TWI874385B - Sealant for organic electroluminescent display element - Google Patents

Abstract

The present invention is a composition, which contains a cationic polymerizable compound having a cationic ring-opening polymerizable group, a vinyl ether compound having a vinyloxy group, and a photo-cationic polymerization initiator, and the content of the vinyl ether compound is greater than 50 parts by mass and less than 95 parts by mass relative to 100 parts by mass of the total of the cationic polymerizable compound and the vinyl ether compound.

Description

Sealant for organic electroluminescent display elements

The present invention relates to a composition.

In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescent (organic EL) display elements has continued to advance.

If the luminescent layer, electrode, etc. of an organic EL display element are exposed to the outside atmosphere, its luminescent properties will deteriorate. Therefore, sealing technology for blocking the outside atmosphere is indispensable. As one of the sealing technologies, photocurable sealants are known (for example, patent documents 1~5).

Prior art literature Patent Literature

Patent document 1: Japanese Patent Publication No. 2001-357973

Patent document 2: Japanese Patent No. 5919574

Patent document 3: Japanese Patent No. 4800247

Patent document 4: Japanese Patent Publication No. 2016-058273

Patent document 5: Japanese Patent No. 4384509

However, when applying a light-curing sealant to a component, if the viscosity of the sealant is low, the workability is improved. Therefore, in order to improve the workability, a method of adjusting the viscosity by adding an organic solvent to the sealant has been adopted, but there is a problem that the residual organic solvent will increase the occurrence of outgassing.

Therefore, the purpose of the present invention is to provide a composition with low viscosity and excellent reliability after curing. In addition, the purpose of the present invention is to provide a sealant for an organic EL display element containing the above composition, a cured body of the sealant for an organic EL display element, a sealant containing the cured body, an organic EL display device containing the sealant, and a method for manufacturing the organic EL display device.

One aspect of the present invention is related to a composition, which contains a cationic polymerizable compound having a cationic ring-opening polymerizable group, a vinyl ether compound having a vinyloxy group, and a photo-cationic polymerization initiator, and the content of the above-mentioned vinyl ether compound is greater than 50 parts by mass and less than 95 parts by mass relative to 100 parts by mass of the total of the above-mentioned cationic polymerizable compound and the above-mentioned vinyl ether compound.

The above composition is a combination of a vinyl ether compound having a vinyloxy group and a cationic polymerizable compound, and the content of the vinyl ether compound is above a certain amount. With this specific composition, the above composition can take into account both low viscosity and excellent moisture resistance and transparency after curing. Therefore, the sealant for organic electroluminescent display containing the above composition is easy to be evenly applied to the component and has excellent workability. In addition, since the moisture resistance and transparency of the above composition after curing are excellent, by using the above composition as a sealant for organic electroluminescent display, an organic electroluminescent display device with excellent reliability can be realized.

In one embodiment, the viscosity of the vinyl ether compound at 25°C may be lower than the viscosity of the cationic polymerizable compound at 25°C.

In one embodiment, the cationic ring-opening polymerizable group can be selected from the group consisting of epoxy groups and cyclohexane groups.

In one embodiment, the content of the photo-cationic polymerization initiator can be 0.1 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the total of the cationic polymerizable compound and the vinyl ether compound.

The composition of one aspect may further contain a hardening delay agent.

In one embodiment, the viscosity can be 2~200cps when measured using an E-type viscometer at 25°C and 10rpm.

In one embodiment, the vinyl ether compound may have two vinyloxy groups and further have a cyclic group.

Another aspect of the present invention relates to a sealant for an organic electroluminescent display element, which contains the above-mentioned composition.

Another aspect of the present invention is related to a hardened body, which is a hardened body of the sealant for the above-mentioned organic electroluminescent display element.

In one embodiment, the total light transmittance at a wavelength of 380-800nm per 10μm thickness can be over 80%.

Another aspect of the present invention is a sealing material for an organic electroluminescent display element, which comprises the above-mentioned hardened body.

Another aspect of the present invention is related to an organic electroluminescent display device, which includes an organic electroluminescent display element and a sealing material for the organic electroluminescent display element.

Another aspect of the present invention is a method for manufacturing an organic electroluminescent display device, which includes the following steps: a step of attaching the organic electroluminescent display element sealant to a first component, a step of irradiating the attached organic electroluminescent display element sealant with light, and a step of bonding the first component to the second component through the organic electroluminescent display element sealant irradiated with light.

According to the present invention, a composition with low viscosity and excellent reliability after curing is provided. In addition, according to the present invention, a sealant for an organic EL display element containing the above-mentioned composition, a cured body of the sealant for an organic EL display element, a sealant containing the cured body, an organic EL display device containing the sealant, and a method for manufacturing the organic EL display device are provided.

Below, one implementation method of the present invention is described in detail.

The composition of this embodiment can be used as a resin composition. The resin composition of this embodiment contains a cationically polymerizable compound (component (A)), a vinyl ether compound (component (B)), and a photocatalytic polymerization initiator (component (C)).

In this embodiment, the cationically polymerizable compound (component (A)) has a cationically ring-opening polymerizable group.

In this embodiment, the vinyl ether compound (component (B)) has a vinyloxy group. In addition, the content of the vinyl ether compound is greater than 50 parts by mass and less than 95 parts by mass relative to 100 parts by mass of the total of the cationically polymerizable compound and the vinyl ether compound.

The resin composition of this embodiment is a combination of a vinyl ether compound having a vinyloxy group and a cationic polymerizable compound, and the content of the vinyl ether compound is above a certain amount. With this specific composition, the resin composition can take into account both low viscosity and excellent moisture resistance and transparency after curing. Therefore, the sealant for an organic electroluminescent (EL) display element (hereinafter also referred to as a sealant) containing the resin composition of this embodiment can form a sealant with excellent reliability, and can realize an organic EL display device with excellent reliability.

((A) Component: Cationic polymerizable compound)

Component (A) is a compound having cationic ring-opening polymerizability, which can also be referred to as a compound having a cationic ring-opening polymerizable group. Examples of the cationic ring-opening polymerizable group include cyclic ether groups (e.g., epoxy groups (ethylene oxide ring)), cyclohexane groups (cyclohexane ring), etc. From the perspective of adhesion and moisture resistance, it is preferably at least one selected from the group consisting of epoxy groups and cyclohexane groups.

Component (A) may be a compound having one cationic ring-opening polymerizable group, or may be a compound having two or more cationic ring-opening polymerizable groups. Component (A) preferably has two or more cationic ring-opening polymerizable groups, and more preferably has two cationic ring-opening polymerizable groups.

As the compound having an epoxy group, from the viewpoint of adhesion and moisture resistance, it is preferably at least one selected from the group consisting of a compound having an epoxy group and an alicyclic group (hereinafter, sometimes referred to as an alicyclic epoxy compound) and a compound having an epoxy group and an aromatic group (hereinafter, sometimes referred to as an aromatic epoxy compound).

<Component (A1): Alicyclic compound with epoxy group>

The component (A1) may be a compound having one epoxy group or a compound having two or more epoxy groups. The component (A1) preferably has two or more epoxy groups, and more preferably has two epoxy groups. The component (A1) may be a compound without an aromatic ring. The component (A1) may be used alone or in combination of two or more.

The component (A1) may be, for example, a compound obtained by epoxidizing a compound having a cycloolefin ring or a derivative thereof. Examples of the cycloolefin ring include cyclohexene ring, cyclopentene ring, and pinene ring. Epoxidation may be performed using an oxidizing agent, for example. Examples of the oxidizing agent include hydrogen peroxide and peracid. Examples of such a component (A1) include: 3',4'-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate, (meth)acrylate 3,4-epoxyepoxyhexylalkyl ester (e.g. (meth)acrylate 3,4-epoxyepoxyhexylmethyl ester, etc.), (3,3',4,4'-bicyclooxy)cyclohexane, etc.

