JP7385722B2 - Encapsulant, cured product, organic electroluminescent display device, and method for manufacturing the device - Google Patents

Description

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

In recent years, organic optical devices using organic thin film elements such as organic electroluminescent (organic EL) display elements (hereinafter also referred to as organic electroluminescent elements, organic EL display elements or organic EL elements) and organic thin film solar cell elements have been developed. Research is underway. Organic thin film elements can be easily manufactured by vacuum evaporation, solution coating, etc., and therefore have excellent productivity.

An organic EL 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, whereby the electrons and holes combine within the organic light emitting material layer to cause self-luminescence. Compared to liquid crystal display elements that require a backlight, they have the advantage of having better visibility, being able to be made thinner, and being able to be driven at a low DC voltage.

However, such an organic EL 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 EL display elements, sealing technology that shields the organic light emitting material layer and electrodes from moisture and oxygen in the atmosphere has become essential for organic EL display elements. There is.

For example, Patent Document 1 discloses a method of filling a photocurable sealant between organic EL display element substrates and irradiating light for sealing in a top-emitting type organic EL display element or the like. . Additionally, Patent Documents 2 to 4 disclose techniques for sealing organic EL display elements to prevent deterioration due to moisture.

On the other hand, Patent Document 5 describes a resin containing (A) an epoxy compound, (B) an epoxy resin, and (C) a photocationic polymerization initiator, and having a water content of 1000 ppm or less and a chlorine content of 1000 ppm or less. Compositions are disclosed. However, Patent Document 5 does not describe how to lower the water vapor permeability by adjusting the specific gravity of the polymerizable monomer.

Patent Document 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a cationic photopolymerization initiator, and a plate-like particulate inorganic filler with a specific shape. However, such a resin composition has a problem in that its transparency is impaired due to the influence of the particulate inorganic filler, making it difficult to apply it to applications that require transparency, such as top-emitting organic EL display elements. Further, Patent Document 6 does not include any description regarding the specific gravity of the polymerizable monomer.

Patent Document 7 contains a polyfunctional cationic polymerizable compound, an organically modified layered silicate, and a curing agent, and the organically modified layered silicate is dispersed in the polyfunctional cationic polymerizable compound, and the organically modified layered silicate is dispersed in the polyfunctional cationic polymerizable compound. For sealing an organic electroluminescent display element with excellent transparency and barrier properties, characterized in that the content of the layered silicate is 20 to 250 parts by weight based on 100 parts by weight of the polyfunctional cationic polymerizable compound. A curable resin composition is disclosed. However, such a resin composition has a problem in that its transparency is impaired due to the influence of the organically modified layered silicate, making it difficult to apply it to applications that require transparency, such as top-emitting organic EL display elements. . Further, Patent Document 7 does not include any description regarding the specific gravity of the polymerizable monomer.

Patent Document 8 describes a transparent compound containing (a) an epoxy compound and (b) a compound having two or more crosslinkable groups reactive with the epoxy compound in a specific ratio, and having a refractive index of 1.6 or more. Furthermore, an epoxy resin composition having low moisture permeability is disclosed. However, such resin compositions have a problem of low transmittance, making it difficult to apply them to applications requiring high transparency, such as lowering the visibility of organic electroluminescent display devices. Further, Patent Document 8 does not include any description regarding the specific gravity of the polymerizable monomer.

Patent Document 9 describes a curable composition containing an organic polymer (A) having a specific reactive silicon group and a polyoxyalkylene polymer (B) having a specific reactive silicon group, which A curable composition is disclosed in which the specific gravity of the curable composition is 0.9 or more and 1.3 or less. However, Patent Document 9 does not describe how to lower the water vapor permeability by adjusting the specific gravity of the polymerizable monomer.

Patent Document 10 discloses a copolymer obtained by photopolymerizing a composition containing 10 to 70% by weight of brominated bisphenol A type epoxy (meth)acrylate having a specific structure, and having a refractive index of 1.58 or more. , a photocurable resin lens having a specific gravity of 1.5 or less and an Abbe number of 30 or more is disclosed. However, Patent Document 10 does not describe how to lower water vapor permeability by adjusting the specific gravity of a polymerizable monomer, nor does it describe anything about sealing an organic EL display element.

U.S. Pat. No. 5,002,201 discloses certain polysiloxane copolymers that are photopolymerized and have functional acrylic groups and have a specific gravity greater than about 1.0 and are suitable for restoring the refractive power of natural crystalline lenses. A polysiloxane copolymer having a refractive index is disclosed. However, Patent Document 11 does not describe how to lower moisture permeability by adjusting the specific gravity of a polymerizable monomer, nor does it describe anything about sealing an organic EL display element.

Patent Document 12 describes an active energy ray-curable compound (A) having one or more ethylenically unsaturated double bonds in one molecule, a photoradical polymerization initiator (C), and/or a photocationic polymerization initiator. An active energy ray-curable resin composition for balancing rotors of motors, which is composed of (D) and has a specific gravity of 1.4 (25°C) or more and a viscosity of 1,000 poise (25°C) or less. Disclosed. However, Patent Document 12 does not describe how to lower moisture permeability by adjusting the specific gravity of a polymerizable monomer, nor does it describe how to seal an organic EL display element.

