TW201900834A - Package composition - Google Patents

Abstract

The present invention provides a sealing composition that comprises: a compound having two or more ethylenically unsaturated groups per molecule; a half-calcined hydrotalcite; and a radical polymerization initiator.

Description

Composition for encapsulation

The present invention relates to a composition for encapsulation, and more particularly to a composition for encapsulation suitable for encapsulation of a light-emitting element such as an organic EL (Electroluminescence) element or a light-receiving element such as a solar cell.

The organic EL element is a light-emitting element using an organic substance as a light-emitting material, and can obtain high-brightness light emission at a low voltage, so it has attracted attention in recent years. However, organic EL elements are extremely weak to moisture. Some light-emitting materials (light-emitting layers) are deteriorated due to moisture, the brightness is reduced or no light is 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. The problem of resistance. Therefore, in order to block the moisture in the outside air, for example, a composition is used to cover the entire surface of the light-emitting layer formed on the substrate to form an encapsulation layer to encapsulate the organic EL element. The packaging layer of such an organic EL element requires a high moisture blocking property. In addition, in applications such as displays, touch panels, and lighting, and a structure in which light is taken out from the packaging surface or a transmissive structure, the packaging layer is also required to have high transparency. In this way, there is a demand for a composition capable of forming an encapsulating layer having both high moisture blocking properties and transparency.

Patent Document 1 describes a composition for adhesive sealing containing a hydrogenated cyclic olefin-based polymer and a polyisobutylene resin. Patent Document 1 describes that a photocurable resin and a photopolymerization initiator are further blended in the composition. Further, Patent Document 2 describes a composition containing a curable compound, a polymerization initiator, a first moisture absorbent having a water absorption of 30% by weight or more, and a second moisture absorbent having a water absorption of 5% by weight or more and less than 30% by weight. Hardening composition. However, neither of Patent Documents 1 and 2 describes an encapsulation layer having both high moisture blocking properties and transparency. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2009-524705 [Patent Document 2] Japanese Patent Publication No. 2016-51700

[Problems to be Solved by the Invention]

This invention aims at providing the composition for encapsulation which can form the encapsulation layer (hardened | cured material layer) excellent in both moisture blocking property and transparency. [Means to solve the problem]

As a result of careful research in order to achieve the above object, the present inventors have found that a composition containing a compound having two or more ethylenically unsaturated groups in one molecule, a semi-fired hydrotalcite, and a radical polymerization initiator can be formed. An encapsulation layer (cured material layer) having excellent moisture blocking properties and transparency. The present invention based on such findings is as follows.

[1] A composition for encapsulation, comprising a compound having two or more ethylenically unsaturated groups in one molecule, a semi-fired hydrotalcite, and a radical polymerization initiator. [2] The composition according to the aforementioned [1], wherein the compound having two or more ethylenically unsaturated groups in one molecule is a compound containing three or more ethylenically unsaturated groups in one molecule. [3] The composition according to the above [1] or [2], wherein the compound having two or more ethylenically unsaturated groups in one molecule is a compound containing two or more ethylenically unsaturated groups in one molecule and an alicyclic ring Formulated compounds. [4] The composition according to any one of [1] to [3], further comprising a diluent. [5] The composition as described in [4] above, wherein the diluent is a compound having one ethylenically unsaturated group in one molecule. [6] The composition according to any one of [1] to [5] above, wherein the ethylenically unsaturated group is a (meth) acrylic fluorenyl group. [7] The composition according to any one of the above [1] to [6], wherein the amount of the compound having two or more ethylenically unsaturated groups in one molecule is 20 to 78 masses in the entire composition %. [8] The composition according to any one of the above [1] to [7], wherein the amount of the semi-calcined hydrotalcite is 10 to 70% by mass in the entire composition. [9] The composition according to any one of the aforementioned [1] to [8], wherein the radical polymerization initiator is a photo radical polymerization initiator and / or a thermal radical polymerization initiator. [10] The composition according to any one of [1] to [9], wherein the amount of the radical polymerization initiator is 0.5 to 10 parts by mass relative to 100 parts by mass of the compound having an ethylenically unsaturated group. . [11] The composition according to any one of [1] to [10], further comprising a silane coupling agent. [12] The composition according to any one of [1] to [11] above, wherein the hardened layer of the composition having a thickness of 20 μm has a total light transmittance of 85% or more under D65 light. [13] The composition according to any one of the aforementioned [1] to [12], wherein the haze of the hardened layer of the composition having a thickness of 20 μm is less than 3.0%. [14] The composition according to any one of [1] to [13] above, which is liquid. [15] The composition according to any one of [1] to [14] above, which is used for packaging an organic EL element. [16] An organic EL device which encapsulates an organic EL element with a hardened body of a composition as described in any one of [1] to [15] above. [Inventive effect]

From the composition of the present invention, an encapsulation layer excellent in both moisture blocking property and transparency can be formed. [Form of Implementing Invention]

<Composition> The composition of the present invention is a compound containing two or more ethylenically unsaturated groups in one molecule, a semi-fired hydrotalcite, and a radical polymerization initiator. Here, the "ethylenically unsaturated group" means a functional group having an ethylenic double bond. The composition of the present invention can be produced by mixing the above-mentioned components and, if necessary, other components using a kneading roller or a rotary mixer.

The composition of the present invention can be used, for example, in electronic components such as semiconductors, solar cells, high-brightness LEDs, LCDs, and EL elements, and is preferably a package of optical semiconductors such as organic EL elements and solar cells. The composition of the present invention is particularly suitable for packaging organic EL devices. Specifically, the composition of the present invention can be used for the upper portion and / or the surrounding (side portion) of the light emitting portion of the organic EL element, and in order to protect the light emitting portion of the organic EL element from the outside.

The composition of the present invention is preferably a liquid composition for encapsulation. Here, the "liquid packaging composition" refers to a packaging composition having flowability at normal temperature (25 ° C) and normal pressure (atmospheric pressure). For example, when the sealing composition containing an inorganic filler has fluidity at normal temperature and pressure, it may correspond to the liquid sealing composition in the present invention. Liquid packaging materials (compositions for packaging), compared with film packaging materials, generally have the embedding property of the light-emitting element surface of the circuit, the suppression of voids when the packaging surface is large, and the film of the packaging layer. The ease of thickness adjustment, the formation of a dam before packaging, and the high alignment accuracy that can be achieved by alignment are often advantageous.

The composition of the present invention is preferably free of volatile components such as solvents. When the composition of the present invention contains a volatile component such as a solvent, the reference amount of each component is a volatile component that does not include a solvent and the like. That is, in the case where the composition of the present invention contains volatile matter, "in the entire composition" based on the amount of each component means "in the entire nonvolatile matter of the composition".

<A compound having two or more ethylenically unsaturated groups in one molecule> 之 The composition of the present invention includes a compound having two or more ethylenically unsaturated groups in one molecule (hereinafter sometimes referred to as "multifunctional ethylenically unsaturated group"). Saturated compound "). The polyfunctional ethylenically unsaturated compound may be used singly or in combination of two or more kinds. The polyfunctional ethylenically unsaturated compound may contain other functional groups, such as an epoxy group, in the range which can exhibit the effect of this invention. Moreover, in the present invention, a polyfunctional ethylenically unsaturated compound containing an epoxy group is classified as a polyfunctional ethylenically unsaturated compound other than an epoxy resin.

The polyfunctional ethylenically unsaturated compound is preferably liquid in order to form the sealing composition of the present invention into a liquid state. Here, "liquid" means the state of a polyfunctional ethylenically unsaturated compound at normal temperature (25 ° C) and normal pressure (atmospheric pressure). When the polyfunctional ethylenically unsaturated compound is a mixture of two or more compounds, it is preferable that these mixtures are liquid. For example, when a solid polyfunctional ethylenically unsaturated compound and a liquid polyfunctional ethylenic compound are used, a mixture of these compounds is preferably liquid.

The polyfunctional ethylenically unsaturated compound has a high-density crosslinked structure and exhibits high moisture-barrier properties, and is preferably a compound containing three or more ethylenically unsaturated groups in one molecule, more preferably 1 A compound having 4 or more ethylenically unsaturated groups in a molecule, and more preferably a compound having 5 or more ethylenically unsaturated groups in one molecule, and particularly preferably a compound having 6 or more ethylenically unsaturated groups in one molecule compound of. Among the polyfunctional ethylenically unsaturated compounds, the upper limit of the number of ethylenically unsaturated groups contained in one molecule is not particularly limited, but the number is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less.