The component (A1) may be, for example, a compound obtained by hydrogenating a compound having an epoxy group and an aromatic ring, or a derivative thereof. Examples of compounds having an epoxy group and an aromatic ring include bisphenol A type epoxy resins and bisphenol F type epoxy resins. Examples of such a component (A1) include hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins.

As component (A1), a compound having a 1,2-epoxycyclohexane structure is preferred. As a compound having a 1,2-epoxycyclohexane structure, for example, a compound represented by formula (A1-1) can be cited.

In formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms).

When X is a single bond, the compound represented by formula (A1-1) is (3,3',4,4'-bicyclooxy)cyclohexane.

X is preferably a linking group. The linking group may be, for example, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group formed by linking multiple of these groups. As a linking group, a group having an ester bond is preferred, and a group formed by linking an ester bond and a divalent hydrocarbon group is more preferred.

As a divalent alkyl group, an alkanediyl group is preferred, and an alkanediyl group having 1 to 3 carbon atoms is more preferred.

As the compound represented by formula (A1-1), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is particularly preferred.

The molecular weight of the component (A1) is preferably 450 or less, more preferably 400 or less, more preferably less than 300, and more preferably 280 or less from the viewpoint of the storage stability of the resin composition and the moisture resistance of the cured product. The molecular weight of the component (A1) may be, for example, 100 or more.

When component (A1) has a molecular weight distribution, it is preferred that the number average molecular weight of component (A1) is within the above range. Furthermore, in this specification, the number average molecular weight represents the polystyrene-converted value measured by gel permeation chromatography (GPC) under the following measurement conditions.

‧Solvent (mobile phase): THF (tetrahydrofuran)

‧Degassing device: ERC-3310 manufactured by ERMA

‧Pump: PU-980 manufactured by Nippon Spectroscopy Corporation

‧Flow rate: 1.0ml/min

‧Automatic sampler: AS-8020 manufactured by Tosoh Corporation

‧Column oven: L-5030 manufactured by Hitachi Ltd.

‧Set temperature: 40℃

‧Column structure: 2 pieces of TSK guardcolumnMP (×L) 6.0mmID×4.0cm manufactured by Tosoh Corporation, and 2 pieces of TSK-GELMULTIPORE HXL-M 7.8mmID×30.0cm manufactured by Tosoh Corporation, a total of 4 pieces

‧Detector: RI (Refractive Index) L-3350 manufactured by Hitachi Ltd.

‧Data processing: SIC480 data station

<(A2) Component: Aromatic compound with epoxy group>

The aromatic epoxy compound may be a compound having one epoxy group or a compound having two or more epoxy groups. The aromatic epoxy compound preferably has two or more epoxy groups, and more preferably has two epoxy groups. The aromatic epoxy compound may be a compound without an alicyclic group. The aromatic epoxy compound may be used alone or in combination of two or more.

As component (A2), for example, there can be listed: 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, and modified products thereof.

As component (A2), it is preferred to use a compound having a bisphenol structure (e.g., bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.), and it is more preferred to use at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

As the component (A2), for example, the compound represented by formula (A2-1) can be listed.

In 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 an alkyl group having 1 to 5 carbon atoms which may have a substituent. When there are plural R ²³ and R ²⁴ , they may be the same or different from each other.

As substituents that an alkyl group may have, for example, fluorine atoms, alkoxy groups, etc. can be listed, among which fluorine atoms are preferred.

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

From the perspective of moisture resistance of the cured product, the molecular weight of the component (A2) is preferably 100 or more, more preferably 150 or more, and further preferably 200 or more. Furthermore, from the perspective of moisture resistance of the cured product, the molecular weight of the component (A2) is preferably 5000 or less, more preferably 1000 or less, and most preferably 450 or less.

When component (A2) has a molecular weight distribution, it is preferred that the number average molecular weight of component (A2) is within the above range. In addition, in this specification, the number average molecular weight represents the value converted to polystyrene measured by gel permeation chromatography (GPC) under the above measurement conditions.

As a compound having an oxacyclobutane group, for example, the following component (A3) can be listed.

<Component (A3): Compounds with cyclobutane groups>

The component (A3) may be a compound having one cyclobutane oxadiazole group or a compound having two or more cyclobutane oxadiazole groups. The component (A3) may be used alone or in combination of two or more.

Examples of the component (A3) include 3-ethyl-3-hydroxymethylcyclohexylbutane (manufactured by Toagosei Co., Ltd., trade name OXT-101, etc.), 1,4-bis[(3-ethyl-3-cyclohexylbutyl)methoxymethyl]benzene (manufactured by Toagosei Co., Ltd., trade name OXT-121, etc.), 3-ethyl-3-(phenoxymethyl)cyclohexylbutane (manufactured by Toagosei Co., Ltd., trade name OXT-211, etc.), di(1-ethyl-(3-cyclohexylbutyl))methyl ether (manufactured by Toagosei Co., Ltd., trade name OXT-221, etc.), and 3-ethyl-3-(2-ethylhexyloxymethyl)cyclohexylbutane (manufactured by Toagosei Co., Ltd., trade name OXT-212, etc.).

Component (A) may be a compound other than component (A1), component (A2) and component (A3). As such a compound, for example, the following component (A4) can be cited.

<(A4) Ingredients>

The component (A4) can be any compound having a cationic ring-opening polymerizable group, for example, a compound having a cyclic ether group. The component (A4) can be a compound having one cationic ring-opening polymerizable group, preferably having two or more cationic ring-opening polymerizable groups. The component (A4) can be a compound without an alicyclic group, an aromatic ring, or an oxycyclobutane group. The component (A4) can be used alone or in combination of two or more.

Among the components (A4), compounds having a cyclic ether group include compounds having an epoxy group (ethylene oxide ring). As the component (A4), a compound having a glycidyloxy group is preferred. The compound having a glycidyloxy group is preferably a compound having two or more glycidyloxy groups.

Examples of compounds having a glycidyloxy group include: diglycidyl ether of alkylene glycol, diglycidyl ether of polyalkylene glycol, diglycidyl ether or triglycidyl ether of glycerol or its alkylene oxide adduct, etc. Examples of alkylene glycol include ethylene glycol, propylene glycol, 1,6-hexanediol, etc. Examples of polyalkylene glycol include polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or its alkylene oxide adduct, etc. Examples of alkylene oxide include ethylene oxide, propylene oxide, etc.

The content of component (A) in the total of 100 parts by mass of components (A) and (B) may be, for example, 5 parts by mass or more. From the perspective of further improving the durability after curing, it is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. In addition, the content of component (A) in the total of 100 parts by mass of components (A) and (B) may be, for example, 49.9 parts by mass or less. From the perspective of further improving the durability after curing, it is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

((B) Vinyl ether compounds)

Component (B) is a compound having an ethyleneoxy group. Component (B) can be used alone or in combination of two or more.

The compound having a vinyloxy group is preferably a compound having a vinyl ether group in which an oxygen atom of a vinyloxy group (CH ₂ =CH-O-) is bonded to a carbon atom. Examples of such compounds include divinyl ether or trivinyl ether compounds such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and trihydroxymethylpropane trivinyl ether; and monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, and hydroxynonyl monovinyl ether.

The component (B) preferably has two vinyloxy groups and further has a cyclic group. Examples of such component (B) include cyclohexanedimethanol divinyl ether and 2,2-adamantanedimethanol divinyl ether.