Japanese Patent Application Publication No. 2001-357973 Japanese Patent Application Publication No. 10-74583 Japanese Patent Application Publication No. 2001-307873 JP2009-37812A International Publication No. 2014/017524 Japanese Patent Application Publication No. 2006-291072 International Publication No. 2015/129783 Japanese Patent Application Publication No. 2010-163566 Japanese Patent Application Publication No. 2010-163566 Japanese Patent Application Publication No. 2001-124903 Special Publication No. 2002-527171 Japanese Patent Application Publication No. 08-109231

In recent years, the required characteristics of electronic devices have increased, and for example, there is a demand for a sealant that can realize higher reliability and durability for organic EL display elements.

However, with the techniques disclosed in Patent Documents 1 to 4, sufficient reliability and durability of the organic EL display element may not be achieved in some cases.

Furthermore, the resin compositions described in Patent Documents 6 and 7 have problems with transparency, making it difficult to apply them to organic EL display elements (particularly top-emitting type organic EL display elements).

Furthermore, the resin composition described in Patent Document 8 has a problem with transparency, making it difficult to apply it to organic EL display elements (particularly top-emitting type organic EL display elements).

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition that is excellent in low moisture permeability and transparency and is suitable as a sealant for organic EL display elements.

That is, the present invention is as follows.
<1> A sealing product containing a polymerizable monomer and a polymerization initiator, having a specific gravity of 1.3 or more in a 23°C atmosphere, and a cured product having a specific gravity of 1.3 to 3.0 in a 23°C atmosphere. Deterrent.
<2> The sealant according to <1>, wherein the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere at 60°C.
<3> The sealant according to <1> or <2>, wherein the cured product has a glass transition temperature of 60° C. or higher.
<4> The sealant according to any one of <1> to <3>, wherein the cured product has a crosslinking density of 1.0×10 ⁻³ mol/cm ³ or more.
<5> The sealant according to any one of <1> to <4>, wherein the polymerizable monomer contains a polymerizable monomer (X) having an element with an atomic number of 9 or more.
<6> The sealant according to <5>, wherein the polymerizable monomer (X) contains a halogen group element.
<7> The sealant according to <5> or <6>, wherein the polymerizable monomer (X) contains at least one selected from the group consisting of elemental fluorine and elemental bromine.
<8> The sealant according to <7>, wherein the content of the halogen group element contained in the polymerizable monomer (X) is 10 to 50% by mass based on the total element amount of the polymerizable monomer.
<9> The sealant according to any one of <1> to <8>, wherein the polymerizable monomer contains a crosslinkable monomer (Y) having two or more polymerizable functional groups.
<10> The sealant according to any one of <1> to <9>, wherein the polymerization initiator is a photopolymerization initiator.
<11> The sealant according to any one of <1> to <10>, wherein the polymerizable monomer contains a monomer having an aromatic ring.
<12> The sealant according to any one of <1> to <11>, wherein the polymerizable monomer has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group.
<13> The sealant according to <12>, wherein the polymerizable monomer contains at least one selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, vinyl ether compounds, and oxetane compounds.
<14> The sealant according to <13>, wherein the polymerization initiator contains an onium salt.
<15> The sealant according to <12>, wherein the polymerizable monomer contains at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide.
<16> The sealant according to <15>, wherein the polymerization initiator contains a photoradical polymerization initiator.
<17> The content of the polymerizable monomer (X) having an atomic number of 9 or more in 100 parts by mass of the polymerizable monomer is 40 to 90 parts by mass, according to any one of <1> to <16>. Sealant.
<18> Any one of <1> to <17>, wherein the content of the crosslinkable monomer (Y) having two or more polymerizable functional groups is 5 to 60 parts by mass in 100 parts by mass of the polymerizable monomer. Encapsulant as described.
<19> The sealant according to any one of <1> to <18>, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass based on 100 parts by mass of the polymerizable monomer.
<20> The cured product has a moisture permeability of 40 g/m ² or less at a thickness of 100 μm, measured at a temperature of 60° C. and a relative humidity of 90%, in accordance with JIS Z0208. <1> to <19 > The sealant according to any one of the above.
<21> The sealant according to any one of <1> to <20>, wherein the cured product has a light transmittance of 95% or more in the ultraviolet-visible light region of 360 nm or more and 800 nm or less per 10 μm thickness.
<22> The sealant according to any one of <1> to <21>, which is a sealant for an organic electroluminescent device.
<23> A method for manufacturing a device including a first member and a second member, an adhesion step of adhering the sealant according to any one of <1> to <22> to the first member. an irradiation step of irradiating the attached sealant with light; and a bonding step of bonding the first member and the second member together via the light-irradiated sealant. manufacturing method.
<24> The method for manufacturing a device according to <23>, wherein the first member is an organic electroluminescent element, the second member is a substrate, and the device is an organic electroluminescent display device.
<25> The method for manufacturing a device according to <23>, wherein the first member is a substrate, the second member is an organic electroluminescent element, and the device is an organic electroluminescent display device.
<26> A cured product of the sealant according to any one of <1> to <22>.
<27> An organic electroluminescent display device comprising an organic electroluminescent element and the cured product according to <26>.
<28> An organic electroluminescent display device comprising a laminate in which an inorganic film and an organic film are laminated, the organic film comprising the cured product according to <26>.
<29> An organic electroluminescent display device including a laminate in which an inorganic film and an organic film are laminated, wherein the organic film directly laminated on the organic electroluminescent element contains the cured product according to <26>.
<30> A composition containing a polymerizable monomer (X) having at least one selected from the group consisting of fluorine element and bromine element, and a polymerization initiator.

