CN117510794A

CN117510794A - Composition and method for producing the same

Info

Publication number: CN117510794A
Application number: CN202311534288.6A
Authority: CN
Inventors: 石田泰则; 栗村启之; 山下幸彦
Original assignee: Denka Co Ltd
Current assignee: Denka Co Ltd
Priority date: 2019-03-27
Filing date: 2020-03-25
Publication date: 2024-02-06
Also published as: KR20210148073A; JPWO2020196669A1; CN113227159B; WO2020196669A1; JP7269323B2; TW202102601A; JP2023012530A; TWI828891B; CN113227159A

Abstract

In one aspect, the present invention provides a composition comprising a polymerizable component and a polymerization initiator, wherein the cured product has an average free volume of 0.1nm ³ The following is given.

Description

Composition and method for producing the same

The present application is a divisional application of chinese invention patent application (PCT application No. PCT/JP 2020/013459) with application No. 202080007209.4 and application name "composition", 25 of 3 months in 2020.

Technical Field

The present invention relates to compositions. For example, the present invention relates to a resin composition and a cured product thereof, a sealing material for an organic electroluminescent display element, an organic electroluminescent display device, and a method for producing the same.

Background

In recent years, organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements have been studied. The organic thin film element can be easily manufactured by a vacuum deposition method, a solution coating method, or the like, and therefore has excellent 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 from one electrode into the organic light emitting material layer, while holes are injected from the other electrode into the organic light emitting material layer, whereby electrons and holes combine in the organic light emitting material layer to perform self-luminescence. The organic EL display element has the following advantages over liquid crystal display elements and the like that require a backlight: the display device has good visibility, can be further thinned, and can realize DC low-voltage driving.

However, such an organic EL display element has the following problems: when the organic light-emitting material layer or the electrode is exposed to the outside air, the light-emitting characteristics thereof are drastically deteriorated, and the lifetime thereof is shortened. Therefore, in the organic EL display element, a sealing technique for blocking the organic light-emitting material layer and the electrode from moisture and oxygen in the atmosphere is essential in order to improve the stability and durability of the organic EL display element.

For example, patent document 1 discloses the following method: in an upper surface emission type organic EL display device or the like, a space between organic EL display device substrates is filled with a photocurable sealing agent, and the sealing is performed by irradiation with light. Patent document 2 describes the following: an organic EL display has a sealing material made of a frit, which seals a light-emitting body.

Patent document 3 discloses a transparent barrier film having an inorganic thin film layer on at least one side of a plastic film, which is usable for packaging materials requiring air tightness, such as electronic components, and is characterized in that the maximum value of S parameter in the inorganic thin film, which is determined for the inorganic layer by positron annihilation, is 0.51 or less.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2001-357973

Patent document 2: japanese patent laid-open No. 10-74583

Patent document 3: japanese patent laid-open No. 2015-42487

Disclosure of Invention

Problems to be solved by the invention

The sealants or sealing materials described in patent documents 1 and 2 have room for further improvement in terms of further improving moisture resistance and achieving sufficient reliability and durability for the organic EL display element.

The barrier film described in patent document 3 has the following problems: the adhesion to the substrate is insufficient, and the following property to the irregularities of the substrate is low.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition capable of forming a sealing material excellent in moisture resistance and adhesion to a substrate.

Means for solving the problems

The present invention provides in some aspects the following <1> to <19>.

<1>Composition comprising polymerizable component and polymerization initiator, wherein the average free volume of the cured product is 0.1nm ³ The following is given.

<2> the composition according to <1>, wherein the porosity of the cured body is 20% by volume or less.

<3> the composition according to <1> or <2>, wherein the glass transition temperature of the cured body is 60 ℃ or higher.

<4>Such as<1>～<3>The composition according to any one of the preceding claims, wherein the cured body has a crosslink density of 1.0X10 ^-3 mol/cm ³ The above.

The composition according to any one of <1> to <4>, wherein the specific gravity of the cured body at 85 ℃ is 1.2 to 3.0.

The composition according to any one of <1> to <5>, wherein the polymerizable component contains a polymerizable monomer containing 1 or more selected from the group consisting of elements having an atomic number of 9 or more.

The composition according to <7> to <6>, wherein the element is a halogen element.

The composition according to <7>, wherein the halogen element is 1 or more selected from the group consisting of chlorine element, fluorine element and bromine element.

The composition according to any one of <6> to <8>, wherein the content of the element is 10 to 50% by mass based on the total amount of the elements contained in the polymerizable monomer.

The composition according to any one of <1> to <9>, wherein the polymerizable component contains a crosslinking agent.

<11>Such as<1>～<10>The composition according to any one of the preceding claims, wherein the cured body has a moisture permeability of 0.01 to 300 g/(m) ² 24 hours), the moisture permeability was measured on a cured product having a thickness of 100 μm in accordance with JIS Z0208 under conditions of a temperature of 85℃and a relative humidity of 85%.

The composition according to any one of <1> to <11>, wherein the cured body has a total light transmittance of 95% or more, and the total light transmittance is measured in a wavelength range of 380 to 1000 nm.

<13> the composition according to any one of <1> to <12>, which is used as a sealant for an organic electroluminescent display element.

<14> an adhesive comprising the composition according to any one of <1> to <13 >.

<15> a cured product obtained by curing the composition according to any one of <1> to <13 >.

<16> a sealing material for an organic electroluminescent display element, comprising an organic layer comprising the cured product of <15 >.

<17> the sealing material for an organic electroluminescent display element according to <16>, further comprising an inorganic layer.

<18> an organic electroluminescent display device comprising: an organic electroluminescent display element; and the sealing material for an organic electroluminescent display element according to <16> or <17 >.

<19> a method for manufacturing an organic electroluminescent display device, comprising the steps of: attaching the composition of any one of <1> to <13> to a substrate and irradiating with light; and a step of bonding the substrate to the organic electroluminescent display element through the resin composition irradiated with light.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a composition capable of forming a sealing material having excellent moisture resistance and excellent adhesion to a substrate can be provided.

Detailed Description

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

In the present specification, (meth) acrylate means acrylate and methacrylate corresponding thereto, and the same applies to other similar expressions. The monofunctional (meth) acrylate means a (meth) acrylate having 1 (meth) acryloyl group. The multifunctional (meth) acrylate means a (meth) acrylate having 2 or more (meth) acryloyl groups.

As the composition according to one embodiment, a resin composition is preferable.

< resin composition >

A resin composition according to one embodiment comprises a polymerizable component and a polymerization initiator, and the cured product of the resin composition has an average free volume of 0.1nm ³ The following is given.

As a method for determining the free volume of a polymer, positron annihilation is known (see polymer, volume 42, month 12 (1993)). Typically, positrons (e ⁺ ) Incident toWhen a polymer is used, positron and electron (e ^- ) Binding to produce positron (Ps).

Positrons are inverse particles of electrons, which are basic particles having the same mass as electrons but having charges of opposite sign. In an amorphous solid such as a polymer, positrons are sometimes paired with electrons, and are called positron elements. When positron annihilates, annihilation gamma rays are emitted in two directions. By measuring the temporal change in intensity of annihilation gamma rays, the lifetime of positrons can be measured.

The positron has a lifetime of about 140ns, and is shortened to 1ns to 5ns when it undergoes an impact process of capturing other electrons in a substance. When positive electron elements exist in the free volume space in the solid, the positive correlation exists between the size of the space and the life of the positive electron elements, and the information of the pore size can be obtained by measuring the life of the positive electron elements based on the annihilation of the impact.

Positron annihilation refers to the following method: the free volume of the polymer was determined by measuring the lifetime (. Tau.3) of a positive electron element (radius 0.1nm, hereinafter also referred to as "o-Ps") accounting for 3/4 of the positron element (Ps) when the positive electron element entered the pores of the polymer. The lifetime (. Tau.3) of an o-Ps is determined by the fact that when an o-Ps collides with the walls of pores present in a polymer, the positrons (e ⁺ ) And electrons (e) in the walls of the pores ^- ) The probability of overlap determines that the larger the porosity of the polymer, the longer the lifetime (τ3) of the o-Ps. The following models are preferably used in the present invention: the pore was regarded as a spherical square trap potential with an infinite height, and the electron layer with a thickness Δr was assumed to exist on the wall surface of the pore, and the positron annihilation velocity obtained by calculating the overlap of the electron layer with the fluctuation function of o-Ps was obtained. When the pore diameter R of the polymer is about 0.16 to 0.8nm, the relationship between the lifetime τ3 of the o-Ps and the pore diameter R is established by the following formula (1).