From the viewpoint of lowering the viscosity, the content of component (B) is preferably greater than 50 parts by mass, more preferably 51 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more, relative to 100 parts by mass of the total of components (A) and (B). Furthermore, from the viewpoint of easily obtaining a hardened body with excellent durability, the content of component (B) is preferably less than 95 parts by mass, more preferably less than 85 parts by mass, and further preferably less than 75 parts by mass, relative to 100 parts by mass of the total of components (A) and (B).

The viscosity (initial viscosity) of component (B) at 25°C is not particularly limited, but from the perspective of lowering the viscosity, it is preferably lower than the viscosity of component (A) at 25°C.

((C) Photocatalytic polymerization initiator)

The component (C) can be activated by light to induce cationic polymerization of the component (A). The component (C) can be used alone or in combination of two or more.

系起始劑、其他鹵化物等酸產生劑等。 Examples of the component (C) include aryl iron salt derivatives (e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by Dow Chemical Company, Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170 and Adeka Optomer SP-172 manufactured by Asahi Electric Corporation, CPI-100P, CPI-101A, CPI-200K, CPI-210S and LW-S1 manufactured by San-Apro, Chivacure-1190 manufactured by Double Bond, etc.), aryl iodonium salt derivatives (e.g., Irgacure 250 and Rhodia Japan Co., Ltd., RP-2074, etc.), aromatic hydrocarbon-ion complex derivatives, diazonium salt derivatives, triazine

Initiators, other halides and other acid generators, etc.

As component (C), an onium salt compound is preferred from the viewpoint of more significantly achieving the above-mentioned effect.

As the onium salt compound of component (C), for example, the onium salt compound represented by formula (C-1) can be listed.

In formula (C-1), A represents an element of group VIA to group VIIA with an atomic valence of m, where m represents 1 or 2. p represents an integer of 0 to 3. R represents an organic group bonded to A. ^X- represents a counter ion of the onium, and its number is (p+1) per molecule. D represents a divalent group represented by the following formula (C-1-1). When there are multiple Rs, they may be the same or different from each other. When there are multiple X ^-s, they may be the same or different from each other. When there are multiple A's, they may be the same or different from each other. When there are multiple D's, they may be the same or different from each other.

In formula (C-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' represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a represents an integer of 0 to 5. a+1 E's and a G's may be the same or different from each other.

R is an organic group bonded to A, representing an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 4 to 30 carbon atoms, an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, or an alkynyl group with 2 to 30 carbon atoms, which may be substituted by one or more selected from the group consisting of alkyl, hydroxyl, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic group, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkoxylene, amino, cyano, nitro, and halogen.

The number of R is (m+p(m-1)+1), and the presence of multiple Rs may be the same or different. In addition, two or more Rs may be directly bonded or bonded via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing the element A. Here, R' represents an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

基、稠四苯基、苯并蒽基、蒽喹啉基、茀基、萘醌基、蒽醌基等縮合多環芳基等。 Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl; naphthyl, anthracenyl, phenanthrenyl, pyrenyl,

condensed polycyclic aromatic groups such as phenyl, fused tetraphenyl, benzanthryl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone.

唑基、噻唑基、吡啶基、嘧啶基、吡

基、吲哚基、苯并呋喃基、苯并噻吩基、喹啉基、異喹啉基、喹

啉基、喹唑啉基、咔唑基、吖啶基、啡噻

基、啡

基、

基、噻嗯基、啡

基、啡

噻基、

基、異

基、二苯并噻吩基、

酮基、9-氧硫

基、二苯并呋喃基等碳數4~20之雜環基；苯氧基、萘氧基等碳數6~10之芳氧基；甲基亞磺醯基、乙基亞磺醯基、丙基亞磺醯基、異丙基亞磺醯基、丁基亞磺醯基、異丁基亞磺醯基、第二丁基亞磺醯基、第三丁基亞磺醯基、戊基亞磺醯基、異戊基亞磺醯基、新戊基亞磺醯基、第三戊基亞磺醯基、辛基亞磺醯基等碳數1~18之直鏈或支鏈之烷基亞磺醯基；苯基亞磺醯基、甲苯基亞磺醯基、萘基亞磺醯基等碳數6~10之芳基亞磺醯基； 甲基磺醯基、乙基磺醯基、丙基磺醯基、異丙基磺醯基、丁基磺醯基、異丁基磺醯基、第二丁基磺醯基、第三丁基磺醯基、戊基磺醯基、異戊基磺醯基、新戊基磺醯基、第三戊基磺醯基、辛基磺醯基等碳數1~18之直鏈或支鏈之烷基磺醯基；苯基磺醯基、甲苯基磺醯基(甲苯磺醯基)、萘基磺醯基等碳數6~10之芳基磺醯基；下述式(C-1-2)所表示之伸烷氧基；未經取代之胺基、及經碳數1~5之烷基及/或碳數6~10之芳基單取代或二取代之胺基；氰基；硝基；氟、氯、溴、碘等鹵基等。 The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms may have one or more substituents. Examples of the substituents include: straight-chain alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; branched-chain alkyl groups having 1 to 18 carbon atoms, such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, and isohexyl; cycloalkyl groups having 3 to 18 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxyl groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, Straight or branched alkoxy groups with 1 to 18 carbon atoms, such as tert-butoxy, hexyloxy, decyloxy, and dodecyloxy; straight or branched alkylcarbonyl groups with 2 to 18 carbon atoms, such as acetyl, propionyl, butyryl, 2-methylpropionyl, heptyl, 2-methylbutyryl, 3-methylbutyryl, octyl, decyl, dodecyl, and octadecyl; arylcarbonyl groups with 7 to 11 carbon atoms, such as benzyl and naphthyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and isobutoxycarbonyl , 2-butoxycarbonyl, 3-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl and other linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms; phenyloxycarbonyl, naphthyloxycarbonyl and other aryloxycarbonyl groups having 7 to 11 carbon atoms; phenylthiocarbonyl, naphthyloxythiocarbonyl and other arylthiocarbonyl groups having 7 to 11 carbon atoms; acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, 2-butylcarbonyloxy, 3-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyl oxy, octadecylcarbonyloxy and other linear or branched acyloxy groups having 2 to 19 carbon atoms; 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) phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-phenylthiophenylthio, 4-phenylthiophenylthio, 4-phenylthio-2-chlorophenylthio, 4-phenylthio-3-chlorophenylthio, 4-phenylthio-3-methylthiophenylthio, 4-phenylthio-2-methylthiophenylthio, 4-(4-methylthiophenylthio)phenylthio, 4-(2-methylthiophenylthio)phenylthio, 4-(p-methylphenylthio)phenylthio, 4-(p-ethylphenylthio)phenylthio 4-(p-isopropylbenzyl)phenylthio, 4-(p-tert-butylbenzyl)phenylthio and the like arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, t-butylthio, pentylthio, isopentylthio, neopentylthio, t-pentylthio, octylthio, decylthio, dodecylthio and the like linear or branched alkylthio groups having 1 to 18 carbon atoms; phenyl, tolyl, dimethylphenyl, naphthyl and the like arylthio groups having 6 to 10 carbon atoms; thienyl, furanyl, pyranyl, pyrrolyl,

Azolyl, thiazolyl, pyridinyl, pyrimidinyl, pyridinyl

yl, indolyl, benzofuranyl, benzothiophenyl, quinolyl, isoquinolyl, quinolyl

Quinoline, quinazoline, carbazolyl, acridinium, phenanthridine

Base, coffee

base,

Thiamine, thiazolidine, phenanthracene

Base, coffee

Thiol,

Base, foreign

1-Benzothiophene,

Keto, 9-oxosulfur

a heterocyclic group having 4 to 20 carbon atoms, such as benzofuranyl and dibenzofuranyl; an aryloxy group having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; a linear or branched alkylsulfinyl group having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, t-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, t-pentylsulfinyl, octylsulfinyl; an arylsulfinyl group having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl; Straight-chain or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, t-pentylsulfonyl, octylsulfonyl, etc.; phenylsulfonyl , tolylsulfonyl (toluenesulfonyl), naphthylsulfonyl and other arylsulfonyl groups having 6 to 10 carbon atoms; an alkoxy group represented by the following formula (C-1-2); an unsubstituted amino group, and an amino group mono- or di-substituted by an alkyl group having 1 to 5 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; a cyano group; a nitro group; a halogen group such as fluorine, chlorine, bromine, iodine, etc.