According to the present invention, a composition suitable as an encapsulant for organic EL display elements, which is excellent in low moisture permeability and transparency, is provided.

Hereinafter, preferred embodiments of the present invention will be described in detail. In this specification, the content of each component is, in principle, in units of mass unless otherwise specified.

The composition according to this embodiment contains a polymerizable monomer and a polymerization initiator. The composition according to this embodiment can be suitably used as a sealant, and can be particularly suitably used as a sealant for organic electroluminescent elements.

It is preferable that the specific gravity of the composition according to this embodiment in a 23° C. atmosphere is 1.3 or more. Further, the composition according to the present embodiment is preferably a composition in which the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere at 23°C.

The composition according to this embodiment is preferably a composition in which the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere at 60°C.

The polymerizable monomer of the composition according to this embodiment is a compound having a polymerizable functional group.

The polymerizable monomer preferably has at least one selected from the group consisting of cationically polymerizable functional groups and radically polymerizable functional groups. The polymerizable monomer having a cationically polymerizable functional group is preferably at least one selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, vinyl ether compounds, and oxetane compounds. The polymerizable monomer having a radically polymerizable functional group is preferably at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide, and (meth)acrylate is more preferred.

The polymerizable monomer of the composition according to the present embodiment preferably contains a polymerizable monomer (X) having an element with an atomic number of 9 or more and a crosslinkable monomer (Y) having two or more polymerizable functional groups. .

It is preferable that the polymerizable monomer (X) has an aromatic ring.

The polymerizable monomer (X) preferably has at least one halogen group element, and more preferably at least one selected from the group consisting of fluorine element and bromine element.

The number of halogen group elements contained in the polymerizable monomer (X) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. The upper limit of the number of halogen group elements contained in the polymerizable monomer (X) is not particularly limited, but is preferably 40 or less, more preferably 30 or less.

Examples of the compound having a cationic polymerizable functional group, which is one of the specific examples of the polymerizable monomer (X), include halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether, brominated cresyl glycidyl ether, and bromine. Examples include brominated bisphenol A type epoxy resin (for example, diglycidyl ether of tetrabromobisphenol A, etc.), brominated bisphenol F type novolac type epoxy resin, brominated phenol novolac type epoxy resin, and the like.

Examples of the compound having a radically polymerizable functional group, which is one of the specific examples of the polymerizable monomer (X), include fluorophenyl (meth)acrylate, trifluorophenyl (meth)acrylate, pentafluorophenyl (meth)acrylate, and chlorophenyl. Halophenyl (meth)acrylates such as (meth)acrylate, trichlorophenyl (meth)acrylate, pentachlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, pentabromorophenyl (meth)acrylate, etc. can be mentioned.

The content of the halogen group element in the polymerizable monomer (X) is preferably 10 to 50% by mass based on the total amount of elements in the polymerizable monomer. If it is 10% or more, the moisture permeability will be lower, and if it is 50% or less, the curability will be further improved.

In this embodiment, the polymerizable monomer may further contain a polymerizable monomer other than the polymerizable monomer (X). The other polymerizable monomer may be, for example, a compound having a polymerizable group copolymerizable with the polymerizable group of the polymerizable monomer (X). The amount of other polymerizable monomers used is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less, based on 100 parts by mass of the polymerizable monomer.

Among other polymerizable monomers other than the polymerizable monomer (X), the cationically polymerizable monomer is preferably at least one selected from the group consisting of epoxy compounds, oxetane compounds, and cationically polymerizable vinyl compounds.

Examples of the epoxy compound include alicyclic compounds having an epoxy group, aromatic compounds having an epoxy group, and glycidyl ether compounds. One or more types of these compounds or derivatives may be used.

Alicyclic compounds having an epoxy group (hereinafter also referred to as alicyclic epoxy compounds) include compounds having at least one cycloalkane ring (e.g., cyclohexene ring, cyclopentene ring, pinene ring, etc.). , hydrogen peroxide, a compound obtained by epoxidizing with a suitable oxidizing agent such as peracid, or a derivative thereof, or an aromatic epoxy compound (e.g., bisphenol A type epoxy compound, bisphenol F type epoxy compound, etc.). Examples include hydrogenated epoxy compounds obtained by One or more types of these compounds may be 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.

In formula (A1-1), X represents a single bond or a connecting group (a divalent group having one or more atoms), and the connecting group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, It is a carbonate group, an amide bond, or a group in which a plurality 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.

The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, even more preferably 300 or less, and even more preferably 100 to 280, in terms of low moisture permeability and storage stability.

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. In this specification, the number average molecular weight indicates a polystyrene equivalent value 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

As the aromatic compound having an epoxy group (hereinafter sometimes referred to as aromatic epoxy compound), any of monomers, oligomers, or polymers can be used, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Examples include epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolac phenol type epoxy resin, cresol novolac type epoxy resin, phenyl glycidyl ether, and modified products thereof. One or more types of these epoxy resins may be 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.

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 alkyl group having 1 to 5 carbon atoms. represents.

R ²¹ , R ²² , R ²³ and R ²⁴ are preferably a hydrogen atom or a methyl group. R ²¹ , R ²² , R ²³ and R ²⁴ are preferably the same.

Among the aromatic epoxy compounds having a bisphenol structure, one or more selected from bisphenol A epoxy resins and bisphenol F epoxy resins are preferred.

The molecular weight of the aromatic epoxy compound is preferably from 100 to 5,000, more preferably from 150 to 1,000, and most preferably from 200 to 450 from the viewpoint of low moisture permeability.