[ mathematics 1]

[ in the above formula (1), τ3 represents the lifetime of the positive electron element (o-Ps) measured, R represents the pore diameter of the polymer, and ΔR represents the thickness of the wall surface of the pore. ]

That is, in the case of using the positron annihilation method, the lifetime (τ3) of the positive electron element (o-Ps) is obtained, whereby the pore diameter R of the polymer can be obtained based on the above formula (1). Further, from the value of the pore diameter R of the polymer obtained, the average free volume (pore volume) of the polymer can be calculated by the following formula (2).

Mean free volume=4/3 pi R ³ (2)

The free volume analyzed by the positron annihilation method indicates a region not occupied by a molecular chain of a cured product of the resin composition, and reflects a volume generated in the vicinity of the molecular chain when the molecular chain of the cured product of the resin composition changes. Specifically, the time from the incidence of a positron to the sample to annihilation can be measured, and information about the atomic pores, the size of free volume, the number density, and the like can be obtained by a nondestructive observation method based on the annihilation lifetime.

As a result of intensive studies, the inventors of the present application have found that, with respect to a resin composition containing a polymerizable component and a polymerization initiator, the average free volume of a cured product is set to 0.1nm ³ Hereinafter, the resin composition is excellent in moisture resistance (hereinafter, also referred to as low moisture permeability), and has good following property of irregularities and excellent adhesion to a substrate such as a glass substrate.

The average free volume of the cured product in the resin composition is preferably 0.1nm from the viewpoint of easy obtaining of a cured product excellent in moisture resistance and adhesion to a substrate ³ Hereinafter, more preferably 0.095nm ³ Hereinafter, it is more preferably 0.09nm ³ Hereinafter, it is particularly preferably 0.085nm ³ Hereinafter, it is more preferably 0.08nm ³ Hereinafter, it is preferably 0.001nm ³ The above is more preferably 0.003nm ³ The above is more preferably 0.005nm ³ The above is particularly preferably 0.01nm ³ The above is more preferably 0.05nm ³ The above. Resin compositionThe average free volume of the cured body of the article is affected by, for example, the size of the van der waals radius of the atoms constituting the monomer. For example, by containing an element having an atomic number of 9 or more in the polymerizable monomer (X) described later, the preferable average free volume can be easily obtained.

From the above point of view, the average free volume of the cured body may be 0.001 to 0.1nm ³ 、0.003～0.1nm ³ 、0.005～0.1nm ³ 、0.01～0.1nm ³ 、0.05～0.1nm ³ 、0.001～0.095nm ³ 、0.003～0.095nm ³ 、0.005～0.095nm ³ 、0.01～0.095nm ³ 、0.05～0.095nm ³ 、0.001～0.09nm ³ 、0.003～0.09nm ³ 、0.005～0.09nm ³ 、0.01～0.09nm ³ 、0.05～0.09nm ³ 、0.001～0.085nm ³ 、0.003～0.085nm ³ 、0.005～0.085nm ³ 、0.01～0.085nm ³ 、0.05～0.085nm ³ 、0.001～0.08nm ³ 、0.003～0.08nm ³ 、0.005～0.08nm ³ 、0.01～0.08nm ³ Or 0.05 to 0.08nm ³ 。

In the resin composition according to the present embodiment, the porosity in the cured body is preferably 20% by volume or less, more preferably 15% by volume or less, and even more preferably 10% by volume or less, from the viewpoint of easily obtaining a cured body having more excellent moisture resistance and also excellent adhesion to a substrate. The porosity of the cured product is preferably 0% by volume or more, more preferably 1% by volume or more. When the lifetime of positrons is 3-component analyzed by the nonlinear least square method, τ1, τ2, τ3 are set from the one with the shorter annihilation lifetime, and the corresponding intensities are I1, I2, I3 (i1+i2+i3=100%), the porosity of the cured body is defined by the following formula (3).

Porosity (vol%) =i3/(i1+i2+i3) (3)

The polymerizable component contained in the resin composition according to the present embodiment contains a compound having a polymerizable functional group. The average free volume of the polymerizable component as long as the cured product is 0.01nm ³ The following components are not limited. One embodiment isThe polymerizable component contains 1 or more polymerizable monomers (hereinafter, also referred to as polymerizable monomers (X)) selected from the group consisting of elements having an atomic number of 9 or more. The polymerizable monomer is a monomer having a polymerizable functional group.

The element having an atomic number of 9 or more contained in the polymerizable monomer (X) may be an element having an atomic number of 53 or less or an element having an atomic number of 35 or less. The element having an atomic number of 9 or more is preferably a halogen element. The halogen element is preferably 1 or more selected from the group consisting of chlorine element, fluorine element and bromine element, and more preferably 1 or more selected from the group consisting of fluorine element and bromine element.

When the polymerizable monomer (X) contains an element having an atomic number of 9 or more, the number of elements having an atomic number of 9 or more is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more per 1 molecular monomer. The upper limit of the number of elements having an atomic number of 9 or more is not particularly limited, and may be, for example, 40 or less or 30 or less per 1-molecule monomer.

The content of the element having an atomic number of 9 or more in the polymerizable monomer (X) is preferably 10 to 50 mass% with respect to the total amount of the elements contained in the polymerizable monomer (X). The content of the element having an atomic number of 9 or more is more preferably 15% by mass or more, and still more preferably 20% by mass or more. When the content of the element is 10 mass% or more, the cured product has low moisture permeability and is more excellent in moisture resistance. The content of the element having an atomic number of 9 or more is more preferably 45 mass% or less, and still more preferably 40 mass% or less, relative to the total amount of elements contained in the polymerizable monomer (X). By setting the content of this element to 50 mass% or less, the resin composition is excellent in curability.

From the above viewpoints, the content of the element having an atomic number of 9 or more in the polymerizable monomer (X) may be 15 to 50 mass%, 20 to 50 mass%, 10 to 45 mass%, 15 to 45 mass%, 20 to 45 mass%, 10 to 40 mass%, 15 to 40 mass%, or 20 to 40 mass% with respect to the total amount of the elements contained in the polymerizable monomer (X).

The polymerizable functional group in the polymerizable monomer (X) is preferably a cationically polymerizable functional group and/or a radically polymerizable functional group. The cationically polymerizable functional group is preferably at least one selected from the group consisting of a glycidyl ether group, an epoxy group, a vinyl ether group, and an oxetane group. The epoxy group may be an alicyclic epoxy group. The radical polymerizable functional group is preferably at least one selected from the group consisting of (meth) acryl groups and (meth) acrylamide groups. As the polymerizable monomer (X), a monomer having 1 polymerizable functional group is preferable.

In the case where the polymerizable monomer (X) is a compound having a cationically polymerizable functional group, examples of the polymerizable monomer (X) include halogenated phenyl glycidyl ethers such as bromophenyl glycidyl ether, dibromophenyl glycidyl ether and brominated tolyl glycidyl ether, brominated bisphenol a-type epoxy resins, brominated bisphenol F-type Novolac-type epoxy resins, brominated phenol Novolac-type epoxy resins, and diglycidyl ethers of tetrabromobisphenol a.

When the polymerizable monomer (X) is a compound having a radical polymerizable functional group, examples of the polymerizable monomer (X) include halogenated phenyl (meth) acrylates such as fluorophenyl (meth) acrylate, trifluorophenyl (meth) acrylate, pentafluorophenyl (meth) acrylate, chlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, pentachlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, and the like.

The content of the polymerizable monomer (X) in the polymerizable component is preferably 50 to 95 parts by mass, more preferably 52.5 to 85 parts by mass, and still more preferably 55 to 80 parts by mass, per 100 parts by mass of the polymerizable component. When the content of the polymerizable monomer (X) is 50 parts by mass or more, the cured product becomes lower in moisture permeability, and when it is 95 parts by mass or less, the curability is excellent.

In another embodiment, the polymerizable component contains a crosslinking agent (Y). The crosslinking agent (Y) is a compound having 2 or more polymerizable functional groups and is a compound (crosslinkable compound) other than the polymerizable monomer (X). The crosslinking agent (Y) may be a compound having a cationically polymerizable functional group and/or a compound having a radically polymerizable functional group.

The compound having a cationically polymerizable group may be 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 alicyclic compounds having an epoxy group, aromatic compounds having an epoxy group, diglycidyl ether compounds, oxetane compounds, and cationically polymerizable vinyl compounds. These compounds may be used in the form of 1 or more.

Examples of the alicyclic compound having an epoxy group (hereinafter, may be referred to as an alicyclic epoxy compound) include: a compound having at least 1 cycloalkane ring (e.g., cyclohexene ring, cyclopentene ring, pinene ring, etc.) or a derivative thereof is epoxidized with an appropriate oxidizing agent such as hydrogen peroxide or peracid. Alternatively, examples of the alicyclic epoxy compound include a hydrogenated epoxy compound obtained by hydrogenating an aromatic epoxy compound (for example, bisphenol a epoxy compound, bisphenol F epoxy compound, etc.). These compounds may be used in the form of 1 or more.