In formula (C-1-2), Q represents a hydrogen atom or a methyl group, and k represents an integer from 1 to 5. The k Qs may be the same or different from each other.

As the onium ion (A ⁺ ) in formula (C-1), cobalt ion, iodine ion, and selenium ion are preferred. Representative examples thereof are disclosed below.

、2-[(二苯基)鋶基]9-氧硫

、4-[4-(4-第三丁基苯甲醯基)苯硫基]苯基二對甲苯基鋶、4-[4-(4-第三丁基苯甲醯基)苯硫基]苯基二苯基鋶、4-[4-(苯甲醯基苯硫基)]苯基二對甲苯基鋶、4-[4-(苯甲醯基苯硫基)]苯基二苯基鋶、5-(4-甲氧基苯基)噻蒽鎓、5-苯基噻蒽鎓、5-甲苯基噻蒽鎓、5-(4-乙氧基苯基)噻蒽鎓、5-(2,4,6-三甲基苯基)噻蒽鎓等三芳基鋶；二苯基苯甲醯甲基鋶、二苯基4-硝基苯甲醯甲基鋶、二苯基苄基鋶、二苯基甲基鋶等二芳基鋶；苯基甲基苄基鋶、4-羥基苯基甲基苄基鋶、4-甲氧基苯基甲基苄基鋶、4-乙醯羰氧基苯基甲基苄基鋶、2-萘基甲基苄基鋶、2-萘基甲基(1-乙氧基羰基)乙基鋶、苯基甲基苯甲醯甲基鋶、4-羥基苯基甲基苯甲醯甲基鋶、4-甲氧基苯基甲基苯甲醯甲基鋶、4-乙醯羰氧基苯基甲基苯甲醯甲基鋶、2-萘基甲基苯甲醯甲基鋶、2-萘基十八烷基苯甲醯甲基鋶、9-蒽基甲基苯甲醯甲基鋶等單芳基鋶； 二甲基苯甲醯甲基鋶、苯甲醯甲基四氫噻吩鎓、二甲基苄基鋶、苄基四氫噻吩鎓、十八烷基甲基苯甲醯甲基鋶等三烷基鋶等。 Examples of the coronium ion include triphenylcoronium, tri-p-tolylcoronium, tri-o-tolylcoronium, tri(4-methoxyphenyl)coronium, 1-naphthyldiphenylcoronium, 2-naphthyldiphenylcoronium, tri(4-fluorophenyl)coronium, tri-1-naphthylcoronium, tri-2-naphthylcoronium, tri(4-hydroxyphenyl)coronium, 4-(phenylthio)phenyldiphenylcoronium, 4-(p-tolylthio)phenyldi-p-tolyl Copper sulfide, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)copper sulfide, 4-(phenylthio)phenylbis(4-fluorophenyl)copper sulfide, 4-(phenylthio)phenylbis(4-methoxyphenyl)copper sulfide, 4-(phenylthio)phenyldi-p-tolylcopper sulfide, bis[4-(diphenylcoppersulfide)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]coppersulfide}phenyl]sulfide ether, bis{4-[bis(4-fluorophenyl)copperyl]phenyl}sulfide, bis{4-[bis(4-methylphenyl)copperyl]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)copperyl]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)copperyl, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylcopperyl, 4-(4- Benzylphenylthio)phenylbis(4-fluorophenyl)copper bis(4-fluorophenyl)copper bis(4-benzoylphenylthio)phenyldiphenylcopper ...

, 2-[(diphenyl)copperyl]9-oxosulfide

, 4-[4-(4-tert-butylbenzyl)phenylthio]phenyl di-p-tolylcopperium, 4-[4-(4-tert-butylbenzyl)phenylthio]phenyl diphenylcopperium, 4-[4-(benzoylphenylthio)]phenyl di-p-tolylcopperium, 4-[4-(benzoylphenylthio)]phenyl diphenylcopperium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, 5-tolylthianthrenium, 5-(4-ethoxyphenyl)thianthrenium, 5-(2,4,6-trimethylphenyl)thianthrenium; diphenylbenzylmethylcopperium, diphenyl 4-nitrobenzylmethylcopperium, diphenyl Diaryl coroniums such as phenylbenzyl coronium and diphenylmethyl coronium; monoaryl coroniums such as phenylmethylbenzyl coronium, 4-hydroxyphenylmethylbenzyl coronium, 4-methoxyphenylmethylbenzyl coronium, 4-acetylcarbonyloxyphenylmethylbenzyl coronium, 2-naphthylmethylbenzyl coronium, 2-naphthylmethyl (1-ethoxycarbonyl)ethyl coronium, phenylmethylbenzylmethyl coronium, 4-hydroxyphenylmethylbenzylmethyl coronium, 4-methoxyphenylmethylbenzylmethyl coronium, 4-acetylcarbonyloxyphenylmethylbenzylmethyl coronium, 2-naphthylmethylbenzylmethyl coronium, 2-naphthyloctadecylbenzylmethyl coronium, and 9-anthrylmethylbenzylmethyl coronium; trialkylcosterniums such as dimethylbenzylcosternium, benzylmethyltetrahydrothiophenium, dimethylbenzylcosternium, benzyltetrahydrothiophenium, and octadecylmethylbenzylcosternium.

、2-[(二苯基)鋶基]9-氧硫

、4-[4-(4-第三丁基苯甲醯基)苯硫基]苯基二對甲苯基鋶、4-[4-(苯甲醯基苯硫基)]苯基二苯基鋶、5-(4-甲氧基苯基)噻蒽鎓、5-苯基噻蒽鎓、二苯基苯甲醯甲基鋶、4-羥基苯基甲基苄基鋶、2-萘基甲基(1-乙氧基羰基)乙基鋶、4-羥基苯基甲基苯甲醯甲基鋶及十八烷基甲基苯甲醯甲基鋶所組成之群中之1種以上。 Among them, preferably selected from triphenylcathionium, tri-p-tolylcathionium, 4-(phenylthio)phenyldiphenylcathionium, bis[4-(diphenylcathionyl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]cathionyl}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)cathionyl]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio) )phenylbis(4-fluorophenyl)copper hydride, 4-(4-benzoylphenylthio)phenyldiphenylcopper hydride, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylcopper hydride, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylcopper hydride, 2-[(di-p-tolyl)copper hydride]9-oxothia-

, 2-[(diphenyl)copperyl]9-oxosulfide

, 4-[4-(4-tert-butylbenzyl)phenylthio]phenyldi-p-tolylcopperium, 4-[4-(benzoylphenylthio)]phenyldiphenylcopperium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, diphenylbenzylmethylcopperium, 4-hydroxyphenylmethylbenzylcopperium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylcopperium, 4-hydroxyphenylmethylbenzylmethylcopperium and octadecylmethylbenzylmethylcopperium.

