TW201936879A - Resin composition for sealing - Google Patents

Abstract

The present invention provides a resin composition for sealing, which has excellent moisture barrier properties and is thus capable of suppressing deterioration of an element such as an EL element due to the moisture taken in the resin composition without performing a drying step before a sealing step. A resin composition for sealing, which contains a hydrotalcite and calcium oxide.

Description

Sealing resin composition

The present invention relates to a resin composition for sealing, and particularly relates to a resin composition for sealing which is suitable for sealing a light-emitting element such as an organic EL (Electroluminescence) element or a light-receiving element such as a solar battery.

In the organic EL element, a light-emitting element using an organic substance for a light-emitting material has been attracting attention in recent years because light emission with low voltage and high luminance can be obtained. However, the organic EL element is extremely weak in moisture, and the luminescent material (light-emitting layer) is deteriorated by moisture, and the brightness is lowered or the light is not emitted, or the interface between the electrode and the light-emitting layer is peeled off due to the influence of moisture, or the metal is oxidized to cause high resistance. The problem. Therefore, in order to block the inside of the element from the moisture in the outside air, for example, a sealing layer is formed by a resin composition so as to cover the entire surface of the light-emitting layer formed on the substrate, thereby sealing the organic EL element. Moreover, in order to prevent moisture intrusion from the edge of the sealing layer of the organic EL device, there is a case where a sealing layer is provided on the edge by a resin composition for sealing which is called a Dam material. Further, it is also known to combine a full seal of a luminescent layer by a liquid sealing material (Fill material) with a dam-filled seal sealed by the edge of the dam material. In such a sealing layer of an organic EL device, high moisture barrier properties (also referred to as barrier properties and moisture permeability resistance) are sought.

Patent Document 1 proposes a sealing resin composition which is excellent in moisture barrier properties using hydrotalcite as a moisture absorbent. However, the resin composition containing the hydrotalcite reversibly penetrates into the resin composition in the production step or the distribution process, and causes deterioration of the organic EL element or the like. As a method for removing moisture which has penetrated into the resin composition, Patent Document 2 discloses a method of drying a sheet for sealing in a short time by using near-infrared rays and heating. However, in this method, there is an increase in the number of steps in the manufacturing process or introduction of a drying device.
[Previous Technical Literature]
[Patent Literature]

[Patent Document 1] WO2015/068787A
[Patent Document 2] WO2016/152756A

[Questions to be solved by the invention]

The present invention has been made in view of the above-mentioned problems, and it is an object to be solved to provide an excellent barrier property against moisture, and it is possible to suppress EL caused by penetration of moisture into the resin composition even if the drying treatment step is not performed before the sealing step. A resin composition for sealing which is deteriorated by components such as elements.

[Means to solve the problem]

As a result of intensive studies to solve the above problems, the present inventors have found that the above-mentioned problems are solved by blending calcium oxide with a resin composition for sealing containing hydrotalcite, and the present invention has been completed. That is, the present invention has the following features.

[1] A resin composition for sealing comprising hydrotalcite and calcium oxide.
[2] The resin composition for sealing according to the above [1], wherein the ratio of the calcium oxide to the hydrotalcite is 0.1 to 1 by mass.
[3] The resin composition for sealing according to the above [1], wherein the content of the hydrotalcite is from 10% by mass to 70% by mass based on 100% by mass of the nonvolatile content of the resin composition.
[4] The resin composition for sealing according to any one of the above [1] to [3], further comprising a resin selected from at least one of an acrylic resin and an epoxy resin.
[5] The resin composition for sealing according to any one of [1] to [3] further comprising at least one type of acrylic resin.
[6] The resin composition for sealing according to the above [4], wherein the acrylic resin is a compound having three or more ethylenically unsaturated groups in one molecule.
[7] The resin composition for sealing according to any one of the above [4], wherein the acrylic resin contains two or more ethylenically unsaturated groups and an alicyclic structure in one molecule. Compound.
[8] The resin composition for sealing according to the above [6], wherein the ethylenically unsaturated group is a (meth) acrylonitrile group.
[9] The resin composition for sealing according to the above [7], wherein the amount of the compound having two or more ethylenically unsaturated groups and an alicyclic structure in one molecule is relative to the resin composition. The whole of the material is 5 to 75% by mass.
[10] The resin composition for sealing according to any one of the above [1], wherein the hydrotalcite is a semi-fired hydrotalcite.
[11] The resin composition for sealing according to any one of [1] to [10] further comprising a radical polymerization initiator.
[12] The resin composition for sealing according to the above [11], wherein the radical polymerization initiator is a photoradical polymerization initiator and/or a thermal radical polymerization initiator.
[13] The resin composition for sealing according to the above [11], wherein the amount of the radical polymerization initiator is 0.5 to 10 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group. Parts by mass.
[14] The resin composition for sealing according to any one of [1] to [13] further comprising a decane coupling agent.
[15] The resin composition for sealing according to any one of the above [1] to [14], which is liquid.
[16] The resin composition for sealing according to any one of the above [1] to [15], which is used for sealing an organic EL element.
[17] An organic EL device, wherein the organic EL device is sealed with a cured product of the sealing resin composition according to any one of the above [1] to [16].

[Effect of the invention]

According to the present invention, it is possible to provide a sealing resin composition which is excellent in moisture barrier properties and which can prevent deterioration of elements such as EL elements due to moisture permeating into the resin composition, even if the drying treatment step is not performed before the sealing step.

<Resin composition for sealing>
The resin composition for sealing of the present invention contains hydrotalcite and calcium oxide. The resin composition for sealing of the present invention can be produced by mixing a resin, hydrotalcite, calcium oxide and, if necessary, other components using a kneading roll or a rotary mixer.

The resin composition for sealing of the present invention is used for, for example, an electronic component such as a semiconductor, a solar cell, a high-brightness LED, an LCD, or an EL element, and is preferably an optical semiconductor such as an organic EL element or a solar cell. The sealing resin composition of the present invention is particularly preferably used for sealing an organic EL element. Specifically, the upper portion of the light-emitting portion of the organic EL element is applied as a filler, and/or is applied as a dam material in the periphery (side portion), and the sealing portion of the present invention can be used in order to protect the light-emitting portion of the organic EL element from the outside. Resin composition.

The resin composition for sealing of the present invention is preferably a liquid resin composition for sealing. Here, the "resin composition for liquid sealing" means a resin composition for sealing which has fluidity at normal temperature (25 ° C) and normal pressure (1 atmosphere). For example, when the sealing resin composition containing an inorganic filler has fluidity at normal temperature and normal pressure, it corresponds to the liquid sealing resin composition of the present invention. In comparison with a film-like sealing material, a liquid sealing material (resin composition for sealing) is generally used for the embedding property of a surface of a light-emitting element having a circuit, the suppression of voids when the sealing surface is large, and the film of the sealing layer. The ease of thickness adjustment is advantageous because the dam is formed before sealing, and the alignment accuracy achieved by the alignment position is advantageous.

The resin composition for sealing of the present invention desirably does not contain a volatile component such as a solvent. When the resin composition for sealing of the present invention contains a volatile component such as a solvent, a volatile component such as a solvent is not included in the content of each component. In other words, when the resin composition for sealing of the present invention contains a volatile component, the term "the total amount of the resin composition" with respect to the content of each component means "the total non-volatile content of the resin composition".

<hydrotalcite>
The resin composition for sealing of the present invention contains hydrotalcite. The hydrotalcite may be classified into an unfired hydrotalcite, a semi-calcined hydrotalcite, and a calcined hydrotalcite, and may be any of these, and may be used alone or in combination of two or more.

The unfired hydrotalcite is, for example, a metal hydroxide having a layered crystal structure represented by natural hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O), for example, a layer as a basic skeleton. [Mg _1-X Al _X (OH) ₂ ] ^X+ is composed of an intermediate layer [(CO ₃ ) _X/2 · mH ₂ O] ^X- . The unfired hydrotalcite of the present invention contains the concept of a hydrotalcite compound such as synthetic hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).

(wherein, M ²⁺ represents a divalent metal ion such as Mg ₂₊ or Zn ²⁺ , M ³⁺ represents a trivalent metal ion such as Al ³⁺ or Fe ³⁺ , and A ^n- represents CO ₃ ^2- or Cl. ^- n-valent anion of NO ₃ ^-, etc., 0 < x < 1, 0 ≦ m < 1, n is a positive number)
In the formula (I), M ^{2+ is} preferably Mg ²⁺ , M ^{3+ is} preferably Al ³⁺ , and A ^{n- is} preferably CO ₃ ^2- .

(wherein, M ²⁺ represents a divalent metal ion such as Mg ²⁺ or Zn ²⁺ , A ^n- represents an n-valent anion such as CO ₃ ^2- , Cl ⁻ or NO ³ , and x is a positive number of 2 or more. , z is a positive number below 2, m is a positive number, and n is a positive number)
In the formula (II), M ^{2+ is} preferably Mg ²⁺ , and A ^{n- is} preferably CO ₃ ^2- .