Examples of the alicyclic epoxy compound include 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexane carboxylate, 3, 4-epoxycyclohexylalkyl (meth) acrylate (e.g., 3, 4-epoxycyclohexylmethyl (meth) acrylate), 3',4' -diepoxy) bicyclohexane, 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 a1, 2-epoxycyclohexane structure is preferable. Among alicyclic epoxy compounds having A1, 2-epoxycyclohexane structure, preferred is a compound represented by the following formula (A1-1).

[ chemical formula 1]

[ in the formula (A1-1), R ¹¹ 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, a carbonate group, an amide bond, or a group formed by connecting a plurality of them.]

R ¹¹ Preferably a linking group. Among the linking groups, a functional group having an ester bond is preferable. Of these, 3, 4-epoxycyclohexylmethyl 3',4' -epoxycyclohexane carboxylate is preferred.

The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, further preferably 300 or less, more preferably less than 300, further more preferably 100 to 280, from the viewpoint of low moisture permeability and storage stability.

When the alicyclic epoxy compound has a molecular weight distribution, the number average molecular weight of the alicyclic epoxy compound is preferably within the above range. In the present specification, the number average molecular weight means a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the following measurement conditions.

Solvent (mobile phase): THF (tetrahydrofuran)

Degassing device: ERMA ERC-3310

Pump: PU-980 manufactured by Japanese spectroscopic Co

Flow rate: 1.0ml/min

Automatic sampler: AS-8020 manufactured by Tosoh corporation

Column incubator: l-5030 manufactured by Hitachi preparation

Set temperature: 40 DEG C

Column composition: TSK protection column MP (. Times.L) of 6.0 mmID. Times.4.0 cm 2 roots of Tosoh corporation, TSK-GELMULTIPORE HXL-M of 7.8 mmID. Times.30.0 cm 2 roots of Tosoh corporation, 4 roots in total

Detector: l-3350 manufactured by Hitachi manufacturing

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, and a polymer may be used, and examples thereof include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, novolac type epoxy resin, cresol Novolac type epoxy resin, and modified products thereof. These epoxy resins may be used in an amount of 1 or more. Among these, aromatic epoxy compounds having a bisphenol structure are preferable. Among the aromatic epoxy compounds having a bisphenol structure, a compound represented by the following formula (A2-1) is preferable.

[ chemical formula 2]

In [ (A2-1), n represents a real number of 0.1-30, R ²¹ 、R ²² 、R ²³ R is R ²⁴ Each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms.]

R ²¹ 、R ²² 、R ²³ 、R ²⁴ Preferably a hydrogen atom or a methyl group. R is R ²¹ 、R ²² 、R ²³ 、R ²⁴ Preferably atoms or groups identical to each other.

Among the aromatic epoxy compounds having a bisphenol structure, 1 or more selected from the group consisting of bisphenol a type epoxy resins and bisphenol F type epoxy resins are preferable.

The molecular weight of the aromatic epoxy compound is preferably 100 to 5000, more preferably 150 to 1000, and even more preferably 200 to 450, from the viewpoint of low moisture permeability of the cured product.

When the aromatic epoxy compound has a molecular weight distribution, the number average molecular weight of the aromatic epoxy compound is preferably within the above range. In the present specification, the number average molecular weight means a value in terms of polystyrene measured by Gel Permeation Chromatography (GPC) under the above measurement conditions.

Examples of the diglycidyl ether compound include diglycidyl ethers of alkylene glycols (for example, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1, 6-hexanediol, etc.), polyglycidyl ethers of polyhydric alcohols (for example, diglycidyl ether of glycerin or alkylene oxide adducts thereof, etc.), diglycidyl ethers of polyalkylene glycols (for example, diglycidyl ether of polyethylene glycol or alkylene oxide adducts thereof, diglycidyl ether of polypropylene glycol or alkylene oxide adducts thereof, etc.). Among them, examples of alkylene oxides include aliphatic series such as ethylene oxide and propylene oxide.

The OXETANE compound is not particularly limited, and examples thereof include 1, 4-bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] benzene (ARON oxide ox-121 and the like), bis (1-ethyl- (3-oxetanyl)) methyl ether (ARON oxide ox-221 and the like) and the like. The oxetane compound used in the crosslinking agent (Y) is a compound having 2 or more oxetane rings in the molecule.

Examples of the cationically polymerizable vinyl compound include a vinyl ether compound and the like. Examples of the vinyl ether compound include di-or trivinyl ether compounds such as ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimethylolpropane trivinyl ether.

As the compound having a cationically polymerizable group, any of monomers, oligomers, or polymers can be used.

Examples of the compound having a radical polymerizable group include a (meth) acrylate compound, an allyl compound, and a radical polymerizable vinyl compound. These compounds may be used in the form of 1 or more. As the compound having a radical polymerizable group, (meth) acrylate compounds are preferably used, and (meth) acrylate compounds having no fluorine atom are more preferably used.

Examples of the (meth) acrylate compound include polyfunctional (meth) acrylates such as 1, 6-hexanediol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate.

Examples of the allyl compound include triallyl (methyl) silane.

Examples of the radical polymerizable vinyl compound include divinylbenzene and the like. The radically polymerizable vinyl compound may be a vinyl ether compound, a vinyl ester compound, or the like.

The content of the crosslinking agent (Y) in the polymerizable component is preferably 5 to 60 parts by mass, more preferably 7.5 to 55 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the polymerizable monomer. When the content of the crosslinking agent (Y) is 5 parts by mass or more, excellent curability can be obtained, and when it is 60 parts by mass or less, adhesion durability is not easily lowered.

The polymerizable component may contain only the polymerizable monomer (X), may contain only the crosslinking agent (Y), and may contain the polymerizable monomer (X) and the crosslinking agent (Y).

The polymerizable component may contain other polymerizable monomers (Z) in addition to the polymerizable monomer (X) and/or the crosslinking agent (Y). The other polymerizable monomer (Z) may be referred to as a polymerizable monomer containing no halogen element in the polymerizable monomer (X).

Examples of the other polymerizable monomer (Z) include oxetane compounds, cationically polymerizable vinyl compounds, and (meth) acrylate compounds.

Examples of OXETANE compounds include monofunctional OXETANE compounds such as 3-ethyl-3-hydroxymethyloxetane (trade name: ARON oxide ox-101, etc. manufactured by eastern synthetic Co., ltd.), 3-ethyl-3- (phenoxymethyl) OXETANE (ARON oxide ox-211, etc.), and 3-ethyl-3- (2-ethylhexyloxymethyl) OXETANE (ARON oxide ox-212, etc.).

Examples of the cationically polymerizable vinyl compound include a monovinyl ether compound such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, a monoglycidyl ether compound such as lauryl glycidyl ether, vinylamine, and styrene.

Examples of the (meth) acrylate compound include monofunctional (meth) acrylates such as ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, and ethoxylated ortho-phenylphenol (meth) acrylate.

The resin composition according to the present embodiment contains a polymerization initiator as an essential component.

The polymerization initiator is preferably a photopolymerization initiator. When a photopolymerization initiator is used, the resin composition of the present embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

The polymerization initiator is preferably a photo-cationic polymerization initiator and/or a photo-radical polymerization initiator. In the case of using a photo-cationic polymerization initiator, polymerization of a cationically polymerizable functional group can be achieved, and in the case of using a photo-radical polymerization initiator, polymerization of a radically polymerizable functional group can be achieved.

Examples of the photo-cation polymerization initiator include, but are not particularly limited to, aryl sulfonium salt derivatives (e.g., cyracure UVI-6990, cyracure UVI-6974, adeka Optomer SP-150, adeka Optomer SP-152, adeka Optomer SP-170, adeka Optomer SP-172, CPI-100P, CPI-101A, CPI-200K, CPI-210S, LW-S1, cibacure 1190, and the like, manufactured by Dow Chemical Co., ltd.), aryl iodonium salt derivatives (e.g., irgacure250, RP-2074, manufactured by RHODIA Japan, and the like, manufactured by Ciba Specialty Chemicals), allene-ion complex derivatives, diazonium salt derivatives, triazine-based initiators, and other acid generators, and the like. As the cationic species of the photo-cationic polymerization initiator, an onium salt represented by the formula (B-1) is preferable.

[ chemical formula 3]

[ A ] represents an element having a valence m from group VIA to group VIIA. 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 represents a divalent group represented by the following formula (B-1-1):

[ chemical formula 4]

In the formula (B-1-1), E represents a divalent group, G represents-O-, -S-, -SO ₂ -, -NH-, -NR '-, -CO-; -COO-, -CONH-, alkylene or phenylene having 1 to 3 carbon atoms (R' is alkyl having 1 to 5 carbon atoms or aryl having 6 to 10 carbon atoms). a represents 0 to 5. a+1E and A G may be the same or different. a is preferably an integer. X is X ^- The number of onium counter ions is p+1 per 1 molecule.]