In formula (C-1), ^X- is a counter ion. The number of counter ions is (p+1) per molecule. The counter ions are not particularly limited, ^and examples thereof include: halogen ions such as F- ^, _Cl- ^, Br- ^, and ^{I- ; OH-} ; _ClO4- ; sulfonate ions such as _FSO3- ^{, ClSO3-} , _CH3SO3- ^{, C6H5SO3-} _, and _{CF3SO3- ;} sulfate ions such as _{HSO4- and SO42-} ; carbonate ions ^{such as} _HCO3- ^and _CO32- ; phosphate ions such ^as _H2PO4- ^, _HPO42- , _and ^PO43- ; fluorophosphate ions such ^as _PF6- ^, _PF5OH- ^, _and fluorinated alkylfluorophosphate ions; _BF4- ^, B _{( C6F5 ) 4-} ^, and B( _C6 H ₄ CF ₃ ) ₄ ^- and other borate ions; AlCl ₄ ^- ; BiF ₆ ^- , SBF ₆ ^- , SBF ₅ OH ^- and other fluoroantimonate ions; AsF ₆ ^- , AsF ₅ OH ^- and other fluoroarsenate ions, etc.

Examples of fluorinated alkyl fluorophosphate ions include fluorinated alkyl fluorophosphate ions represented by formula (C-1-3) and the like.

[Chemical 6] [(R ^f ) _b PF _6-b ] ^- (C-1-3)

In formula (C-1-3), ^Rf represents a fluorinated alkyl group. b represents the number of ^Rf , which is an integer from 1 to 5. The b ^Rfs may be the same as or different from each other.

b is preferably 2~4, more preferably 2~3.

^Rf fluorinated alkyl means a group in which a part or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms. The number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 4. Examples of the alkyl group include: straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched chain alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Specific examples of the fluorinated alkyl group 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 -, and (CF ₃ ) ₃ C -.

Specific examples of preferred fluorinated alkyl fluorophosphate ions 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 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 ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- etc.

In this embodiment, as component (C), tris(pentafluoroethyl)diphenyl 4-thiophenoxyphenylcopperium trifluorophosphate represented by formula (C-2) and triarylcopperium hexafluoroantiphonate represented by formula (C-3) can be used preferably. Among them, triarylcopperium hexafluoroantiphonate represented by formula (C-3) is more preferred.

[Chemistry 7]

In order to facilitate mixing with other components such as component (A), component (C) may be used that has been dissolved in a solvent in advance. The solvent is not particularly limited, and examples thereof include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

From the perspective of the photocurability of the resin composition, the content of component (C) is preferably 0.1 parts by mass or more, and more preferably 0.15 parts by mass or more, relative to 100 parts by mass of the total of components (A) and (B). In addition, from the perspective of the adhesion durability of the cured product, the content of component (C) is preferably 5.0 parts by mass or less, and more preferably 1.0 parts by mass or less, relative to 100 parts by mass of the total of components (A) and (B).

The resin composition may further contain other components besides component (A), component (B) and component (C).

As other components, for example, a hardening retarder (component (X)) can be cited. The so-called hardening retarder refers to a compound that suppresses the increase in viscosity after light irradiation and prolongs the applicable time by temporarily capturing active species related to the reaction.

((X) ingredient: hardening retarder)

The curing retarder is preferably a curing retarder selected from the group consisting of a phosphate-based curing retarder (component (D)) and an ether-based curing retarder (component (E)). The curing retarder may be used alone or in combination of two or more.

<(D) Component: Phosphoric acid-based hardening retarder>

The phosphoric acid-based hardening retarder is a hardening retarder selected from the group consisting of phosphate ester (component (D1)) and phosphite ester (component (D2)). Component (D) can be used alone or in combination of two or more.

Examples of the component (D1) include diethyl benzyl phosphate, trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, tri(butoxyethyl) phosphate, tri(2-ethylhexyl) phosphate, (RO) ₃ P=O (R is octyl, lauryl, cetyl, stearyl or oleyl), tri(2-chloroethyl) phosphate, tri(2-dichloropropyl) phosphate, triphenyl phosphate, butyl pyrophosphate, tricresyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl diphosphate, monobutyl phosphate, dibutyl phosphate, di(2-ethylhexyl) phosphate, monoisodecyl phosphate, ethyl ammonium acid phosphate, and 2-ethylhexyl acid phosphate. The component (D1) may be used alone or in combination of two or more.

From the viewpoint of appropriate reactivity to cations and reduced outgassing, component (D1) preferably contains at least one selected from the group consisting of compounds represented by formula (D1-1), compounds represented by formula (D1-2), and compounds represented by formula (D1-3), and more preferably contains a compound represented by formula (D1-2).

[Chemistry 10]

In formula (D1-1), formula (D1-2) and formula (D1-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a alkyl group which may have a substituent.

R ² , R ³ and R ⁴ in formula (D1-2) and R ⁵ and R ⁶ in formula (D1-3) are preferably the same group in each formula.

Examples of the substituent that the alkyl group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may have include an alkoxy group, etc. The alkyl group in ^{R 1} , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an unsubstituted alkyl group.

The alkyl group in R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group, and still more preferably an alkyl group. The number of carbon atoms in the alkyl group may be, for example, 1 to 18, preferably 4 to 13.

The compound represented by formula (D1-1) may be, for example, a monoalkyl phosphate (i.e., a compound in which ^R1 is an alkyl group), and specific examples thereof include monoethyl phosphate, mono-n-butyl phosphate, mono(butoxyethyl) phosphate, and mono(2-ethylhexyl) phosphate.

The compound represented by formula (D1-2) is preferably a trialkyl phosphate (i.e., a compound in which R ² , R ³ and R ⁴ are alkyl groups). In this case, the carbon number 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 trialkyl phosphates include triethyl phosphate, tri-n-butyl phosphate, tri(butoxyethyl) phosphate, tri(2-ethylhexyl) phosphate, (RO) ₃ P=O (R is lauryl, cetyl, stearyl or oleyl), and the like.

Examples of the compound represented by formula (D1-3) include dialkyl phosphates (i.e., compounds in which R ⁵ and R ⁶ are alkyl groups). Specific examples of dialkyl phosphates include dibutyl phosphate and bis(2-ethylhexyl) phosphate.

(D2) component is a phosphite. Examples of the (D2) component include trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tri(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tri(tridecyl) phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tri(nonylphenyl) phosphite, tri(2,4-di-tert-butylphenyl) phosphite, phenyl diisooctyl 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 diphenyl phosphite, trilauryl trithiophosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, di(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono(tridecyl) phosphite, and the like. Component (D2) can be used alone or in combination of two or more.

From the viewpoint of appropriate reactivity to cations, component (D2) preferably contains at least one selected from the group consisting of compounds represented by formula (D2-1), compounds represented by formula (D2-2), compounds represented by formula (D2-3), compounds represented by formula (D2-4), compounds represented by formula (D2-5), and compounds represented by formula (D2-6).

In formula (D2-1) to formula (D2-6), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a alkyl group which may have a substituent.

Examples of the substituent that the alkyl group in ^R7 , R8, ^R9 , ^R10 , ^R11 , ^R12 , ^R13 , ^R14 , ^R15 , ^R16 and ^R17 may have include an alkoxy group and the ^like . The alkyl group in R7, ^R8 , ^R9 , ^R10 , ^R11 , ^R12 , ^R13 , ^R14 , ^{R15 , R16 and R17} is preferably an unsubstituted alkyl group.

The alkyl 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, more preferably an alkyl group or a phenyl group, and further 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 (D2-2), R ¹⁰ , R ¹¹ and R ¹² in formula (D2-3), R ¹³ and R ¹⁴ in formula (D2-4), and R ¹⁵ and R ¹⁶ in formula (D2-5) are preferably the same in each formula.

Examples of the compound represented by formula (D2-1) include monoalkyl phosphites (i.e., compounds in which R ⁷ is an alkyl group) and the like.

Examples of the compound represented by formula (D2-2) include dialkyl phosphites (ie, compounds in which R ⁸ and R ⁹ are alkyl groups).

