JPWO2020149384A1 - Encapsulant, cured product, organic electroluminescence display device, and manufacturing method of the device - Google Patents

Abstract

Provided is a composition suitable as a sealing agent for an organic EL display element, which has excellent low moisture permeability and transparency. An organic electroluminescence element containing a polymerizable monomer and a polymerization initiator, having a specific density of 1.3 or more in an atmosphere of 23 ° C. and a specific gravity of 1.3 to 3.0 in an atmosphere of 23 ° C. of a cured product. For sealant.

Description

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

In recent years, an organic optical device using an organic thin film element such as an organic electroluminescence (organic EL) display element (hereinafter, also referred to as an organic electroluminescence element, an organic EL display element or an organic EL element) or an organic thin film solar cell element. Research is underway. Since the organic thin film device can be easily manufactured by vacuum vapor deposition, solution coating, etc., it is excellent in productivity.

The 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 the organic light emitting material layer from one electrode and holes are injected from the other electrode, so that electrons and holes are combined in the organic light emitting material layer to perform self-luminous emission. Compared to a liquid crystal display element or the like that requires a backlight, it has the advantages of better visibility, thinner size, and low DC voltage drive.

However, such an organic EL display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outside air, its light emitting characteristics are rapidly deteriorated and its life is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technology that shields the organic light emitting material layer and the electrode from the moisture and oxygen in the atmosphere is indispensable for the organic EL display element. There is.

For example, Patent Document 1 discloses a method of filling an organic EL display element substrate with a photocurable sealant and irradiating it with light to seal it in a top-emitting organic EL display element or the like. .. Further, Patent Documents 2 to 4 disclose a technique for sealing an organic EL display element and preventing deterioration due to moisture.

On the other hand, Patent Document 5 contains (A) an epoxy compound, (B) an epoxy resin, and (C) a photocationic polymerization initiator, and has a water content of 1000 ppm or less and a chlorine content of 1000 ppm or less. The composition is disclosed. However, Patent Document 5 does not describe reducing the moisture permeability by adjusting the specific gravity of the polymerizable monomer.

Patent Document 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a photocationic polymerization initiator, and a plate-shaped fine particle inorganic filler having a specific shape. However, such a resin composition has a problem that transparency is impaired by the influence of the fine particle inorganic filler, and it is difficult to apply it to an application requiring transparency, for example, a top light emitting type organic EL display element. Further, Patent Document 6 does not describe the specific gravity of the polymerizable monomer.

Patent Document 7 contains a polyfunctional cationically polymerizable compound, an organicized layered silicate, and a curing agent, and the organicized layered silicate is dispersed in the polyfunctional cationically polymerizable compound, and the organic is said. For encapsulating an organic electroluminescence display element having excellent transparency and barrier properties, wherein the content of the layered silicate is 20 to 250 parts by weight with respect to 100 parts by weight of the polyfunctional cationically polymerizable compound. Curable resin compositions are disclosed. However, such a resin composition has a problem that transparency is impaired by the influence of the organic layered silicate, and it is difficult to apply it to applications requiring transparency, for example, a top-emitting organic EL display element. .. Further, Patent Document 7 does not describe the specific gravity of the polymerizable monomer.

Patent Document 8 contains (a) an epoxy compound and (b) a compound having two or more crosslinkable groups reactive with the epoxy compound in a specific ratio, and has a refractive index of 1.6 or more. Moreover, a low moisture permeability epoxy resin composition is disclosed. However, such a resin composition has a problem that the transmittance is low and it is difficult to apply it to an application requiring high transparency, for example, the visibility of an organic electroluminescence display device is lowered. Further, Patent Document 8 does not describe 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. A curable composition characterized by having a specific gravity of 0.9 or more and 1.3 or less is disclosed. However, Patent Document 9 does not describe reducing the moisture permeability by adjusting the specific gravity of the polymerizable monomer.

Patent Document 10 describes a copolymer obtained by photopolymerizing a composition containing 10 to 70% by weight of a bromine-added bisphenol A type epoxy (meth) acrylate having a specific structure, and has 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 reducing the moisture permeability by adjusting the specific gravity of the polymerizable monomer, nor does it describe the encapsulation of the organic EL display element.

Patent Document 11 describes a specific polysiloxane copolymer that is photopolymerized and has a functional acrylic group, and is suitable for restoring a specific gravity greater than about 1.0 and the refractive index of a natural crystalline lens. A polysiloxane copolymer having a refractive index is disclosed. However, Patent Document 11 does not describe that the moisture permeability is lowered by adjusting the specific gravity of the polymerizable monomer, and there is no description about sealing the organic EL display element.

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

Japanese Unexamined Patent Publication No. 2001-357973 Japanese Unexamined Patent Publication No. 10-74583 Japanese Unexamined Patent Publication No. 2001-307873 Japanese Unexamined Patent Publication No. 2009-37812 International Publication No. 2014/017524 Japanese Unexamined Patent Publication No. 2006-291072 International Publication No. 2015/129783 Japanese Unexamined Patent Publication No. 2010-163566 Japanese Unexamined Patent Publication No. 2010-163566 Japanese Unexamined Patent Publication No. 2001-124903 Special Table 2002-527171 Japanese Unexamined Patent 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 capable of achieving higher reliability and durability for an organic EL display element.

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

Further, the resin compositions described in Patent Documents 6 to 7 have a problem in transparency, and it is difficult to apply them to an organic EL display element (particularly, a top light emitting type organic EL display element).

Further, the resin composition described in Patent Document 8 has a problem in transparency, and it is difficult to apply it to an organic EL display element (particularly, a top light emitting type organic EL display element).