The semi-fired hydrotalcite is a metal hydroxide having a layered crystal structure obtained by firing uncalcined hydrotalcite with a reduced or eliminated amount of interlayer water. The term "interlayer water" as used in the composition formula refers to the "H ₂ O" described in the composition formula of the unfired natural hydrotalcite and hydrotalcite-like compound.

Further, the calcined hydrotalcite is a metal oxide having an amorphous structure which is obtained by firing uncalcined hydrotalcite or semi-baked hydrotalcite, and not only inter-layer water but also hydroxyl groups are dehydrated by condensation.

Unfired hydrotalcite, semi-fired hydrotalcite and calcined hydrotalcite can be distinguished by saturated water absorption. The saturated water absorption rate of the semi-fired hydrotalcite is 1% by mass or more and less than 20% by mass. Further, the saturated water absorption of the unfired hydrotalcite is less than 1% by mass, and the saturated water absorption of the calcined hydrotalcite is 20% by mass or more.

The "saturated water absorption rate" in the present invention means that the unsintered hydrotalcite, the semi-calcined hydrotalcite or the calcined hydrotalcite is measured in an amount of 1.5 g on a scale, and after the initial mass is measured, it is set at atmospheric pressure at 60 ° C. The mass increase rate with respect to the initial mass when the small environmental tester (SH-222 manufactured by Espec Co., Ltd.) of 90% RH (relative humidity) was allowed to stand for 200 hours can be obtained by the following formula (i).
Saturated water absorption (% by mass)
=100×(mass after moisture absorption - initial quality) / initial quality (i)

The saturated water absorption rate of the semi-fired hydrotalcite is preferably 3% by mass or more and less than 20% by mass, more preferably 5% by mass or more and less than 20% by mass.

Further, the unfired hydrotalcite, the semi-fired hydrotalcite, and the calcined hydrotalcite can be distinguished by the thermal weight reduction rate measured by thermogravimetric analysis. The semi-calcined hydrotalcite has a thermal weight reduction rate of less than 15% by mass at 280 ° C and a thermal weight reduction rate of 138 ° C or more at 12% by mass or more. Further, the thermogravimetric reduction rate of the unfired hydrotalcite at 280 ° C was 15% by mass or more, and the thermal weight loss rate of the calcined hydrotalcite at 380 ° C was less than 12% by mass.

The thermogravimetric analysis was carried out using a TG/DTA EXSTAR 6300 manufactured by Hitachi High-Tech Co., Ltd., and a 5 mg hydrotalcite was weighed in a sample tray made of aluminum, and opened in an uncovered state. From 30 ° C to 550 in a nitrogen flow rate of 200 mL/min. °C was carried out under the conditions of a temperature increase rate of 10 ° C /min. The heat weight reduction rate can be obtained by the following formula (ii).


Thermal weight reduction rate (% by mass)
=100× (mass before heating - mass at the specified temperature) / mass before heating (ii)

Further, the unfired hydrotalcite, the semi-fired hydrotalcite, and the calcined hydrotalcite can be distinguished by the peak and relative intensity ratios measured by powder X-ray diffraction. Semi-calcined hydrotalcite means that by powder X-ray diffraction, it has a peak split into two at 2θ around 8 to 18 ,, or has a shoulder peak by synthesis of two peaks, on the low angle side. The relative intensity ratio of the peak or shoulder diffraction intensity (= low angle side diffraction intensity), the peak appearing at the high angle side, or the diffraction intensity of the shoulder (= high angle side diffraction intensity) (low angle side) The diffraction intensity/high-angle side diffraction intensity is 0.001 to 1,000. In addition, the unfired hydrotalcite has only one peak near 8 to 18 ,, or the peak value appearing on the low angle side or the relative intensity ratio of the peak or the diffraction intensity of the shoulder on the high angle side becomes the aforementioned Out of scope. The calcined hydrotalcite has no characteristic peaks in the area of 8 ̊ to 18 , and a characteristic peak at 43 ̊. The powder X-ray diffraction measurement was performed by a powder X-ray diffraction device (manufactured by PANalytical Co., Ltd., Empyrean), a cathode CuKα (1.5405 Å), a voltage of 45 V, a current of 40 mA, a sampling width of 0.0260 Torr, and a scanning speed of 0.0657. ̊ / s, measurement of the diffraction angle range (2θ): 5.0131 ~ 79.9711 ̊ conditions. The peak search system uses the peak search function of the software attached to the diffractive device. The minimum significance: 0.50, minimum peak chip: 0.01 ̊, maximum peak chip: 1.00 ̊, peak bottom width The condition of :2.00 ̊, method: minimum value of 2 times of differentiation is performed.

Hydrotalcite BET specific surface area is preferably 1 ~ 250m ² / g, more preferably 5 ~ 200m ² / g. The BET specific surface area of the hydrotalcite was measured by the BET method using a specific surface area measuring apparatus (manufactured by Macsorb HM Model 1210 MOUNTECH Co., Ltd.) to adsorb the nitrogen gas on the surface of the sample, and the BET multipoint method was used.

The average particle diameter of the hydrotalcite is preferably from 1 to 1,000 nm, more preferably from 10 to 800 nm. The average particle diameter of the hydrotalcite is determined by a laser diffraction scattering particle size distribution (JIS Z 8825), and the median diameter of the particle size distribution when the particle size distribution is prepared on a volume basis.

Hydrotalcite can be used as a surface treatment agent for surface treatment. As the surface treatment agent used for the surface treatment, for example, a higher fatty acid, a alkyl decane, a decane coupling agent, or the like can be used, and among them, a higher fatty acid or a alkyl decane is preferable. One type or two or more types of surface treatment agents can be used.

Examples of the higher fatty acid include higher fatty acids having 18 or more carbon atoms such as stearic acid, montanic acid, myristic acid, and palmitic acid. Among them, stearic acid is preferred. These may be used alone or in combination of two or more.

Examples of the alkyl decanes include methyltrimethoxydecane, ethyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, and octadecyltrimethoxy. Decane, dimethyldimethoxydecane, octyltriethoxydecane, n-octadecyldimethyl(3-(trimethoxydecyl)propyl)ammonium chloride, and the like. These may be used alone or in combination of two or more.

Examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl (dimethyl). Epoxy decane coupling agent of oxy)methyl decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyl a decyl decane coupling agent such as triethoxy decane, 3-mercaptopropylmethyldimethoxydecane or 11-decylundecyltrimethoxydecane; 3-aminopropyltrimethoxydecane, 3-Aminopropyltriethoxydecane, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N-methylaminopropyl Trimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane and N-(2-aminoethyl)-3-aminopropyldimethoxymethyl Amino decane coupling agent such as decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane and vinyl Vinyl decane coupling agent such as bis-ethoxy decane; p-styryl trimethoxy a styrene-based decane coupling agent such as decane; an acrylate-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane or 3-methylpropoxypropyltrimethoxydecane; a sulfide such as an isocyanate-based decane coupling agent such as isocyanatepropyltrimethoxydecane, bis(triethoxydecylpropyl)disulfide or bis(triethoxydecylpropyl)tetrasulfide A decane coupling agent; phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium, triazine decane, and the like. These may be used alone or in combination of two or more.

The surface treatment of the hydrotalcite can be carried out, for example, by adding the spray surface treatment agent to the untreated hydrotalcite while stirring and dispersing the mixture at room temperature, and stirring for 5 to 60 minutes. As the mixer, a known mixer can be used, and examples thereof include a mixer such as a V mixer, a ribbon mixer, a bubble cone mixer, a mixer such as a Henschel mixer and a concrete mixer, a ball mill, a honing machine, and the like. Further, when pulverizing by a ball mill or the like, the above-mentioned higher fatty acid, alkyldecane or decane coupling agent may be added to carry out surface treatment. The amount of the surface treatment agent used varies depending on the type of the hydrotalcite or the type of the surface treatment agent, and is preferably from 1 to 10 parts by mass based on 100 parts by mass of the hydrotalcite which is not surface-treated. In the present invention, the surface-treated hydrotalcite is also included in the "hydrotalcite" of the present invention.

The content of the hydrotalcite of the resin composition for sealing of the present invention is not particularly limited as long as the effect of the present invention is exerted, but the nonvolatile content of the resin composition is preferably 100% by mass, preferably 10 to 70%. The mass % is more preferably 15 to 60% by mass, still more preferably 30 to 50% by mass. Hydrotalcite is excellent in moisture absorption performance, and if it is increased in content, the moisture barrier property of the obtained cured product is improved. However, when the content is more than 70% by mass, the viscosity of the resin composition is increased, and the adhesion between the substrate to be sealed and the like is lowered due to a decrease in wettability, and the strength of the cured product is lowered to become brittle. The tendency of the problem. Further, by the inter-layer water of the hydrotalcite, the amount of water in the sealing layer (that is, the cured product) is increased, for example, in the production of an organic EL device, the luminescent material (light-emitting layer) or the electrode layer is caused by moisture in the sealing layer. The adverse effects are obvious, and there are suspense in which the black spots in the initial stage increase.