When a compound having three or more ethylenically unsaturated groups in one molecule is used, the amount of the compound exhibits a high moisture blocking property. The entire composition is preferably 2% by mass or more, and more preferably 3% by mass or more. It is more preferably 4% by mass or more, more preferably 70% by mass or less, more preferably 65% by mass or less, and still more preferably 60% by mass 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 two in one molecule, from the viewpoint of improving the moisture blocking property. A compound of ethylenically unsaturated group and 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 tricyclic [5.2.1.0 ^2,6 ] decane ring, a bornane ring, an isoxane ring, a cyclohexane ring, a bicyclooctane ring, a norbornane ring, Cyclodecane ring, adamantane ring, cyclopentane ring and the like. The alicyclic structure may have a hetero atom. The alicyclic structure may be substituted with a substituent such as an alkyl group, an alkoxy group, or an alkylene group.

When using a compound having two or more ethylenically unsaturated groups and alicyclic structures in one molecule (especially a compound having two ethylenically unsaturated groups and alicyclic structures in one molecule), the amount is based on the composition Of the total material, it is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, more preferably 75 mass% or less, more preferably 70 mass% or less, and even more preferably 65 Mass% or less.

The ethylenically unsaturated group is preferably a (meth) acrylfluorenyl group. That is, the compound having an ethylenically unsaturated group is preferably a (meth) acrylate having a (meth) acrylfluorenyl group. In this specification, "(meth) acrylfluorenyl" means "acrylfluorenyl and / or methacrylfluorenyl", and "(meth) acrylate" means "acrylate and / or methacrylate" . In addition, a (meth) acrylate having two or more (meth) acrylfluorenyl groups in one molecule may be simply referred to as "multifunctional (meth) acrylate" hereinafter. In addition, a (meth) acrylate having two (meth) acrylfluorenyl groups in one molecule may be simply referred to simply as "difunctional (meth) acrylate".

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

Examples of the bifunctional (meth) acrylate include "DPGDA" (dipropylene glycol diacrylate), "HDDA" (1,6-hexanediol diacrylate), and "TPGDA" (tripropylene glycol) manufactured by DAICEL-ALLNEX Corporation. Diacrylate), `` EBECRYL145 '' (PO modified neopentyl glycol diacrylate), `` EBECRYL150 '' (modified bisphenol A diacrylate), `` IRR214-K '' (tricyclodecane dimethanol diacrylate) ), `` EBECRYL11 '' (PEG600 diacrylate), `` HPNDA '' (neopentyl glycol hydroxypivalate diacrylate), `` LIGHT ESTEREG '' (ethylene glycol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd. , "LIGHT ESTERNP-A" (neopentyl glycol dimethacrylate), "LIGHT ESTER2EG" (diethylene glycol dimethacrylate), "LIGHT ESTER1.6HX" (1,6-hexanediol di (Methacrylate), `` LIGHT ESTER1.9ND '' (1, 9-nonanediol dimethacrylate), `` LIGHT ESTERG-101P '' (glycerol dimethacrylate), `` LIGHT ESTER BP-2EMK "(EO adduct of bisphenol A dimethacrylate)," Light AcrylateNP-A "(neopentyl glycol diacrylate)," Light Acrylate1.9ND-A "(1, 9-nonanediol diacrylate)," Light Acrylate BP-4EAL "(EO adduct diacrylate of bisphenol A)," Light Acrylate BP-4PA "(PO adduct of bisphenol A Diacrylate), `` NK Ester701A '' (2-hydroxy-3-methacryl propyl propyl acrylate), `` NK EsterA-200 '' (polyethylene glycol # 200 diacrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd. "NK EsterAPG-400" (polypropylene glycol # 400 diacrylate), "NK EsterA-PTMG-65" (polyethylene glycol # 650 diacrylate), "NK EsterA-1206PE" (polyethylene polymer Propylene glycol diacrylate), `` NK Ester ester A-BPEF '' (9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene diacrylate), `` NK Ester ester A-BPE30 '' (ethyl Oxylated bisphenol A diacrylate), `` NK EsterA-BPP-3 '' (propoxylated bisphenol A diacrylate), `` NK EsterBG '' (1,3-butanediol dimethacrylate) `` NK Ester701 '' (2-hydroxy-1,3-dimethylpropylene methoxypropane), `` NK Ester3PG '' (tripropylene glycol dimethacrylate), `` NK Ester ester 1206PE '' (polyethylene polypropylene glycol di Methacrylate), "NK EsterDCP" ( Cyclodecane dimethanol dimethacrylate), `` KAYARAD FM-400 '', `` KAYARAD HX-220 '', `` KAYARAD HX-620 '' (neopentyl modified diacrylate), `` KAYARAD '' "R-604", (dioxane ethylene glycol diacrylate), "KAYARAD UX-3204" (oligomer with two acryl fluorene groups in one molecule), "Viscoat # 195" manufactured by Osaka Organic Chemical Industry Co., Ltd. (1,4-butanediol diacrylate), "Viscoat # 540" (bisphenol A diglycidyl ether acrylic acid adduct), "CD406" (cyclohexanedimethanol diacrylate) manufactured by arkema, `` SR562 '' (alkoxylated hexamethylene glycol diacrylate), `` EBECRYL600 '' made by DAICEL-ALLNEX (bisphenol A type epoxy acrylate with two acryl fluorenyl groups in one molecule), `` EBECRYL210 '' (1 Aromatic urethane oligomer with two acryl fluorenyl groups in the molecule), "EBECRYL230" (aliphatic urethane oligomer with two acryl fluorenyl groups in one molecule), "EBECRYL436" (Ester oligomer with two acryl fluorenyl groups in one molecule), "CN959" manufactured by Arkema Corporation (urethane oligomer with two acryl fluorenyl groups in one molecule ), "ART RESIN UN-9000PEP" (urethane oligomer with 2 acryl fluorene groups in 1 molecule), "ART RESIN UN-333" (2 propylene fluorene in 1 molecule) Based oligomers).

(Meth) acrylates having three or more (meth) acrylfluorenyl groups in one molecule include, for example, "LIGHT ESTERTMP" (trimethylolpropane trimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., and Light AcrylatePE-3A "(Pentaerythritol Triacrylate)," Light AcrylatePE-4A "(Pentaerythritol Tetraacrylate)," Light AcrylateDGE-4A "(EO Adduct Modified Diglycerol Tetraacrylate), DAICEL-ALLNEX Corporation Made of "PETIA" (pentaerythritol (tri / tetra) acrylate), TMPTA (trimethylolpropane triacrylate), TMPEOTA (trimethylolpropane ethoxy triacrylate), "EBECRYL135" (trimethylol Propane propoxy triacrylate), `` PETA '' (pentaerythritol (tri / tetra) acrylate), `` DPHA '' (dipentaerythritol hexaacrylate), `` NK EsterA-TMPT '' (trimethylol) manufactured by Shin Nakamura Chemical Industry Co., Ltd. Propane triacrylate), `` NK EsterA-TMPT-3PO '' (propoxylated trimethylolpropane triacrylate), `` NK EsterA-GLY-6E '' (ethoxylated glycerol triacrylate) , "NK EsterA-GLY-6P" (propoxylated glycerol triacrylate), "NK Este "rA-9300" (tri- (2-propenyloxyethyl) isocyanurate), "NK EsterA-9200" (bis / tri- (2-propenyloxyethyl) isocyanurate) ), `` NK EsterA-9300-1CL '' (caprolactone modified tri- (2-propenyloxyethyl) isocyanurate), `` NK EsterATM-4EL '' (ethoxylated pentaerythritol (tri / 4) Acrylate), `` KAYARAD DPCA-20 '' (6-functional acrylate), `` KAYARAD DPCA-60 '' (6-functional acrylate), `` T-1420 (T) '' (4-functional acrylate) ), "DPEA-12" (6-functional acrylate), "KAYARAD DPHA-40H" (oligomer with 10 acryl fluorenyl groups in one molecule), "Viscoat # 802" (Pentaerythritol Acrylic Acid) manufactured by Osaka Organic Chemical Industry Co., Ltd. (Ester), "Viscoat # 1000" (Dendrimer acrylate), "CN989NS" (ark fatty urethane oligomer with 3 acryl fluorenyl groups in one molecule), " CN9039 "(aliphatic urethane oligomer with 6 acrylamino groups in 1 molecule)," UN-3320HA "," UN-3320HC "," UN-906S "(1 molecule) Aliphatic amine group with 6 acrylyl groups Formate oligomer), "DICLITE UE-8740" (a phenol novolac epoxy acrylate having three acryl fluorenyl groups in one molecule) manufactured by DIC Corporation, and the like. The "pentaerythritol (tri / tetra) acrylate" refers to a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The same applies to other "(3/4)" etc.

Examples of the polyfunctional (meth) acrylate having an alicyclic structure include, for example, "IRR214-K" (tricyclodecanedi) manufactured by DAICEL-ALLNEX Corporation having a tricyclic [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 amount of the polyfunctional ethylenically unsaturated compound in the entire composition is preferably 20 to 78% by mass, more preferably 25 to 75% by mass, and still more preferably 30 to 70% by mass.