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

That is, the present invention is as follows.
<1> A seal containing a polymerizable monomer and a polymerization initiator, having a specific gravity of 1.3 or more in an atmosphere of 23 ° C. and a cured product having a specific gravity of 1.3 to 3.0 in an atmosphere of 23 ° C. Initiator.
<2> The sealant according to <1>, wherein the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere of 60 ° C.
<3> The sealant according to <1> or <2>, wherein the glass transition temperature of the cured product is 60 ° C. or higher.
<4> The sealant according to any one of <1> to <3>, wherein the crosslinked density of the cured product is 1.0 × 10 ^-3 mol / cm ^{3 or more.}
<5> The encapsulant according to any one of <1> to <4>, wherein the polymerizable monomer contains a polymerizable monomer (X) having an element having an atomic number of 9 or more.
<6> The encapsulant according to <5>, wherein the polymerizable monomer (X) has a halogen group element.
<7> The encapsulant according to <5> or <6>, wherein the polymerizable monomer (X) has at least one selected from the group consisting of a fluorine element and a bromine element.
<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 with respect to the total element amount of the polymerizable monomer.
<9> The encapsulant 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 encapsulant according to any one of <1> to <9>, wherein the polymerization initiator is a photopolymerization initiator.
<11> The encapsulant according to any one of <1> to <10>, wherein the polymerizable monomer contains a monomer having an aromatic ring.
<12> The encapsulant 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 a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound and an oxetane compound.
<14> The encapsulant according to <13>, wherein the polymerization initiator contains an onium salt.
<15> The encapsulant according to <12>, wherein the polymerizable monomer contains at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide.
<16> The encapsulant according to <15>, wherein the polymerization initiator contains a photoradical polymerization initiator.
<17> The description according to any one of <1> to <16>, wherein the content of the polymerizable monomer (X) having an element having an atomic number of 9 or more in 100 parts by mass of the polymerizable monomer is 40 to 90 parts by mass. Encapsulant.
<18> In 100 parts by mass of the polymerizable monomer, the content of the crosslinkable monomer (Y) having two or more polymerizable functional groups is 5 to 60 parts by mass according to any one of <1> to <17>. The sealant described.
<19> The encapsulant according to any one of <1> to <18>, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass with respect to 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 under the conditions of a temperature of 60 ° C. and a relative humidity of 90% in accordance with JIS Z0208 <1> to <19. > The encapsulant according to any one of.
<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 electroluminescence device.
<23> A method for manufacturing an apparatus including a first member and a second member, wherein the sealing agent according to any one of <1> to <22> is attached to the first member. An apparatus including an irradiation step of irradiating the attached sealant with light and a bonding step of bonding the first member and the second member via the light-irradiated sealant. Manufacturing method.
<24> The method for manufacturing an apparatus according to <23>, wherein the first member is an organic electroluminescence element, the second member is a substrate, and the apparatus is an organic electroluminescence display device.
<25> The method for manufacturing an apparatus according to <23>, wherein the first member is a substrate, the second member is an organic electroluminescence element, and the apparatus is an organic electroluminescence display device.
<26> The cured product of the encapsulant according to any one of <1> to <22>.
<27> An organic electroluminescence display device including an organic electroluminescence element and the cured product according to <26>.
<28> An organic electroluminescence display device comprising a laminate in which an inorganic film and an organic film are laminated, and the organic film contains the cured product according to <26>.
<29> An organic electroluminescence display device comprising a laminate in which an inorganic film and an organic film are laminated, and the organic film directly laminated on an organic electroluminescence element includes the cured product according to <26>.
<30> A composition containing a polymerizable monomer (X) having at least one selected from the group consisting of a fluorine element and a bromine element, and a polymerization initiator.

According to the present invention, there is provided a composition suitable as a sealing agent for an organic EL display element, which has excellent low moisture permeability and transparency.

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

The composition according to this embodiment contains a polymerizable monomer and a polymerization initiator. The composition according to the present embodiment can be suitably used as a sealing agent, and can be particularly preferably used as a sealing agent for an organic electroluminescence device.

The specific gravity of the composition according to this embodiment under an atmosphere of 23 ° C. is preferably 1.3 or more. Further, the composition according to the present embodiment is preferably a composition having a specific gravity of the cured product in an atmosphere of 23 ° C. of 1.3 to 3.0.

The composition according to the present embodiment is preferably a composition having a specific gravity of the cured product in an atmosphere of 60 ° C. of 1.3 to 3.0.

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

The polymerizable monomer preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group. The polymerizable monomer having a cationically polymerizable functional group is preferably at least one selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound and an oxetane compound. 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 preferable.

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

The polymerizable monomer (X) preferably has an aromatic ring.

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

The number of halogen group elements contained in the polymerizable monomer (X) is preferably 1 or more, more preferably 2 or more, still 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 cationically 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 thereof include brominated bisphenol A type epoxy resin (for example, diglycidyl ether of tetrabromobisphenol A), brominated bisphenol F type novolak type epoxy resin, brominated phenol novolak type epoxy resin and the like.

Examples of the compound having a radically polymerizable functional group, which is one of 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) acrylates, trichlorophenyl (meth) acrylates, pentachlorophenyl (meth) acrylates, bromophenyl (meth) acrylates, tribromophenyl (meth) acrylates, pentabromolophenyl (meth) acrylates, etc. Can be mentioned.

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

In the present 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 the other polymerizable monomer used is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, further preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, out of 100 parts by mass of the polymerizable monomer.