Specific examples of the semi-calcined hydrotalcite include "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm), and "DHT-4A-2" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400nm) and so on. In addition, examples of the calcined hydrotalcite include "KW-2200" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter: 400 nm), and examples of the unfired hydrotalcite include "DHT-4A" (Kyowa Chemical Industry Co., Ltd.). Company system, average particle size: 400nm).

<calcium oxide>
The resin composition for sealing of the present invention contains calcium oxide. The ratio of the calcium oxide to the hydrotalcite in the resin composition for sealing of the present invention is not particularly limited as long as the effect of the present invention is exerted, but the mass ratio is preferably 0.1 to 1, more preferably the mass. The ratio is 0.1 to 0.75, and more preferably 0.1 to 0.55 by mass. When the mass ratio is lower than 0.1, the effect of the present invention tends to be insufficient. When the mass ratio is higher, the water content of the resin composition tends to increase, and the water barrier property tends to decrease.

The particle form of the calcium oxide is not particularly limited, and a branched shape such as a slightly spherical shape, a rectangular parallelepiped shape, a plate shape, or a fiber shape, or a branched branch shape can be used.

The average particle diameter of the calcium oxide is preferably from 0.1 to 20 μm, more preferably from 0.1 to 15 μm. The average particle diameter of calcium oxide is a median diameter of the particle size distribution when the particle size distribution is prepared on a volume basis by a laser diffraction scattering type particle size distribution measurement (JIS Z 8825).

<Resin constituting the resin composition>
The resin constituting the resin composition for sealing of the present invention is not particularly limited as long as it is used for the resin composition for sealing in the field, and one type or two or more types may be used, but it is preferably selected from acrylic acid. The resin of at least one of the resin and the epoxy resin is more preferably at least one type of acrylic resin.

When the resin is an acryl resin, the resin composition for sealing of the present invention contains, for example, a compound having two or more ethylenically unsaturated groups in one molecule (having two or more (meth) acrylonitriles in one molecule). Base (meth) acrylate) and radical polymerization initiators.

<Compound having two or more ethylenically unsaturated groups in one molecule>
The compound having two or more ethylenically unsaturated groups in one molecule (hereinafter, abbreviated as "polyfunctional ethylenically unsaturated compound") may be used alone or in combination of two or more. The polyfunctional ethylenically unsaturated compound may contain other functional groups such as an epoxy group in the range in which the effects of the present invention are exerted. Further, the polyfunctional ethylenically unsaturated compound containing an epoxy group is not an epoxy resin in the present invention, but is classified into a polyfunctional ethylenically unsaturated compound.

The polyfunctional ethylenically unsaturated compound is preferably in a liquid form because the resin composition for sealing of the present invention is made into a liquid form. The term "liquid" as used herein refers to a state of a polyfunctional ethylenically unsaturated compound at normal temperature (25 ° C) and normal pressure (1 atmosphere). When the polyfunctional ethylenically unsaturated compound is a mixture of two or more kinds of compounds, it is preferred that the mixture is liquid. For example, when a solid polyfunctional ethylenically unsaturated compound and a liquid polyfunctional ethylenic compound are used, it is preferred that the mixture of such compounds be in a liquid form.

The polyfunctional ethylenically unsaturated compound is preferably a compound having three or more ethylenically unsaturated groups in one molecule, from the viewpoint of forming a high-density crosslinked structure and exhibiting high moisture blocking property. In order to have four or more ethylenically unsaturated groups in one molecule, and more preferably a compound having five or more ethylenically unsaturated groups in one molecule, it is particularly preferable to have six or more ethylenic unsaturation in one molecule. Base compound. In the polyfunctional ethylenically unsaturated compound, the upper limit of the number of ethylenically unsaturated groups contained in one molecule is not particularly limited, but the number thereof is preferably 15 or less, more preferably 12 or less, still more preferably 10 or less.

The polyfunctional ethylenically unsaturated compound is preferably a compound having two or more ethylenically unsaturated groups and an alicyclic structure in one molecule, and more preferably one molecule, from the viewpoint of improving water blocking properties. A compound having two ethylenically unsaturated groups and an alicyclic structure. Examples of the alicyclic structure include a structure having an alicyclic hydrocarbon ring having 5 to 12 carbon atoms. Examples of the alicyclic hydrocarbon ring include a tricyclo[5.2.1.0 ^2,6 ]decane ring, a decane ring, an isodecane ring, a cyclohexane ring, a bicyclooctane ring, a norbornane ring, and a ring. A decane ring, an adamantane ring, a cyclopentane ring, and the like. It may have a hetero atom in the alicyclic structure. Further, the alicyclic structure may bond a substituent such as an alkyl group, an alkoxy group or an alkylene group.

When used in a compound having two or more ethylenically unsaturated groups and an alicyclic structure in one molecule (especially a compound having two ethylenically unsaturated groups and an alicyclic structure in one molecule), the content thereof is relative to The total amount of the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, more preferably 75% by mass or less, still more preferably 70% by mass or less, and still more preferably 65 mass% or less.

<Compound having three or more ethylenically unsaturated groups in one molecule>
When the compound having three or more ethylenically unsaturated groups in one molecule is used, the content thereof is preferably 2% by mass or more, more preferably 2% by mass or more, based on the total amount of the resin composition. 3 mass% or more, more preferably 4 mass% or more, preferably 70 mass% or less, more preferably 65 mass% or less, still more preferably 60 mass% or less.

As the ethylenically unsaturated group, a (meth) acrylonitrile group is preferred. That is, as the compound having an ethylenically unsaturated group, a (meth) acrylate having a (meth) acrylonitrile group is preferred. In the present specification, the term "(meth)acryloyl group" means "acryloyl fluorenyl group and/or methacryl fluorenyl group", and "(meth) acrylate" means "acrylate" and / Or methacrylate." Further, a (meth) acrylate having two or more (meth) acrylonitrile groups in one molecule may be simply referred to as "polyfunctional (meth) acrylate" below. Further, a (meth) acrylate having two (meth) acrylonitrile groups in one molecule may be simply referred to as "bifunctional (meth) acrylate".

As the polyfunctional (meth) acrylate, an oligomer can be used. Examples of the oligomer include a polyester oligomer synthesized by a reaction of a polyester polyol and acrylic acid, a urethane oligomer having a urethane bond, and a glycidyl ether. An epoxy oligomer or the like synthesized by a reaction of an acrylate of an acrylic acid or a carboxyl group.