<Compound having one ethylenically unsaturated group in one molecule> 封装 The encapsulating composition of the present invention may contain a compound having one ethylenically unsaturated group in one molecule (hereinafter sometimes referred to simply as "monofunctional ethylene" Sexually unsaturated compounds "). The "monofunctional ethylenically unsaturated compound" is a case where it may be contained in the sealing composition of the present invention as a diluent as described later. The monofunctional ethylenically unsaturated compound may contain other functional groups such as an epoxy group within the range in which the effects of the present invention are exhibited. Examples of such a compound include compounds having one or more epoxy groups and one ethylenically unsaturated group in one molecule. Moreover, in the present invention, a monofunctional ethylenically unsaturated compound containing an epoxy group is not an epoxy resin, but is not classified as a monofunctional ethylenically unsaturated compound.

Commercial products of compounds having an epoxy group and one ethylenically unsaturated group in one molecule include, for example, "CyclomerM100" (3,4-epoxycyclohexyl methacrylate) manufactured by DAICEL-ALLNEX Corporation. "UVACURE1561" (mixture of a compound having an epoxy group and a propenyl 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 glycidyl ether) and the like manufactured by Nippon Kasei Corporation.

When the encapsulating composition of the present invention contains a monofunctional ethylenically unsaturated compound, the amount is in the entire composition, preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. It is preferably 55 mass% or less, more preferably 50 mass% or less, and still more preferably 40 mass% or less.

<The compound which has an ethylenically unsaturated group> The said "multifunctional ethylenically unsaturated compound" and "monofunctional ethylenically unsaturated compound" are called "the compound which has an ethylenically unsaturated group." The amount of the compound having an ethylenically unsaturated group is preferably 30 to 80% by mass, more preferably 35 to 80% by mass, and even more preferably 40 to 80% by mass in the entire composition.

<Diluent> The sealing composition of the present invention is a liquid sealing composition, and may contain a diluent in order to achieve a suitable viscosity. The viscosity of the diluent measured with a B-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, and still more preferably 0.1 to 1000 mPa ･ s.

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

In addition, in the present invention, a compound having two ethylenically unsaturated groups in one molecule is classified as a "multifunctional ethylenically unsaturated compound" (sometimes referred to as "bifunctional ethylenically unsaturated compounds"), As long as it is in the above viscosity range, it may function as a reactive diluent. When the difunctional ethylenically unsaturated compound is blended with the function of a reactive diluent, the diluent can be dispensed or the amount of the diluent can be reduced. Examples of difunctional ethylenically unsaturated compounds that function as diluents 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 ESTERNP '' (made by Kyoeisha Chemical Co., Ltd.) Neopentyl glycol dimethacrylate), `` LIGHT ESTEREG '' (ethylene glycol dimethacrylate), `` LIGHT ESTER2EG '' (diethylene glycol dimethacrylate), `` LIGHT ESTER1.6HX '' (1 , 6-hexanediol dimethacrylate), "LIGHT ESTER1.9ND" (1, 9-nonanediol dimethacrylate), "Light AcrylateNP-A" (neopentyl glycol diacrylate), "Light Acrylate 1.9ND-A" (1, 9-nonanediol diacrylate), "NK Ester701A" (2-hydroxy-3-methacryl propyl propyl acrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd., " "NK EsterA-200" (polyethylene glycol # 200 diacrylate), "NK EsterAPG-400" (polypropylene glycol # 400 diacrylate), "NK EsterBG" (1,3-butanediol dimethacrylate), `` NK Ester701 '' (2-hydroxy-1,3-dimethylpropylene ethoxypropane), `` NK Ester3PG '' (tripropylene glycol dimethacrylate) ), "Viscoat # 195" (1,4-butanediol diacrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd., "SR562" (alkoxylated hexanediol diacrylate) manufactured by arkema Corporation, and the like. The ethylenically unsaturated group is preferably a (meth) acrylfluorenyl group, and a reactive diluent, especially a (meth) acrylic acid ester having one (meth) acrylfluorenyl group in one molecule is more preferable (there is When it is simply called "monofunctional (meth) acrylate").

Examples of the monofunctional (meth) acrylate used as a diluent include, for example, "ODA-N" (octyl / decyl acrylate, that is, monofunctional acrylate having a long-chain alkyl group) manufactured by DAICEL-ALLNEX Corporation. ), `` EBECRYL 110 '', `` EBECRYL1114 '' (ethoxylated phenyl acrylate), `` LIGHT ESTERE '' (ethyl methacrylate), `` LIGHT ESTERNB '' (n-butyl methacrylic acid) manufactured by Kyoeisha Chemical Co., Ltd. Ester), LIGHT ESTERIB (isobutyl methacrylate), LIGHT ESTERTB (t-butyl methacrylate), LIGHT ESTEREH (2-ethylhexyl methacrylate), LIGHT ESTERID (iso Decyl methacrylate), LIGHT ESTERL (n-lauryl methacrylate), LIGHT ESTERS (n-octadecyl methacrylate), LIGHT ESTERCH (cyclohexyl methacrylate) (Ester), `` LIGHT ESTERTHF (1000) '' (tetrahydrofurfuryl methacrylate), `` LIGHT ESTERBZ '' (benzyl methacrylate), `` LIGHT ESTERPO '' (benzylphenoxyethyl methacrylate) ), "LIGHT ESTERIB-X" (isofluorenyl methacrylate), "LIGHT ESTERHO-250" (2 -Hydroxyethyl methacrylate), "LIGHT ESTERHOA" (hydroxyethyl acrylate), "LIGHT ESTERG" (epoxypropyl methacrylate), "Light AcrylateIAA" (isoamyl acrylate, also known as , Monofunctional acrylate with branched alkyl group), "Light AcrylateS-A" (octadecyl acrylate), "Light AcrylateEC-A" (ethoxy-diethylene glycol acrylate), "Light AcrylateEHDG- "AT" (2-ethylhexyl-diethylene glycol acrylate), "Light AcrylateDPM-A" (methoxydipropylene glycol acrylate), "Light AcrylateIB-XA" (isoamyl methacrylate, also known as , A monofunctional methacrylate having an alicyclic group), "Light AcrylatePO-A" (phenoxyethyl acrylate, that is, a monofunctional acrylate having an aromatic ring), "Light AcrylateP2H-A" ( Phenoxy diethylene glycol acrylate), "Light AcrylateP-200A" (phenoxy-polyethylene glycol acrylate), "Light AcrylatePOB-A" (m-phenoxybenzyl acrylate), "Light "AcrylateTFH-A" (tetrahydrofurfuryl acrylate), "LIGHT ESTERHOP-A (N)" (2-hydroxypropyl propylene Acid ester), "HOA-MS (N)" (2-propenyloxyethyl-succinic acid), "epoxy ester M-600A" (2-hydroxy-3-phenoxypropyl acrylate), Osaka "IDAA" (isodecyl acrylate), "Viscoat # 155" (cyclohexyl acrylate), "Viscoat # 160" (benzyl acrylate), "Viscoat # 150" (tetrahydrofurfuryl) Acrylate), "Viscoat # 190" (ethyl carbitol acrylate), "OXE-10" (3-ethyl-3-oxetanyl methacrylate), that is, acrylate. Acrylate with oxetane ring), "MEDOL-10" (2-methyl-2-ethyl-1, 3-dioxolane-4-yl) methacrylate, that is, Acrylate with dioxolane), "AronixM-101A" (phenol EO modified acrylate) manufactured by Toa Kosei, "NK EsterA-LEN-10" (ethoxy group) manufactured by Shin Nakamura Chemical Industry Co., Ltd. O-phenylphenol acrylate), NK EsterEH-4E (ethoxylated ethylhexyl polyethylene glycol methacrylate), Hitachi Chemical Co., Ltd. "FA-511AS" (dicyclopentenyl acrylate) ), "FA-512AS" (dicyclopentenyloxyethyl acrylate), "FA-513AS" (dicyclopentyl acrylate), "SR217NS" (4-tert-butylcyclohexanol) manufactured by arkema Acrylate), "SR420NS" (3,3,5-trimethylcyclohexanol acrylate), "SR531" (cyclotrimethylolpropane acetal acrylate), "CD421" (3,3,5- Trimethylcyclohexanol methacrylate), "CD535" (dicyclopentadienyl methacrylate), "VEEA" (2- (2-vinyloxyethoxy) acrylate) made by Japan Catalyst Corporation Ethyl), VEEM (2- (2-vinyloxy methacrylate) Yloxy) ethyl) and the like. The "octyl / decyl acrylate" refers to a mixture of octyl acrylate and decyl acrylate.