Examples of the compound represented by formula (D2-3) include trialkyl phosphites (i.e., compounds in which R ¹⁰ , R ¹¹ , and R ¹² are alkyl groups). Specific examples of the compound represented by formula (D2-3) include triethyl phosphite, tri(2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, tri(tridecyl) phosphite, and trioleyl phosphite.

Examples of the compound represented by formula (C2-4) include bis(alkyl)pentaerythritol diphosphite (i.e., a compound in which ^R13 and ^R14 are alkyl groups). Specific examples of the compound represented by formula (D2-4) include bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, and distearylpentaerythritol diphosphite.

Examples of the compound represented by formula (D2-5) include dialkyl hydrogen phosphites (i.e., compounds in which R ¹⁵ and R ¹⁶ are alkyl groups). Specific examples of the compound represented by formula (D2-5) 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 (D2-6) include monoalkyl hydrogen phosphite (i.e., a compound in which R ¹⁷ is an alkyl group). Specific examples of the compound represented by formula (D2-6) include monoethyl hydrogen phosphite, mono(2-ethylhexyl) hydrogen phosphite, monolauryl hydrogen phosphite, and monooleyl hydrogen phosphite.

As the component (D2), it is preferred to contain a phosphite selected from trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tri(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tritridecyl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, tri(nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, di(tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, At least one selected from the group consisting of dimethyl hydrogen phosphate, dibutyl hydrogen phosphite, di(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, and dioleyl hydrogen phosphite, more preferably at least one selected from the group consisting of trimethyl phosphite, triethyl phosphite, tri-n-butyl phosphite, tri(2-ethylhexyl) phosphite, triisooctyl phosphite, tridecyl phosphite, triisodecyl phosphite, tritridecyl phosphite, trioleyl phosphite, tristearyl phosphite, triphenyl phosphite, and tri(nonylphenyl) phosphite.

When the resin composition contains component (D), the content of component (D) is preferably 0.01 parts by mass or more, and more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of obtaining a longer application time. In addition, the content of component (D) is preferably 2 parts by mass or less, and more preferably 1 part by mass or less, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of moisture resistance and bonding strength of the cured product.

When the resin composition contains component (D), the content of component (D) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of component (C), from the viewpoint of obtaining a longer application time. In addition, the content of component (D) is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less, relative to 100 parts by mass of component (C), from the viewpoint of photocurability.

<(E) Component: Ether-based curing retarder>

Component (E) is a hardening retarder having an ether bond. Component (E) can be used alone or in combination of two or more.

Component (E) may be a chain ether or a cyclic ether. Examples of chain ethers include polyoxyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol. Examples of cyclic ethers include crown ethers, etc.

From the viewpoint of appropriate reactivity to cationic ions, the component (E) is preferably a cyclic ether, and more preferably a crown ether.

When the resin composition contains component (E), the content of component (E) is preferably 0.1 parts by mass or more, and more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of obtaining a longer application time. In addition, the content of component (E) is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the total of components (A) and (B), from the viewpoint of moisture resistance and bonding strength of the cured product.

When the resin composition contains component (E), the content of component (E) is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of component (C), from the viewpoint of obtaining a longer application time. In addition, the content of component (E) is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less, relative to 100 parts by mass of component (C), from the viewpoint of photocurability.

The resin composition may further contain other components other than component (A), component (B), component (C) and component (X).

As other components, for example, photosensitizers can be cited. The so-called photosensitizer refers to a compound that absorbs energy rays and efficiently generates cations from photo-cationic polymerization initiators.

衍生物、苯基酮衍生物、萘衍生物、蒽衍生物、菲衍生物、稠四苯衍生物、

衍生物、苝衍生物、稠五苯衍生物、吖啶衍生物、苯并噻唑衍生物、苯偶姻衍生物、茀衍生物、萘醌衍生物、蒽醌衍生物、

衍生物、

酮衍生物、硫

衍生物、9-氧硫

衍生物、香豆素衍生物、酮基香豆素衍生物、花青衍生物、吖

衍生物、噻

衍生物、

衍生物、吲哚啉衍生物、薁衍生物、三烯丙基甲烷衍生物、酞菁衍生物、螺吡喃衍生物、螺

衍生物、硫代螺吡喃衍生物、有機釕錯合物等。該等中，較佳為選自由9,10-二丁氧基蒽等蒽衍生物、2-羥基-2-甲基-1-苯基-丙烷-1-酮等苯基酮衍生物所組成之群中之至少一種，更佳為9,10-二丁氧基蒽等蒽衍生物。光敏劑可單獨使用1種或組合2種以上使用。 There is no particular limitation on the photosensitizer, but examples thereof include benzophenone derivatives, phenanthridine

derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetraphenylene derivatives,

derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives,

derivative,

Ketone derivatives, sulfur

Derivatives, 9-oxosulfur

Derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, acridine

Derivatives, Thiamine

derivative,

derivatives, indoline derivatives, azulene derivatives, triallyl methane derivatives, phthalocyanine derivatives, spiropyran derivatives, spiropyran derivatives

Derivatives, thiospiropyran derivatives, organic ruthenium complexes, etc. Among them, at least one selected from the group consisting of anthracene derivatives such as 9,10-dibutoxyanthracene and phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one is preferred, and anthracene derivatives such as 9,10-dibutoxyanthracene are more preferred. The photosensitizer can be used alone or in combination of two or more.

When the resin composition contains a photosensitizer, the content of the photosensitizer is preferably 0.01 parts by mass or more, and more preferably 0.02 parts by mass or more, relative to 100 parts by mass of the total of the components (A) and (B). In addition, the content of the photosensitizer is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (B). By setting it within this range, better curability and storage stability can be obtained.

As other components, silane coupling agents can be cited. By including silane coupling agents, the adhesion and adhesion durability of the resin composition tend to be improved.

The silane coupling agent is not particularly limited, and examples thereof include: γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tri(β-methoxyethoxy)silane, γ-(methyl)acryloyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- Glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl triethoxysilane, γ-butyl propyl trimethoxysilane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-ureidopropyl triethoxysilane, etc. Among them, at least one selected from the group consisting of β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidyloxypropyl trimethoxysilane, γ-glycidyloxypropyl triethoxysilane and γ-(meth)acryloxypropyl trimethoxysilane is preferred. Silane coupling agents can be used alone or in combination of two or more.

When the resin composition contains a silane coupling agent, the content of the silane coupling agent is preferably 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the total of the components (A) and (B). The content of the silane coupling agent is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the total of the components (A) and (B). By setting the content within this range, higher adhesion and adhesion durability can be obtained.

In this embodiment, the method for producing the resin composition is not particularly limited, for example, the above-mentioned components can be mixed. The mixing method is not particularly limited as long as it is a method that can fully mix the above-mentioned components. Examples of the mixing method include: a stirring method using the stirring force accompanying the rotation of the screw, a method using a common disperser such as a planetary stirrer based on rotation and revolution, etc. Such mixing methods are preferred in terms of low cost and the ability to mix stably.

The resin composition of this embodiment can be used, for example, to contribute to the sealing of an organic EL display element. For example, the resin composition can be used to form a coating material that covers an organic EL display element, and can also be used as an adhesive for bonding components that constitute an organic EL display device.

The viscosity of the resin composition of this embodiment increases moderately after light irradiation, and then hardens as the polymerization reaction of the cationic polymerizable compound proceeds. The resin composition after light irradiation can also be quickly hardened by heating.

There is no particular limitation on the light source for irradiating the resin composition, and examples thereof include: halogen lamps, metal halogen lamps, high-power metal halogen lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, light-emitting diodes (hereinafter referred to as LEDs), etc. Such light sources are preferred in that they can efficiently irradiate energy lines corresponding to the reaction wavelength of the photo-ion polymerization initiator.