The onium ion of the formula (B-1-1) is not particularly limited, and examples thereof include 4- (phenylthio) phenyldiphenyl sulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenyl) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenyl sulfonium, 7-isopropyl-9-oxo-10-thiohetero-9, 10-dihydro-2-xylyl sulfonium, 7-isopropyl-9-oxo-10-thiohetero-9, 10-dihydro-2-diphenylsulfonium, 2- [ (di-p-tolyl) sulfonium ] thioxanthone, 2- [ (diphenyl) sulfonium ] thioxanthone, 4- [4- (4-t-butylbenzoyl) phenyldiphenyl) sulfonium, 4- (4-benzoylphenylthiosulfonium, 4-methylbenzyl) phenylsulfonium, 5-benzylthiosulfonium, 4-benzylphenylthiosulfonium, 5-benzylphenylthiosulfonium and 5-benzylthiosulfonium, octadecyl methyl benzoylmethyl sulfonium, and the like.

R is an organic group bonded to A. R represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, or a heterocyclic group having 1 to 30 carbon atomsAn alkyl group, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one member selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocycle, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen. The number of R is m+p (m-1) +1, and each may be the same or different from each other. More than 2R may be directly bonded to each other or through-O-; -S-, -SO ₂ -, -NH-, -NR' -, -CO-; -COO-, -CONH-, an alkylene group or a phenylene group having 1 to 3 carbon atoms is bonded to form a ring structure containing the element A. Wherein R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, and the like, Condensed polycyclic aryl groups such as a group, a naphto naphthyl group, a benzo anthryl group, an anthraquinone group, a fluorenyl group, a naphthoquinone group, and an anthraquinone group.

The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and examples of the substituent include: straight-chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a hydroxyl group; straight-chain or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy and dodecyloxy groups; straight-chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as acetyl, propionyl, butyryl, 2-methylpropanoyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl and octadecanoyl groups; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octoxycarbonyl, tetradecyloxycarbonyl and octadecyloxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthyloxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthyloxy thiocarbonyl; straight-chain or branched acyloxy groups having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy and octadecylcarbonyloxy; phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl ] phenylthio, 4- [4- (phenylthio) phenoxy ] phenylthio, 4- [4- (phenylthio) phenyl ] phenylthio arylthio groups having 6 to 20 carbon atoms, such as 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-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 and 4- (p-tert-butylbenzoyl) phenylthio; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms such as methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio and dodecylthio; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl and the like; thienyl, furyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathianyl, benzodihydrofuranyl, isobenzodihydrofuranyl, dibenzothiophenyl, xanthonyl, thioxanthonyl, dibenzofuranyl and other heterocyclic groups having 4 to 20 carbon atoms; aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthoxy; linear or branched alkyl sulfinyl groups having 1 to 18 carbon atoms such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl and the like; arylsulfinyl having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl and the like; arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl groups; an alkyleneoxy group represented by the formula (B-1-2) (Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5); unsubstituted amino; an amino group monosubstituted or disubstituted with an alkyl group having 1 to 5 carbon atoms and/or an aryl group having 6 to 10 carbon atoms; cyano group; a nitro group; halogen such as fluorine, chlorine, bromine, iodine, etc.; etc

[ chemical formula 5]

P in formula (B-1) represents [ D-A ] ⁺ R _m-1 ]The number of repeating units of the bond is preferably an integer of 0 to 3.

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

Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris (4-fluorophenyl) sulfonium, tris-1-naphthylsulfonium, tris-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylsulfanyl) phenyldiphenylsulfonium, 4- (p-tolylsulfanyl) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylsulfanyl) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylsulfanyl) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylsulfanyl) phenylbis (4-methoxyphenyl) sulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] phenyl } sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, bis {4- [ bis { 4-methylphenyl ] sulfide, bis { 4-chlorophenyl } phenyl } sulfide, bis { 4-chlorophenyl } 4-bis (4-methoxyphenyl) sulfide, bis { 4-chlorophenyl } sulfide, bis (4-methoxyphenyl) sulfide, bis [ 4-p-methylphenyl ] sulfide, bis [ 4-phenylsulfide ] sulfide, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thioxo-9, 10-dihydro-anthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thioxo-9, 10-dihydro-anthracene-2-yldiphenylsulfonium, 2- [ (di-p-tolyl) sulfonium ] thioxanthone, 2- [ (diphenyl) sulfonium ] thioxanthone, 4- [4- (4-t-butylbenzoyl) phenylthio ] phenyldi-p-tolylsulfonium, 4- [4- (4-t-butylbenzoyl) phenylthio ] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio) ] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio) ] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thianthracenium, 5-phenylthianthracene, 5-tolylthio-nium, 5- (4-t-butylphenylthioxolium) or 5- (6, 6-trimethylphenylthioxolium, etc.; diaryl sulfonium such as diphenyl benzoylmethylsulfonium, diphenyl 4-nitrobenzoylmethylsulfonium, diphenyl benzylsulfonium and diphenyl methylsulfonium; monoaryl sulfonium such as phenylmethylbenzyl sulfonium, 4-hydroxyphenylmethylbenzyl sulfonium, 4-methoxyphenylmethylbenzyl sulfonium, 4-acetylcarbonyloxyphenylmethylbenzyl sulfonium, 2-naphthylmethylbenzyl sulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylbenzoyl methylsulfonium, 4-hydroxyphenylmethylbenzoyl methylsulfonium, 4-methoxyphenylmethylbenzoyl methylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzoyl methylsulfonium, 2-naphthylmethylbenzoyl methylsulfonium, 2-naphthyloctadecyl benzoylmethylsulfonium, 9-anthracenylmethylbenzoylmethylsulfonium, and the like; and trialkylsulfonium such as dimethylbenzoyl methyl sulfonium, benzoylmethyl tetrahydrothiophenium, dimethylbenzyl sulfonium, benzyltetrahydrothiophenium, octadecyl methylbenzoyl methyl sulfonium, and the like.

Among these onium ions, 1 or more of sulfonium ions and iodonium ions are preferably contained, and sulfonium ions are more preferably contained. As sulfonium ions, preference is given to those selected from the group consisting of triphenylsulfonium, tri-p-tolylthio, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonium) phenyl ] sulfide, bis [4- { bis [4- (2-hydroxyethoxy) phenyl ] sulfonium } phenyl ] sulfide, bis {4- [ bis (4-fluorophenyl) sulfonium ] phenyl } sulfide, 4- (4-benzoyl-2-chlorophenyl) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thiohetero-9, 10-dihydro-2-anthracenedi-p-tolylthio, 7-isopropyl-9-oxo-10-thiohetero-9, 10-dihydro-anthracene-2-yldiphenylsulfonium, 2- [ (di-p-tolyl) sulfonium ] thioxanthone, 2- [ (diphenyl) thioxanthone, 4- [4- (4-t-butylbenzoyl) phenylthiobis (4-fluorophenyl) phenylsulfonium, 4- (4-benzoylphenylthiothi) phenylsulfonium, 4- (4-benzylphenylthiosulfonium), 5-benzylthiothium, 4-phenylthiothium, 5-benzylthiothium, 5-phenylthiosulfonium, 4-hydroxyphenylmethyl benzoylmethyl sulfonium and octadecyl methyl benzoylmethyl sulfonium.

In the formula (B-1), X ^- Is a counter ion. The number of the molecules is p+1 per 1 molecule. Counter ionExamples thereof include, but are not particularly limited to, halides and methylated compounds such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds. As X ^- Examples thereof include: f (F) ^- 、Cl ^- 、Br ^- 、I ^- A halogen ion; OH (OH) ^- ；ClO ₄ ^- ；FSO ₃ ^- 、ClSO ₃ ^- 、CH ₃ SO ₃ ^- 、C ₆ H ₅ SO ₃ ^- 、CF ₃ SO ₃ ^- And the class of sulfonate ions; HSO (high speed oxygen) ₄ ^- 、SO ₄ ^2- A class of plasma sulfate ions; HCO (hydrogen chloride) ₃ ^- 、CO ₃ ^2- And carbonate ions; h ₂ PO ₄ ^- 、HPO ₄ ^2- 、PO ₄ ^3- Isophosphate ions; PF (physical filter) ₆ ^- 、PF ₅ OH ^- Fluorophosphate ions such as fluoroalkyl fluorophosphate ions; BF (BF) ₄ ^- 、B(C ₆ F ₅ ) ₄ ^- 、B(C ₆ H ₄ CF ₃ ) ₄ ^- Iso-borate ion species; alCl ₄ ^- ；BiF ₆ ^- Etc. Further, sbF can be mentioned ₆ ^- 、SbF ₅ OH ^- Isofluoroantimonate ions, asF ₆ ^- 、AsF ₅ OH ^- And the class of iso-fluoro arsenate ions.