Examples of the bifunctional (meth) acrylate include "DPGDA" (dipropylene glycol diacrylate) manufactured by Daicel Orneex Co., Ltd., "HDDA" (1,6-hexanediol diacrylate), and "TPGDA" (three Propylene glycol diacrylate), "EBECRYL145" (PO modified neopentyl glycol diacrylate), "EBECRYL150" (modified bisphenol A diacrylate), "IRR214-K" (tricyclodecane dimethanol diacrylate Ester), "EBECRYL11" (PEG600 diacrylate), "HPNDA" (neopentyl glycol hydroxypivalate diacrylate), "LIGHT ESTER EG" manufactured by Kyoeisha Chemical Co., Ltd. (ethylene glycol dimethacrylate) Ester), "LIGHT ESTER NP-A" (neopentylene glycol dimethacrylate), "LIGHT ESTER 2EG" (diethylene glycol dimethacrylate), "LIGHT ESTER 1.6HX" (1,6- Hexane diol dimethacrylate), "LIGHT ESTER 1.9ND" (1,9-decanediol dimethacrylate), "LIGHT ESTER G-101P" (glycerol dimethacrylate), " LIGHT ESTER BP-2EMK" (EO addition product dimethacrylate of bisphenol A), "LIGHT ACRYLATE NP-A" (neopentylene glycol diacrylate), "LIGH T ACRYLATE 1.9ND-A" (1,9-nonanediol diacrylate), "LIGHT ACRYLATE BP-4EAL" (EO addition product diacrylate of bisphenol A), "LIGHT ACRYLATE BP-4PA" ( "NK ESTER 701A" (2-hydroxy-3-methylpropenyl propyl acrylate), "NK ESTER A-200" manufactured by Shin-Nakamura Chemical Co., Ltd. PEG Ether APG-400, NK ESTER A-PTMG-65, polytetramethylene glycol #650 diacrylate ), "NK ESTER A-1206PE" (polyethylene polypropylene glycol diacrylate), "NK ESTER ESTERA-BPEF" (9,9-bis[4-(2-hydroxyethoxy)phenyl]indole diacrylate ), "NK ESTER ESTERA-BPE30" (ethoxylated bisphenol A diacrylate), "NK ESTER A-BPP-3" (propoxylated bisphenol A diacrylate), "NK ESTER BG" ( 1,3-butanediol dimethacrylate), "NK ESTER 701" (2-hydroxy-1,3-dimethylpropenyloxypropane), "NK ESTER 3PG" (tripropylene glycol dimethyl) Acrylate), "NK ESTER ESTER Ester 1206PE" (polyethylene polypropylene glycol II) "Acrylate", "NK ESTER DCP" (tricyclodecane dimethanol dimethacrylate), "KAYARAD FM-400" manufactured by Nippon Kayaku Co., Ltd., "KAYARAD HX-220", "KAYARAD HX-620" ( Neopentyl modified diacrylate), "KAYARAD R-604" (dioxane diol diacrylate), "KAYARAD UX-3204" (oligomer having 2 propylene sulfhydryl groups in one molecule), Osaka Chemical Industry Co., Ltd. "BISCOAT #195" (1,4-butanediol diacrylate), "BISCOAT #540" (bisphenol A diglycidyl ether acrylic acid adduct), Arkema "CD406" (cyclohexanedimethanol diacrylate), "SR562" (alkoxylated hexanediol diacrylate), "EBECRYL600" manufactured by Daicel Orneex Co., Ltd. (having 2 acrylonitrile groups in one molecule) Bisphenol A type epoxy acrylate), "EBECRYL210" (an aromatic urethane oligomer having two propylene groups in one molecule), "EBECRYL230" (having two propylene in one molecule) "Ethyl urethane oligomer of sulfhydryl group", "EBECRYL436" (an ester oligomer having two propylene groups in one molecule), "C of Arkema Co., Ltd." N959" (amino acrylate oligomer having two acrylonitrile groups in one molecule), "Art Resin UN-9000PEP" manufactured by Kokuwon Industrial Co., Ltd. (Amino group having two propylene groups in one molecule) An acid ester oligomer), "Art Resin UN-333" (an oligomer having two propylene groups in one molecule), and the like.

For example, "LIGHT ESTER TMP" (trimethylolpropane trimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd. is used as the (meth) acrylate having three or more (meth) acrylonitrile groups in one molecule. , LIGHT ACRYLATE PE-3A" (pentaerythritol triacrylate), "LIGHT ACRYLATE PE-4A" (pentaerythritol tetraacrylate), "LIGHT ACRYLATE DGE-4A" (EO adduct modified diglycerol tetraacrylate), Daicel "PETIA" (pentaerythritol (tri/tetra) acrylate), TMPTA (trimethylolpropane triacrylate), TMPEOTA (trimethylolpropane ethoxy triacrylate), "EBECRYL135" (trihydroxyl) "Methylpropane propoxy triacrylate", "PETA" (pentaerythritol (tri/tetra) acrylate), "DPHA" (dipentaerythritol hexaacrylate), "NK ESTER A-TMPT" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. ( Trimethylolpropane triacrylate), "NK ESTER A-TMPT-3PO" (propoxylated trimethylolpropane triacrylate), "NK ESTER A-GLY-6E" (ethoxylated glycerol) Acrylate), "NK ESTER A-GLY-6P" (propoxylated triglyceride), "NK ES TER A-9300" (para-(2-propenyloxyethyl) isocyanurate), "NK ESTER A-9200" (bis/gin-(2-propenyloxyethyl) isocyanurate Acid ester), "NK ESTER A-9300-1CL" (caprolactone modified ginseng-(2-propenyloxyethyl) isocyanurate), "NK ESTER ATM-4EL" (ethoxylated) Pentaerythritol (tri/tetra) acrylate), "KAYARAD DPCA-20" (6-functional acrylate) manufactured by Nippon Kayaku Co., Ltd., "KAYARAD DPCA-60" (6-functional acrylate), "T-1420(T)" ( 4-functional acrylate), "DPEA-12" (6-functional acrylate), "KAYARAD DPHA-40H" (oligomer having 10 acrylonitrile groups in one molecule), and "BISCOAT #" manufactured by Osaka Organic Chemical Industry Co., Ltd. 802" (pentaerythritol acrylate), "BISCOAT #1000" (dendrimer acrylate), "CN989NS" manufactured by Arkema Co., Ltd. (an aliphatic carbamic acid having 3 acrylonitrile groups in one molecule) "Ester oligomer"), "CN9039" (an aliphatic urethane oligomer having 6 acrylonitrile groups in one molecule), "UN-3320HA" manufactured by Gensal Industries Co., Ltd., "UN-3320HC", " UN-906S" (6 acrylonitrile in 1 molecule) The aliphatic urethane oligomer), DIC Corporation "DICLITE UE-8740" (a phenolic novolac Bing Xixi three groups of novolak type epoxy acrylate in the molecule) and the like. Further, the term "pentaerythritol (tri/tetra) acrylate" means a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. Other "(three/four)" and so on are also of the same meaning.

Examples of the polyfunctional (meth) acrylate having an alicyclic structure include "IRR214-K" (Tricyclodecane II) manufactured by Daicel Orneex Co., Ltd. having a tricyclo[5.2.1.0 ^2,6 ]decane ring structure. Methanol diacrylate), 1,3-adamantanediol diacrylate manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like.

The content of the polyfunctional ethylenically unsaturated compound is preferably from 20 to 78% by mass, more preferably from 25 to 75% by mass, still more preferably from 30 to 70% by mass, based on the total of the resin composition.

<Compound having one ethylenically unsaturated group in one molecule>
A compound having one ethylenically unsaturated group in one molecule (hereinafter sometimes referred to simply as "monofunctional ethylenically unsaturated compound") may be contained. The "monofunctional ethylenically unsaturated compound" is a case where it is contained in the sealing resin composition of the present invention as a diluent as will be described later. The monofunctional ethylenically unsaturated compound may include other functional groups such as an epoxy group in the range in which the effects of the present invention are exerted. As such a compound, for example, a compound having one or more epoxy groups and one ethylenically unsaturated group in one molecule can be mentioned. Further, a monofunctional ethylenically unsaturated compound containing an epoxy group is classified as a monofunctional ethylenically unsaturated compound in the present invention instead of an epoxy resin.

As a commercially available product of an epoxy group and a compound having one ethylenic unsaturated group in one molecule, for example, "CYCLOMER M100" (3,4-epoxycyclohexylmethyl methacrylate) manufactured by Daicel Orneex Co., Ltd. ), "UVACURE 1561" (a mixture of an epoxy group and a compound having one propylene fluorenyl group in one molecule (content: 78 to 82% by mass) and a bisphenol A type epoxy resin (content: 18 to 22% by mass) ), "4HBAGE" (4-hydroxybutyl acrylate epoxy propyl ether) manufactured by Nippon Kasei Co., Ltd., and the like.

When the resin composition for sealing of the present invention contains a monofunctional ethylenically unsaturated compound, the content thereof is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 1.5% by mass based on the entire resin composition. The above is preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less.

<Compounds having an ethylenically unsaturated group>
The above-mentioned "polyfunctional ethylenically unsaturated compound" and "monofunctional ethylenically unsaturated compound" are collectively described as "a compound having an ethylenically unsaturated group". The content of the compound having such an ethylenically unsaturated group is preferably from 30 to 80% by mass, more preferably from 35 to 80% by mass, still more preferably from 40 to 80% by mass, based on the total of the resin composition.

<Free radical polymerization initiator>
The radical polymerization initiator may be used alone or in combination of two or more. The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator. That is, the radical polymerization initiator is a photoradical polymerization initiator and/or a thermal radical polymerization initiator. The radical polymerization initiator is preferably a photoradical polymerization initiator or a thermal radical polymerization initiator. The photoradical polymerization initiator and the thermal radical polymerization initiator may be used alone or in combination of two or more.

Examples of the photoradical polymerization initiator include acetophenone, diethoxyacetophenone, and 2-[4-(methylthio)methyl-1-phenyl]-2-morpholinylacetone. Benzoin, benzoin ethyl ether, benzyl methyl ketal, benzophenone, 2-ethyl onion, thioxanthone, diethyl thioxanthone, 2,4,6-trimethylbenzylidene Diphenylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylethoxyphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2 -hydroxy-2-methyl-1-phenylpropan-1-one, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone , 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 2-methyl-2-morpholinyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, N,N'-octamethylbisacridine, propylene benzophenone, 2-(benzylideneoxyimido)-1-[4'-(benzene Thio)phenyl]-1-octanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2 -methyl-1-phenylpropan-1-one, 1 -[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl) -propenyl)-benzyl]phenyl}-2-methylpropan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-dimethylamine 2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butanone, bis(2,4,6-trimethylbenzylidene)phenyl oxide Phosphine, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro- 3-(1H-pyrrol-1-yl)phenyl)titanium, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1 -[6-(2-Methylbenzylidene)-9-ethyl-9H-indazol-3-yl]ethanone O-acetonitrile.