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.

In this embodiment, the cationically polymerizable monomer can be a monomer, an oligomer, or a polymer.

As the glycidyl ether compound, a polyglycidyl ether compound is preferred. Examples of the polyglycidyl ether compound include, but are not particularly limited to, 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 alkylene glycol, etc. Polyglycidyl ethers of alcohols (e.g. di- or triglycidyl ethers of glycerin or its alkylene oxide adducts), diglycidyl ethers of polyalkylene glycols (e.g. diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, polypropylene glycol or diglycidyl ether of its alkylene oxide adduct, 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.

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

Vinyl ether compounds include, but are not limited to, 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, Di- or trivinyl ether compounds such as vinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, 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, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, etc. Can be mentioned.

Among other polymerizable monomers other than the polymerizable monomer (X), the radically polymerizable monomer is at least one selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, and a vinyl ester group. A radically polymerizable monomer having a radically polymerizable functional group of

As the radically polymerizable monomer, a radically polymerizable monomer having a (meth)acryloyl group can be suitably used. That is, the composition according to the present embodiment does not contain an element having an atomic number of 9 or more such as a fluorine atom, and may further contain a radically polymerizable monomer having a (meth)acryloyl group.

Examples of radically polymerizable monomers having a (meth)acryloyl group include monofunctional monofunctional monomers such as ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, ethoxylated-o-phenylphenol acrylate, and phenyl (meth)acrylate. Examples include polyfunctional (meth)acrylates such as (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. It will be done.

The content of the polymerizable monomer (X) is preferably 20 to 100 parts by mass, more preferably 40 to 90 parts by mass, even more preferably 52.5 to 85 parts by mass, and 55 to 80 parts by mass, based on 100 parts by mass of the polymerizable monomer. Parts by mass are more preferred. When the amount is 20 parts by mass or more, the moisture permeability of the cured product is further reduced.

The polymerizable monomer according to this embodiment preferably contains a crosslinkable monomer (Y). The crosslinkable monomer (Y) is a compound having two or more polymerizable functional groups. The crosslinkable monomer (Y) is preferably a monomer other than the polymerizable monomer (X) (that is, a monomer that does not contain an element with an atomic number of 9 or more).

Examples of the crosslinkable monomer (Y) include compounds having two or more polymerizable functional groups among the compounds described above.

The content of the crosslinkable monomer (Y) is preferably 0 to 80 parts by weight, more preferably 5 to 60 parts by weight, most preferably 7.5 to 55 parts by weight, and 10 to 50 parts by weight, based on 100 parts by weight of the polymerizable monomer. Parts by mass are more preferred. If the amount is 80 parts by mass or less, the adhesive durability will be further improved.

The composition according to this embodiment includes a polymerization initiator as an essential component.

As the polymerization initiator, a photopolymerization initiator is preferred. When using a photopolymerization initiator, the composition according to this embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

The polymerization initiator is preferably at least one selected from the group consisting of cationic photopolymerization initiators and radical photopolymerization initiators. When using a photocationic polymerization initiator, polymerization of cationically polymerizable functional groups becomes possible. When using a photoradical polymerization initiator, it becomes possible to polymerize radically polymerizable functional groups.

Examples of photocationic polymerization initiators include, but are not limited to, arylsulfonium salt derivatives (for example, Cylacure UVI-6990, Cylacure UVI-6974 manufactured by Dow Chemical Co., Ltd., Adeka Optomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., Adeka Opto Mar SP-152, ADEKA OPTOMER SP-170, ADEKA OPTOMER SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1 manufactured by Sun-Apro, Cibacure 1190 manufactured by Double Bond etc.), aryliodonium salt derivatives (for example, Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan), arene-ion complex derivatives, diazonium salt derivatives, triazine initiators and other halides. Examples include acid generators such as. The cationic species of the photocationic polymerization initiator is preferably an onium salt represented by formula (B-1).

Examples of the photocationic polymerization initiator include, but are not limited to, onium salts represented by formula (B-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分子当たりｐ＋１である。 A represents an element of group VIA to group VIIA with valence m. m represents 1 to 2. p represents 0 to 3. m and p are preferably integers. R represents an organic group bonded to A. D is the following formula (B-1-1):

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. The a+1 E's and A's 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-1-1) is not particularly limited, but includes 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-fluoro phenyl)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, diphenylphena Examples include silsulfonium, 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 A ring structure containing element A may be formed by bonding via one to three 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, examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone, etc. Examples include fused 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 It may have various substituents. Substituents include straight chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, ocdadecyl; isopropyl, isobutyl, sec-butyl, tert-butyl Branched alkyl groups having 1 to 18 carbon atoms such as , isopentyl, neopentyl, tert-pentyl, isohexyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; hydroxy groups; methoxy, ethoxy, propoxy , isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy and other linear or branched alkoxy groups having 1 to 18 carbon atoms; acetyl, propionyl, butanoyl, 2-methylpropionyl, Straight chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl; 7 to 11 carbon atoms such as benzoyl and naphthoyl Arylcarbonyl group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc. Straight chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms; Aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl Arylthiocarbonyl group; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyl Straight chain or branched acyloxy group having 2 to 19 carbon atoms such as oxy; phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenyl thio, 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, 4-(p-ethylbenzoyl)phenylthio 4-(p Arylthio groups having 6 to 20 carbon atoms such as -isopropylbenzoyl)phenylthio, 4-(p-tert-butylbenzoyl)phenylthio; methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, Straight chain or branched alkylthio groups having 1 to 18 carbon atoms such as pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio; 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl, etc. Aryl group; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, C4-C20 heterocyclic groups such as phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl; C6-C10 aryloxy groups such as phenoxy, naphthyloxy; methyl 1 carbon number such as sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, etc. ~18 linear or branched alkylsulfinyl groups; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, Straight chain or branched alkylsulfonyl groups having 1 to 18 carbon atoms such as sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl; phenylsulfonyl, tolylsulfonyl (tosyl group), arylsulfonyl group having 6 to 10 carbon atoms such as 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. Examples include dialkylsulfonium or trialkylsulfonium.