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

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

As the alicyclic compound having an epoxy group (hereinafter, also referred to as an alicyclic epoxy compound), a compound having at least one cycloalcan ring (for example, cyclohexene ring, cyclopentene ring, pinen ring, etc.) is used. , Hydrogen peroxide, a compound obtained by epoxidation with an appropriate oxidizing agent such as peracid, or a derivative thereof, or an aromatic epoxy compound (for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, etc.) is hydrogenated. Examples thereof include hydrided epoxy compounds obtained from the above. One or more of these compounds may be used.

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

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

In the formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms), and the linking group is a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, and the like. A carbonate group, an amide bond, or a group in which a plurality of these are linked.

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

The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, further preferably 300 or less, still 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 in the above range. In the present 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
・ Degassing device: ERC-3310 manufactured by ERMA
-Pump: PU-980 manufactured by JASCO Corporation
-Flow velocity: 1.0 ml / min
・ Autosampler: AS-8020 manufactured by Tosoh Corporation
-Column oven: Hitachi, Ltd. L-5030
・ Set temperature: 40 ℃
-Column configuration: Tosoh TSKquadcolumn MP (xL) 6.0 mm ID x 4.0 cm 2 pieces, Tosoh TSK-GELMULTIPORE HXL-M 7.8 mm ID x 30.0 cm 2 pieces, total 4 pieces-Detector: RI Hitachi L-3350
-Data processing: SIC480 data station

As the aromatic compound having an epoxy group (hereinafter, also referred to as an aromatic epoxy compound), any of a monomer, an oligomer or a polymer can be used, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol S type can be used. Examples thereof include epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolak phenol type epoxy resin, cresol novolac type epoxy resin, phenylglycidyl ether, and modified products thereof. One or more of these epoxy resins may be used.
Among these, aromatic epoxy compounds having a bisphenol structure are preferable. Among the aromatic epoxy compounds having a bisphenol structure, the compound represented by the following formula (A2-1) is preferable.

In the formula (A2-1), n represents a real number from 0 to 30, and R ²¹ , R ²² , R ²³ and R ²⁴ are independently hydrogen atoms or substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms, respectively. Represents.

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

Among the aromatic epoxy compounds having a bisphenol structure, one or more selected from bisphenol A type epoxy resin and bisphenol F type epoxy resin is preferable.

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

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 in the above range. In the present specification, the number average molecular weight indicates a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.

In the present embodiment, the cationically polymerizable monomer may be any of a monomer, an oligomer or a polymer.

As the glycidyl ether compound, a polyglycidyl ether compound is preferable. The polyglycidyl ether compound is not particularly limited, but is a multivalent alkylene glycol diglycidyl ether (for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.). Polyglycidyl ether of alcohol (eg, di or triglycidyl ether of glycerin or its alkylene oxide adduct), diglycidyl ether of polyalkylene glycol (eg, diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or Diglycidyl ether of the alkylene oxide adduct, etc.) can be mentioned. Here, examples of the alkylene oxide include aliphatic systems such as ethylene oxide and propylene oxide.

The oxetane compound is not particularly limited, but is limited to 3-ethyl-3-hydroxymethyloxetane (trade name: Aronoxetane OXT-101 manufactured by Toa Synthetic Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanyl, etc.). ) Ethylmethyl] benzene (same as OXT-121 etc.), 3-ethyl-3- (phenoxymethyl) oxetane (same as OXT-211 etc.), di (1-ethyl- (3-oxetanyl)) methyl ether (same as OXT-) 221 etc.), 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane (OXT-212 etc.) and the like. The oxetane compound means a compound having one or more oxetane rings in the molecule.

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

The vinyl ether compound is not particularly limited, but is 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, and cyclohexanedimethanol diethanol. 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 and other monovinyl ether compounds. Can be mentioned.

Among the 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 the above is preferable.

As the radically polymerizable monomer, a radically polymerizable monomer having a (meth) acryloyl group can be preferably used. That is, the composition according to the present embodiment may further contain a radically polymerizable monomer having an atomic number 9 or more such as a fluorine atom and having a (meth) acryloyl group.

Examples of the radically polymerizable monomer having a (meth) acryloyl group include monofunctionals 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 tricyclodecanedimethanol di (meth) acrylate. 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, still more preferably 52.5 to 85 parts by mass, and 55 to 80 parts by mass in 100 parts by mass of the polymerizable monomer. Parts by mass are more preferred. When it is 20 parts by mass or more, the moisture permeability of the cured product is further lowered.

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 having no element having 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 mass, more preferably 5 to 60 parts by mass, most preferably 7.5 to 55 parts by mass, and 10 to 50 parts by mass in 100 parts by mass of the polymerizable monomer. Parts by mass are more preferred. If it is 80 parts by mass or less, the adhesive durability is further improved.

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

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

As the polymerization initiator, at least one selected from the group consisting of a photocationic polymerization initiator and a photoradical polymerization initiator is preferable. When a photocationic polymerization initiator is used, the cationically polymerizable functional group can be polymerized. When a photoradical polymerization initiator is used, the radically polymerizable functional group can be polymerized.

The photocationic polymerization initiator is not particularly limited, but is limited to an aryl sulfonium salt derivative (for example, Cyracure UVI-6990, Cyracure UVI-6974, Asahi Denka Kogyo Co., Ltd. Mar SP-152, Adecaca Ptomer SP-170, Adecao Ptomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1, Double Bond Ciba Cure 1190 Etc.), aryliodonium salt derivatives (eg, Irgacure 250 manufactured by Ciba Specialty Chemicals, RP-2074 manufactured by Rhodia Japan), allen-ion complex derivatives, diazonium salt derivatives, triazine initiators and other halides. Such as an acid generator and the like. As the cationic species of the photocationic polymerization initiator, an onium salt represented by the formula (B-1) is preferable.