Examples of the commercially available product of the photoradical polymerization initiator include "Omnirad 651", "Omnirad 184", "Omnirad 1173", "Omnirad 500", "Omnirad 2959", and "Omnirad 127" manufactured by IGM Resins. "Omnirad 754", "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO", "Omnirad 784", "Irgacure OXE-01" by BASF, "Irgacure OXE-02" "Irgacure 1173" and so on.

Examples of the thermal radical polymerization initiator include an azo compound, an organic peroxide, and the like.
Examples of the azo compound include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis. (2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methyl)dihydrochloride, 1,1'- Azobis(1-ethenyloxy-1-phenylethane, 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (iso) Butyrate), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2, 2'-Azobis(2-methylbutyronitrile), 1-[(1-cyano-1-methylethyl)azo]carbamamine, 2-phenylazo-4-methoxy -2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(N-butyl-2-methyl Propylamine and the like.

Examples of the organic peroxide include benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, and methyl ethyl ketone peroxide. 1,1-di(t-hexylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-di(t-butylperoxy) Pivalate, 2,2-bis(4,4-bis(t-butylperoxy)cyclohexyl)propane, p-menthane hydrogen peroxide, diisopropoxybenzene Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, bis(2-t-butylperoxyisopropyl) Benzene, cumene diperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylperoxybenzene, di-t-hexyl Oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane-3, diisobutylphosphonate peroxide, bis(3,5,5-t-methylhexyl) Mercapto) peroxide, dilauroyl peroxide, disuccinic acid peroxide, bis(3-methylbenzhydryl) peroxide, benzhydryl peroxide, di-n- Propylperoxycarbonate, di-isopropylperoxydicarbonate, di(4) -t-butylcyclohexyl)peroxycarbonate, di(2-ethylhexyl)peroxycarbonate, di-sec-butylperoxycarbonate, cumene peroxy neodecanoic acid Ester, 1,1,3,3-tetramethylbutylperoxy neodecanoate, t-hexylperoxy neodecanoate, t-butylperoxy neodecanoate, t-hexyl Oxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl Base-2,5-di(t-ethylhexylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexyl Acid ester, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t- Butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2, 5-bis(benzimidylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate and t-butylperoxy a mixture of benzoates, t-butylperoxybenzoate, t-butylperoxyallyl monocarbonate, 3,3',4, 4'-tetrakis(t-butylperoxycarbonyl)benzophenone or the like.

For example, "AIBN" (2,2'-azobis(isobutyronitrile)) and "V-40" (1,1) manufactured by Wako Pure Chemical Industries, Ltd., as a commercial product of the thermal radical polymerization initiator. '-Azobis(cyclohexane-1-carbonitrile), "VAm-110" (2,2'-azobis(N-butyl-2-methylpropanamide), "V-601" (Dimethyl 2,2'-azobis(isobutyrate)), "OTAZO-15" manufactured by Otsuka Chemical Co., Ltd. (1,1'-azobis(1-ethenyloxy-1-phenyl) Ethane), "MAIB" (dimethyl 2,2'-azobisisobutyrate), and the like.

The content of the radical polymerization initiator is preferably from 0.5 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, even more preferably from 0.5 to 6 parts by mass, per 100 parts by mass of the "compound having an ethylenically unsaturated group". Share. Here, the "compound having an ethylenically unsaturated group" includes the "polyfunctional ethylenically unsaturated compound" and the "monofunctional ethylenically unsaturated compound" as described above.

When the photo-radical polymerization initiator is used, the content thereof is preferably from 0.5 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, even more preferably from 100 to 8 parts by mass, more preferably from 100 parts by mass of the "compound having an ethylenically unsaturated group". 0.5 to 6 parts by mass.

When the thermal radical polymerization initiator is used, the content thereof is preferably from 0.5 to 10 parts by mass, more preferably from 0.5 to 8 parts by mass, even more preferably from 100 to 8 parts by mass, more preferably from 100 parts by mass of the "compound having an ethylenically unsaturated group". 0.5 to 6 parts by mass.

<Epoxy resin>
The epoxy resin may be used alone or in combination of two or more. An epoxy resin having one epoxy group in one molecule is simply referred to as a "monofunctional epoxy resin", and an epoxy resin having two epoxy groups in one molecule is simply referred to as a "2-functional epoxy resin". "." Epoxy resins having three or more epoxy groups in one molecule are also abbreviated as abbreviations.

As described above, a compound having one or more epoxy groups and two or more ethylenically unsaturated groups in one molecule is classified into the above-mentioned ones because it can be used as the polyfunctional ethylenically unsaturated compound in the present invention. A polyfunctional ethylenically unsaturated compound. Further, as described above, a compound having one or more epoxy groups and one ethylenically unsaturated group in one molecule is classified into a monofunctional ethylenically unsaturated compound in the present invention.

Examples of the epoxy resin include hydrogenated epoxy resin (hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.), fluorine-containing epoxy resin, chain aliphatic epoxy resin, and ring. Aliphatic epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, bisphenol F Epoxy resin, epoxy resin containing phosphorus, bisphenol S type epoxy resin, aromatic epoxy propyl amine type epoxy resin (for example, tetra-epoxypropyldiaminodiphenylmethane, tri-epoxypropyl group) -p-aminophenol, toluidine, diepoxypropyl aniline, etc., alicyclic epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin , bisphenol A novolak type epoxy resin, epoxy resin with butadiene structure, diepoxypropyl etherate of bisphenol, diepoxypropyl etherate of naphthalenediol, phenolic epoxy A propylene ether compound and a diepoxypropyl ether compound of an alcohol, and an alkyl substituent of the epoxy resin or the like.

The epoxy equivalent of the epoxy resin is preferably from 50 to 1,000, more preferably from 50 to 750, still more preferably from 100 to 750, particularly preferably from 100 to 500, from the viewpoint of reactivity and the like. Further, the "epoxy equivalent" is a number of grams (g/eq) of a resin containing 1 gram equivalent of an epoxy group, and is measured in accordance with the method specified in JIS K 7236.

The epoxy resin is preferably one or more selected from the group consisting of hydrogenated epoxy resins, fluorine-containing epoxy resins, chain aliphatic epoxy resins, and cyclic aliphatic epoxy resins, and more preferably selected from hydrogenated rings. One or more of the oxygen resin, the fluorine-containing epoxy resin, and the cyclic aliphatic epoxy resin are more preferably one or more selected from the group consisting of hydrogenated epoxy resins and cyclic aliphatic epoxy resins. Here, the term "hydrogenated epoxy resin" means an epoxy resin obtained by hydrogenating an epoxy resin containing an aromatic ring. The hydrogenation ratio of the hydrogenated epoxy resin is preferably 50% or more, more preferably 70% or more. The "chain aliphatic epoxy resin" means an epoxy resin having a linear or branched alkyl chain or an alkyl ether chain, and is a "cyclic aliphatic epoxy resin". It means an epoxy resin having a cyclic aliphatic skeleton such as a cycloalkane skeleton in the molecule.

Examples of the hydrogenated bisphenol A type epoxy resin include a liquid hydrogenated bisphenol A type epoxy resin (for example, "YX8000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 205), "DENACOL EX-252" (Nagase) Manufactured by ChemteX Co., Ltd., epoxy equivalent: about 213)), solid hydrogenated bisphenol A type epoxy resin (for example, "YX8040" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 1000)).

As the epoxy resin containing fluorine, for example, a fluorine-containing epoxy resin described in WO2011/089947 can be used.

Examples of the chain-like aliphatic epoxy resin include polyglycerol polyepoxypropyl ether (for example, "DENACOL EX-512", "DENACOL EX-521", manufactured by Nagase ChemteX), and pentaerythritol polyepoxypropyl ether. (for example, "DENACOL EX-411", manufactured by Nagase ChemteX), diglycerol polyepoxypropyl ether (for example, "DENACOL EX-421", manufactured by Nagase ChemteX), and glycerol polyepoxypropyl ether (for example, "DENACOL EX" -313", "DENACOL EX-314", manufactured by Nagase ChemteX), trimethylolpropane polyepoxypropyl ether (for example, "DENACOL EX-321", manufactured by Nagase ChemteX), neopentyl glycol epoxide Propyl ether (for example, "DENACOL EX-211", manufactured by Nagase ChemteX Co., Ltd.), 1,6-hexanediol diepoxypropyl ether (for example, "DENACOL EX-212", manufactured by Nagase ChemteX Co., Ltd.), ethylene glycol Di-glycidyl ether (eg "DENACOL EX-810", "DENACOL EX-811", manufactured by Nagase ChemteX), diethylene glycol diglycidyl ether (eg "DENACOL EX-850", "DENACOL EX" -851", manufactured by Nagase ChemteX Co., Ltd.), polyethylene glycol diglycidyl ether (eg "DENACOL EX-821", "DENACOL EX-83" 0", "DENACOL EX-832", "DENACOL EX-841", "DENACOL EX-861", manufactured by Nagase ChemteX), propylene glycol diepoxypropyl ether (for example, "DENACOL EX-911", manufactured by Nagase ChemteX ), polypropylene glycol diglycidyl ether (for example, "DENACOL EX-941", "DENACOL EX-920", "DENACOL EX-931", manufactured by Nagase ChemteX).