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 ^- ; Sulfate ions such as HSO ₄ ^- , SO ₄ ^2- ; Carbonate ions such as HCO ₃ ^- , CO ₃ ^2- ; H ₂ PO ₄ ^- , HPO ₄ ^2- , PO ₄ ^3- ; fluorophosphate ions such as PF ₆ ^- , PF ₅ OH ^- , fluorinated alkylfluorophosphate ions; BF ₄ ^- , B(C ₆ F ₅ ) ₄ ^- , Examples include borate ions such as B(C ₆ H ₄ CF ₃ ) ₄ ^- ; 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, 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.

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 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 used. Among these, fluorides are preferred because they have excellent photocurability and improve adhesiveness and adhesive durability. Among the fluorides, hexafluoroantimonate is preferred.

Among the photocationic polymerization initiators, triarylsulfonium salt hexafluoroantimonate represented by formula (B-2) and diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl) represented by formula (B-3) are preferred. ) At least one selected from the group consisting of trifluorophosphates is preferred, and triarylsulfonium salt hexafluoroantimonate is more preferred.

Although the photoradical polymerization initiator is not particularly limited,
Benzophenone and its derivatives;
Benzyl and its derivatives;
Anthraquinone and its derivatives;
Benzoin-type photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal;
Acetophenone type photopolymerization initiator such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;
2-dimethylaminoethylbenzoate;
p-dimethylaminoethylbenzoate;
Diphenyl disulfide;
Thioxanthone and its derivatives;
Camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1] Heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2 , 3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride and other camphorquinone type photopolymerization initiators;
α of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, etc. -Aminoalkylphenone type photoinitiator;
Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine Acyl phosphine oxide type photopolymerization initiator such as oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;
2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone , 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and other α-hydroxyalkylphenone type photopolymerization initiators;
Phenyl-glyoxylic acid-methyl ester;
Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester;
Oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester;
etc.

The content of the polymerization initiator is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polymerizable monomer. If the content of the polymerization initiator is 0.01 parts by mass or more, the photocurability will be better, and if the content is 5 parts by mass or less, the adhesive durability will be further improved.

The composition according to 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 5 parts by mass, and 0.02 parts by mass based on 100 parts by mass of the polymerizable monomer, since the photocurability is further improved and the storage stability is further improved. ~3 parts by mass is more preferred.

The composition according to this embodiment may contain a silane coupling agent. By containing the silane coupling agent, the composition according to 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 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 content of the silane coupling agent is preferably 0.1 to 10 parts by mass, and 0.2 to 5 parts by mass, based on 100 parts by mass of the polymerizable monomer, in terms of further improving adhesiveness and adhesive durability. More preferred.

The composition according to this embodiment may contain an inorganic filler. By containing an inorganic filler, the low moisture permeability of the sealant is further improved.

Examples of inorganic fillers include silica, mica, kaolin, talc, and aluminum oxide. Among these, talc is preferred.

The average particle size (hereinafter also referred to as particle size) of the inorganic filler is preferably 1 to 50 μm. The average particle diameter is preferably measured by Microtrack (laser diffraction/scattering method). The average particle diameter is preferably the median diameter (d50).

The content of the inorganic filler is preferably 1 to 80 parts by weight, more preferably 20 to 40 parts by weight, based on 100 parts by weight of the polymerizable monomer, in terms of further improving low moisture permeability.

The composition according to the present embodiment may further contain known additives used in the technical field as other components.

A cured body is obtained by curing the composition according to this embodiment.

Light sources used for curing and adhesion of the composition according to 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, Examples include high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like. These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelength of each photopolymerization 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 photopolymerization initiator and the like. 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 according to this embodiment may be subjected to a post-heat treatment in order to accelerate the curing speed after light irradiation. The temperature of the post-heating is preferably 150° C. or lower, more preferably 100° C. or lower, from the viewpoint of not damaging the organic electroluminescent device when used for sealing the organic electroluminescent device. The temperature of post-heating is preferably 50°C or higher.

The composition according to this embodiment may be used as an adhesive. The adhesive according to this embodiment can be suitably used for bonding packages such as organic electroluminescent devices.

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 the present embodiment includes, for example, a step of applying the composition to the entire surface or part of one of the substrates, and a step of applying light to the composition of the substrate coated with the composition. a step of irradiating, and a step of laminating the other base material to the one base material until the composition irradiated with the light is cured, and curing the base material laminated with the composition. By having the step of exposing the base material to light or heat, the base material can be bonded without exposing it 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.

A method of applying the composition of this embodiment to one substrate, bonding the other substrate through the composition, and irradiating the composition of this embodiment with light using the composition of this embodiment. An organic electroluminescent display device can be manufactured using the organic electroluminescent display device.

