Sealing agent, cured body, organic electroluminescence display device, and method for manufacturing organic electroluminescence display device

Abstract

A sealant comprising a polymerizable compound, a polymerization initiator, and an inorganic filler, the polymerizable compound containing a compound having a specific gravity of 1.3 to 4.0.

Description

TECHNICAL FIELD

[0001] The present application relates to a sealant, a cured body, an organic electroluminescence display device, and a method for manufacturing an organic electroluminescence display device. BACKGROUND

[0002] In recent years, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been progressing. Organic thin film elements can be easily produced by vacuum evaporation, solution coating, and the like, and thus have excellent productivity.

[0003] An organic EL display element is a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. By injecting electrons from one electrode into the organic light emitting material layer and injecting holes from the other electrode into the organic light emitting material layer, the electrons and the holes combine in the organic light emitting material layer to emit light spontaneously. Compared with liquid crystal display elements and the like that require a backlight, the organic EL display element has the advantages of good visual recognition, further thinness, and direct current low voltage driving.

[0004] However, such an organic EL display element has the problem that if the organic light emitting material layer and the electrodes are exposed to external gases, the light emitting properties thereof are drastically deteriorated and the lifetime thereof is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technique that blocks moisture and oxygen in the atmosphere from the organic light emitting material layer and the electrodes is essential.

[0005] For example, Patent Literature 1 discloses a method in which a photocurable sealant is filled between organic EL display element substrates in an upper surface light emitting type organic EL display element and the like, and light is irradiated to seal. In addition, Patent Literatures 2 to 4 disclose techniques for sealing an organic EL display element and preventing deterioration caused by moisture.

[0006] On the other hand, Patent Literature 5 discloses a resin composition containing (A) an epoxy compound, (B) an epoxy resin, and (C) a photocationic polymerization initiator, and having a moisture content of 1000 ppm or less and a chlorine content of 1000 ppm or less. However, Patent Literature 5 does not describe the specific gravity of the polymerizable compound.

[0007] Patent Literature 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a photocationic polymerization initiator, and a plate-shaped microparticle inorganic filler having a specific shape. However, the composition described in Patent Literature 6 does not have sufficient moisture permeability, and thus is difficult to be applied to an organic electroluminescence display element. In addition, Patent Literature 6 does not describe the specific gravity of the polymerizable compound.

[0008] Patent Document 7 discloses a curable resin composition for sealing an organic electroluminescence display element, which is excellent in transparency and barrier properties, characterized by containing a multifunctional cationically polymerizable compound, an organo-coated layered silicate, and a curing agent, the aforementioned organo-coated layered silicate being dispersed in the aforementioned multifunctional cationically polymerizable compound, the content of the aforementioned organo-coated layered silicate being 20 to 250 parts by weight with respect to 100 parts by weight of the aforementioned multifunctional cationically polymerizable compound. However, in the case of the resin composition described in Patent Document 7, there is a case where sufficient moisture permeability cannot be obtained. In addition, Patent Document 7 does not describe the specific gravity of the polymerizable compound.

[0009] Patent Document 8 discloses an epoxy resin composition which is excellent in transparency and low in moisture permeability, containing (a) an epoxy compound and (b) a compound having two or more crosslinkable groups reactive with the aforementioned epoxy compound, at a specific ratio, the refractive index of the composition being 1.6 or more. However, in the case of the resin composition described in Patent Document 8, there is a case where sufficient moisture permeability cannot be obtained. In addition, Patent Document 8 does not describe the specific gravity of the polymerizable compound.

[0010] Patent Document 9 discloses a curable composition characterized by containing an organic polymer (A) having a specific reactive silicon group and a polyoxyalkylene polymer (B) having a specific reactive silicon group, the specific gravity of the curable composition being 0.9 or more and 1.3 or less. However, Patent Document 9 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound.

