evaluation]
〔initial〕
A voltage of 6 V was applied for 10 seconds to the organic EL element immediately after fabrication, and the light emitting state of the organic EL element was observed visually and with a microscope, and the diameter of the dark spot was measured.

[High temperature and high humidity]
After exposing the organic EL element immediately after fabrication for 1000 hours under conditions of a temperature of 85°C and a relative humidity of 85% by mass, a voltage of 6V was applied for 10 seconds, and the luminescence state of the organic EL element was observed visually and with a microscope. The diameter of the dark spot was then measured.

The diameter of the dark spot is preferably 300 μm or less, more preferably 150 μm or less, most preferably 100 μm or less, even more preferably 50 μm or less, and even more preferably no dark spot.

[Storage stability evaluation]
After measuring the initial viscosity of the sealant (V0, viscosity immediately after preparation of the sealant), after 4 weeks in an accelerated test in a high temperature environment of approximately 40°C with the container covered (closed system). The viscosity (V4) of the sealant was measured. Then, the viscosity change rate was determined according to the formula: V4/V0. The viscosity change rate is preferably 1.5 or less in terms of good storage stability.

The composition of this embodiment does not easily generate outgas when irradiated with light, so it has good durability and does not deteriorate the device. From this result, it was confirmed that the composition of this embodiment is suitable as a sealant for organic electroluminescent elements.

Claims (13)

(A) a cationic polymerizable compound, (B) a cationic photopolymerization initiator, and (C1) a phosphoric acid ester ;
The cationic polymerizable compound (A) contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group,
The aromatic compound having an epoxy group (A-2) contains (A-2-1) a bisphenol A type epoxy resin and (A-2-2) a bisphenol F type epoxy resin,
The ratio A 1 /A 2 (mass ratio) between the content A ₁ of the bisphenol A type epoxy resin (A-2-1) and the content A ₂ of the bisphenol F type epoxy resin (A- _2-2 ) _is , 0.2-5. The phosphoric acid ester (C1) is selected from the group consisting of a compound represented by formula (C1-1), a compound represented by formula (C1-2), and a compound represented by formula (C1-3). The composition according to claim 1 , comprising at least one of:
[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 composition according to claim 1 or 2 , wherein the amount of the phosphoric acid ester (C1) used is 0.1 to 5 parts by mass based on 100 parts by mass of the cationically polymerizable compound (A). The composition according to any one of claims 1 to 3 , wherein the photocationic polymerization initiator (B) is an onium salt. Any one of claims 1 to 4 , wherein the content of the cationic photopolymerization initiator (B) is 0.05 to 5.0 parts by mass based on 100 parts by mass of the cationically polymerizable compound (A). The composition described in . The composition according to any one of claims 1 to 5 , further comprising a photosensitizer. The composition according to any one of claims 1 to 6 , further comprising a silane coupling agent. A sealing agent for an organic electroluminescent device, comprising the composition according to any one of claims 1 to 7 . A cured product of the composition according to any one of claims 1 to 7 . A sealing material for an organic electroluminescent element, comprising the cured product according to claim 9 . an organic electroluminescent element,
The sealing material for an organic electroluminescent device according to claim 10 ,
An organic electroluminescent display device, including: an adhesion step of adhering the composition according to any one of claims 1 to 7 to a first member;
an irradiation step of irradiating the adhered composition with light;
a bonding step of bonding the first member and the second member via the light-irradiated composition;
A method for manufacturing an organic electroluminescent display device, comprising: the first member is a substrate,
The method for manufacturing an organic electroluminescent display device according to claim 12 , wherein the second member is an organic electroluminescent element.