The photocationic polymerization initiator is not particularly limited, and examples thereof include an onium salt represented by the 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 having a valence m of Group VIA to Group VIIA. m indicates 1 to 2. p indicates 0 to 3. Integers are preferable for m and p. R indicates an organic group attached to A. D is the following formula (B-1-1) :.

Indicates a divalent group represented by. In formula (B-1-1), E represents a divalent group and G is -O-, -S-, -SO-, -SO _2- , -NH-, -NR'-, -CO-. , -COO-, -CONH-, an alkylene or phenylene group having 1 to 3 carbon atoms (R'is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms). a indicates 0 to 5. The a + 1 E and the A G may be the same or different. a is preferably an integer. X ⁻ is a counterion of onium, and the number thereof is p + 1 per molecule.

The onium ion of the formula (B-1-1) is not particularly limited, but is limited to 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, and bis [4- {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-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9 -Oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonate] thioxanthone, 4- [4-( 4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthlenium, 5-phenylthiaanthrenium, diphenylphena Examples thereof include sylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, octadecylmethylphenacilsulfonium and the like.

R is an organic group attached 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 represent alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl. , Arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and at least one selected from the group consisting of halogens. The number of R is m + p (m-1) + 1, and they may be the same or different from each other. Also, two or more R may bond directly or -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH-, carbon It may be bonded via an alkylene or phenylene group of the number 1 to 3 to form a ring structure containing the element A. Here, R'is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

In the above, examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, naphthyl, anthraquinone, phenanthrenyl, pyrenyl, chrysenyl, naphthalsenyl, benzanthrasenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone and the like. Examples thereof 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-mentioned 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 is at least one. It may have a species substituent. As the substituent, a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like; isopropyl, isobutyl, sec-butyl, tert-butyl , Isopentyl, neopentyl, tert-pentyl, isohexyl and other branched alkyl groups having 1 to 18 carbon atoms; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like having 3 to 18 carbon atoms; 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, A linear or branched alkylcarbonyl group having 2 to 18 carbon atoms such as heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyle, dodecanoyl, octadecanoyl; and 7 to 11 carbon atoms such as benzoyl and naphthoyl. Arylcarbonyl group of; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc. A linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms; an aryloxycarbonyl group having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl. Arylthiocarbonyl groups; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyl A linear 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-bromofu Enilthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2- Naftilthio, 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-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc. Arylthio groups with 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, Linear or branched alkylthio groups with 1 to 18 carbon atoms such as dodecylthio; aryl groups with 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, Pyrimidyl, pyrazinyl, indrill, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantrenyl, phenoxadinyl, phenoxatiynyl, chromanyl, isochromanyl, dibenzothienyl Heterocyclic groups with 4 to 20 carbon atoms such as dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec -Phenylsulfinyl, tert-butylsulfinyl, pinch Linear or branched alkylsulfinyl groups with 1-18 carbon atoms such as rusulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl; 6-10 carbon atoms such as phenylsulfinyl, trillsulfinyl, naphthylsulfinyl. Aryl sulfinyl groups; methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl, isobutyl sulfonyl, sec-butyl sulfonyl, tert-butyl sulfonyl, pentyl sulfonyl, isopentyl sulfonyl, neopentyl sulfonyl, tert-pentyl sulfonyl, octyl. Linear or branched alkylsulfonyl groups with 1-18 carbon atoms such as sulfonyls; arylsulfonyl groups with 6-10 carbon atoms such as phenylsulfonyls, tolylsulfonyls (tosyl groups), naphthylsulfonyls; formula (B-1-2) )

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

P in the 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.

Sulfonium, iodonium, and selenium are preferable as ^{the onium ion [A +} ] in the formula (B-1), and the following are typical examples.

Examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and 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- (diphenylsulfonate) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [Bis (4-fluorophenyl) sulphonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulphonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulphonio] 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-dihydroanthracene-2-yldi-p-tolylsulfonium, 7- Isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonate] thioxanthone, 4-[ 4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio) ] Phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaanthrenium, 5-trilciaanthrenium, 5 -Triarylsulfoniums such as (4-ethoxyphenyl) thiaanthrenium, 5- (2,4,6-trimethylphenyl) thiaanthrenium; diphenylphenacilsulfonium, diphenyl4-nitrophenacilsulfonium, diphenylbenzylsulfonium, diphenyl Diarylsulfoniums such as methylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl ( 1-ethoxycarbonyl) Ethylsulfonium, phenylmethylphenacilsulfonium, 4-hydroxyphenylmethylphenacilsulfonium, 4-methoxyphenylmethylphenacilsulfonium, 4-acetcarbonyloxyphenylmethylphenacilsulfonium, 2-naphthylmethylphenacilsulfonium , 2-naphthyl octadecylphenacil sulfonium, monoaryl sulfonium such as 9-anthrasenyl methyl phenacil sulfonate; dimethyl phenacil sulfonium, phenacil tetrahydrothiophenium, dimethyl benzyl sulfonium, benzyl tetrahydrothiophenium, octadecyl methyl phenacil Examples thereof include dialkylsulfonium such as sulfonium and trialkylsulfonium.