The monofunctional (meth) acrylate used as a diluent is preferably a monofunctional methacrylate having an alicyclic structure. The alicyclic structure is synonymous with the foregoing. Commercially available monofunctional (meth) acrylates having an alicyclic structure include, for example, "LIGHT ESTERIB-X" (isofluorenyl methacrylate), "Light" "AcrylateIB-XA" (isoamyl methacrylate), "LIGHT ESTERCH" (cyclohexyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd. with a cyclohexyl structure, and "Viscoat # 155" (manufactured by Osaka Organic Chemical Industry Co., Ltd.) Cyclohexyl acrylate), "SR217NS" (4-tert-butylcyclohexanol acrylate), "SR420NS" (3,3,5-trimethylcyclohexanol acrylate), "CD421" (manufactured by arkema) 3,3,5-trimethylcyclohexanol methacrylate), "CD535" (dicyclopentadienyl methacrylate), "FA-511AS" (two manufactured by Hitachi Chemical Co., Ltd.) (Cyclopentenyl acrylate), "FA-512AS" (dicyclopentenyl ethyl acrylate), "FA-513AS" (dicyclopentyl acrylate), "CD535" (dicyclopentyl) manufactured by arkema Dienyl methacrylate), "VEEA" (2- (2-vinyloxyethoxy) ethyl acrylate), "VEEM" (2-methacrylic acid 2- (2-vinyloxyethoxy) ethyl ester) and the like.

When a diluent is used, its amount (including the amount of "difunctional ethylenically unsaturated compound" which functions as a diluent is also included) is preferably 2% by mass or more in the entire composition, and more preferably 5 mass% or more, more preferably 10 mass% or more, preferably 60 mass% or less, more preferably 55 mass% or less, and even more preferably 50 mass% or less.

<Semi-fired hydrotalcite> The composition of the present invention contains semi-fired hydrotalcite. The semi-calcined hydrotalcite may be used alone or in combination of two or more.

Hydrotalcite can be classified into unfired hydrotalcite, semi-fired hydrotalcite, and fired hydrotalcite.

Unfired hydrotalcites, such as metal hydroxides with a layered crystalline structure represented by natural hydrotalcites (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ ･ 4H ₂ O), such as a layer with a basic skeleton [Mg _{1 -X} Al _X (OH) ₂ ] ^{X +} and intermediate layer [(CO ₃ ) _{X / 2} ･ mH ₂ O] ^X- . The unfired hydrotalcite in the present invention includes the concept of synthetic hydrotalcite-like compounds such as hydrotalcite. Examples of the hydrotalcite-like compound include those represented by the following formula (I) and the following formula (II).

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

(In the formula, M ²⁺ represents Mg ^2+, Zn ²⁺ and other divalent metal ions of, A ^n- represents _{^{CO 3 2-, Cl -, NO}} 3- , etc. The n-valent anion, x is a positive number of 2 or more, z is a positive number of 2 or less, m is a positive number, and n is a positive number.) In formula (II), M ^{2+ is} preferably Mg ²⁺ and A ^{n- is} preferably CO ₃ ^2- .

The semi-calcined hydrotalcite refers to a metal hydroxide having a layered crystal structure in which the amount of interlayer water obtained by firing an uncalcined hydrotalcite is reduced or disappeared. "Interlayer water" refers to the "H ₂ O" described in the composition formula of the unfired natural hydrotalcite and hydrotalcite-like compounds when explained using the composition formula. One of the features of the present invention is the use of this semi-fired hydrotalcite.

In addition, the calcined hydrotalcite is obtained by firing an uncalcined hydrotalcite or a semi-calcined hydrotalcite, and not only interlayer water, but also a metal oxide having an amorphous structure that disappears due to condensation and dehydration.

Uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by saturated water absorption. The saturated water absorption of the semi-calcined hydrotalcite is 1 mass% or more and less than 20 mass%. In addition, the saturated water absorption of the uncalcined 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 refers to measuring 1.5 g of uncalcined hydrotalcite, semi-calcined hydrotalcite or calcined hydrotalcite using a balance, and after measuring the initial mass, it is set to 60 ° C, 90 ° C under atmospheric pressure. The mass increase rate relative to the initial mass in a small-scale environmental tester (SH-222 manufactured by ESPEC) at% RH (relative humidity) can be used for the following formula (i): Saturated water absorption (mass%) = 100 × (mass after moisture absorption-initial mass) / initial mass (i).

The saturated water absorption of the semi-calcined hydrotalcite is preferably from 3% by mass to 20% by mass, and more preferably from 5% by mass to 20% by mass.

In addition, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the thermal weight reduction rate measured by thermogravimetric analysis. The thermal weight reduction rate of the semi-calcined hydrotalcite at 280 ° C. is less than 15% by mass, and the thermal weight reduction rate thereof at 380 ° C. is 12% by mass or more. In addition, the thermal weight reduction rate of the unfired hydrotalcite at 280 ° C is 15 mass% or more, and the thermal weight reduction rate of the fired hydrotalcite at 380 ° C is less than 12 mass%.

For thermogravimetric analysis, TG / DTA EXSTAR6300 manufactured by Hitachi High-Tech Science can be used to measure 5 mg of hydrotalcite with aluminum sample pan. Under the condition of no cover and baking, the nitrogen flow rate is 200mL / min. The process is carried out at a temperature-raising rate of 10 ° C / min to 550 ° C. The thermal weight reduction rate can be obtained by the following formula (ii): Thermal weight reduction rate (mass%) = 100 × (mass before heating-mass when reaching a predetermined temperature) / mass before heating (ii).

In addition, uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction. The semi-calcined hydrotalcite, which is diffracted by powder X-rays, shows two peaks splitting around 2θ from 8 to 18 °, or a peak with a shoulder by the combination of the two peaks. Relative intensity ratio (low) of diffraction intensity of peaks or shoulders on the low-angle side (= diffraction intensity on the low-angle side) and diffraction intensity of peaks or shoulders on the high-angle side (= diffraction intensity on the high-angle side) Angle side diffraction intensity / high angle side diffraction intensity) is 0.001 to 1,000. On the other hand, the uncalcined hydrotalcite has only one peak near 8 to 18 °, or the relative intensity ratio of the diffraction intensity of the peak or shoulder that appears on the low-angle side to the peak or shoulder that appears on the high-angle side Outside the aforementioned range. The calcined hydrotalcite does not have characteristic peaks in the region of 8 ° -18 °, and has characteristic peaks at 43 °. For powder X-ray diffraction measurement, a powder X-ray diffraction device (Empyrean, manufactured by PANalytical Corporation) can be used for the cathode CuKα (1.5405Å), voltage: 45V, current: 40mA, sampling width: 0.0260 °, scanning speed: 0.0657 ° / S, measurement of diffraction angle range (2θ): 5.0131 to 79.9711 °. The peak search can use the peak search function of the software attached to the diffraction device to "minimum significance: 0.50, minimum peak chip: 0.01 °, maximum peak chip: 1.00 °, peak bottom width: 2.00 °, method: 2 times of differential "Minimum" condition.

Semi calcined hydrotalcite BET specific surface area is based at 1 ~ 250m ² / g is preferable, more preferably 5 ~ 200m ² / g. The BET specific surface area of the semi-calcined hydrotalcite is based on the BET method, and a specific surface area measuring device (Macsorb HM Model 1210 MOUNTECH Co., Ltd.) is used to adsorb nitrogen on the surface of the sample.

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

The semi-calcined hydrotalcite can be used as a surface treatment agent with a surface treatment agent. Examples of the surface treatment agent used for the surface treatment include higher fatty acids, alkylsilanes, and silane coupling agents. Among them, higher fatty acids and alkylsilanes are preferred. The surface treatment agent may be used singly or in combination of two or more kinds.

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

Examples of the alkylsilanes include methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, and octadecyltrimethoxysilane. , Dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, and the like. These may be used singly or in combination of two or more kinds.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyl (dimethoxy) ) Epoxy-based silane coupling agents such as methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethyl Mercapto-based silane coupling agents such as methoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-amine Propyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Amine-based silane coupling agents; urea-based silane coupling agents such as 3-ureidopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxy Silane and other vinyl silane coupling agents; p-styryltrimethoxy Styryl-based silane coupling agents such as alkane; 3-acrylic methoxypropyltrimethoxysilane and 3-methacrylic methoxypropyltrimethoxysilane; acrylate-based silane coupling agents; 3-isocyanate Isocyanate-based silane coupling agents such as propyltrimethoxysilane, thioether-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide, and bis (triethoxysilylpropyl) tetrasulfide Mixture; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, etc. These may be used singly or in combination of two or more kinds.