[0011] Patent Document 10 discloses a lens made of a photocurable resin having a refractive index of 1.58 or more, a specific gravity of 1.5 or less, and an Abbe number of 30 or more, the lens being formed of a copolymer obtained by photopolymerizing a composition containing 10 to 70% by weight of a specific structure of bromine-addition type bisphenol A type epoxy (meth)acrylate. However, Patent Document 10 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing of an organic EL display element.

[0012] Patent Document 11 discloses a polysiloxane copolymer which is photopolymerized and has a specific polysiloxane copolymer having a functional acryloyl group, has a specific gravity of more than about 1.0, and a refractive index suitable for restoring the refractive power of a natural crystalline lens. However, Patent Document 11 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing of an organic EL display element.

[0013] Patent Literature 12 discloses a resin composition for an equalizing property of a rotor of an electric motor, which contains a reactive energy ray-curable compound (A) having one or more ethylenic unsaturated double bonds in one molecule, a photoradical polymerization initiator (C) and / or a photocationic polymerization initiator (D), and the specific gravity of the resin composition is 1.4 (25°C) or more and the viscosity is 1,000 poise (25°C) or less. However, in Patent Literature 12, there is no description about lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, and there is no description about sealing of an organic EL display element.

[0014] Prior Art Documents

[0015] Patent Literature

[0016] Patent Literature 1: Japanese Patent Application Laid-Open (JP-A) No. 2001-357973

[0017] Patent Literature 2: Japanese Patent Application Laid-Open (JP-A) No. 10-74583

[0018] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2001-307873

[0019] Patent Literature 4: Japanese Patent Application Laid-Open (JP-A) No. 2009-37812

[0020] Patent Literature 5: International Publication No. 2014 / 017524

[0021] Patent Literature 6: Japanese Patent Application Laid-Open (JP-A) No. 2006-291072

[0022] Patent Literature 7: International Publication No. 2015 / 129783

[0023] Patent Literature 8: Japanese Patent Application Laid-Open (JP-A) No. 2010-163566

[0024] Patent Literature 9: Japanese Patent Application Laid-Open (JP-A) No. 2010-163566

[0025] Patent Literature 10: Japanese Patent Application Laid-Open (JP-A) No. 2001-124903

[0026] Patent Literature 11: Japanese Patent Application Laid-Open (JP-A) No. 2002-527171

[0027] Patent Literature 12: Japanese Patent Application Laid-Open (JP-A) No. 08-109231 SUMMARY

[0028] PROBLEMS TO BE SOLVED BY THE INVENTION

[0029] In recent years, the required characteristics of electronic devices have been improved, and for example, sealing materials capable of achieving higher reliability and durability for organic EL display elements are required.

[0030] The present application has been made in view of the above circumstances, and aims to provide a sealing agent capable of forming a sealing material excellent in moisture resistance and adhesion to a glass substrate or the like. In addition, the present application aims to provide a cured body of the sealing agent, a manufacturing method of an organic electroluminescent display device using the sealing agent, and an organic electroluminescent display device having a sealing material formed by the sealing agent.

[0031] Means for solving the problem

[0032] That is, the present application is as described below.

[0033] <1> A sealing agent comprising a polymerizable compound, a polymerization initiator, and an inorganic filler material, the polymerizable compound containing a compound having a specific gravity of 1.3 to 4.0.

[0034] <2> The sealing agent according to <1>, wherein when the sealing agent is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the cured body has a specific gravity of 1.35 to 19.0.

[0035] <3> The sealing agent according to <1> or <2>, wherein when the sealing agent is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the polymer has a glass transition temperature of 85°C or higher.

[0036] <4> The sealing agent according to any one of <1> to <3>, wherein when the sealing agent is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the cured body has a crosslinking density of 1.5 x 10 -3 mol / cm 3 or more.

[0037] <5> The sealing agent according to any one of <1> to <4>, wherein the polymerizable compound contains a polymerizable compound (X) having an element having an atomic number of 9 or more.

[0038] <6> The sealing agent according to <5>, wherein the polymerizable compound (X) has a halogen element.