Among these onium ions, one or more kinds composed of sulfonium ions and iodonium ions are preferable, and sulfonium ions are more preferable. Examples of the sulfonium ion include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, and bis [4- {bis [4- (2- (2- (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-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo- 10-Chia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonate] thioxanthone, 2-[(diphenyl) sulfonate] thioxanthone, 4- [4- (4-tert) -Butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthlenium, 5-phenylthiaanthrenium, diphenylphenacil One or more of sulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, 4-hydroxyphenylmethylphenacilsulfonium and octadecylmethylphenacilsulfonium is preferred.

In equation (B-1), X ⁻ is a counterion. The number is p + 1 per molecule. The counterion is not particularly limited, and examples thereof include a halide such as a boron compound, a phosphorus compound, an antimony compound, an arsenic compound, and an alkylsulfonic acid compound, and a methide compound. As X ⁻ , halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , I ^{−, etc .; OH −} ; ClO ₄ ⁻ ; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , Sulfonate 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- phosphate ions of _PO ^{4 3-} and the _{^{like; PF 6 -, PF 5 OH}} -, fluorophosphate ions such as fluorinated alkyl fluorophosphate _{^{ion; BF 4 -, B (C}} 6 F 5) 4 -, _{B (C 6 H 4 CF 3} ) 4 - borate ions such as; AlCl ₄ ^-; BiF ₆ ^-, and the like. Other examples thereof include fluoroantimony acid 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 a fluorinated alkylfluorophosphate ion represented by the 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, and most preferably 2 to 3.

In the fluorinated alkylfluorophosphate ion represented by the formula (B-1--3), Rf represents an alkyl group substituted with a fluorine atom, and the preferred carbon number is 1 to 8, and the more preferable carbon number is 1 to 4. Is. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl group 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). ₃ ) CF, (CF ₃ ) ₃ C and the like can be mentioned.

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 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] - and [(CF _{3 CF 2 CF 2 CF 2) 3} PF 3] - , and the like.

As the photocationic polymerization initiator, one that has been previously dissolved in a solvent may be used in order to facilitate dissolution in an epoxy compound or an 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.

Examples of the anion species of the photocationic polymerization initiator (B) include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds and alkyl sulfonic acid compounds. One or more of these anion species may be used. Among these, fluoride is preferable because it has excellent photocurability and improves adhesiveness and adhesive durability. Among the fluorides, hexafluoroantimonate is preferred.

Among the photocationic polymerization initiators, the triarylsulfonium salt hexafluoroantimonate represented by the formula (B-2) and the diphenyl4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) represented by the formula (B-3). ) At least one selected from the group consisting of trifluorophosphate is preferable, and triarylsulfonium salt hexafluoroantimonate is more preferable.

The photoradical polymerization initiator is not particularly limited, but is not 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, and benzyl dimethyl ketal;
Acetophenone-type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;
2-Dimethylaminoethylbenzoate;
p-Dimethylaminoethylbenzoate;
Diphenyl disulfide;
Thioxanthone and its derivatives;
Conferquinone, 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] Heptan-1-carboxylic acid chloride and other camphorquinone-type photopolymerization initiators;
Α such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 -Aminoalkylphenylone-type photopolymerization initiator;
Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine Acylphosphine oxide-type photopolymerization initiators 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-hydroxycyclohexylphenylketone , 2-Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and other α-hydroxyalkylphenone-type photopolymerization initiators;
Phenyl-glioxylic 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;
And so on.

The content of the polymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the content of the polymerization initiator is 0.01 parts by mass or more, the photocurability is further improved, and when the content is 5 parts by mass or less, the adhesive durability is further improved.

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

The photosensitizer is not particularly limited, but is not limited to a benzophenone derivative, a phenothiazine derivative, a phenylketone derivative, a naphthalene derivative, an anthracene derivative, a phenanthrene derivative, a naphthacene derivative, a chrysene derivative, a perylene derivative, a pentacene derivative, an acrydin derivative, a benzothiazole derivative, Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, xanthone derivative, thioxanthene derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, azine derivative, thiazine derivative, oxazine derivative, indolin derivative, azulene derivative, tri Examples thereof include an allylmethane derivative, a phthalocyanine derivative, a spiropyran derivative, a spiroxazine derivative, a thiospiropirane derivative, and an organic ruthenium complex. Among these, a phenylketone derivative such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one and / or an anthracene derivative such as 9,10-dibutoxyanthracene are preferable, and anthracene derivative is more preferable. Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferable.

The amount of the photosensitizer used is preferably 0.01 to 5 parts by mass, preferably 0.02 with respect to 100 parts by mass of the polymerizable monomer, in that the photocurability is further improved and the storage stability is further improved. ~ 3 parts by mass is more preferable.

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

The silane coupling agent is not particularly limited, but is limited to γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltricrolsilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, and 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 And so on. One or more of these silane coupling agents may be used. Among these, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxy One or more selected from the group consisting of silanes is preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable.

The content of the silane coupling agent is preferably 0.1 to 10 parts by mass, and 0.2 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer, in that the adhesiveness and the adhesive durability are further improved. More preferred.

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

Examples of the inorganic filler include silica, mica, kaolin, talc, aluminum oxide and the like. Of these, talc is preferred.

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

The content of the inorganic filler is preferably 1 to 80 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the polymerizable monomer, in that the low moisture permeability is further improved.

The composition according to the present embodiment may further contain a known additive used in the art as another component.

A cured product can be obtained by curing the composition according to the present embodiment.

The light source used for curing or adhering the composition according to the present embodiment is not particularly limited, but is limited to a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium or the like), a low pressure mercury lamp, a high pressure mercury lamp, and an ultra. Examples thereof include high-pressure mercury lamps, xenon lamps, xenon excima lamps, xenon flash lamps, and light-emitting diodes (hereinafter referred to as LEDs). These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective photopolymerization initiators.