For surface treatment of semi-calcined hydrotalcite, for example, untreated semi-calcined hydrotalcite can be stirred and dispersed at room temperature using a mixer, and a surface treatment agent is added for spraying, followed by stirring for 5 to 60 minutes. Mixing mixer known mixer can be used include, for example, V blender, ribbon blender (ribbon blender), blender, etc. double cone blender, V type blender and concrete mixer etc. Machine, ball mill, cutting knife, etc. When the semi-calcined hydrotalcite is pulverized using a ball mill or the like, the above-mentioned higher fatty acid, alkylsilane, or silane coupling agent may be added for surface treatment. The amount of the surface treatment agent used varies depending on the type of the semi-calcined hydrotalcite or the type of the surface treatment agent, and is preferably 1 to 10 parts by mass relative to 100 parts by mass of the semi-calcined hydrotalcite without surface treatment. In the present invention, the surface-treated semi-fired hydrotalcite is also included in the "semi-fired hydrotalcite" of the present invention.

The amount of the semi-calcined hydrotalcite in the composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but the entire composition is preferably 10 to 70% by mass, more preferably 25 to 60% by mass. %, And more preferably 30 to 50% by mass. The semi-calcined hydrotalcite is excellent in moisture absorption performance, so when the amount is increased, the moisture blocking property of the obtained hardened product is improved. However, when the amount exceeds 70% by mass, the viscosity of the composition increases, and the wettability decreases, which causes problems such as a decrease in adhesion between the substrate to be packaged and the composition, a decrease in the strength of the hardened material, and brittleness. In addition, since the interlayer water of the semi-fired hydrotalcite increases the amount of water in the encapsulation layer (that is, the hardened material), for example, in the manufacture of organic EL devices, due to the moisture in the encapsulation layer, the light-emitting material (light emitting Layer) or the electrode layer, and there is a concern that dark spots may increase in the initial stage.

The composition of the present invention may contain uncalcined hydrotalcite if the effect of the present invention is not hindered. The amount is in the entire composition, preferably 0 to 20% by mass, and more preferably 0. That is, it is preferable that the composition of the present invention does not contain unfired hydrotalcite. Uncalcined hydrotalcite does not affect the transmittance of the hardened material of the composition, but the moisture content is reduced due to the increase in moisture content. For example, when the amount exceeds the mass%, it is the same as semi-calcined hydrotalcite. Initially, There are many doubts about the dark spots of the stage. The mass ratio of semi-calcined hydrotalcite: uncalcined hydrotalcite is preferably 70:30 to 100: 0.

Examples of the semi-calcined hydrotalcite include "DHT-4C" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm), "DHT-4A-2" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm), and the like. Examples of the calcined hydrotalcite include "KW-2200" (manufactured by Kyowa Chemical Industry Co., Ltd., average particle size: 400 nm). Examples of the uncalcined hydrotalcite include "DHT-4A" (manufactured by Kyowa Chemical Industry Co., Ltd.). Particle size: 400 nm).

<Radical polymerization initiator> The composition system of this invention contains a radical polymerization initiator. The radical polymerization initiator may be only one kind, or two or more kinds. The radical polymerization initiator may be a photo radical polymerization initiator or a thermal radical polymerization initiator. That is, the radical polymerization initiator is a photo radical polymerization initiator and / or a thermal radical polymerization initiator. The radical polymerization initiator is preferably a photo radical polymerization initiator or a thermal radical polymerization initiator. Each of a photoradical polymerization initiator and a thermal radical polymerization initiator may be only one kind, and may be two or more kinds.

Examples of the photoradical polymerization initiator include acetophenone, diethoxyacetophenone, 2- [4- (methylthio) methyl-1-phenyl] -2-morpholinylacetone Benzoin, benzoin ether, benzylmethyl acetal, benzophenone, 2-ethylanthraquinone, thioxanthone, diethylthioxanthone, 2,4,6-trimethylbenzene Formamyl diphenyl phosphorus oxide, 2,4,6-trimethylbenzyl diphenylethoxy phosphorus oxide, bis (2,4,6-trimethylbenzyl) phenyl oxide Phosphorus, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) one, 1-hydroxycyclohexyl Phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl Propane-1-one, 2-methyl-2-morpholinyl (4-thiomethylphenyl) propane-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinylphenyl) -butanone, N, N'-octamethylenebisacridine, allyl benzophenone, 2- (benzyloxyimino) -1- [4 ' -(Phenylthio) phenyl] -1-octanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4 -(2-hydroxyethoxy) phenyl] -2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propanone) ) -Benzyl] phenyl} -2-methylpropane-1-one, benzoic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone, 2-dimethylamino-2- (4- Methylbenzyl) -1- (4-morpholine-4-phenyl) -butanone, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, 2,4,6 -Trimethylbenzylidene-diphenylphosphine oxide, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole 1-yl) phenyl) titanium, 1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzidineoxime), 1- [6- (2 -Methylbenzylidene) -9-ethyl-9H-carbazol-3-yl] ethanone O-acetamidooxime and the like.

Examples of commercially available photoradical polymerization initiators include "Omnirad651", "Omnirad184", "Omnirad1173", "Omnirad500", "Omnirad2959", "Omnirad127", "Omnirad754", "Omnirad907" manufactured by IGM Resins. "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO", "Omnirad784", "Irgacure OXE-01", "Irgacure OXE-02" made by BASF, etc.

Examples of the thermal radical polymerization initiator include azo compounds and organic peroxides. 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'-couple Azobis (1-acetamido-1-phenylethane, 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl2,2'-azobis (isobutyl Acid ester), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2 '-Azobis (2-methylbutyronitrile), 1-[(1-cyano-1-methylethyl) azo] formamidine, 2-phenylazo-4-methoxy- 2,4-dimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (N-butyl-2-methylpropane) Amidine and so on.

Examples of the organic peroxide include benzyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-butyl peroxide, and methyl ethyl ketone peroxide. , 1,1-bis (t-hexylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, n-butyl4,4-bis (t-butylperoxy) Pivalate, 2,2-bis (4,4-bis (t-butylperoxy) cyclohexyl) propane, p-menthane hydroperoxide, diisopropoxybenzene peroxide, 1, 1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, bis (2-t-butylperoxyisopropyl) benzene, di Cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2 , 5-dimethyl-2,5-bis (t-butylperoxy) hexane-3, diisobutylfluorenyl peroxide, bis (3,5,5-t-methylhexyl) peroxide Compounds, dilauryl methoxide, disuccinic acid peroxide, bis (3-methylbenzyl) peroxide, benzamidine dioxide, di-n-propyl peroxycarbonate, Di-isopropylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxycarbonic acid Ester, bis (2-ethylhexyl) peroxycarbonate, di-sec-butylperoxycarbonate, cumylperoxyneodecanate, 1,1,3,3-tetramethylbutylperoxy Neodecanoate, t-hexylperoxynedecanoate, t-butylperoxynedecanoate, t-hexylperoxytrimethylacetate, t-butylperoxytrimethylacetate , 1,1,3,3-tetramethylbutylperoxyfluoren-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (t-ethylhexylperoxy) hexyl Alkane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy- 3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate Ester, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzylideneperoxy) hexane, t-butylperoxyacetate, t-butyl Mixture of peroxy-3-methylbenzoate and third butyl peroxybenzoate, third butyl peroxybenzoate, t-butylperoxyallyl monocarbonate, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like.

Commercial products of the thermal radical polymerization initiator include, for example, "AIBN" (2,2'-azobis (isobutyronitrile)), "V-40" (1,1 ') manufactured by Wako Pure Chemical Industries, Ltd. -Azobis (cyclohexane-1-carbonitrile), "VAm-110" (2,2'-Azobis (N-butyl-2-methylpropanamide), "V-601" ( Dimethyl 2,2'-azobis (isobutyrate)), "OTAZO-15" (1,1'-azobis (1-ethoxyl-1-phenylethyl), manufactured by Otsuka Chemical Co., Ltd. Alkane), "MAIB" (dimethyl 2,2'-azobisisobutyrate) and the like.

The amount of the radical polymerization initiator is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and still more preferably 0.5 to 6 parts with respect to 100 parts by mass of the "compound having an ethylenically unsaturated group". Parts by mass. Here, the "compound having an ethylenically unsaturated group" refers to the "multifunctional ethylenically unsaturated compound" and the "monofunctional ethylenically unsaturated compound" as described above.

When a photoradical polymerization initiator is used, the amount is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and more preferably 100 parts by mass of the "compound having an ethylenically unsaturated group". It is 0.5 to 6 parts by mass.

When a thermal radical polymerization initiator is used, the amount is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and more preferably 100 parts by mass of the "compound having an ethylenically unsaturated group". It is 0.5 to 6 parts by mass.