[0039] <7> The sealing agent according to <6>, wherein the polymerizable compound (X) has at least one halogen element selected from the group consisting of a fluorine element and a bromine element.

[0040] <8> The sealing agent according to <6> or <7>, wherein the content of the halogen element in the polymerizable compound (X) is 10 to 50 mass% relative to the total element amount of the polymerizable compound.

[0041] <9> The sealing agent according to any one of <1> to <8>, wherein the aforementioned polymerizable compound contains a crosslinkable compound (Y) having two or more polymerizable functional groups.

[0042] <10> The sealing agent according to any one of <1> to <9>, wherein the aforementioned polymerizable compound contains at least one selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound, and an oxetane compound.

[0043] <11> The sealing agent according to any one of <1> to <10>, wherein the aforementioned polymerizable compound has a radical polymerizable functional group.

[0044] <12> The sealing agent according to any one of <1> to <11>, wherein the aforementioned polymerization initiator is a photopolymerization initiator.

[0045] <13> The sealing agent according to any one of <1> to <12>, wherein the aforementioned polymerization initiator contains an onium salt.

[0046] <14> The sealing agent according to any one of <1> to <12>, wherein the aforementioned polymerization initiator is a radical polymerization initiator.

[0047] <15> The sealing agent according to any one of <1> to <14>, wherein the true specific gravity of the aforementioned inorganic filler material is 1.5 to 5.0.

[0048] <16> The sealing agent according to any one of <1> to <15>, wherein the aforementioned inorganic filler material contains at least one selected from the group consisting of silicon dioxide, mica, kaolin, talc, and alumina.

[0049] <17> The sealing agent according to any one of <1> to <16>, wherein the aforementioned inorganic filler material contains talc.

[0050] <18> The sealing agent according to any one of <1> to <17>, wherein the aforementioned inorganic filler material contains inorganic particles having an average particle diameter of 0.01 to 30 μm.

[0051] <19> The sealing agent according to any one of <1> to <18>, further comprising resin particles.

[0052] <20> The sealing agent according to <19>, wherein the aforementioned resin particles contain at least one selected from the group consisting of crosslinked poly(methyl) methacrylate particles, crosslinked polystyrene particles, and crosslinked poly(methyl) methacrylate-polystyrene copolymer particles.

[0053] <21> The sealing agent according to any one of <19> to <20>, wherein the average particle diameter of the resin particles is 1 μm to 100 μm.

[0054] <22> The sealing agent according to any one of <19> to <21>, wherein the standard deviation of the particle volume distribution with respect to the particle diameter (μm) of the resin particles when the particle diameter is expressed in logarithm is 0.25 or less.

[0055] <23> The sealing agent according to any one of <19> to <22>, wherein the content of the resin particles is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.

[0056] <24> The sealing agent according to any one of <1> to <23>, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.

[0057] <25> The sealing agent according to any one of <1> to <24>, wherein the content of the inorganic filler is 5 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound.

[0058] <26> The sealing agent according to any one of <1> to <25>, wherein the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound is 500 to 30,000 mPa-s.

[0059] <27> The sealing agent according to any one of <1> to <26>, wherein the viscosity at 25°C is 50,000 to 1,000,000 mPa-s.

[0060] <28> The sealing agent according to any one of <1> to <27>, wherein the ratio (η2 / η1) of the viscosity at 25°C and 0.1 rpm (η2) to the viscosity at 25°C and 1 rpm (η1) is 1.1 to 10.0.

[0061] <29> The sealing agent according to any one of <1> to <28>, wherein when a cured body containing a polymer of the polymerizable compound and the inorganic filler is produced by curing the sealing agent, the average free volume of the cured body is 1 nm 3 or more.

[0062] <30> The sealing agent according to any one of <1> to <29>, wherein when a cured body containing a polymer of the polymerizable compound and the inorganic filler is produced by curing the sealing agent, the porosity of the cured body is less than 20%.