Examples of the cyclic aliphatic epoxy resin include "EHPE-3150" manufactured by Daicel Chemical Industries, Ltd., and the like.

When the epoxy resin is used, the content thereof is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, still more preferably 5 to 30% by mass based on the total amount of the resin composition.

<Other ingredients>
The resin composition for sealing of the present invention may contain other components different from the above components insofar as the effects are not impaired.

Diluent The resin composition for sealing of the present invention may contain a diluent to achieve an appropriate viscosity as a resin composition for liquid sealing. The viscosity of the diluent measured by an E-type viscosity meter at a temperature of 25 ° C is preferably 0.1 to 5000 mPa·s, more preferably 0.1 to 2500 mPa·s, still more preferably 0.1 to 1000 mPa·s.

As the diluent, a reactive diluent is preferred. The reactive diluent is preferably a compound having one ethylenically unsaturated group in one molecule (hereinafter, simply referred to as a "monofunctional ethylenically unsaturated compound").

In the present invention, a compound having two ethylenically unsaturated groups in one molecule (hereinafter, simply referred to as "bifunctional ethylenically unsaturated compound") is classified into a "polyfunctional ethylenically unsaturated compound". If it is the above viscosity range, it is also used as a reactive diluent. When the bifunctional ethylenically unsaturated compound used as the reactive diluent is blended, the blending amount can be reduced without blending the diluent or blending. Examples of the bifunctional ethylenically unsaturated compound which can also be used as a diluent include "DPGDA" (dipropylene glycol diacrylate), "HDDA" (1,6-hexanediol diacrylate), and "TPGDA". (Tripropylene glycol diacrylate), "EBECRYL145" (PO modified neopentyl glycol diacrylate), "HPNDA" (neopentyl glycol hydroxypivalate diacrylate), "LIGHT" ESTER NP" (neopentylene glycol dimethacrylate), "LIGHT ESTER EG" (ethylene glycol dimethacrylate), "LIGHT ESTER 2EG" (diethylene glycol dimethacrylate), "LIGHT ESTER 1.6HX" (1,6-hexanediol dimethacrylate), "LIGHT ESTER 1.9ND" (1,9-decanediol dimethacrylate), "LIGHT ACRYLATE NP-A" ( Neopentyl glycol diacrylate), "LIGHT ACRYLATE 1.9ND-A" (1,9-nonanediol diacrylate), "NK ESTER 701A" (2-hydroxy-3-A) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Acryl propyl propyl acrylate), "NK ESTER A-200" (polyethylene glycol #200 diacrylate), "NK ESTER APG-400" (polypropylene glycol #400 dipropylene) Ester), "NK ESTER BG" (1,3-butanediol dimethacrylate), "NK ESTER 701" (2-hydroxy-1,3-dimethylpropenyloxypropane), "NK ESTER 3PG" (tripropylene glycol dimethacrylate), "BISCOAT #195" (1,4-butanediol diacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., and "SR562" (alkoxy) manufactured by Arkema Co., Ltd. Hexanediol diacrylate) and the like. The ethylenically unsaturated group is preferably a (meth) acrylonitrile group, and the reactive diluent is preferably a (meth) acrylate having one (meth) acryl fluorenyl group in one molecule (hereinafter, , sometimes referred to simply as "monofunctional (meth) acrylate").

Examples of the monofunctional (meth) acrylate used as the diluent include "ODA-N" (octyl/mercapto acrylate, that is, a monofunctional acrylate having a long-chain alkyl group) manufactured by Daicel Orneex Co., Ltd., "EBECRYL 110", "EBECRYL 1114" (ethoxylated phenyl acrylate), "LIGHT ESTER E" (ethyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "LIGHT ESTER NB" (n-butyl methyl group) Acrylate), "LIGHT ESTER IB" (isobutyl methacrylate), "LIGHT ESTER TB" (t-butyl methacrylate), "LIGHT ESTER EH" (2-ethylhexyl methacrylate), "LIGHT ESTER ID" (isodecyl methacrylate), "LIGHT ESTER L" (n-lauryl methacrylate), "LIGHT ESTER S" (n-stearyl methacrylate), "LIGHT ESTER CH" (cyclohexyl methacrylate), "LIGHT ESTER THF (1000)" (tetrahydrofurfuryl methacrylate), "LIGHT ESTER BZ" (benzyl methacrylate), "LIGHT ESTER PO" (benzyl Phenyloxyethyl methacrylate), "LIGHT ESTER IB-X" (isodecyl methacrylate), "LIGHT ESTER HO" -250" (2-hydroxyethyl methacrylate), "LIGHT ESTER HOA" (2-hydroxyethyl acrylate), "LIGHT ESTER G" (epoxypropyl methacrylate), "LIGHT ACRYLATE IAA" (Isoamyl acrylate, that is, a monofunctional acrylate having a branched alkyl group), "LIGHT ACRYLATE SA" (stearyl acrylate), "LIGHT ACRYLATE EC-A" (ethoxy-diethylene) Alcohol acrylate), "LIGHT ACRYLATE EHDG-AT" (2-ethylhexyl-diethylene glycol acrylate), "LIGHT ACRYLATE DPM-A" (methoxydipropylene glycol acrylate), "LIGHT ACRYLATE IB-XA" (isodecyl methacrylate, ie monofunctional methacrylate with alicyclic group), "LIGHT ACRYLATE PO-A" (phenoxyethyl acrylate, ie monofunctional acrylic with aromatic ring) Ester), "LIGHT ACRYLATE P2H-A" (phenoxy diethylene glycol acrylate), "LIGHT ACRYLATE P-200A" (phenoxy-polyethylene glycol acrylate), "LIGHT ACRYLATE POB-A" ( M-phenoxybenzyl acrylate), "LIGHT ACRYLATE TFH-A" (tetrahydrofurfuryl acrylate), "LIGHT ESTER HOP-A(N)" (2-hydroxyl) Acrylate), "HOA-MS(N)" (2-propenyloxyethyl-succinic acid), "epoxy ester M-600A" (2-hydroxy-3-phenoxypropyl acrylate) "IDAA" (isodecyl acrylate), "BISCOAT #155" (cyclohexyl acrylate), "BISCOAT #160" (benzyl acrylate), "BISCOAT #150" (tetrahydrogen) manufactured by Osaka Organic Chemical Industry Co., Ltd. Mercaptoacrylate), "BISCOAT #190" (ethyl carbitol acrylate), "OXE-10" (3-ethyl-3-epoxypropane methacrylate, ie having a propylene oxide ring Acrylate), "MEDOL-10" (2-methyl-2-ethyl-1,3-dioxolane-4-yl)methacrylate, ie having dioxolane ( Dioxolane), "ARONIX M-101A" (phenolic EO modified acrylate) manufactured by Toagosei Co., Ltd., "NK ESTER A-LEN-10" manufactured by Shin-Nakamura Chemical Industry Co., Ltd. (ethoxylated o-benzene) "Acetyl acrylate", "NK ESTER EH-4E" (ethoxylated ethylhexyl polyethylene glycol methacrylate), "FA-511AS" (dicyclopentenyl acrylate) manufactured by Hitachi Chemical Co., Ltd., "FA-512AS" (dicyclopentenyloxyethyl acrylate ), "FA-513AS" (dicyclopentyl acrylate), "SR217NS" manufactured by Arkema Co., Ltd. (4-Tert-butylcyclohexanol acrylate), "SR420NS" (3,3,5-Third Cyclohexanol acrylate), "SR531" (cyclic trimethylolpropane acetal acrylate), "CD421" (3,3,5-trimethylcyclohexanol methacrylate), "CD535 (Dicyclopentadienyl methacrylate), "VEEA" (2-(2-vinyloxyethoxy)ethyl acrylate), "VEEM" (2-(2) methacrylate) -vinyloxyethoxy)ethyl ester) and the like. Further, the term "octyl/mercapto acrylate" means a mixture of octyl acrylate and methacrylate.