Examples of the fluoroalkyl fluorophosphate ion include fluoroalkyl fluorophosphate ions represented by the formula (B-1-3) and the like.

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

In the formula (B-1-3), rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is preferably an integer of 1 to 5. 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 fluoroalkyl fluorophosphate ion represented by the formula (B-1-3), rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably having 1 to 4 carbon atoms. As a means of Examples of the alkyl group include: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl, and the like; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. 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, etc.

Preferred fluoroalkyl fluorophosphoric acid 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 ] ^- [ (CF) ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- Etc.

For easy dissolution in the epoxy compound or the epoxy resin, a photo cation polymerization initiator may be used which is dissolved in a solvent in advance. Examples of the solvent include carbonates such as propylene carbonate, ethylene carbonate, 1, 2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

These photo cation polymerization initiators may be used in the form of 1 or more kinds.

Examples of the anionic species of the (B) photo-cationic polymerization initiator include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds. These anionic species may be used in an amount of 1 or more. Among these, fluoride is preferable in view of excellent photocurability, adhesion, and improvement of adhesion durability. Of the fluorides, hexafluoroantimonate is preferred.

(B) Among the photo-cation polymerization initiators, preferred are 1 or more of the group consisting of triarylsulfonium salt hexafluoroantimonate represented by the formula (B-2) and diphenyl 4-thiophenoxyphenyl sulfonium tris (pentafluoroethyl) trifluorophosphate represented by the formula (B-3), and more preferred is triarylsulfonium salt hexafluoroantimonate.

[ chemical formula 6]

[ chemical formula 7]

The photo radical polymerization initiator is not particularly limited, and examples thereof include: benzophenone and derivatives thereof; benzil and derivatives thereof; anthraquinone and its derivatives; benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; α -hydroxyalkylphenone type photopolymerization initiators such as 1-hydroxycyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and the like; acetophenone type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone; 2-dimethylaminoethyl benzoate; p-dimethylaminoethyl benzoate; diphenyl disulfide; thioxanthone and derivatives thereof; camphorquinone photopolymerization initiators such as camphorquinone, 7-dimethyl-2, 3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7-dimethyl-2, 3-dioxobicyclo [2.2.1] heptane-1-carboxyl-2-bromoethyl ester, 7-dimethyl-2, 3-dioxobicyclo [2.2.1] heptane-1-carboxyl-2-methyl ester, and 7, 7-dimethyl-2, 3-dioxobicyclo [2.2.1] heptane-1-formyl chloride; α -aminoalkylbenzophenone photopolymerization initiators such as 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acyl phosphine oxide type photopolymerization initiators such as benzoyl diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, benzoyl diethoxy phosphine oxide, 2,4, 6-trimethylbenzoyl dimethoxy phenyl phosphine oxide, 2,4, 6-trimethylbenzoyl diethoxy phenyl phosphine oxide, and bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphine oxide; methyl benzoate; 2- [ 2-oxo-2-phenyl-acetoxy-ethoxy ] ethyl oxy-phenylacetate; 2- [ 2-hydroxyethoxy ] ethyl oxyphenylacetate; etc.

The content of the polymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable component. When the content of the polymerization initiator is 0.01 parts by mass or more, deterioration of curability can be suppressed, and when it is 5 parts by mass or less, deterioration of adhesion durability can be suppressed.

The resin composition of the present embodiment may contain a photosensitizer. The photosensitizer is a compound that absorbs energy rays to efficiently generate cations from the photo-cationic polymerization initiator. The photosensitizer preferably does not include a polymerization initiator, more preferably does not include a photo-cationic polymerization initiator.

The photosensitizer is not particularly limited, and examples thereof include benzophenone derivatives, phenothiazine derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, and the like,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, indolines Derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, organoruthenium complexes and the like. Among these, phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and anthracene derivatives such as 9, 10-dibutoxyanthracene are preferable, and anthracene derivatives are more preferable. Among the anthracene derivatives, 9, 10-dibutoxyanthracene is preferable.

The content of the photosensitizer is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, relative to 100 parts by mass of the polymerizable component, from the viewpoint of no deterioration in photocurability and no deterioration in storage stability.

The resin composition of the present embodiment may contain a silane coupling agent. The resin composition of the present embodiment exhibits excellent adhesion and adhesion durability by containing the silane coupling agent.

The silane coupling agent is not particularly limited, and examples thereof include gamma-chloropropyl trimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (. Beta. -methoxyethoxy) silane, gamma- (meth) acryloxypropyl trimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-mercaptopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-. Beta. -aminoethyl) -gamma-aminopropyl trimethoxysilane, N-. Beta. -aminoethyl) -gamma-aminopropyl methyldimethoxy silane, and gamma-ureidopropyl triethoxysilane. These silane coupling agents may be used in an amount of 1 or more. Among these, 1 or more selected from the group consisting of β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -glycidoxypropyl triethoxysilane, and γ - (meth) acryloxypropyl trimethoxysilane is preferable, and γ -glycidoxypropyl trimethoxysilane is more preferable.

The amount of the silane coupling agent used is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the polymerizable component, from the viewpoint of obtaining adhesion and adhesion durability.

The resin composition of the present embodiment may contain an antioxidant. By containing an antioxidant, the storage stability of the resin composition tends to be improved.

Examples of the antioxidant include methylhydroquinone, hydroquinone, octadecyl 3- [3, 5-di-t-butyl-4-hydroxyphenyl ] propionate, 2-methylenebis (4-methyl-6-t-butylphenol), catechol, hydroquinone monomethyl ether, mono-t-butylhydroquinone, 2, 5-di-t-butylhydroquinone, p-benzoquinone, 2, 5-diphenyl-p-benzoquinone, 2, 5-di-t-butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, t-butylcatechol, 2-butyl-4-hydroxyanisole, and 2, 6-di-t-butyl-p-cresol. The antioxidant may be used in an amount of 1 or 2 or more.

The antioxidant is preferably a phenol antioxidant, and more preferably a hindered phenol antioxidant, from the viewpoints of storage stability of the resin composition and transparency of the cured product.

The hindered phenol antioxidant preferably contains at least one selected from the group consisting of octadecyl 3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate and 2, 2-methylenebis (4-methyl-6-tert-butylphenol), and more preferably contains both octadecyl 3- [3, 5-di-tert-butyl-4-hydroxyphenyl ] propionate and 2, 2-methylenebis (4-methyl-6-tert-butylphenol). As octadecyl 3- [3, 5-di-t-butyl-4-hydroxyphenyl ] propionate, "Irganox 1076" manufactured by BASF Japan Co., ltd. Examples of the 2, 2-methylenebis (4-methyl-6-t-butylphenol) include "SUMILIZER MDP-S" manufactured by Sumitomo chemical industry Co.

The content of the antioxidant is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, per 100 parts by mass of the polymerizable component. This tends to significantly improve the storage stability of the resin composition. The content of the antioxidant is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable monomers (X). This tends to further improve the adhesiveness and curability of the resin composition.

The resin composition of the present embodiment may contain an inorganic filler. By containing the inorganic filler, the cured product of the resin composition tends to be lower in moisture permeability and further improved in moisture resistance.

Examples of the inorganic filler include particles such as silica, mica, kaolin, talc, and alumina.

The average particle diameter (hereinafter, also referred to as particle diameter) of the inorganic filler is preferably 1 to 50. Mu.m. The average particle diameter is preferably measured by Microtrac (laser diffraction/scattering method). The average particle diameter is preferably the cumulative 50% particle diameter (d 50) in the particle diameter distribution.

The content of the inorganic filler is preferably 1 to 80 parts by mass, more preferably 20 to 40 parts by mass, per 100 parts by mass of the polymerizable component, in view of obtaining low moisture permeability of the cured product.

The resin composition according to the present embodiment may further contain known additives used in the art as other components. Examples of the additive include a metal deactivator, a stabilizer, a neutralizer, a lubricant, and an antimicrobial agent.

The method for producing the resin composition of the present embodiment is not particularly limited as long as the above-described components can be sufficiently mixed. The method of mixing the components is not particularly limited, and examples thereof include: a stirring method using stirring force accompanied by rotation of a propeller; a method using a general dispersing machine such as a planetary mixer based on rotation and revolution; etc. These mixing methods are preferable in view of low cost and stable mixing.