[0063] <31> The sealing material according to any one of <1> to <30>, wherein when the aforementioned sealing material is cured to produce a cured body containing a polymer of the aforementioned polymerizable compound and the aforementioned inorganic filler material, the moisture permeability of the cured body, measured according to JIS Z0208 under conditions of a temperature of 85°C and a relative humidity of 85%, is 50 (g / m 2 or less.

[0064] <32> The sealing material according to any one of <1> to <31>, which is a sealing material for an organic electroluminescent display element.

[0065] <33> The sealing material according to any one of <1> to <32>, which is a sealing material for a dam formation.

[0066] <34> A cured body, which is a cured body of the sealing material according to any one of <1> to <33>.

[0067] <35> A method for producing an organic electroluminescent display device, which includes a step of applying the sealing material according to any one of <1> to <33> and curing to form a dam,

[0068] The aforementioned organic electroluminescent display device has a dam and filler sealing structure.

[0069] <36> An organic electroluminescent display device having a dam and filler sealing structure provided with a dam and a filler, the dam including a cured body of the sealing material according to any one of <1> to <33>.

[0070] Effects of the Invention

[0071] According to the present application, it is possible to provide a sealing material that can form a sealing material having excellent moisture resistance and adhesion to a glass substrate or the like. In addition, according to the present application, it is possible to provide a cured body of the sealing material, a method for producing an organic electroluminescent display device using the sealing material, and an organic electroluminescent display device having a sealing material formed by the sealing material. DETAILED DESCRIPTION

[0072] Hereinafter, a preferred embodiment of the present application will be described in detail.

[0073] The composition of the present embodiment contains a polymerizable compound, a polymerization initiator, and an inorganic filler material. In the present embodiment, the polymerizable compound contains a high specific gravity compound having a specific gravity of 1.3 to 4.0.

[0074] The composition according to the present embodiment can form a sealing material that is excellent in moisture resistance and adhesion to a glass substrate or the like. Thus, the composition of the present embodiment can be suitably used as a sealing agent (preferably, a sealing agent for an organic electroluminescent display element). In addition, the composition of the present embodiment can be particularly suitably used as a coffer forming sealing agent for forming a coffer and a filled sealing structure.

[0075] In the present embodiment, the polymerizable compound can refer to a compound having a polymerizable functional group. One kind of polymerizable compound can be used alone, or two or more kinds of polymerizable compounds can be used in combination.

[0076] The polymerizable compound preferably has at least one selected from the group consisting of a cationic polymerizable functional group and a radical polymerizable functional group. As the polymerizable compound having a cationic polymerizable functional group, at least one selected from the group consisting of an epoxy compound (for example, a glycidyl ether compound, an alicyclic epoxy compound, and the like), a cationic polymerizable vinyl compound (for example, a vinyl ether compound, and the like), and an oxetane compound is preferable. As the polymerizable compound having a radical polymerizable functional group, a compound having at least one radical polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group is exemplified, and a compound having a (meth)acryloyl group is preferable. As the compound having a (meth)acryloyl group, at least one selected from the group consisting of a (meth)acrylate and a (meth)acrylamide is preferable.

[0077] The high specific gravity compound can refer to a compound having a polymerizable functional group and having a specific gravity of 1.3 to 4.0. The specific gravity of the high specific gravity compound is preferably 1.4 or higher, and more preferably 1.5 or higher. In addition, the specific gravity of the high specific gravity compound is preferably 3.0 or lower, more preferably 2.5 or lower, and further preferably 2.0 or lower. That is, the specific gravity of the high specific gravity compound can be, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0, 1.4 to 3.0, 1.4 to 2.5, 1.4 to 2.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5, or 1.5 to 2.0. Note that the specific gravity of the high specific gravity compound is a value measured using a Hubber-type specific gravity bottle in accordance with JIS K0061.