The radiation wavelength and energy distribution of the above light sources are different. Therefore, the above light sources can be appropriately selected according to the reaction wavelength of the photo-ion polymerization initiator. In addition, natural light (sunlight) can also be used as the reaction initiation light source of the resin composition.

As the irradiation method, direct irradiation, condensed irradiation using a reflector, etc., condensed irradiation using fibers, etc. can be performed. Irradiation using a low-wavelength cutoff filter, a heat-ray cutoff filter, a cold mirror, etc. can also be performed.

The light irradiation dose is not particularly limited and can be appropriately adjusted according to the thickness of the resin composition coating film, etc. The light irradiation dose can be, for example, 50 to 20,000 mJ/cm ² , preferably 100 to 10,000 mJ/cm ² .

When heating after light irradiation (also called post-heating) is performed, the heating temperature is preferably below 150°C, and more preferably below 80°C, from the perspective of avoiding damage to the organic EL display element. When post-heating is performed, the heating temperature is preferably above 50°C.

The viscosity of the resin composition of this embodiment measured using an E-type viscometer at 25°C and 10rpm is preferably 2cps or more, and more preferably 5cps or more, from the perspective of preventing unintentional dripping from a dispenser, inkjet device, or other device used for spraying. In addition, the above viscosity is preferably 200cps or less, more preferably 50cps or less, and further preferably 30cps or less from the perspective of ease of coating and spraying. If the viscosity is 30cps or less, it is easier to spray using an inkjet device at 25°C.

The viscosity of the resin composition of this embodiment is preferably 1.2 times or more and less than 10 times the viscosity before the light irradiation 20 minutes after the light irradiation. For example, the viscosity of the resin composition applied in a coating amount of ¹⁰ mg/ ^cm2 per unit area after irradiation with ultraviolet light for 10 seconds using a high-pressure mercury lamp at an irradiation amount of 100 mW/cm2 is preferably 1.2 times or more and less than 10 times the viscosity before the ultraviolet irradiation 20 minutes after the ultraviolet irradiation.

The resin composition of this embodiment is preferably irradiated with light and aged in a high temperature environment for 10 minutes, and the viscosity is preferably 3 times or more compared to the viscosity before the aging. For example, when the aging is carried out in an environment of 80°C, the viscosity after 10 minutes of aging is preferably 3 times or more compared to the viscosity before the aging.

The resin composition of this embodiment can fully extend the applicable time after light irradiation. In addition, since the viscosity of the resin composition of this embodiment increases moderately after light irradiation, it becomes easy to bond the components and the workability is excellent. Furthermore, the resin composition of this embodiment has excellent moisture resistance and adhesion after curing. Therefore, the resin composition of this embodiment can form a sealing material with excellent sealing properties, and can also manufacture an organic electroluminescent display device with excellent reliability.

In this embodiment, the sealant may contain a resin composition.

The moisture permeability of the cured body of the sealant of this embodiment at a thickness of 0.1m is preferably 250g/(m ² .24hr) or less, and more preferably 200g/(m ² .24hr) or less. In this specification, the moisture permeability of the cured body refers to the value measured in accordance with JIS Z0208 "Test method for moisture permeability of moisture-proof packaging materials (cup method)" using calcium chloride (anhydrous) as a moisture absorbent at an ambient temperature of 60°C and a relative humidity of 90%.

The hardened sealant of this embodiment preferably has excellent transparency. Specifically, the total light transmittance of the hardened sealant at a wavelength of 380-800nm per 10μm thickness is preferably 60% or more, more preferably 80% or more, and further preferably 95% or more.

The method of using the sealant of this embodiment is not particularly limited. For example, the sealant can be applied to an object (such as a component constituting an organic EL display device) and the sealant can be cured on the object to form a sealant containing a cured body.

Furthermore, the sealant can be hardened into a predetermined shape (e.g., a film, a sheet, etc.) to form a sealant having a predetermined shape. In this case, for example, when assembling an organic EL display device, the organic EL display element can be sealed by placing the sealant on the organic EL display element.

In this embodiment, the sealing material may be composed of a hardened body of a sealant, or may include a hardened body of a sealant and other constituent materials. Other constituent materials include, for example: inorganic layers such as silicon nitride film, silicon oxide film, silicon oxynitride; inorganic fillers such as silicon dioxide, mica, kaolin, talc, aluminum oxide, etc.

By using the sealant of this embodiment, an organic EL display device including an organic EL display element and a sealant can be easily manufactured.

The manufacturing method of the organic EL display device may include, for example, the following steps: an attaching step of attaching the sealant to the first component, an irradiation step of irradiating the attached sealant with light, and a bonding step of bonding the first component to the second component via the sealant irradiated with light. By this manufacturing method, the joint surface of the first component and the second component constituting the organic EL display device can be sealed with a sealant.

In the attachment step, the sealant disposed on the first component is viscous by light irradiation. In the bonding step, the first component and the second component are bonded before the sealant irradiated with light is hardened, so that the first component and the second component are connected by the sealant. The sealant between the first component and the second component is hardened by post-heating as needed to form a sealant.

In the above manufacturing method, the steps after the irradiation step can also be performed by shielding the light. In this way, the second component can be connected to the first component without being exposed to light.

There is no particular limitation on the method of attaching the sealant, and it may be, for example, an inkjet method or a method using a dispenser.

The first component and the second component are not particularly limited as long as they are components constituting an organic EL display device.

In one embodiment, the first component may be an organic EL display element, and the second component may be a substrate.

Furthermore, in another embodiment, the first component may be a substrate, and the second component may be an organic EL display element.

The type of substrate is not particularly limited, and examples thereof include: glass substrate, silicon substrate, plastic substrate, etc. Among them, glass substrate and plastic substrate are preferred, and glass substrate is more preferred.

The above describes the preferred implementation of the present invention, but the present invention is not limited to the above implementation.

[Implementation example]

The present invention is described in more detail below by way of examples, but the present invention is not limited to the examples. Unless otherwise specified, the process is carried out at 25°C.

(Examples 1 to 13 and Comparative Examples 1 to 3)

<Preparation of sealant>

The components shown in Table 1 were mixed in the composition ratio (mass parts) recorded in Table 1 to prepare the sealant of the embodiment. The viscosity of the sealant and the sprayability in the inkjet device were evaluated according to the evaluation method shown below. In addition, the sealant was cured under the light curing conditions shown below to form a hardened body, and the moisture permeability, yellowness, transmittance and organic EL evaluation of the hardened body were measured according to the evaluation method shown below.

[Table 1]

The components shown in Table 1 have the following meanings.

((A) Component: Cationic polymerizable compound)

(a-1) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" manufactured by Cellulose Chemical Co., Ltd., viscosity: 200cps)

(a-2) Hydrogenated bisphenol A epoxy resin ("YX8000" manufactured by Mitsubishi Chemical Corporation, viscosity: 18,500cps)

(a-3) 3,4-Epoxycyclohexylmethyl methacrylate ("Cyclomer M100" manufactured by Celluloid Corporation, viscosity: 100cps)

(a-4) Di(1-ethyl-(3-oxacyclobutyl)) methyl ether ("ARONOXETANE OXT-221" manufactured by Toa Gosei Co., Ltd., viscosity: 9~14cps)

((B) component: vinyl ether compound)

(b-1) Cyclohexanedimethanol divinyl ether ("CHDVE" manufactured by Nippon Carbide, viscosity: 4.5cps)

(b-2) 1,4-Butanediol divinyl ether ("BDVE" manufactured by Nippon Carbide, viscosity: 1.2cps)

(b-3) Triethylene glycol divinyl ether (TEGDVE manufactured by Nippon Carbide, viscosity: 3.4cps)

(b-4) Cyclohexyl vinyl ether ("CHVE" manufactured by Nippon Carbide, viscosity: 1.3cps)

(b-5) 4-Hydroxyvinyl bromide ether ("HBVE" manufactured by Nippon Carbide, viscosity: 5.2cps)

((C) Component: Photocatalytic polymerization initiator)

(c-1) Diphenyl[4-(phenylthio)phenyl]copperium hexafluoroantimonate ("CPI-110A" manufactured by San-Apro)

((X) ingredient: hardening retarder)

(x-1) Trioctyl phosphate (manufactured by Daihachi Chemical Co., Ltd.)