<Other components> 之 The composition of the present invention may contain other components different from those described above, as long as the effect is not impaired.

The composition of the present invention may contain an epoxy resin for the purpose of suppressing shrinkage of the cured product and the like. The epoxy resin may be only one kind, or two or more kinds. An epoxy resin having one epoxy group in one molecule is sometimes referred to as "monofunctional epoxy resin", and an epoxy resin having two epoxy groups in one molecule is sometimes referred to as "bifunctional epoxy resin". An epoxy resin having three or more epoxy groups in one molecule is similarly abbreviated.

As described above, a compound having one or more epoxy groups and two or more ethylenically unsaturated groups in one molecule can function as a polyfunctional ethylenically unsaturated compound in the present invention. Therefore, in the present invention, it is classified It becomes the above-mentioned polyfunctional ethylenically unsaturated compound. As described above, a compound having one or more epoxy groups and one ethylenically unsaturated group in one molecule is classified as a monofunctional ethylenically unsaturated compound in the present invention.

Examples of the epoxy resin include a hydrogenated epoxy resin (hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc.), a fluorine-containing epoxy resin, a chain aliphatic epoxy resin, and a cyclic fat. Family epoxy resin, bisphenol A epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, bisphenol F ring Oxygen resin, phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, aromatic epoxypropylamine type epoxy resin (e.g., tetraglycidylaminodiphenylmethane, triglycidyl- p-aminophenol, diglycidyl toluidine, diglycidyl aniline, etc.), alicyclic epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic Varnish-type epoxy resin, epoxy resin with butadiene structure, diglycidyl etherate of bisphenol, diglycidyl etherate of naphthalenediol, diglycidyl etherate of phenols, and alcohols Dipropylene oxide ethers, and alkyl substituents of these epoxy resins.

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

The epoxy resin is preferably one or more selected from hydrogenated epoxy resin, fluorine-containing epoxy resin, chain aliphatic epoxy resin, and cyclic aliphatic epoxy resin, and more preferably selected from hydrogenated ring One or more kinds of oxygen resin, fluorine-containing epoxy resin, and cyclic aliphatic epoxy resin, and more preferably one or more kinds selected from hydrogenated epoxy resin and cyclic aliphatic epoxy resin. Here, the "hydrogenated epoxy resin" refers to an epoxy resin obtained by hydrogenating an epoxy resin containing an aromatic ring. The hydrogenation rate of the hydrogenated epoxy resin is preferably 50% or more, and more preferably 70% or more. "Chained aliphatic epoxy resin" refers to an epoxy resin having a linear or branched alkyl chain or alkyl ether chain, and "cyclic aliphatic epoxy resin" refers to a cyclic molecule in the molecule. Aliphatic backbones, such as epoxy resins with a naphthenic backbone.

Examples of the hydrogenated bisphenol A epoxy resin include liquid hydrogenated bisphenol A epoxy resin (for example, "YX8000" (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 205)), "Denacol EX-252" ( Nagasechemtex Corporation, epoxy equivalent: about 213)), solid hydrogenated bisphenol A type epoxy resin (for example, "YX8040" (Mitsubishi Chemical Corporation, epoxy equivalent: about 1000)).

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

Examples of the chain aliphatic epoxy resin include polyglycerol polyglycidyl ether (for example, "Denacol EX-512", "Denacol EX-521", manufactured by Nagasechemtex), pentaerythritol polyglycidyl ether ( For example, "Denacol EX-411", manufactured by nagasechemtex), diglycerol polyglycidyl ether (e.g., "Denacol EX-421", manufactured by nagasechemtex), glycerol polyglycidyl ether (e.g., " Denacol EX-313 '', `` Denacol EX-314 '', manufactured by nagasechemtex), trimethylolpropane polyoxypropylene ether (e.g., `` Denacol EX-321 '', manufactured by nagasechemtex), neopentyl glycol diepoxy Propylene ether (for example, "Denacol EX-211", manufactured by Nagasechemtex), 1,6-hexanediol diglycidyl ether (for example, "Denacol EX-212", manufactured by Nagasechemtex), ethylene glycol diepoxy Propyl ether (e.g., "Denacol EX-810", "Denacol EX-811", manufactured by nagasechemtex), diethylene glycol diglycidyl ether (e.g., "Denacol EX-850", "Denacol EX-851", (manufactured by Nagasechemtex), polyethylene glycol diglycidyl ether (e.g., "Denacol EX-821", "Denacol EX-830" , "Denacol EX-832", "Denacol EX-841", "Denacol EX-861", manufactured by nagasechemtex), propylene glycol diglycidyl ether (e.g., "Denacol EX-911", manufactured by nagasechemtex), polypropylene glycol Dipropylene oxide (for example, "Denacol EX-941", "Denacol EX-920", "Denacol EX-931", manufactured by Nagasechemtex), and the like.

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

When an epoxy resin is used, the amount is 5 to 40% by mass, more preferably 5 to 35% by mass, and still more preferably 5 to 30% by mass in the entire composition.

The composition of the present invention may contain a photocationic polymerization initiator. The photocationic polymerization initiator may be only one kind, or two or more kinds.

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

Examples of the aromatic sulfonium salt include bis (4- (diphenyldihydrothio) phenyl) sulfide, dihexafluorophosphate, and bis (4- (diphenyldihydrothio) phenyl) sulfide. Bishexafluoroantimonate, bis (4- (diphenyldihydrothio) phenyl) sulfide, bistetrafluoroborate, bis (4- (diphenyldihydrothio) phenyl) sulfide, tetra (Pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl 4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetra (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis (4- (bis (4- (2-hydroxyethoxy)) ) Phenyldihydrothio) phenyl) sulfide bishexafluorophosphate, bis (4- (bis (4- (2-hydroxyethoxy)) phenyldihydrothio) phenyl) sulfide bis Hexafluoroantimonate, bis (4- (bis (4- (2-hydroxyethoxy)) phenyldihydrothio) phenyl) sulfide, bistetrafluoroborate, bis (4- (bis (4 -(2-hydroxyethoxy)) phenyldihydrothio) phenyl) sulfide tetrakis (pentafluorophenyl) borate and the like.

Examples of the aromatic sulfonium salt include diphenylsulfonium hexafluorophosphate, diphenylsulfonium hexafluoroantimonate, diphenylsulfonium tetrafluoroborate, diphenylsulfonium tetrakis (pentafluorophenyl) borate, Bis (dodecylphenyl) fluorene hexafluorophosphate, bis (dodecylphenyl) fluorene hexafluoroantimonate, bis (dodecylphenyl) fluorene tetrafluoroborate, bis (dodecyl Alkylphenyl) fluorene tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenylfluorene hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenylsulfonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenylsulfonium tetrafluoroborate, 4-methylphenyl-4 -(1-methylethyl) phenylphosphonium tetrakis (pentafluorophenyl) borate and the like.

Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenylazonium tetrakis (pentafluorobenzene). Group) borate and the like.

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

Examples of (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2,4-cyclopentadien-1-yl) ((1- (Methylethyl) benzene) -Fe (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) hexafluoroantimony Acid salt, (2,4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (II) tetrafluoroborate, (2,4-cyclopentadiene-1- Group) ((1-methylethyl) benzene) -Fe (II) tetrakis (pentafluorophenyl) borate and the like.

Examples of commercially available photocationic polymerization initiators include "SP-150", "SP-170", "SP-082", "SP-103", and "CPI-100P" manufactured by San-apro Corporation. "," CPI-101A "," CPI-200K "," Omnirad270 "and" Omnirad290 "made by IGM resins.

When a photocationic polymerization initiator is used, the amount is 100 parts by mass with respect to the total of the compound having an epoxy group (for example, the total of the (meth) acrylate having an epoxy group and an epoxy resin), preferably 0.5. ~ 10 parts by mass, more preferably 1.0 ~ 8 parts by mass, and even more preferably 2.0 ~ 6 parts by mass.

The composition of the present invention may contain a silane coupling agent. The silane coupling agent may be only one kind, or two or more kinds.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropyl (dimethoxy) ) Epoxy-based silane coupling agents such as methylsilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethyl Mercapto-based silane coupling agents such as methoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 11-mercaptoundecyltrimethoxysilane; 3-aminopropyltrimethoxysilane, 3-amine Propyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxy Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane Amine-based silane coupling agents; Urea-based silane coupling agents such as 3-ureidopropyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxy Silane and other vinyl silane coupling agents; p-styryltrimethoxy Styryl-based silane coupling agents such as alkane; 3-acrylic methoxypropyltrimethoxysilane and 3-methacrylic methoxypropyltrimethoxysilane; acrylate-based silane coupling agents; 3-isocyanate Isocyanate-based silane coupling agents such as propyltrimethoxysilane; thioether-based silane coupling agents such as bis (triethoxysilylpropyl) disulfide and bis (triethoxysilylpropyl) tetrasulfide Mixture; phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, imidazolesilane, triazinesilane, etc. Among these, an acrylate-based silane coupling agent is preferred.