The monofunctional (meth) acrylate used as a diluent is particularly preferably a monofunctional methacrylate having an alicyclic structure. The alicyclic structure is synonymous with the foregoing. For example, "LIGHT ESTER IB-X" (isodecyl methacrylate) manufactured by Kyoei Chemical Co., Ltd. having a decane ring structure is exemplified as a monofunctional (meth) acrylate having a alicyclic structure. "LIGHT ACRYLATE IB-XA" (isodecyl methacrylate), "LIGHT ESTER CH" (cyclohexyl methacrylate) manufactured by Kyoei Chemical Co., Ltd., which has a cyclohexyl structure, and Osaka Organic Chemical Industry Co., Ltd. BISCOAT #155" (cyclohexyl acrylate), "SR217NS" manufactured by Arkema Co., Ltd. (4-Tert-butylcyclohexanol acrylate), "SR420NS" (3,3,5-trimethylcyclohexanol acrylic acid) Ester), "CD421" (3,3,5-trimethylcyclohexanol methacrylate), "CD535" (biscyclopentadienyl methacrylate), and Hitachi Chemical Co., Ltd. "FA-511AS" (dicyclopentenyl acrylate), "FA-512AS" (dicyclopentenyloxyethyl acrylate), "FA-513AS" (dicyclopentyl acrylate), Arco "CD535" (biscyclopentadienyl methacrylate) manufactured by Nippon Co., Ltd., "VEEA" (2-(2-vinyloxyethoxy)ethyl acrylate) manufactured by Nippon Shokubai Co., Ltd., " VEEM" (2-(2-vinyloxyethoxy)ethyl methacrylate) and the like.

When a diluent is used, the content (including the content of the "bifunctional ethylenically unsaturated compound" used as a diluent) is preferably 2% by mass or more, and more preferably 5% by mass based on the total amount of the resin composition. More preferably, it is 10% by mass or more, more preferably 60% by mass or less, still more preferably 55% by mass or less, and still more preferably 50% by mass or less.

Photocationic polymerization initiator The sealing resin composition of the present invention may contain a photocationic polymerization initiator. The photocationic polymerization initiator may be used alone or in combination of two or more.

Examples of the photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and (2,4-cyclopentadien-1-yl). ((1-methylethyl)benzene)-Fe salt or the like.

Examples of the aromatic onium salt include bis(4-(diphenyldithio)(sulfonio)phenyl)sulfide dihexafluorophosphate and bis(4-(diphenyldihydrothio)benzene. Sulfide dihexafluoroantimonate, bis(4-(diphenyldihydrothio)phenyl) sulfide ditetrafluoroborate, bis(4-(diphenyldihydrothio)benzene Sulfide quinone (pentafluorophenyl) borate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylphosphonium hexafluorophosphate Citrate, diphenyl-4-(phenylthio)phenylphosphonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylhydrazine(pentafluorophenyl)borate, three Phenylphosphonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium (pentafluorophenyl) borate, bis (4-(di) 4-(2-hydroxyethoxy))phenyldihydrothio)phenyl)sulfide dihexafluorophosphate, bis(4-(di(4-(2-hydroxyethoxy))phenyl) Hydrogenthio)phenyl)sulfide dihexafluoroantimonate, bis(4-(di(4-(2-hydroxyethoxy))phenyldihydrothio)phenyl)sulfide bistetrafluoroboron Acid ester, bis(4-(di(4-(2-hydroxyethoxy))phenyldihydrothio)phenyl) sulfide (Pentafluorophenyl) borate.

Examples of the aromatic iodonium salt include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, and diphenyliodonium (five). Fluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl) Iodine tetrafluoroborate, bis(dodecylphenyl)iodonium (pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyl iodide Hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl) Phenyl iodonium tetrafluoroborate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium (pentafluorophenyl) borate, and the like.

Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium (pentafluorophenyl). Borate esters, etc.

Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, and 1-benzyl-2-cyanide. Pyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium (pentafluorophenyl) borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate , 1-(Naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl) -2-cyanopyridinium (pentafluorophenyl) borate or the like.

As the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl) (1) -methylethyl)benzene)-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoro Citrate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadiene- 1-yl)((1-methylethyl)benzene)-Fe(II)肆(pentafluorophenyl)borate or the like.

For example, "SP-150", "SP-170", "SP-082", "SP-103" manufactured by ADEKA Co., Ltd., and "CPI-" manufactured by San-Apro Co., Ltd. are available as a commercial product of the photo-cationic polymerization initiator. 100P", "CPI-101A", "CPI-200K", "Omnirad 270" and "Omnirad 290" manufactured by IGM resins.

When a photocationic polymerization initiator is used, the content thereof is 100 parts by mass, preferably 0.5, based on the total of the epoxy group-containing compound (for example, a total of (meth) acrylate having an epoxy group and an epoxy resin). ～10 parts by mass, more preferably 1.0 to 8 parts by mass, still more preferably 2.0 to 6 parts by mass.

The decane coupling agent The sealing resin composition of the present invention may contain a decane coupling agent. The decane coupling agent may be used alone or in combination of two or more.

Examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl (dimethyl). Epoxy decane coupling agent of oxy)methyl decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane; 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyl a decyl decane coupling agent such as triethoxy decane, 3-mercaptopropylmethyldimethoxydecane or 11-decylundecyltrimethoxydecane; 3-aminopropyltrimethoxydecane, 3-Aminopropyltriethoxydecane, 3-aminopropyldimethoxymethylnonane, N-phenyl-3-aminopropyltrimethoxydecane, N-methylaminopropyl Trimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane and N-(2-aminoethyl)-3-aminopropyldimethoxymethyl Amino decane coupling agent such as decane; urea-based decane coupling agent such as 3-ureidopropyltriethoxy decane; vinyl trimethoxy decane, vinyl triethoxy decane and vinyl Vinyl decane coupling agent such as bis-ethoxy decane; p-styryl trimethoxy a styrene-based decane coupling agent such as decane; an acrylate-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane or 3-methylpropoxypropyltrimethoxydecane; - an isocyanate-based decane coupling agent such as isocyanate propyl trimethoxy decane; a sulfide of bis(triethoxydecylpropyl) disulfide or bis(triethoxydecylpropyl) tetrasulfide; A decane coupling agent; phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium, triazine decane, and the like. Among these, an acrylate-based decane coupling agent is preferred.

For example, "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", "KBM-" manufactured by Shin-Etsu Chemical Co., Ltd. are available as a commercial product of the decane coupling agent. 5803" and so on.

When the decane coupling agent is used, the content thereof is preferably 0.10 to 5.00% by mass, more preferably 0.25 to 3.00% by mass, still more preferably 0.30 to 2.00% by mass, based on the entire resin composition.

Inhibitor The sealing resin composition of the present invention may contain a polymerization inhibitor. The polymerization inhibitor may be used alone or in combination of two or more.

Examples of the polymerization inhibitor include t-butylhydroquinone, p-benzoquinone, hydroquinone, p-methoxyphenol, N,N-diethylhydroxylamine, and N-nitroso-N-phenyl. Hydroxylamine ammonium salt and the like. As a commercial product of the polymerization inhibitor, "Q-1101", "TBHQ", "PBQ2", "DEHA", "MEHQ", and "QS-10" manufactured by Kawasaki Kasei Kogyo Co., Ltd., are available from Wako Pure Chemical Industries, Ltd. Wait.

When the polymerization inhibitor is used, the content thereof is preferably from 10 to 200 ppm, more preferably from 50 to 100 ppm, per 100 parts by mass of the "compound having an ethylenically unsaturated group". Still, the aforementioned "ppm" is a quality standard. Here, the "compound having an ethylenically unsaturated group" includes the "polyfunctional ethylenically unsaturated compound" and the "monofunctional ethylenically unsaturated compound" as described above.

<Organic EL device>
In the organic EL device in which the organic EL device is sealed with the cured product of the resin composition for sealing of the present invention, for example, the resin composition for sealing of the present invention can be applied from the organic EL device on the substrate, and then the resin can be applied. The composition is hardened to be manufactured.

When the resin composition for sealing of the present invention contains a photoradical polymerization initiator, the curing can be carried out by irradiating the resin composition with ultraviolet rays. Examples of the apparatus for irradiating ultraviolet rays include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a low pressure mercury lamp, an LED light source, and the like. The temperature of the resin composition at the time of ultraviolet irradiation is preferably from 20 to 120 ° C, more preferably from 25 to 110 ° C. The total amount of irradiation of ultraviolet rays is preferably from 500 to 4,000 mJ/cm ² , more preferably from 1,000 to 3,500 mJ/cm ² .

When the resin composition for sealing of the present invention contains a thermal radical polymerization initiator, the curing can be carried out by heating the resin composition using a dryer or the like. The heating temperature is preferably from 80 to 120 ° C, more preferably from 100 to 110 ° C, and the heating time is preferably from 15 to 120 minutes, more preferably from 30 to 90 minutes. This heating can be carried out in an atmosphere or in an inert gas such as a nitrogen gas atmosphere.