The glass transition temperature (Tg) of the cured product of the composition according to this embodiment is preferably 60°C or higher, more preferably 70°C or higher, and most preferably 85°C or higher.

In this specification, the glass transition temperature (Tg) of a cured product indicates a value determined from a dynamic viscoelastic spectrum. In the dynamic viscoelastic spectrum, stress and strain are applied to the cured product at a constant heating rate, and the temperature at which the peak top of the loss tangent (hereinafter abbreviated as tan δ) occurs can be determined as the glass transition temperature. If the tan δ peak does not appear even when the temperature is raised from a sufficiently low temperature of about -150°C to a certain temperature (Ta°C), the glass transition temperature is considered to be below -150°C or above a certain temperature (Ta°C). However, since a cured product with a glass transition temperature of −150° C. or lower cannot be considered, it can be determined that the temperature is higher than a certain temperature (Ta° C.).

The cured product of the composition according to the present embodiment preferably has a crosslink density of 1.0×10 ⁻³ mol/cm ³ or more, and 2.0×10 ⁻³ to 1.0 mol/cm ³ . It is more preferable that there be. It is preferable that the crosslinking density is 1.0×10 ⁻³ mol/cm ³ or more because the cured product has many bonding points, suppresses micro-Brownian motion in the polymer, and has excellent low moisture permeability. When the crosslinking density is 1.0 mol/cm ³ or less, the cured product does not become brittle. The crosslinking density can be calculated from the results of dynamic viscoelasticity measurement of the cured product of the composition.

In this specification, the crosslinking density of the cured product indicates a value determined from a dynamic viscoelastic spectrum. A cured product with a thickness of 100 μm is cut out into a piece of width 5 mm x length 25 mm to be used as a test piece. Dynamic viscoelasticity measurements are performed on this test piece under the conditions of a temperature range of -50 to 200°C, a heating rate of 2°C/min, and a tensile mode to understand the relationship between temperature and storage modulus (G'). The crosslinking density is calculated using the following formula, where the temperature at Tg+40°C is T(K), the storage modulus (G') at T(K) is G' _Tg+40 , the gas constant is R, and the front coefficient is φ (=1). Calculated.
Crosslink density (ρ)=G' _Tg+40 /3φRT

In accordance with JIS Z 0208:1976, the cured product of the composition according to the present embodiment has a moisture permeability of 40 g/m at a thickness of 100 μm, which was measured by exposing it to an environment of 60° C. and 90% RH for 24 hours. It is preferably ² or less, more preferably 35 g/m ² or less, and even more preferably 30 g/m ² or less. When the moisture permeability is low, when used for sealing an organic electroluminescent element, the generation of dark spots due to moisture reaching the organic light emitting material layer can be further suppressed. From the viewpoint of productivity, the moisture permeability is preferably 0.01 g/m ² or more.

The cured product of the composition according to this embodiment preferably has excellent transparency. Specifically, the cured product preferably has a light transmittance of 95% or more, more preferably 97% or more, in the ultraviolet-visible light region of 360 nm or more and 800 nm or less, per 10 μm thickness. Most preferably it is 99% or more. When this light transmittance is 95% or more, when used for sealing an organic electroluminescent element, it becomes easy to obtain an organic EL display device with excellent brightness and contrast.

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 embodiment of the present invention may be a cured product obtained by curing the above-mentioned composition.

Another aspect of the embodiment of the present invention may be a sealing material including the above-mentioned cured body. As the sealing material, a sealing material for organic electroluminescent elements is preferable. This sealing material may be made of a cured material, or may include a cured material of the sealing material and other constituent materials. Examples of other constituent materials include a silicon nitride film, a silicon oxide film, and an inorganic layer such as silicon nitride oxide.

Yet another aspect of the embodiment of the present invention may be an organic electroluminescent display device including an organic electroluminescent element and the above-described sealing material for the organic electroluminescent element.

In the present invention, a method for manufacturing an organic electroluminescent display device includes an adhesion step of attaching the above-mentioned sealant for an organic electroluminescent element to a first member, and a step of attaching a sealant for an organic electroluminescent element to the attached organic electroluminescent element. and a bonding step of bonding the first member and the second member together via the irradiated sealant for organic electroluminescent elements. In this manufacturing method, for example, the first member may be a substrate, and the second member may be an organic electroluminescent device. In this manufacturing method, for example, the first member may be an organic electroluminescent device, and the second member may be a substrate. Conditions for each step in this manufacturing method may be appropriately selected based on the description of the above-mentioned embodiments.

The substrate may be a color filter. There may be no inorganic film on the outermost surface of the organic electroluminescent device.
The organic electroluminescent display device may include a laminate in which an inorganic film and an organic film are stacked. The organic film may include a cured product of the composition according to this embodiment. In the organic electroluminescent display device, the organic film directly laminated on the organic electroluminescent element may include a cured product of the composition according to the present embodiment.

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.