Examples of commercially available silane coupling agents include "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", and "KBM-5803" manufactured by Shin-Etsu Chemical Co., Ltd. Wait.

When a silane coupling agent is used, the amount is in the entire composition, preferably 0.10 to 5.00 mass%, more preferably 0.25 to 3.00 mass%, and even more preferably 0.30 to 2.00 mass%.

The composition of the present invention may contain a polymerization inhibitor. The polymerization inhibitor may be only one kind, or two or more kinds.

Examples of the polymerization inhibitor include t-butylhydroquinone, p-benzoquinone, hydroquinone, p-methoxyphenol, N, N-diethylhydroxylamine, and N-nitroso-N. -Phenylhydroxylamine ammonium salts and the like. Examples of commercially available polymerization inhibitors include "Q-1301", "TBHQ", "PBQ2", "DEHA", "MEHQ", and "QS-10" manufactured by Kawasaki Chemical Industries, Ltd., manufactured by Wako Pure Chemical Industries, Ltd. .

When a polymerization inhibitor is used, the amount is preferably 10 to 200 ppm, and more preferably 50 to 100 ppm, based on 100 parts by mass of the "compound having an ethylenically unsaturated group". The "ppm" is a mass standard. Here, the "compound having an ethylenically unsaturated group" refers to the "multifunctional ethylenically unsaturated compound" and the "monofunctional ethylenically unsaturated compound" as described above.

<Total light transmittance of hardened material layer> 全 The total light transmittance of the hardened material layer (thickness: 20 μm) of the composition of the present invention under D65 light (daylight) is preferably 85% or more, more preferably Above 88%, and more preferably above 90%.

The total light transmittance of the hardened material layer under D65 light is as described in the examples described later. It is calculated by forming a laminated body with a hardened material composition between the glass plates and using air as a reference. . In addition, the value of the total light transmittance under the above D65 light is a measured value of a hardened material layer having a thickness of 20 μm, but the thickness of the hardened material layer is generally 3 to 200 μm.

<Haze of hardened material layer> The haze of the hardened material layer (thickness: 20 μm) of the composition of the present invention is preferably less than 3.0%.

The haze of the hardened material layer is as described in the examples described later, and is calculated by forming a laminated body of the hardened material with the composition between the glass plates and using air as a reference. The value of the haze is a measured value of a hardened material layer having a thickness of 20 μm, but the thickness of the hardened material layer is generally 3 to 200 μm.

The total light transmittance is 85% or more, and the hardened layer with a haze of less than 3.0% can be visually recognized as transparent.

<Organic EL device> 的 An organic EL device in which an organic EL device is encapsulated with a cured product of the composition of the present invention, for example, the composition of the present invention can be applied to the organic EL element on a substrate, and then the composition can be cured. To make.

When the composition of the present invention contains a photo-radical polymerization initiator, curing can be performed by irradiating the composition with ultraviolet rays. Examples of the device for ultraviolet irradiation include high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-output metal halide lamps, low-pressure mercury lamps, and LED light sources. The temperature of the composition at the time of ultraviolet irradiation is preferably 20 to 120 ° C, and more preferably 25 to 110 ° C. The total amount of ultraviolet irradiation is preferably 500 to 4000 mJ / cm ² , and more preferably 1000 to 3500 mJ / cm ² .

When the composition of the present invention contains a thermal radical polymerization initiator, curing can be performed by heating the composition using a dryer or the like. The heating temperature is preferably 80 to 120 ° C, more preferably 100 to 110 ° C, and the heating time is preferably 15 to 120 minutes, and more preferably 30 to 90 minutes. This heating may be performed in an atmospheric environment, or in an inert gas (such as nitrogen) environment.

[Example]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples. Of course, the present invention can be appropriately modified and implemented within a range that meets the above-mentioned gist. All of them are included in the present invention. Within technology. In addition, the "parts" in the quantities described below and the "%" in the saturated water absorption and thermal weight reduction ratios, unless otherwise noted, represent "mass parts" and "mass%", respectively. The "room temperature" means 20 to 30 ° C.

In the following examples and comparative examples, the viscosity of a monofunctional acrylate ("Light AcrylateIB-XA" manufactured by Kyoeisha Chemical Co., Ltd.) used as a diluent was measured using a B-type viscometer at a temperature of 25 ° C. As a result, the viscosity was 10 mPa ･ s.

<Example 1> 20 parts of a 6-functional acrylate ("KAYARAD DPCA-60" manufactured by Nippon Kayaku Co., Ltd.) and 100 parts of a 2-functional acrylate having an alicyclic skeleton ("IRR214-K" manufactured by DAICEL-ALLNEX) 2, 50 parts of a bifunctional acrylate (bisphenol A epoxy acrylate, "EBECRYL600" manufactured by DAICEL-ALLNEX Corporation), 2 parts of a silane coupling agent ("KBM-5103" manufactured by Shin-Etsu Silicone Co., Ltd.) 96 parts of hydrotalcite (BET specific surface area: 15 m ² / g, average particle size: 400 nm) were kneaded, and then dispersed using a three-roll mill to obtain a mixture. 50 parts of a monofunctional acrylate ("Light AcrylateIB-XA" manufactured by Kyoeisha Chemical Co., Ltd.) (diluent) and a bifunctional acrylate (manufactured by Kyoeisha Chemical Co., Ltd. " Light AcrylateNP-A ") (also functions as a diluent) 50 parts, 2 parts of thermal radical polymerization initiator (" V-601 "manufactured by Wako Pure Chemical Industries, Ltd.), and then uniformly dispersed using a high-speed rotary mixer, A composition was obtained.

<Example 2> A composition was obtained in the same manner as in Example 1 except that the amount of the semi-calcined hydrotalcite was changed to 170 parts.

<Example 3> 20 parts of a 6-functional acrylate ("KAYARAD DPCA-60" manufactured by Nippon Kayaku Co., Ltd.) and 80 parts of a 2-functional acrylate having an alicyclic skeleton ("IRR214-K" manufactured by DAICEL-ALLNEX) , UVACURE1561 (manufactured by DAICEL-ALLNEX Corporation, a mixture of a compound having an epoxy group and an acryl fluorenyl group in one molecule (content: 78 to 82%) and a bisphenol A type epoxy resin (content: 18 to 22%) ) 20 parts, liquid hydrogenated bisphenol A type epoxy resin ("YX8000" manufactured by Mitsubishi Chemical Corporation) 30 parts, 2 parts of silane coupling agent ("KBM-5103" manufactured by Shin-Etsu Silicone Co., Ltd.), commercially available semi-burned water After 150 parts of talc (BET specific surface area: 15 m ² / g, average particle diameter: 400 nm) were kneaded, they were dispersed using a three-roll mill to obtain a mixture. 100 parts of a monofunctional acrylate ("Light AcrylateIB-XA" manufactured by Kyoeisha Chemical Co., Ltd.) and a thermal radical polymerization initiator ("V manufactured by Wako Pure Chemical Industries, Ltd." -601 ″) 2 parts, and then uniformly dispersed using a high-speed rotary mixer to obtain a composition.

<Example 4> Except changing the amount of semi-calcined hydrotalcite to 96 parts and changing 2 parts of the thermal radical polymerization initiator to a photo radical polymerization initiator ("Omnirad OXE-01" manufactured by BASF) 2 A composition was obtained in the same manner as in Example 3 except for the rest.

<Example 5> A composition was obtained in the same manner as in Example 4 except that 2 parts of a photocationic polymerization initiator ("SP-152" manufactured by ADEKA Corporation) was further added.

<Comparative Example 1> A composition was obtained in the same manner as in Example 1 except that 96 parts of the semi-calcined hydrotalcite was changed to 96 parts of magnesium oxide (BET specific surface area: 8.9 m ² / g, average particle size: 500 nm).

<Comparative Example 2> 100 parts of a bifunctional epoxy resin ("EP4088SS" manufactured by ADEKA Corporation) having an alicyclic skeleton, 20 parts of a 4-functional epoxy resin ("jER604" manufactured by Mitsubishi Chemical Corporation), and a bifunctional epoxy resin ( 100 parts of "Nippon Steel & Sumitomo Chemical Co., Ltd." (ZX-1059)), 2 parts of a silane coupling agent ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.), and commercially available semi-fired hydrotalcite (BET specific surface area: 15 m ² / g (Average particle diameter: 400 nm) 96 parts were kneaded, and then dispersed using a three-roll mill to obtain a mixture. Next, 50 parts of a monofunctional epoxy resin ("EX-121" manufactured by Nagasechemtex) and 2 parts of a thermal anion polymerization initiator ("TBPDA" manufactured by Beixing Chemical Industry Co., Ltd.) were prepared in the obtained mixture, and a high-speed rotary mixer was used. Disperse uniformly to obtain a composition.