In view of low moisture permeability, the glass transition temperature (Tg) of the cured product of the resin composition according to the present embodiment is preferably 60 ℃ or higher, more preferably 70 ℃ or higher, and still more preferably 85 ℃ or higher. The glass transition temperature (Tg) is preferably 300℃or lower, more preferably 200℃or lower.

In the present specification, the glass transition temperature (Tg) of the cured product means a value obtained from a dynamic viscoelasticity spectrum. In the dynamic viscoelasticity spectrum, the cured body may be subjected to stress and strain at a constant temperature rise rate, and the temperature at the peak top exhibiting a loss tangent (hereinafter, abbreviated as tan δ) may be referred to as the glass transition temperature. When the peak of tan δ does not occur even when the temperature is raised from a sufficiently low temperature of about-150 ℃ to a certain temperature (Ta ℃), the glass transition temperature is considered to be equal to or lower than-150 ℃ or equal to or higher than a certain temperature (Ta ℃), but the glass transition temperature is not considered to be equal to or lower than-150 ℃ and therefore the temperature (Ta ℃) can be determined to be equal to or higher than a certain temperature.

In the resin composition according to the present embodiment, the crosslink density of the cured product is preferably 1.0X10 ^-3 mol/cm ³ The above is more preferably 2.0X10 ^-3 mol/cm ³ The above is more preferably 3.0X10 ^-3 mol/cm ³ The above. Crosslink density of 1.0X10 ^-3 mol/cm ³ In the above case, the number of bonding points in the cured product is large, and the micro-Brownian motion in the polymer is suppressed, so that the cured product is preferably low in moisture permeability. The crosslinking density is preferably 1.0mol/cm ³ The following (1000X 10) ^-3 mol/cm ³ Hereinafter), more preferably 0.1mol/cm ³ The following (100X 10) ^-3 mol/cm ³ Hereinafter), more preferably 0.05mol/cm ³ The following (50X 10) ^-3 mol/cm ³ The following are described below). The crosslink density was 1.0mol/cm ³ In the following, the cured product is not brittle, and is preferable.

From the above point of view, the crosslinked density of the cured body may be 1.0X10 ^-3 ～1.0mol/cm ³ 、2.0×10 ^-3 ～1.0mol/cm ³ 、3.0×10 ^-3 ～1.0mol/cm ³ 、1.0×10 ^-3 ～0.1mol/cm ³ 、2.0×10 ^-3 ～0.1mol/cm ³ 、3.0×10 ^-3 ～0.1mol/cm ³ 、1.0×10 ^-3 ～0.05mol/cm ³ 、2.0×10 ^-3 ～0.05mol/cm ³ Or 3.0X10 ^-3 ～0.05mol/cm ³ 。

In the present specification, the crosslink density of the cured product means a value obtained from a dynamic viscoelasticity spectrum, and can be obtained by the following method. A cured body having a thickness of 100 μm was cut into test pieces having a width of 5 mm. Times.length of 25 mm. The test piece was stretched at a temperature ranging from-50 ℃ to 200 ℃ and a heating rate of 2 ℃/minDynamic viscoelasticity measurement was performed under the condition of the mode, and the relationship between the temperature and the storage elastic modulus (G') was grasped. Regarding the crosslinking density, the temperature of Tg+40℃was set as T (K), and the storage elastic modulus (G ') at T (K) was set as G' _Tg+40 Let the gas constant be R, and the pre-factor be RCalculated by the following formula (4).

Crosslink Density

The specific gravity of the cured product of the resin composition according to the present embodiment is preferably 1.2 to 3.0, more preferably 1.3 to 3.0, and even more preferably 1.3 to 2.0.

In the resin composition according to the present embodiment, the moisture permeability of the cured product is preferably 0.01 to 300 g/(m) ² 24 hours). The moisture permeability is preferably 200 g/(m) ² 24 hours) or less, more preferably 150 g/(m) ² 24 hours) or less, more preferably 120 g/(m) ² 24 hours) or less. The moisture permeability can be 0.1 g/(m) ² 24 hours) or more, 1 g/(m) ² 24 hours) or more, or 10 g/(m) ² 24 hours) or more. In the present specification, the moisture permeability is a value measured at a temperature of 85℃and a relative humidity of 85% in accordance with JIS Z0208 for a cured product having a thickness of 100. Mu.m, which is obtained from the resin composition. When the moisture permeability is low, the cured product can be used for a sealing material for an organic electroluminescent element (hereinafter, the sealing material may also include layers such as an organic layer and an inorganic layer), and occurrence of dark spots due to moisture reaching the organic luminescent material layer can be suppressed.

From the above point of view, the moisture permeability of the cured body may be 0.1 to 300 g/(m) ² 24 hours), 1 to 300 g/(m) ² 24 hours), 10 to 300 g/(m) ² 24 hours), 0.01 to 200 g/(m) ² 24 hours), 0.1 to 200 g/(m) ² 24 hours), 1 to 200 g/(m) ² 24 hours), 10 to 200 g/(m) ² 24 hours), 0.01 to 150 g/(m) ² 24 hours), 0.1 to 150 g/(m) ² 24 hours), 1 to 150 g/(m) ² 24 hours), 10 to 150 g/(m) ² 24 hours), 0.01 to 120 g/(m) ² 24 hours), 0.1 to 120 g/(m) ² 24 hours), 1 to 120 g/(m) ² 24 hours), or 10 to 120 g/(m) ² 24 hours).

The resin composition according to the present embodiment is also excellent in transparency of a cured product. Specifically, the cured product of the resin composition preferably has a total light transmittance of 95% or more, more preferably 97% or more, and still more preferably 99% or more per 10 μm thickness, measured in the ultraviolet-visible light range having a wavelength of 380 to 1000nm or less. When the light transmittance is 95% or more, an organic EL display device excellent in brightness and contrast can be easily obtained when the cured product is used as a sealing material for an organic electroluminescent element.

The preferable range of the characteristics (average free volume, porosity, glass transition temperature, etc.) of the cured product described in the above item < resin composition > means a preferable range of the characteristics of the cured product obtained by curing the resin composition under the conditions described in examples described later.

< cured body >

The cured product of the resin composition can be obtained by irradiating the resin composition with light.

The light source used for curing the resin composition of the present embodiment is not particularly limited, and examples thereof include halogen lamps, metal halide lamps, high-power metal halide lamps (including indium and the like), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury 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 irradiation of energy rays corresponding to the reaction wavelength of each photopolymerization initiator can be efficiently performed.

The light sources have different emission wavelengths and energy distributions. Therefore, the light source may be appropriately selected according to the reaction wavelength of the photopolymerization initiator, and the like. In addition, natural light (sunlight) may also be a light source that initiates the reaction.

The irradiation by the light source may be direct irradiation or concentrated light irradiation by a mirror, an optical fiber, or the like. A low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like may also be used.

In order to accelerate the curing rate after the light irradiation, the resin composition of the present embodiment may be subjected to post-heat treatment. In the case where the resin composition is used for sealing an organic electroluminescent element, the post-heating temperature is preferably 150 ℃ or less, more preferably 100 ℃ or less, from the viewpoint of not damaging the organic electroluminescent element. The post-heating temperature is preferably 40℃or higher.

The average free volume of the cured product is preferably 0.1nm from the viewpoints of more excellent moisture resistance and more excellent adhesion to a substrate such as a glass substrate ³ Hereinafter, more preferably 0.095nm ³ Hereinafter, it is more preferably 0.09nm ³ Hereinafter, it is particularly preferably 0.085nm ³ Hereinafter, it is more preferably 0.08nm ³ Hereinafter, it is preferably 0.001nm ³ The above is more preferably 0.003nm ³ The above is more preferably 0.005nm ³ The above is particularly preferably 0.01nm ³ The above is more preferably 0.05nm ³ The above.

From the viewpoint of easy obtaining of a cured product having more excellent moisture resistance and also excellent adhesion to a substrate, the porosity of the cured product is preferably 20% by volume or less, more preferably 15% by volume or less, and even more preferably 10% by volume or less, based on the total volume of the cured product.

The glass transition temperature (Tg) of the cured product is preferably 60℃or higher, more preferably 70℃or higher, and still more preferably 85℃or higher.

The crosslink density of the cured body is preferably 1.0X10 ^-3 mol/cm ³ The above is more preferably 2.0X10 ^-3 mol/cm ³ The above is more preferably 3.0X10 ^-3 mol/cm ³ The above. Crosslink density of 1.0X10 ^-3 mol/cm ³ In the above case, the number of bonding points in the cured product is large, and the micro-Brownian motion in the polymer is suppressed, so that the cured product is preferably low in moisture permeability. The crosslinking density is preferably 1.0mol/cm ³ The following (1000X 10) ^-3 mol/cm ³ Hereinafter), more preferably 0.1mol/cm ³ The following (100X 10) ^-3 mol/cm ³ Hereinafter), more preferably 0.05mol/cm ³ The following (50X 10) ^-3 mol/cm ³ The following are described below). The crosslink density was 1.0mol/cm ³ In the following, the cured product is not brittle, and is preferable.