[0078] In the present embodiment, the polymerizable compound can further contain a low specific gravity compound having a specific gravity of less than 1.3. The low specific gravity compound can refer to a compound having a polymerizable functional group and a specific gravity of less than 1.3. The specific gravity of the low specific gravity compound is preferably 0.7 or greater, more preferably 0.8 or greater, and can be 0.9 or greater, 1.0 or greater, or 1.1 or greater. That is, the specific gravity of the low specific gravity compound can be, for example, 0.7 or greater and less than 1.3, 0.8 or greater and less than 1.3, 0.9 or greater and less than 1.3, 1.0 or greater and less than 1.3, or 1.1 or greater and less than 1.3. Note that the specific gravity of the low specific gravity compound is a value measured using a Hubber bottle in accordance with JIS K0061.

[0079] The proportion of the high specific gravity compound in the polymerizable compound can be, for example, 30% by mass or greater, preferably 40% by mass or greater, more preferably 45% by mass or greater, and further preferably 50% by mass or greater, and more preferably 55% by mass or greater. Thereby, the above-described effects can be obtained remarkably. In addition, the proportion of the high specific gravity compound in the polymerizable compound can be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, more preferably 75% by mass or less, more further preferably 70% by mass or less, and particularly preferably 65% by mass or less. That is, the proportion of the high specific gravity compound in the polymerizable compound can be, for example, 30 to 100% by mass, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 30 to 75% by mass, 30 to 70% by mass, 30 to 65% by mass, 40 to 100% by mass, 40 to 90% by mass, 40 to 85% by mass, 40 to 80% by mass, 40 to 75% by mass, 40 to 70% by mass, 40 to 65% by mass, 45 to 100% by mass, 45 to 90% by mass, 45 to 85% by mass, 45 to 80% by mass, 45 to 75% by mass, 45 to 70% by mass, 45 to 65% by mass, 50 to 100% by mass, 50 to 90% by mass, 50 to 85% by mass, 50 to 80% by mass, 50 to 75% by mass, 50 to 70% by mass, 50 to 65% by mass, 55 to 100% by mass, 55 to 90% by mass, 55 to 85% by mass, 55 to 80% by mass, 55 to 75% by mass, 55 to 70% by mass, or 55 to 65% by mass.

[0080] The proportion of the low specific gravity compound in the polymerizable compound may be, for example, 0% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, more preferably 25% by mass or more, more further preferably 30% by mass or more, and particularly preferably 35% by mass or more. In addition, the proportion of the low specific gravity compound in the polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, more preferably 45% by mass or less. Thus, the above-described effects are more remarkably obtained.

[0081] That is, the proportion of the low specific gravity compound in the polymerizable compound may be, for example, 0 to 70% by mass, 0 to 60% by mass, 0 to 55% by mass, 0 to 50% by mass, 0 to 45% by mass, 10 to 70% by mass, 10 to 60% by mass, 10 to 55% by mass, 10 to 50% by mass, 10 to 45% by mass, 15 to 70% by mass, 15 to 60% by mass, 15 to 55% by mass, 15 to 50% by mass, 15 to 45% by mass, 20 to 70% by mass, 20 to 60% by mass, 20 to 55% by mass, 20 to 50% by mass, 20 to 45% by mass, 25 to 70% by mass, 25 to 60% by mass, 25 to 55% by mass, 25 to 50% by mass, 25 to 45% by mass, 30 to 70% by mass, 30 to 60% by mass, 30 to 55% by mass, 30 to 50% by mass, 30 to 45% by mass, 35 to 70% by mass, 35 to 60% by mass, 35 to 55% by mass, 35 to 50% by mass, or 35 to 45% by mass.

[0082] In the present embodiment, the polymerizable compound preferably contains a polymerizable compound (X) having an element having an atomic number of 9 or more. The polymerizable compound (X) can be a high specific gravity compound or a low specific gravity compound, and is preferably a high specific gravity compound.

[0083] The polymerizable compound (X) preferably has a halogen element, and more preferably has at least one selected from the group consisting of a fluorine element and a bromine element.