<Water absorption of hydrotalcite> (1) The hydrotalcite used in the examples and comparative examples was measured on a scale with a weight of 1.5 g, and the initial mass was measured. In a small-scale environmental tester (SH-222, manufactured by ESPEC) set at 60 ° C and 90% RH (relative humidity) under atmospheric pressure, let stand for 200 hours, measure the mass after moisture absorption, and use the formula (i) to obtain saturation. Water absorption. The results are shown in Table 1.

<Thermal weight reduction rate of hydrotalcite> 热 The hydrotalcite used in Examples and Comparative Examples was subjected to thermogravimetric analysis using TG / DTA EXSTAR 6300 manufactured by Hitachi High-Tech Science. An aluminum sample pan weighed 10 mg of hydrotalcite, and the temperature was increased from 30 ° C. to 550 ° C. at 10 ° C./min under a nitrogen flow rate of 200 mL / min in an uncovered and baked state. Using the above formula (ii), the thermal weight reduction rates at 280 ° C and 380 ° C were determined. The results are shown in Table 1.

<Powder X-ray diffraction> Powder X-ray diffraction is measured using a powder X-ray diffraction device (Empyrean, manufactured by PANalytical, Inc.) for the cathode CuKα (1.5405Å), voltage: 45V, current: 40mA, sampling width : 0.0260 °, scanning speed: 0.0657 ° / S, measurement of diffraction angle range (2θ): 5.0131 to 79.9711 °. The crest search uses the crest search function of the software attached to the diffractive device to "minimum significance: 0.50, minimum crest chip: 0.01 °, maximum crest chip: 1.00 °, peak bottom width: 2.00 °, method: 2nd derivative "Minimum" condition. Detect peaks split into two peaks that appear in the range of 2θ from 8 to 18 °, or peaks that have shoulders by combining the two peaks, and measure the peaks or shoulders that appear on the low-angle side Calculate the relative intensity ratio (diffraction intensity on the low-angle side / diffraction angle on the high-angle side) and diffraction intensity (= diffraction intensity on the high-angle side) of the peak or shoulder on the high-angle side. Side diffraction intensity). The results are shown in Table 1.

From the results of saturated water absorption, thermal weight reduction, and powder X-ray diffraction, it was confirmed that the hydrotalcites used in the examples and comparative examples were "semi-fired hydrotalcites".

<Total light transmittance and haze of the hardened material layer of the composition> The compositions prepared in the examples and comparative examples were dropped onto an alkali-free glass plate (length 50 mm, width 50 mm, thickness 700 μm, Nippon Electric Glass Co., Ltd.) After the production of OA-10G), an alkali-free glass plate of the same size was stacked to produce a laminated body (alkali-free glass plate / resin composition layer / alkali-free glass plate). Next, in Examples 1 to 3 and Comparative Examples 1 and 2, the composition was cured by heating the laminated body at 100 ° C. for 30 minutes to prepare a sample for evaluation (thickness of the cured product: 20 μm). In addition, Examples 4 and 5 used UV-LEDs (produced by Oxtail Corporation, wavelength 365 nm) at room temperature to set the cumulative exposure to 3,000 mJ / cm ² and irradiated ultraviolet rays to the laminate to make the composition The material was cured and a sample for evaluation (thickness of the cured material: 20 μm) was produced.

The haze meter HZ-V3 (halogen lamp) manufactured by SUGA Testing Machine Co., Ltd. was used to measure the total light transmittance and haze of the sample for evaluation with D65 light using air as a reference, and evaluated based on the following criteria. The results are shown in Table 2. (Baseline for total light transmittance) Good (○): 90% or more acceptable (△): Less than 90%, 85% or more Defective (×): Less than 85% (baseline of haze) Good (○): Less than 2.5% OK (△): 2.5% or more and less than 3.0% Poor (×): 3.0% or more

<Device reliability test (residual light-emitting area ratio)> The organic EL device was used to evaluate the sealing performance of the composition. Specifically, first, an organic EL element was formed on a glass substrate (manufactured by GEOMATEC) with indium tin oxide (ITO) with a light emitting area of 4 mm ² (thickness of organic film: 110 nm, thickness of Al cathode: 100 nm) . Next, a chemical vapor deposition method (CVD method) is used on the organic EL element to form a nitride film (thickness: 500 nm).

Next, the composition prepared in Examples 2 to 5 was dropped onto the organic EL element with a nitride film, and then an alkali-free glass plate was superposed thereon to prepare a laminated body (alkali-free glass plate / composition layer / nitride film Organic EL element / with ITO glass substrate). In Examples 2 and 3, the laminated body was heated at 100 ° C. for 30 minutes to harden the composition to produce a laminated body (thickness of the hardened body: 100 μm) in which the organic EL element was encapsulated. In Examples 4 and 5, at room temperature, UV-LEDs (manufactured by Oxtail Corporation, wavelength: 365 nm) were used to make the cumulative exposure to 3,000 mJ / cm ² , and the laminated body was irradiated with ultraviolet rays to harden the composition. A laminated body (thickness of hardened material: 100 μm) in which the organic EL element was encapsulated was manufactured.

A voltage was applied to the packaged organic EL device, and the initial light-emitting area before storage in a constant-humidity and constant-temperature bath was measured. Next, the laminated body in which the organic EL element was encapsulated was stored in a constant-humidity constant-temperature bath set at a temperature of 85 ° C. and a humidity of 85% RH. 1,000 hours after the start of storage, the laminate was taken out from the constant-humidity thermostatic bath, a voltage was applied to the organic EL element, and the light-emitting area after storage was measured.

As an index for comparing the barrier properties of the encapsulation layer (cured material), the following formula is used: Residual light-emitting area ratio (%) = 100 × (Light-emitting area after storage) / (Initial light-emitting area) , And evaluated based on the following benchmarks. The results are shown in Table 2. (Baseline of residual luminous area ratio) Very good (◎): 95% or more Good (○): 85% or more and less than 95% Yes (△): 75% or more and less than 85% Poor (×): less than 75%

[Industrial availability]

When the composition for encapsulation according to the present invention is used, it is possible to form an encapsulation layer excellent in both moisture blocking properties and transparency. Therefore, the composition for encapsulation of the present invention can be suitably used for encapsulation of components that are relatively weak to moisture, such as organic EL elements.

This case is based on Japanese Patent Application No. 2017-071985, the contents of which are included in the description of this case.

Claims (16)

A composition for encapsulation, comprising a compound having two or more ethylenically unsaturated groups in one molecule, a semi-fired hydrotalcite, and a radical polymerization initiator. For example, the composition according to claim 1, wherein the compound having two or more ethylenically unsaturated groups in one molecule is a compound containing three or more ethylenically unsaturated groups in one molecule. For example, the composition of claim 1 or 2, wherein the compound having two or more ethylenically unsaturated groups in one molecule is a compound containing two or more ethylenically unsaturated groups in one molecule and an alicyclic structure. The composition according to any one of claims 1 to 3, further comprising a diluent. The composition according to claim 4, wherein the diluent is a compound having one ethylenically unsaturated group in one molecule. The composition according to any one of claims 1 to 5, wherein the ethylenically unsaturated group is a (meth) acrylfluorenyl group. For example, the composition of any one of claims 1 to 6, wherein the amount of the compound having two or more ethylenically unsaturated groups in one molecule is 20 to 78% by mass in the entire composition. According to the composition of any one of claims 1 to 7, the amount of the semi-calcined hydrotalcite is 10 to 70% by mass in the entire composition. The composition according to any one of claims 1 to 8, wherein the radical polymerization initiator is a photo radical polymerization initiator and / or a thermal radical polymerization initiator. The composition according to any one of claims 1 to 9, wherein the amount of the radical polymerization initiator is 0.5 to 10 parts by mass relative to 100 parts by mass of the compound having an ethylenically unsaturated group. The composition according to any one of claims 1 to 10, further comprising a silane coupling agent. For example, the composition of any one of claims 1 to 11, wherein the hardened layer of the composition having a thickness of 20 μm has a total light transmittance of 85% or more under D65 light. For example, the composition of any one of claims 1 to 12, wherein the haze of the hardened layer of the composition having a thickness of 20 μm is less than 3.0%. The composition of any one of claims 1 to 13 is liquid. The composition according to any one of claims 1 to 14 is for packaging an organic EL element. An organic EL device in which an organic EL element is encapsulated with a hardened body of a composition as claimed in any one of claims 1 to 15.