The specific gravity of the cured product is preferably 1.2 to 3.0, more preferably 1.3 to 3.0, and even more preferably 1.3 to 2.0.

The moisture permeability of the cured product is preferably 0.01 to 300 g/(m) ² 24 hours). The moisture permeability is preferably 200 g/(m) ² 24 hours) or less, more preferably 150 g/(m) ² 24 hours) or less, more preferably 120 g/(m) ² 24 hours) or less. Moisture permeabilityMay be 0.1 g/(m) ² 24 hours) or more, 1 g/(m) ² 24 hours) or more, or 10 g/(m) ² 24 hours) or more.

The moisture permeability of the cured body may be 0.1 to 300 g/(m) ² 24 hours), 1 to 300 g/(m) ² 24 hours), 10 to 300 g/(m) ² 24 hours), 0.01 to 200 g/(m) ² 24 hours), 0.1 to 200 g/(m) ² 24 hours), 1 to 200 g/(m) ² 24 hours), 10 to 200 g/(m) ² 24 hours), 0.01 to 150 g/(m) ² 24 hours), 0.1 to 150 g/(m) ² 24 hours), 1 to 150 g/(m) ² 24 hours), 10 to 150 g/(m) ² 24 hours), 0.01 to 120 g/(m) ² 24 hours), 0.1 to 120 g/(m) ² 24 hours), 1 to 120 g/(m) ² 24 hours), or 10 to 120 g/(m) ² 24 hours).

The total light transmittance of the cured product measured in the ultraviolet-visible light region having a wavelength of 380 to 1000nm or less is preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more per 10 μm thickness. When the light transmittance is 95% or more, an organic EL display device excellent in brightness and contrast can be easily obtained when the cured product is used as a sealing material for an organic electroluminescent element.

While the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

Another aspect of the present invention may be a sealing material for an organic electroluminescent display element, which contains the cured product described above. The sealing material may be formed of an organic layer containing only a cured body, or may contain a cured body of a resin composition and other constituent materials. Examples of the other constituent materials include a silicon nitride film, a silicon oxide film, an inorganic layer such as silicon nitride oxide, and the like. In this case, the sealing material for an organic electroluminescent display element includes an organic layer containing a cured product of the resin composition and an inorganic layer.

In addition, another aspect of the present invention may be an organic electroluminescent display device including an organic electroluminescent element and the sealing material for an organic electroluminescent element.

In the present invention, the method for manufacturing an organic electroluminescent display device may include the steps of: an irradiation step of, after attaching the resin composition to a substrate, irradiating the attached resin composition with light; and a bonding step of bonding the substrate to the organic electroluminescent display element through the resin composition irradiated with light. In the manufacturing method, the substrate may be a glass substrate or the like. The conditions and the like of each step in the production method can be appropriately selected based on the description of the embodiment described above.

More specifically, as a method for manufacturing an organic electroluminescent display device using the resin composition of the present embodiment, for example, the following method can be mentioned: the resin composition of the present embodiment is applied to one substrate (back plate), the resin composition is activated by irradiation with light, and then light is blocked, and the back plate is bonded to the substrate on which the electroluminescent display element is formed via the composition; etc. With this method, sealing can be performed without exposing the organic electroluminescent display element to light or heat.

The resin composition according to the present embodiment can be used as an adhesive. The adhesive of the present embodiment can be suitably used for adhesion of packages and the like such as organic electroluminescent display elements.

As a method for bonding a substrate using the resin composition of the present embodiment, for example, the following steps are provided: a coating step of coating the resin composition on the entire surface or a part of the one substrate; an irradiation step of irradiating a resin composition of a substrate coated with the resin composition with light; a bonding step of bonding another substrate to the one substrate during a period before the resin composition irradiated with light is cured; and a curing step of curing the substrate bonded with the resin composition. This makes it possible to bond the substrates without exposing the substrates to light or heat.

The organic electroluminescent display device may also be manufactured using the following method: with the resin composition of the present embodiment, the resin composition of the present embodiment is applied to one substrate, and the other substrate is bonded via the resin composition, and the resin composition of the present embodiment is irradiated with light.

Examples

Hereinafter, this embodiment will be described in more detail with reference to experimental examples. The present embodiment is not limited to these examples. In the following examples, the test was performed in an environment of 23℃and 50% by mass relative humidity unless otherwise specified.

In examples and comparative examples, the following compounds were used.

[ polymerizable component ]

[ polymerizable monomer (X) ]

(X-1): dibromophenyl glycidyl ether (BR-250, manufactured by Japanese chemical Co., ltd., bromine content: 51% by mass, monomer specific gravity: 1.8)

(X-2): brominated tolylglycidyl ether (BROC, manufactured by Japanese chemical Co., ltd., bromine content: 50% by mass, monomer specific gravity: 1.8)

(X-3): TBBPA epoxy resin (diglycidyl ether of tetrabromobisphenol A, "epiclone 152" manufactured by DIC Co., ltd., bromine content of 48% by mass, specific gravity of 1.7)

(X-4): brominated phenol Novolac epoxy resin (BREN-105, manufactured by Japanese chemical Co., ltd., bromine content of 36% by mass, specific gravity of 1.7)

(X-5) Pentafluorophenyl acrylate (Tokyo chemical industry Co., ltd. "Pentafluorophenyl acrylate", specific gravity 1.5)

(X-6) 2,4, 6-tribromophenyl acrylate (Tokyo chemical industry Co., ltd. "Tribromophenyl acrylate", specific gravity 2.1)

[ Cross-linker (Y) ]

(Y-1): 3, 4-epoxycyclohexane carboxylic acid 3',4' -epoxycyclohexyl methyl ester (Daicel chemical company "Celloxide 2021P", specific gravity 1.2)

(Y-2): bisphenol A epoxy resin (JiER 828, manufactured by Mitsubishi chemical corporation, molecular weight 360-390, specific gravity 1.2)

(Y-3): cyclohexane dimethanol divinyl ether (Nippon Carbide Co., ltd. "CHDVE", specific gravity 0.9)

(Y-4): polyoxyalkylene diglycidyl ether (Nagase ChemteX Co., ltd. "EX-946L", specific gravity 0.9)

(Y-5): 1, 6-hexanediol dimethacrylate (New Zhongcun chemical company "HD-N", specific gravity 1.0)

(Y-6): tricyclodecane dimethanol dimethacrylate (DCP, new Zhongcun chemical Co., ltd., specific gravity 1.1)

[ other polymerizable monomer (Z) ]

(Z-1) lauryl glycidyl ether (Epogosey LA (D) manufactured by Sichuan Synthesis Co., ltd.) having a specific gravity of 0.9

(Z-2) lauryl acrylate (manufactured by Osaka organic Co., ltd. "LA", specific gravity 1.1)

[ polymerization initiator ]

Triarylsulfonium salt hexafluoroantimonate (Adeka Optomer SP-170, inc. of ADEKA), anionic species hexafluoroantimonate

Triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, manufactured by San-Apro Co., ltd. "CPI-200K", anionic species phosphorus compound)

2,4, 6-trimethylbenzoyl diphenylphosphine oxide (TPO manufactured by BASF Japan Co.)

1-hydroxycyclohexyl phenyl ketone, "I-184", BASF Japan Co., ltd.)

[ photosensitizer ]

9, 10-dibutoxyanthracene (Kawasaki chemical industry Co., ltd. "Anthraceue UVS-1331')

[ silane coupling agent ]

Gamma-glycidoxypropyl trimethoxysilane (KBM-403 from Shin-Etsu Silicones Co.)

[ inorganic filler ]

Talc particulate, particle size (d 50): 4.5 μm (Songcun industries Co., ltd. #5000 PJ)

Experimental example

Resin compositions of examples and comparative examples were prepared by mixing the raw materials of the types shown in tables 1 to 2 in the composition ratios shown in tables 1 to 2. The unit of the composition ratio is parts by mass. Examples 1-1 to 1-7 and comparative examples 1-1 to 1-3 use a compound having a cationically polymerizable functional group as a polymerizable component, and examples 2-1 to 2-2 and comparative examples 2-1 to 2-2 use a compound having a radically polymerizable functional group as a polymerizable component.

The following measurements were performed on the resin compositions of examples and comparative examples. The results are shown in tables 1 to 2.

[ viscosity ]

The viscosity (shear viscosity) of the resin composition was measured using an E-type viscometer (1℃34'. Times.R24 conical rotor) at a temperature of 25℃and a rotation speed of 10 rpm.