(X) The following was used as the polymerizable monomer.
(X-1) Dibromophenyl glycidyl ether (“BR-250” manufactured by Nippon Kayaku Co., Ltd., bromine element content 51% by mass)
(X-2) Brominated cresyl glycidyl ether (“BROC” manufactured by Nippon Kayaku Co., Ltd., bromine element content 50% by mass)
(X-3) TBBPA epoxy resin (diglycidyl ether of tetrabromobisphenol A, “Epiclon 152” by DIC, bromine element content 48% by mass)
(X-4) Brominated phenol novolac type epoxy resin (“BREN-105” manufactured by Nippon Kayaku Co., Ltd., bromine element content 36% by mass)
(X'-1) Phenyl glycidyl ether (Sakamoto Pharmaceutical Co., Ltd. "PEG")
(X-5) Pentafluorophenyl acrylate (“Pentafluorophenyl acrylate” manufactured by Tokyo Kasei Kogyo Co., Ltd.)
(X-6) 2,4,6-tribromophenyl acrylate (“Tribromophenyl acrylate” manufactured by Tokyo Kasei Kogyo Co., Ltd.)
(X'-2) Phenyl acrylate ("Phenyl acrylate" manufactured by Tokyo Kasei Kogyo Co., Ltd.)
(X'-3) Isobornyl acrylate (Kyoeisha Chemical Co., Ltd. "Light Acrylate IB-XA")
(X'-4) Isobornyl methacrylate ("Light Ester IB-X" manufactured by Kyoeisha Chemical Co., Ltd.)

(Y) The following was used as the crosslinkable monomer.
(Y-1) 3',4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxide 2021P" manufactured by Daicel Chemical Co., Ltd.)
(Y-2) Bisphenol A type epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, molecular weight 360-390)
(Y-3) Di(1-ethyl-(3-oxetanyl)) methyl ether (“Aronoxetane OXT-221” manufactured by Toagosei Co., Ltd.)
(Y-4) Cyclohexane dimethanol divinyl ether (“CHDVE” manufactured by Nippon Carbide Co., Ltd.)
(Y-5) 1,6-hexanediol dimethacrylate (“HD-N” manufactured by Shin Nakamura Chemical Co., Ltd.)
(Y-6) Tricyclodecane dimethanol dimethacrylate (“DCP” manufactured by Shin Nakamura Chemical Co., Ltd.)

The following was used as a polymerization initiator.
・Triarylsulfonium salt hexafluoroantimonate (“ADEKA Optomer SP-170” manufactured by ADEKA, the anion species is hexafluoroantimonate)
・Triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl) trifluorophosphate, "CPI-200K" manufactured by San-Apro, the anion species is a phosphorus compound)
・2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“TPO” manufactured by BASF Japan)
・1-Hydroxycyclohexyl phenyl ketone, “I-184” manufactured by BASF Japan)

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

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

The following was used as the inorganic filler.
Particulate talc, particle size (d50): 4.5 μm (Matsumura Sangyo Co., Ltd. "#5000PJ")

(Experiment example 1)
A polymerizable monomer having a cationically polymerizable functional group was tested. 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 compositions of experimental examples and used as sealants. The unit of composition ratio is parts by mass.
The following measurements were performed on the composition of the experimental example. The results are shown in Tables 1 and 2.

(Experiment example 2)
A polymerizable monomer having a radically polymerizable functional group was tested. The raw materials of the types shown in Table 3 were mixed in the composition ratios shown in Table 3 to prepare a composition of an experimental example, which was used as a sealant. The unit of composition ratio is parts by mass.
The following measurements were performed on the composition of the experimental example. The results are shown in Table 3.

〔viscosity〕
The viscosity (shear viscosity) of the composition 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.

[Specific gravity of polymerizable monomer (monomer specific gravity)]
The specific gravity of the polymerizable monomer was measured using a Herbert type pycnometer according to JIS K0061.
[Specific gravity of composition]
The specific gravity of the composition was measured using a Herbert type pycnometer according to JIS K0061.

[Light curing conditions]
When evaluating the curability and adhesiveness of the composition, the composition was cured under the following light irradiation conditions. The composition was photocured using a UV curing device equipped with an electrodeless discharge metal halide lamp (manufactured by Fusion) under conditions of an integrated light intensity of 4,000 mJ/ ^cm2 at a wavelength of 365 nm, and then heated in an oven at 80°C for 30 minutes. A post-heat treatment was performed for a minute to obtain a cured product.

[Cured product specific gravity (23℃)]
A sheet-like cured product having a thickness of 1 mm was produced under the above photocuring conditions, and the specific gravity of the cured product was measured in accordance with JIS K7112 B method. Water at a temperature of 23°C was used as the immersion liquid.

[Cured product specific gravity (60℃)]
A sheet-like cured product having a thickness of 1 mm was produced under the above photocuring conditions, and the specific gravity of the cured product was measured in accordance with JIS K7112 B method. Water at a temperature of 60°C was used as the immersion liquid.

[Tg]
A sheet-like cured product with a thickness of 0.1 mm was produced under the above-mentioned photocuring conditions, and the cured product with a thickness of 100 μm was cut out to a size of 5 mm in width and 25 mm in length to obtain a test piece. Dynamic viscoelasticity measurements were performed on this test piece under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and a tensile mode. The temperature at the peak top of tan δ (loss tangent) measured in the above dynamic viscoelasticity measurement was defined as the glass transition temperature (Tg) of the cured product.

[Crosslink density]
A sheet-like cured product with a thickness of 0.1 mm was produced under the above-mentioned photocuring conditions, and the cured product with a thickness of 100 μm was cut out to a size of 5 mm in width and 25 mm in length to obtain a test piece. Dynamic viscoelasticity measurements were performed on this test piece under the conditions of a temperature range of -50 to 200°C, a heating rate of 2°C/min, and a tensile mode. The crosslinking density is calculated using the following formula, where the temperature at Tg+40°C is T(K), the storage modulus (G') at T(K) is G' _Tg+40 , the gas constant is R, and the front coefficient is φ (=1). Calculated.
Crosslink density (ρ)=G' _Tg+40 /3φRT

〔transparency〕
Using the composition, two glass plates (size: 40 mm x 20 mm) were bonded together so that the thickness of the cured product was 10 μm. A test piece was prepared by curing the composition under the photocuring conditions described above. Light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (JASCO Corporation).