[Examples]

The present invention is not limited by the following examples, but the present invention is not limited by the following examples, and may be appropriately modified and implemented in the scope of the above-mentioned and the following, and these are also included in the present invention. The scope of technology.
In addition, the "parts" of the amounts described below are intended to mean "parts by mass" unless otherwise specified.

<Example 1>
90 parts of a bifunctional alicyclic acrylate ("IRR214-K" manufactured by Daicel Orneex Co., Ltd.), 30 parts with a 6-functional acrylate ("DPCA-60" manufactured by Nippon Kayaku Co., Ltd.), and a bifunctional aliphatic acrylate 30 parts ("1.9ND-A" manufactured by Xierongshe Chemical Co., Ltd.), 0.05 parts with a polymerization inhibitor ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.), and commercially available hydrotalcite A (semi-fired hydrotalcite, BET specific surface area: 13 m ² /g, average particle diameter: 400 nm)) 90 parts, and 30 parts of commercially available calcium oxide (manufactured by Kitamura Co., Ltd.) were uniformly dispersed by a high-speed rotary mixer. Then, 11 parts of a polymerization initiator ("Irgacure 1173" manufactured by BASF Corporation) was added, and the mixture was further dispersed to obtain a resin composition.

<Example 2>
The semi-calcined hydrotalcite A and the commercially available hydrotalcite D (unfired hydrotalcite, average particle diameter: 400 nm) were used, and the components described in Table 1 were stirred and mixed at a predetermined blending ratio to obtain a resin composition. Things.

<Example 3>
The semi-calcined hydrotalcite A and the commercially available hydrotalcite C (calcined hydrotalcite, average particle diameter: 400 nm) were used, and the components described in Table 1 were stirred and mixed at a predetermined blending ratio to obtain a resin composition. .

<Examples 4 to 6 and Comparative Examples 1 to 4>
In the same manner as in Example 1, the components described in Table 1 were stirred and mixed at a predetermined blending ratio to obtain the resin compositions of Examples 4 to 6 and Comparative Examples 1 to 4.

<Water absorption rate of hydrotalcite>
Each hydrotalcite was weighed 1.5 g on Libra, and the initial mass was measured. The sample was placed in a small environmental tester (SH-222 manufactured by Espec Co., Ltd.) at atmospheric pressure, 60 ° C, and 90% RH (relative humidity) for 200 hours, and the mass after moisture absorption was measured, and saturation was obtained using the above formula (i). Water absorption rate. The results are shown in Table 1.

<The thermal weight reduction rate of hydrotalcite>
The thermogravimetric analysis of each hydrotalcite was carried out using a TG/DTA EXSTAR 6300 manufactured by Hitachi High-Tech Co., Ltd. The sample disc prepared by AL was weighed 10 mg of hydrotalcite, and was opened without being covered, and was heated from 30 ° C to 550 ° C at 10 ° C / min in an environment of a nitrogen flow rate of 200 mL / min. Using the above formula (ii), the thermal weight reduction rate at 280 ° C and 380 ° C was determined. The results are shown in Table 1.

<Powder X-ray diffraction>
The powder X-ray diffraction was measured by a powder X-ray diffraction device (manufactured by PANalytical Co., Ltd., Empyrean), a cathode CuKα (1.5405 Å), a voltage: 45 V, a current: 40 mA, a sampling width: 0.0260 ̊, and a scanning speed: 0.0657 ̊ / s, measurement of the diffraction angle range (2θ): 5.0131 ~ 79.9711 ̊ conditions are carried out. The peak search system uses the peak search function of the software attached to the diffractive device to "minimum saliency: 0.50, minimum peak wafer: 0.01 ̊, maximum peak chip: 1.00 ̊, peak bottom width: 2.00 ̊, method : The condition of the minimum value of 2 times of differentiation is performed. The two peaks of the split appearing in the range of 8 to 18 检 are detected, or the peak of the shoulder is formed by the synthesis of the two peaks, and the peak of the low angle side or the diffraction intensity of the shoulder is measured. (= low angle side diffraction intensity), peak with high angle side or diffraction intensity of shoulder (= high angle side diffraction intensity), calculate relative intensity ratio (= low angle side diffraction intensity / high angle side diffraction strength). The results are shown in Table 1.

From the results of saturated water absorption, thermal weight reduction, and powder X-ray diffraction, hydrotalcite A is "semi-fired hydrotalcite", hydrotalcite C is "burned hydrotalcite", and hydrotalcite D is "unfired water". talc".

<water content>
The resin composition prepared in the examples and the comparative examples was stored in an oven at 80 ° C for one week, and then the moisture contained in the resin composition was measured using a Karl Fischer moisture measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., CA-200). . The moisture content detected when heated in a furnace at 130 ° C was evaluated on the basis of the following criteria. The results are shown in Table 2.
Good (○): less than 1000ppm
(△): 1000ppm or more and less than 1500ppm
Bad (×): 1500ppm or more

<Ca deterioration evaluation>
After Ca 200 nm was formed on the glass substrate, the prepared resin composition was coated on Ca to carry out a hardening treatment. It was confirmed whether or not the deterioration of the Ca film surface after heating at 100 ° C for 30 minutes was evaluated by the following criteria. The results are shown in Table 2.
Good (○): poor deterioration of the surface of the Ca-free film (×): significant deterioration of the surface of the Ca film

From the results of Table 2, it was confirmed that the compositions of Examples 1 to 6 have a low water content, and the Ca deterioration evaluation is good, that is, the initial deterioration at the time of suppressing the organic EL sealing can be suppressed, and deterioration of the element can be prevented by a long period of time. Sealing layer.

<Device Seal Test>
First, an organic EL device (thickness of organic film: 110 nm, thickness of cathode: 10 nm) was formed on a glass substrate (manufactured by GEOMATEC Co., Ltd.) with indium tin oxide (ITO) so that the light-emitting area was 4 mm ² . Next, a nitride film (thickness: 500 nm) was formed on the organic EL device by a chemical vapor deposition method (CVD method). Next, the composition prepared in Example 1 was applied so as to surround the organic EL element to which the nitride film was attached, and the alkali-free glass plate was superposed thereon to prepare a laminate (alkali-free glass plate/composition) Layer/organic EL element with nitride film/glass substrate with ITO). The composition was cured by heating the laminate at 100 ° C for 30 minutes to produce a laminate of a sealed organic EL element (thickness of the cured product: 10 μm).

[Industrial availability]

The sealing resin composition of the present invention is excellent in the deterioration of the moisture-blocking property and the element such as the organic EL. Therefore, it can be suitably used for sealing a light-emitting element such as an organic EL element or a light-receiving element such as a solar cell.

This case is based on the Japanese Patent Application No. 2018-033850, the contents of which are all included in the present specification.

Claims (17)

A resin composition for sealing comprising hydrotalcite and calcium oxide. The sealing resin composition of claim 1, wherein the ratio of the calcium oxide to the hydrotalcite is 0.1 to 1 by mass. The resin composition for sealing according to claim 1 or 2, wherein the content of the hydrotalcite is from 10% by mass to 70% by mass based on 100% by mass of the nonvolatile content of the resin composition. The resin composition for sealing according to any one of claims 1 to 3, further comprising a resin selected from at least one of an acrylic resin and an epoxy resin. The sealing resin composition according to any one of claims 1 to 3, further comprising at least one type of acrylic resin. The sealing resin composition of claim 4 or 5, wherein the acrylic resin contains a compound having three or more ethylenically unsaturated groups in one molecule. The resin composition for sealing according to any one of claims 4 to 6, wherein the acrylic resin is a compound having two or more ethylenically unsaturated groups and an alicyclic structure in one molecule. The sealing resin composition of claim 6 or 7, wherein the ethylenically unsaturated group is a (meth)acryl fluorenyl group. The resin composition for sealing according to claim 7 or 8, wherein the amount of the compound having two or more ethylenically unsaturated groups and an alicyclic structure in one molecule is from 5 to 75% by mass based on the total amount of the resin composition. . The sealing resin composition according to any one of claims 1 to 9, wherein the hydrotalcite is a semi-fired hydrotalcite. The resin composition for sealing according to any one of claims 1 to 10, further comprising a radical polymerization initiator. The resin composition for sealing according to claim 11, wherein the radical polymerization initiator is a photoradical polymerization initiator and/or a thermal radical polymerization initiator. The sealing resin composition of claim 11 or 12, wherein the amount of the radical polymerization initiator is 0.5 to 10 parts by mass based on 100 parts by mass of the compound having an ethylenically unsaturated group. The resin composition for sealing according to any one of claims 1 to 13, further comprising a decane coupling agent. The resin composition for sealing according to any one of claims 1 to 14, which is in the form of a liquid. The sealing resin composition according to any one of claims 1 to 15, which is used for sealing an organic EL element. An organic EL device that seals an organic EL device with a cured product of the sealing resin composition according to any one of claims 1 to 16.