The resin composition was cured under the following conditions, and the following measurements were performed on the cured body obtained. The results are shown in tables 1 to 2. The resin compositions of comparative examples 1 to 3 and comparative examples 2 to 2 were not cured, and thus, the respective physical properties could not be evaluated.

[ photo curing conditions ]

In evaluating the physical properties and adhesiveness of the cured product of the resin composition, the resin composition was cured under the following light irradiation conditions. The cumulative light amount at 365nm was 4,000mJ/cm by a UV curing apparatus (manufactured by Fusion Co.) equipped with an electrodeless discharge metal halide lamp ² The resin composition was photo-cured, and then post-heat treatment was performed in an oven at 80℃for 30 minutes to obtain a cured product.

[ average free volume and porosity ]

A sheet-like cured body having a thickness of 0.1mm was produced under the above-mentioned photo-curing conditions, the cured body having a thickness of 10.1mm was cut into pieces having a width of 10 mm. Times.length of 10mm, and 10 pieces of the pieces were stacked and fixed to obtain a test sample.

The positron annihilation lifetime and the relative intensity were measured under the following conditions, with the radiation source being 22 NaCl.

Positron emitting sources: 22NaCl (intensity 0.6 MBq),

gamma ray detector: a barium fluoride scintillator and a photomultiplier tube,

device resolution: the time period of the 250ps,

measuring temperature: 25 c,

count value: 1,000,000,

the positron emission sources were sandwiched on both sides between 2 test samples for measurement. The positron lifetime was measured under the above measurement conditions, and the average free volume and the porosity were calculated.

[ specific gravity of cured article (85 ℃ C.)

A sheet-like cured product having a thickness of 1mm was produced under the above-mentioned photo-curing conditions, and the specific gravity of the cured product was measured according to JIS K7112B method. As the impregnating solution, water at a temperature of 85℃was used.

[ Tg, elastic modulus at Tg+40℃ ]

A sheet-like cured body having a thickness of 0.1mm was produced under the above-mentioned photo-curing conditions, and the cured body having a thickness of 100 μm was cut into test pieces having a width of 5 mm. Times.25 mm. The test piece was subjected to dynamic viscoelasticity measurement at a temperature ranging from-50 to 200℃and a heating rate of 2℃per minute in a stretching mode (frequency: 1Hz, strain: 0.05%) to determine the storage elastic modulus. The temperature of the peak top of tan δ (loss tangent) measured by the dynamic viscoelasticity measurement was used as the glass transition temperature (Tg) of the cured product. Dynamic viscoelasticity is measured using a dynamic viscoelasticity measuring device "DMS210" manufactured by the precision electronics industry company.

[ Cross-Linked Density ]

The crosslink density was calculated from the dynamic viscoelasticity measurement described above. Regarding the crosslinking density, the temperature of Tg+40℃was set as T (K), and the storage elastic modulus (G ') at T (K) was set as G' _Tg+40 Let the gas constant be R, and the pre-factor be RCalculated by the following formula.

[ transparency ]

For the resin composition, a 0.1mm spacer was used, and bonding was performed with 2 glass plates (size: 40 mm. Times.20 mm). The resin composition was cured under the above-mentioned photo-curing conditions, and the obtained article was used as a test piece. The light transmittance (%) at a wavelength of 400nm was measured using a spectrophotometer (manufactured by Japanese Spectrophotometer Co., ltd.).

[ moisture permeability ]

A sheet-like cured product having a thickness of 0.1mm was produced under the above-mentioned photo-curing conditions, and the sheet-like cured product was measured under conditions of an atmosphere temperature of 85℃and a relative humidity of 85% by using calcium chloride (anhydrous) as a moisture absorbent in accordance with JIS Z0208 "moisture permeability test method (cup method)". The moisture permeability is 300 g/(m) ² 24 hours) or less, it can be said that the cured product is excellent in moisture resistance.

[ tensile shear bond Strength ]

Using 2 borosilicate glass test pieces (25 mm long by 25mm wide by 2.0mm thick, tempax (registered trademark) glass), 0.5cm in length ² The resin composition was cured under the above-mentioned photo-curing conditions, with an adhesive area of 80. Mu.m. After curing, the tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in an environment at a temperature of 23℃and a relative humidity of 50% using test pieces bonded with the resin composition. The tensile shear bond strength was measured using a universal tester.

[ evaluation of organic EL ]

[ production of organic EL element substrate ]

The glass substrate with the ITO electrode was cleaned using acetone and isopropyl alcohol, respectively. Then, the following compounds were sequentially deposited as thin films by vacuum deposition to obtain an organic EL element substrate including an anode/a hole injection layer/a hole transport layer/a light emitting layer/an electron injection layer/a cathode. The constitution of each layer is as follows.

Anode ITO, film thickness of anode 250nm

Hole injection layer copper phthalocyanine thickness of 30nm

Hole transport layer N, N '-diphenyl-N, N' -dinaphthyl benzidine (. Alpha. -NPD) with a thickness of 20nm

Luminescent layer tris (8-hydroxyquinoline) aluminum (metal complex-based material), film thickness of luminescent layer

The thickness of the lithium fluoride of the electron injection layer is 1nm

Cathode aluminum, anode film thickness of 250nm

[ production of organic EL element ]

The resin compositions obtained in examples and comparative examples were applied to glass by a coating apparatus under a nitrogen atmosphere, and then bonded to an organic EL display element substrate, and the resin composition was cured under the above-mentioned photo-curing conditions at a bonding thickness of 10 μm to produce an organic EL display element. The anode side of the organic EL display element substrate was adhered to glass via the resin composition.

[ evaluation of organic EL ]

[ initially ]

The organic EL element immediately after fabrication was applied with a voltage of 6V, and the light-emitting state of the organic EL element was observed visually and microscopically to measure the diameter of the dark spot.

[ high temperature and high humidity ]

The organic EL element immediately after fabrication was exposed to 85 ℃ and 85 mass% relative humidity for 1000 hours, then a voltage of 6V was applied, and the light-emitting state of the organic EL element was observed visually and microscopically, and the diameter of the dark spot was measured.

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

TABLE 1

TABLE 2

/>

Claims

1. A composition comprising a polymerizable component and a polymerization initiator,

mean free volume of cured bodyIs 0.1nm ³ The following is given.

2. The composition according to claim 1, wherein the porosity of the cured body is 20% by volume or less.

3. The composition according to claim 1 or 2, wherein the cured body has a glass transition temperature of 60 ℃ or higher.

4. The composition according to any one of claims 1 to 3, wherein the cured body has a crosslink density of 1.0X10 ^- ³ mol/cm ³ The above.

5. The composition according to any one of claims 1 to 4, wherein the specific gravity of the cured body at 85 ℃ is 1.2 to 3.0.

6. The composition according to any one of claims 1 to 5, wherein the polymerizable component contains a polymerizable monomer containing 1 or more selected from the group consisting of elements having an atomic number of 9 or more.

7. The composition of claim 6, wherein the element is a halogen element.

8. The composition according to claim 7, wherein the halogen element is 1 or more selected from the group consisting of chlorine element, fluorine element and bromine element.

9. The composition according to any one of claims 6 to 8, wherein the content of the element is 10 to 50% by mass relative to the total amount of the elements contained in the polymerizable monomer.

10. The composition according to any one of claims 1 to 9, wherein the polymerizable component contains a crosslinking agent.

11. The composition according to any one of claims 1 to 10, wherein the cured body has a moisture permeability of 0.01 to 300 g/(m) ² 24 hours),

the moisture permeability was measured on the cured body having a thickness of 100 μm according to JIS Z0208 at a temperature of 85℃and a relative humidity of 85%.

12. The composition according to any one of claim 1 to 11, wherein the cured body has a total light transmittance of 95% or more,

The total light transmittance is measured in a wavelength range of 380 to 1000 nm.

13. The composition according to any one of claims 1 to 12, which is used as a sealing material for an organic electroluminescent display element.

14. An adhesive comprising the composition of any one of claims 1 to 13.

15. A cured body obtained by curing the composition according to any one of claims 1 to 13.

16. A sealing material for an organic electroluminescent display element, comprising an organic layer comprising the cured product according to claim 15.

17. The sealing material for an organic electroluminescent display element according to claim 16, further comprising an inorganic layer.

18. An organic electroluminescent display device is provided with:

an organic electroluminescent display element; and, a step of, in the first embodiment,

the sealing material for an organic electroluminescent display element as claimed in claim 16 or 17.

19. A method for manufacturing an organic electroluminescent display device, comprising the steps of:

a step of adhering the composition according to any one of claims 1 to 13 to a substrate and irradiating with light; and, a step of, in the first embodiment,

and bonding the substrate to the organic electroluminescent display element through the composition irradiated with light.