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

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

The composition according to this embodiment may be subjected to post-heat treatment in order to accelerate the curing rate after light irradiation. When used for sealing the organic electroluminescence device, the postheating temperature is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, in that it does not damage the organic electroluminescence device. The temperature of the 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 adhering packages such as organic electroluminescence devices.

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

As a method for adhering a base material using the composition of the present embodiment, for example, a step of applying the composition to the entire surface or a part of one base material and light is applied to the composition of the base material to which the composition is applied. Between the step of irradiating and the step of bonding the other base material to the one base material until the composition irradiated with the light is cured, and the step of bonding the base material bonded by the composition is cured. By having the step of making the substrate, the substrate can be adhered without being exposed to light or heat.

As a method of manufacturing an organic electroluminescence display device using the composition of the present embodiment, for example, the composition of the present embodiment is applied on one substrate (back plate), and the composition is irradiated with light. After activation, light is blocked, and a method of adhering the back plate and the substrate on which the electroluminescence element is formed to each other through the composition can be mentioned. By this method, the organic electroluminescence device can be sealed without being exposed to light or heat.

A method of applying the composition of the present embodiment to one substrate using the composition of the present embodiment, laminating the other substrate via the composition, and irradiating the composition of the present embodiment with light. It can be used to manufacture an organic electroluminescence display device.

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

In the present specification, the glass transition temperature (Tg) of the cured product indicates a value obtained from the dynamic viscoelastic spectrum. In the dynamic viscoelastic spectrum, stress and strain are applied to the cured product at a constant temperature rise rate, and the temperature showing the peak top of the loss tangent (hereinafter abbreviated as tan δ) can be set as the glass transition temperature. If the peak of tan δ does not appear even if 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 −150 ° C or lower or a certain temperature (Ta ° C) or higher. However, since a cured product having a glass transition temperature of −150 ° C. or lower cannot be considered, it can be determined that the temperature is above 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, preferably 2.0 × 10 ^{-3 to} 1.0 mol / cm ³ . It is more preferable to have. When the crosslink density is 1.0 × 10 ^-3 mol / cm ³ or more, there are many bonding points in the cured product, microBrownian motion in the polymer is suppressed, and low moisture permeability is more excellent, which is preferable. When the crosslink density is 1.0 mol / cm ³ or less, the cured product does not become brittle. The crosslink density can be calculated from the result of dynamic viscoelasticity measurement of the cured product of the composition.

In the present specification, the crosslink density of the cured product indicates a value obtained from the dynamic viscoelastic spectrum. A cured product having a thickness of 100 μm is cut into pieces having a width of 5 mm and a length of 25 mm to obtain test pieces. For this test piece, dynamic viscoelasticity measurement is performed under the conditions of a temperature range of -50 to 200 ° C., a heating rate of 2 ° C./min, and a tensile mode, and the relationship between the temperature and the storage elastic modulus (G') is grasped. The crosslink density is calculated by the following equation, where the temperature at Tg + 40 ° C. is T (K), the storage elastic 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

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 measured by exposing it to an environment of 60 ° C. and 90% RH for 24 hours in accordance with JIS Z 0208: 1976. preferably ² or less, more preferably 35 g / ^{m 2} or less, further preferably 30 g / ^{m 2} or less. When the moisture permeability is low, the generation of dark spots due to the arrival of moisture on the organic light emitting material layer can be further suppressed when used for encapsulating the organic electroluminescence element. The moisture permeability is preferably 0.01 g / m ² or more from the viewpoint of productivity.

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

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

For example, one aspect of the 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 containing the above-mentioned cured product. As the sealing material, a sealing material for an organic electroluminescence element is preferable. The encapsulant may be made of a cured product, or may include a cured product of the encapsulant and other constituent materials. Examples of other constituent materials include an inorganic layer such as a silicon nitride film, a silicon oxide film, and silicon nitride.

Yet another aspect of the embodiment of the present invention may be an organic electroluminescence display device comprising an organic electroluminescence element and the above-mentioned encapsulant for an organic electroluminescence element.

In the present invention, the method for manufacturing an organic electroluminescence display device is a bonding step of adhering the above-mentioned sealing agent for an organic electroluminescence element to a first member, and light to the adhering sealing agent for an organic electroluminescence element. It may have an irradiation step of irradiating with light and a bonding step of bonding the first member and the second member via the light-irradiated sealant for the organic electroluminescence element. In this manufacturing method, for example, the first member may be a substrate and the second member may be an organic electroluminescence device. In this manufacturing method, for example, the first member may be an organic electroluminescence device, and the second member may be a substrate. The conditions and the like of each step in this production method may be appropriately selected based on the description of the above-described embodiment.

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

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

In the experimental example, the following compounds were used.

The following was used as the (X) polymerizable monomer.
(X-1) Dibromophenylglycidyl ether (“BR-250” manufactured by Nippon Kayaku Co., Ltd., content of bromine element 51% by mass)
(X-2) Brominated cresyl glycidyl ether (“BROC” manufactured by Nippon Kayaku Co., Ltd., content of bromine element 50% by mass)
(X-3) TBBPA Epoxy Resin (Diglycidyl Ether of Tetrabromobisphenol A, "Epiclon 152" by DIC, Content of bromine element 48% by mass)
(X-4) Brominated phenol novolac type epoxy resin (“BREN-105” manufactured by Nippon Kayaku Co., Ltd., content of bromine element 36% by mass)
(X'-1) Phenylglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd. "PEG")
(X-5) Pentafluorophenyl acrylate ("Pentafluorophenyl acrylate" manufactured by Tokyo Chemical Industry Co., Ltd.)
(X-6) Acrylic acid 2,4,6-tribromophenyl ("Tribromophenyl acrylate" manufactured by Tokyo Chemical Industry Co., Ltd.)
(X'-2) Phenyl Acrylate ("Phenyl Acrylate" manufactured by Tokyo Chemical Industry Co., Ltd.)
(X'-3) Isobornyl acrylate ("Light Acrylate IB-XA" manufactured by Kyoeisha Chemical Co., Ltd.)
(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 ("Selokiside 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 ("Aron Oxetane OXT-221" manufactured by Toagosei Co., Ltd.)
(Y-4) Cyclohexanedimethanol 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) Tricyclodecanedimethanol dimethacrylate (“DCP” manufactured by Shin-Nakamura Chemical Co., Ltd.)