(x-2) 18-crown ether-6 ("crown ether O-18" manufactured by Japan Soda Co., Ltd.)

[Viscosity measurement method]

The viscosity was measured using an E-type viscometer (conical rotor: 1°34'×R24, "DV3T" manufactured by BROOKFIELD) at a temperature of 25°C and a rotation speed of 10 rpm.

[Jetability in inkjet device]

The obtained composition was sprayed onto a 70mm×70mm×0.7mmt substrate (alkaline-free glass (Eagle XG manufactured by Corning)) using an inkjet spraying device (MID500B manufactured by Musashi Engineering, solvent-based spray head "MID spray head"). The sprayability was evaluated according to the following criteria.

A: The nozzle is not blocked and can spray.

B: The nozzle is clogged and cannot spray.

[Hardening conditions]

The sealant was photocured using a UV (Ultraviolet) curing device (manufactured by Fusion) equipped with an electrodeless discharge metal halogen lamp at a wavelength of 365nm and a cumulative light dose of 1,000mJ/ ^cm2 . Then, it was heated in an oven at 80°C for 30 minutes to produce a cured product.

[Moisture permeability]

Under the above curing conditions, a sheet-shaped cured product with a thickness of 0.1 mm was prepared. According to JIS Z0208 "Test method for moisture permeability of moisture-proof packaging materials (cup method)", calcium chloride (anhydrous) was used as a moisture absorbent, and the moisture permeability of the cured product was measured under the conditions of an ambient temperature of 60°C and a relative humidity of 90%. In addition, the moisture permeability is preferably less than 250g/(m ² .24hr).

[Transmittance and yellowness]

Two borosilicate glass test pieces (25 mm in length × 25 mm in width × 2.0 mm in thickness, TEMPAX (registered trademark) glass) were used to cure the resin composition under the above-mentioned light curing conditions with a bonding thickness of 10 μm. After curing, the test pieces bonded with an adhesive containing the resin composition were used to measure the total light transmittance of light with a wavelength of 300 to 800 nm using an ultraviolet-visible spectrophotometer (UV2550 manufactured by Shimadzu Corporation) and the yellowness (b value) in accordance with JIS K 7373:2006 Plastics - Yellowness and Yellowing Degree Determination Method.

[Production of organic EL display element substrate]

Use acetone and isopropyl alcohol to clean the glass substrate with ITO (Indium Tin Oxides) electrode. Then, use vacuum evaporation to sequentially evaporate the following compounds into thin films to obtain an organic EL element substrate including anode/hole injection layer/hole transport layer/luminescent layer/electron injection layer/cathode. The composition of each layer is as follows.

‧Anode ITO, anode film thickness 250nm

‧Hole injection layer: copper phthalocyanine, thickness 30nm

‧The hole transport layer N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD) has a thickness of 20nm

‧Luminescent layer: tris(8-hydroxyquinolyl)aluminum (metal complex material), film thickness of luminescent layer 1000Å

‧Electron injection layer: lithium fluoride, thickness 1nm

‧Anode aluminum, anode film thickness 250nm

[Production of organic EL display components]

The resin composition obtained in the embodiment and the comparative example was applied on glass using a coating device in a nitrogen atmosphere, and the resin composition was irradiated with ultraviolet light of 365 nm wavelength and 100 mW/ ^cm2 for 10 seconds using an ultraviolet irradiation device (ultra-high pressure mercury lamp irradiation device manufactured by HOYA Corporation, "UL-750"). After 20 minutes, it was bonded to an organic EL display element substrate with a bonding thickness of 10 μm, and cured for 30 minutes in an environment of 80°C to cure the adhesive containing the resin composition to produce an organic EL display element. The cathode side of the organic EL element substrate was bonded to the glass via a sealant. The obtained organic EL display element was evaluated for organic EL according to the evaluation method shown below.

[Evaluation of organic EL: Evaluation of initial luminescence state]

Apply 6V voltage to the newly manufactured organic EL display element for 10 seconds, observe the luminescence state of the organic EL display element visually and under a microscope, and measure the diameter of the dark spot.

[Evaluation of organic EL: Evaluation of luminescence status after high temperature and high humidity test]

After exposing the newly manufactured organic EL display element to 60°C and 90% relative humidity for 1000 hours, a voltage of 6V was applied for 10 seconds. The luminescence state of the organic EL display element was observed visually and under a microscope, and the diameter of the dark spot was measured. The diameter of the dark spot is preferably less than 300μm, more preferably less than 50μm, and preferably no dark spot.

The above evaluation results are shown in Table 1. It shows that the sealant of the embodiment has low viscosity and excellent reliability after curing. In addition, it is shown that when the content of component (A) is less than 50 parts by mass in the total of 100 parts by mass of components (A) and (B), the viscosity of the sealant becomes high and the coating and spraying properties decrease (Comparison Examples 1 and 2). Furthermore, it is shown that when component (C) is not used, the sealant does not cure (Comparison Example 3).

The resin composition of this embodiment can be used, for example, to prepare a sealant for an organic electroluminescent (EL) display element containing the resin composition, a sealant for an organic EL display element containing a hardened body of the sealant, and an organic EL display device containing the sealant.

Claims (9)

A sealant for an organic electroluminescent display element, comprising: a cationic polymerizable compound having a 1,2-epoxycyclohexane structure, a vinyl ether compound having a vinyloxy group, a photo-cationic polymerization initiator, and one or more curing retardants selected from the group consisting of a phosphate curing retarder and an ether curing retarder, wherein the content of the vinyl ether compound is greater than 50 parts by mass and less than 95 parts by mass relative to 100 parts by mass of the total of the cationic polymerizable compound and the vinyl ether compound, and the content of the photo-cationic polymerization initiator is greater than 0.1 parts by mass and less than 1.0 parts by mass relative to 100 parts by mass of the total of the cationic polymerizable compound and the vinyl ether compound. As in claim 1, the sealant for an organic electroluminescent display element, wherein the viscosity of the vinyl ether compound at 25°C is lower than the viscosity of the cationic polymerizable compound at 25°C. For example, the viscosity of the sealant for organic electroluminescent display elements in claim 1 or 2 is 2~200cps when measured using an E-type viscometer at 25°C and 10rpm. As in claim 1 or 2, the sealant for an organic electroluminescent display element, wherein the vinyl ether compound has two vinyloxy groups and further has a cyclic group. A hardened body, which is a hardened body of a sealant for an organic electroluminescent display element as claimed in any one of claims 1 to 4. For example, the hardened body of claim 5 has a total light transmittance of more than 80% at a wavelength of 380-800nm per 10μm thickness. A sealing material for an organic electroluminescent display element, comprising a hardened body as claimed in claim 5 or 6. An organic electroluminescent display device, comprising: an organic electroluminescent display element, and a sealing material for the organic electroluminescent display element as claimed in claim 7. A method for manufacturing an organic electroluminescent display device, comprising the following steps: a step of attaching an organic electroluminescent display element sealant as in any one of claims 1 to 4 to a first component, a step of irradiating the attached organic electroluminescent display element sealant with light, and a step of bonding the first component to the second component via the organic electroluminescent display element sealant irradiated with light.