[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 the composition was made under the above photocuring conditions. Hardened things. After curing, the tensile shear adhesive strength (unit: MPA) of the test piece bonded with the composition was measured at a tensile rate of 10 mm/min at a temperature of 23° C. and a relative humidity of 50%.

[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 sealant obtained in the experimental example was applied to glass using a coating device under a nitrogen atmosphere, and then bonded to an organic EL element substrate. It was cured to produce an organic EL device. The anode 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 to the organic EL element immediately after fabrication, 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 device immediately after fabrication for 1000 hours under the conditions of 85° C. and relative humidity of 85% by mass, a voltage of 6 V was applied, and the light emitting state of the organic EL device was observed visually and with a microscope. The diameter of the spot was measured.

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

This embodiment has low moisture permeability even without using a filler. This embodiment has high permeability because no filler is used.
This embodiment is used for encapsulating electronic devices, organic EL elements, and the like.
According to the present embodiment, a low moisture permeability resin composition is provided that can form a sealant that has excellent moisture resistance without impairing transparency, has excellent adhesion to glass substrates, etc., and has excellent permeability to irregularities. can get.
According to the embodiments of the present invention, a sealant for organic EL elements and an organic EL display device can be obtained.

Claims (21)

Contains a polymerizable monomer and a polymerization initiator,
The specific gravity in a 23°C atmosphere is 1.3 or more,
The specific gravity of the cured product in a 23°C atmosphere is 1.3 to 3.0,
The polymerizable monomer has at least one polymerizable monomer (X) selected from the group consisting of halophenyl glycidyl ether, brominated cresyl glycidyl ether, and halophenyl (meth)acrylate, and two or more polymerizable functional groups. and a crosslinkable monomer (Y) that does not have an element with an atomic number of 9 or more,
The sealing monomer (Y) contains at least one selected from the group consisting of an alicyclic epoxy compound, an aromatic epoxy compound having a bisphenol structure, an oxetane compound, a cationically polymerizable vinyl compound, and a radically polymerizable monomer. Deterrent. The sealant according to claim 1, wherein the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere at 60°C. The sealant according to claim 1 or 2, wherein the cured product has a glass transition temperature of 60°C or higher. The sealant according to any one of claims 1 to 3, wherein the cured product has a crosslinking density of 1.0×10 ⁻³ mol/cm ³ or more. The sealant according to any one of claims 1 to 4, wherein the polymerizable monomer (X) contains at least one selected from the group consisting of fluorine element and bromine element. The seal according to any one of claims 1 to 5 , wherein the content of the halogen group element contained in the polymerizable monomer (X) is 10 to 50% by mass based on the total element amount of the polymerizable monomer. Deterrent. The sealant according to any one of claims 1 to 6 , wherein the polymerization initiator is a photopolymerization initiator. The sealant according to any one of claims 1 to 7 , wherein the polymerization initiator contains an onium salt. The sealant according to any one of claims 1 to 8 , wherein the content of the polymerizable monomer (X) is 40 to 90 parts by mass in 100 parts by mass of the polymerizable monomer. The sealant according to any one of claims 1 to 9 , wherein the content of the crosslinkable monomer (Y) is 5 to 60 parts by mass in 100 parts by mass of the polymerizable monomer. The sealant according to any one of claims 1 to 10 , wherein the content of the polymerization initiator is 0.01 to 5 parts by mass based on 100 parts by mass of the polymerizable monomer. Any one of claims 1 to 11 , wherein the cured product has a moisture permeability of 40 g/m ² or less at a thickness of 100 μm, measured under conditions of a temperature of 60° C. and a relative humidity of 90%, in accordance with JIS Z0208. The sealant according to item 1. The sealant according to any one of claims 1 to 12 , wherein the cured product has a light transmittance of 95% or more in the ultraviolet-visible light region of 360 nm or more and 800 nm or less per 10 μm thickness. The encapsulant according to any one of claims 1 to 13 , which is an encapsulant for organic electroluminescent devices. A method for manufacturing a device including a first member and a second member,
an adhesion step of adhering the sealant according to any one of claims 1 to 14 to the first member;
an irradiation step of irradiating the attached sealant with light;
a bonding step of bonding the first member and the second member via the light-irradiated sealant;
A method for manufacturing a device, comprising: The first member is an organic electroluminescent device,
the second member is a substrate,
the device is an organic electroluminescent display device;
A method for manufacturing the device according to claim 15 . the first member is a substrate,
the second member is an organic electroluminescent element,
the device is an organic electroluminescent display device;
A method for manufacturing the device according to claim 15 . A cured product of the sealant according to any one of claims 1 to 14 . An organic electroluminescent display device comprising an organic electroluminescent element and the cured product according to claim 18 . Including a laminate in which an inorganic film and an organic film are stacked,
An organic electroluminescent display device, wherein the organic film contains the cured product according to claim 18 . Including a laminate in which an inorganic film and an organic film are stacked,
An organic electroluminescent display device, wherein an organic film directly laminated on an organic electroluminescent element contains the cured product according to claim 18 .