The following was used as the polymerization initiator.
-Triarylsulfonium salt hexafluoroantimonate ("ADEKA PTOMER SP-170" manufactured by ADEKA, anion species is hexafluoroantimonate)
-Triarylsulfonium salt (diphenyl4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, "CPI-200K" manufactured by San-Apro, anion species is a phosphorus compound)
-2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("TPO" manufactured by BASF Japan Ltd.)
1-Hydroxycyclohexylphenyl ketone, "I-184" manufactured by BASF Japan Ltd.)

The following was used as a photosensitizer.
9,10-Dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Kasei Chemicals Co., Ltd.)

The following was used as the silane coupling agent.
γ-glycidoxypropyltrimethoxysilane (“KBM-403” manufactured by Shinetsu Silicone Co., Ltd.)

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

(Experimental Example 1)
Polymerizable monomers with cationically polymerizable functional groups were tested. The raw materials of the types shown in Tables 1 and 2 were mixed at the composition ratios shown in Tables 1 and 2 to prepare the composition of the experimental example and used as a sealing agent. The unit of composition ratio is parts by mass.
The following measurements were made for the composition of the experimental example. The results are shown in Tables 1 and 2.

(Experimental Example 2)
Polymerizable monomers having radically polymerizable functional groups were tested. The raw materials of the types shown in Table 3 were mixed at the composition ratios shown in Table 3 to prepare the composition of the experimental example, which was used as a sealing agent. The unit of composition ratio is parts by mass.
The following measurements were made for 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'x R24 cone rotor) under the conditions of 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 specific gravity bottle according to JIS K0061.
[Specific gravity of composition]
The specific gravity of the composition was measured using a Herbert type specific gravity bottle according to JIS K0061.

[Photo-curing conditions]
In the evaluation of the curability and the adhesiveness of the composition, the composition was cured under the following light irradiation conditions. ^{The composition was photocured under the condition of an integrated light amount of 4,000 mJ / cm 2} with a wavelength of 365 nm using a UV curing device (manufactured by Fusion) equipped with an electrodeless discharge metal halide lamp, and then 30 in an oven at 80 ° C. After a minute of heat treatment, a cured product was obtained.

[Hardened Relative Density (23 ° C)]
A sheet-shaped cured product having a thickness of 1 mm was prepared under the above photocuring conditions, and the specific gravity of the cured product was measured in accordance with the JIS K7112 B method. Water having a temperature of 23 ° C. was used as the dipping solution.

[Hardened Relative Density (60 ° C)]
A sheet-shaped cured product having a thickness of 1 mm was prepared under the above photocuring conditions, and the specific gravity of the cured product was measured in accordance with the JIS K7112 B method. Water having a temperature of 60 ° C. was used as the dipping solution.

[Tg]
A sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above-mentioned photocuring conditions, and the cured product having a thickness of 100 μm was cut into a width of 5 mm and a length of 25 mm to obtain a test piece. This test piece was subjected to dynamic viscoelasticity measurement 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 by the above dynamic viscoelasticity measurement was defined as the glass transition temperature (Tg) of the cured product.

[Crosslink density]
A sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above-mentioned photocuring conditions, and the cured product having a thickness of 100 μm was cut into a width of 5 mm and a length of 25 mm to obtain a test piece. This test piece was subjected to dynamic viscoelasticity measurement under the conditions of a temperature range of −50 to 200 ° C., a heating rate of 2 ° C./min, and a tensile mode. The crosslink density is calculated by the following equation, where the temperature at Tg + 40 ° C. is T (K), the storage elastic 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 × 20 mm) were bonded together so that the thickness of the cured product was 10 μm. A test piece was obtained by curing the composition under the above photocuring conditions. The light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (JASCO Corporation).

[Humidity permeability]
A sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above-mentioned photocuring conditions, and calcium chloride (anhydrous) was used as a hygroscopic agent in accordance with JIS Z0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Material (Cup Method)". The measurement was performed under the conditions of an atmospheric temperature of 60 ° C. and a relative humidity of 90%. Moisture permeability 120g ^/ (m 2 · 24hr) or less.

[Tension 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 ^{composition is 0.5 cm 2} in adhesion area and 80 μm in adhesion thickness under the above photocuring conditions. The thing was hardened. After curing, the tensile shear adhesive strength (unit: MPA) was measured at a tensile speed of 10 mm / min in an environment of a temperature of 23 ° C. and a relative humidity of 50% using a test piece bonded with the composition.

[Evaluation of organic EL]
[Manufacturing of organic EL element substrate]
The glass substrate with ITO electrode was washed with acetone and isopropanol, respectively. Then, the following compounds were sequentially vapor-deposited into a thin film by a vacuum vapor deposition method to obtain an organic EL element substrate composed 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 250 nm
・ Hole injection layer Copper phthalocyanine Thickness 30 nm
-Hole transport layer N, N'-diphenyl-N, N'-dinaphthylbenzidine (α-NPD) 20 nm thick
-Light emitting layer Tris (8-hydroxyquinolinato) aluminum (metal complex material), film thickness of light emitting layer 1000 Å
・ Electron injection layer Lithium fluoride Thickness 1 nm
・ Cathode aluminum, anode film thickness 250 nm

[Manufacturing of organic EL element]
The sealant obtained in the experimental example is applied to glass in a nitrogen atmosphere with a coating device, bonded to an organic EL element substrate, and this sealant is applied under the above photocuring conditions with an adhesive thickness of 10 μm. It was cured to produce an organic EL element. The anode side of the organic EL element substrate was bonded to the glass via a sealing agent.

[Organic EL evaluation]
〔initial〕
A voltage of 6 V was applied to the organic EL element immediately after the production, and the light emitting state of the organic EL element was visually and microscopically observed, and the diameter of the dark spot was measured.

[High temperature and high humidity]
The organic EL element immediately after being manufactured is exposed to the conditions of 85 ° C. and a relative humidity of 85% by mass for 1000 hours, then a voltage of 6 V is applied, and the light emitting state of the organic EL element is visually observed and observed 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 without using a filler. Since this embodiment does not use a filler, it has high permeability.
This embodiment is used for sealing an electronic device, sealing an organic EL element, and the like.
According to the present embodiment, there is a low moisture permeable resin composition capable of forming a sealing agent having excellent moisture resistance without impairing transparency, adhesiveness to a glass substrate or the like, and excellent unevenness permeability. can get.
According to the embodiment of the present invention, a sealing agent for an organic EL element and an organic EL display device can be obtained.

Claims (30)

Contains a polymerizable monomer and a polymerization initiator,
The specific gravity in an atmosphere of 23 ° C is 1.3 or more,
A sealant having a specific gravity of the cured product in an atmosphere of 23 ° C. of 1.3 to 3.0. The sealant according to claim 1, wherein the cured product has a specific gravity of 1.3 to 3.0 in an atmosphere of 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 crosslinked density of the cured product is 1.0 × 10 ^-3 mol / cm ^{3 or more.} The sealant according to any one of claims 1 to 4, wherein the polymerizable monomer contains a polymerizable monomer (X) having an element having an atomic number of 9 or more. The encapsulant according to claim 5, wherein the polymerizable monomer (X) has a halogen group element. The sealant according to claim 5 or 6, wherein the polymerizable monomer (X) has at least one selected from the group consisting of a fluorine element and a bromine element. The sealant according to claim 7, wherein the content of the halogen group element contained in the polymerizable monomer (X) is 10 to 50% by mass with respect to the total element amount of the polymerizable monomer. The sealant according to any one of claims 1 to 8, wherein the polymerizable monomer contains a crosslinkable monomer (Y) having two or more polymerizable functional groups. The sealant according to any one of claims 1 to 9, wherein the polymerization initiator is a photopolymerization initiator. The encapsulant according to any one of claims 1 to 10, wherein the polymerizable monomer contains a monomer having an aromatic ring. The sealant according to any one of claims 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. The sealant according to claim 12, wherein the polymerizable monomer contains at least one selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound and an oxetane compound. The sealant according to claim 13, wherein the polymerization initiator contains an onium salt. The encapsulant according to claim 12, wherein the polymerizable monomer contains at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide. The encapsulant according to claim 15, wherein the polymerization initiator contains a photoradical polymerization initiator. The sealant according to any one of claims 1 to 16, wherein the content of the polymerizable monomer (X) having an element having an atomic number of 9 or more in 100 parts by mass of the polymerizable monomer is 40 to 90 parts by mass. .. The seal according to any one of claims 1 to 17, wherein the content of the crosslinkable monomer (Y) having two or more polymerizable functional groups in 100 parts by mass of the polymerizable monomer is 5 to 60 parts by mass. Stopping agent. The sealant according to any one of claims 1 to 18, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Any one of claims 1 to 19 of the cured product, which is measured under the conditions of a temperature of 60 ° C. and a relative humidity of 90% according to JIS Z0208, and has a moisture permeability of 40 g / m ^{2 or less at a thickness of 100 μm.} The sealant according to the section. The sealant according to any one of claims 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. The sealant according to any one of claims 1 to 21, which is a sealant for an organic electroluminescence device. A method of manufacturing an apparatus including a first member and a second member.
The bonding step of adhering the sealant according to any one of claims 1 to 22 to the first member,
The irradiation process of irradiating the attached sealant with light,
The bonding process of bonding the first member and the second member via a light-irradiated sealant,
A method of manufacturing an apparatus. The first member is an organic electroluminescence element,
The second member is the substrate,
The device is an organic electroluminescence display device,
The method for manufacturing an apparatus according to claim 23. The first member is the substrate,
The second member is an organic electroluminescence element,
The device is an organic electroluminescence display device,
The method for manufacturing an apparatus according to claim 23. The cured product of the encapsulant according to any one of claims 1 to 22. An organic electroluminescence display device comprising an organic electroluminescence element and the cured product according to claim 26. Includes a laminate in which an inorganic film and an organic film are laminated,
An organic electroluminescence display device in which the organic film comprises the cured product according to claim 26. Includes a laminate in which an inorganic film and an organic film are laminated,
The organic electroluminescence display device, wherein the organic film directly laminated on the organic electroluminescence element contains the cured product according to claim 26. A composition containing a polymerizable monomer (X) having at least one selected from the group consisting of a fluorine element and a bromine element, and a polymerization initiator.