[0084] The number of halogen elements contained in one molecule of the polymerizable compound (X) is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. The upper limit of the number of halogen elements contained in one molecule of the polymerizable compound (X) is not particularly limited, and may be, for example, 40 or less, preferably 30 or less. That is, the number of halogen elements contained in one molecule of the polymerizable compound (X) may be, for example, 1 to 40, 1 to 30, 2 to 40, or 2 to 30.

[0085] The polymerizable compound (X) preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group. As the polymerizable compound (X) having a cationically polymerizable functional group, at least one selected from the group consisting of an epoxy compound (for example, a glycidyl ether compound, an alicyclic epoxy compound, and the like), a cationically polymerizable vinyl compound (for example, a vinyl ether compound, and the like), and an oxetane compound is preferable. As the polymerizable compound (X) having a radically polymerizable functional group, a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group is citable, and a compound having a (meth)acryloyl group is preferable. As the compound having a (meth)acryloyl group, at least one selected from the group consisting of a (meth)acrylate and a (meth)acrylamide is preferable.

[0086] As the polymerizable compound (X) having a cationically polymerizable functional group, as one of specific examples, a halogenated phenyl glycidyl ether such as bromophenyl glycidyl ether, dibromophenyl glycidyl ether, a brominated bisphenol A type epoxy resin, a brominated bisphenol F type Novolac type epoxy resin, a brominated phenol Novolac type epoxy resin, and the like is citable.

[0087] As the polymerizable compound (X) having a radically polymerizable compound, as one of specific examples, a (meth)acrylic acid halogenated phenyl ester such as (meth)acrylic acid fluorophenyl ester, (meth)acrylic acid trifluorophenyl ester, (meth)acrylic acid pentafluorophenyl ester, (meth)acrylic acid chlorophenyl ester, (meth)acrylic acid trichlorophenyl ester, (meth)acrylic acid pentachlorophenyl ester, (meth)acrylic acid bromophenyl ester, (meth)acrylic acid tribromophenyl ester, (meth)acrylic acid pentabromophenyl ester, and the like is citable.

[0088] The content of the halogen element in the polymerizable compound (X) is preferably 10 to 50 mass% relative to the total elemental amount of the polymerizable compound. If it is 10 mass% or more, there is a tendency that the moisture resistance of the cured body is further improved, and if it is 50 mass% or less, there is a tendency that the curability of the composition is further improved.

[0089] The proportion of the polymerizable compound (X) in the polymerizable compound may be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and more preferably 55% by mass or more. Thus, there is a tendency that the moisture resistance of the cured body is further improved. In addition, the proportion of the polymerizable compound (X) in the polymerizable compound may be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, more preferably 75% by mass or less, more further preferably 70% by mass or less, and particularly preferably 65% by mass or less. Thus, there is a tendency that the adhesion to a glass substrate or the like is further improved, and the reliability of the sealing material is further improved. That is, the proportion of the polymerizable compound (X) in the polymerizable compound may be, for example, 30 to 100% by mass, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 30 to 75% by mass, 30 to 70% by mass, 30 to 65% by mass, 40 to 100% by mass, 40 to 90% by mass, 40 to 85% by mass, 40 to 80% by mass, 40 to 75% by mass, 40 to 70% by mass, 40 to 65% by mass, 45 to 100% by mass, 45 to 90% by mass, 45 to 85% by mass, 45 to 80% by mass, 45 to 75% by mass, 45 to 70% by mass, 45 to 65% by mass, 50 to 100% by mass, 50 to 90% by mass, 50 to 85% by mass, 50 to 80% by mass, 50 to 75% by mass, 50 to 70% by mass, 50 to 65% by mass, 55 to 100% by mass, 55 to 90% by mass, 55 to 85% by mass, 55 to 80% by mass, 55 to 75% by mass, 55 to 70% by mass, or 55 to 65% by mass.

[0090] In the present embodiment, the polymerizable compound can further contain a polymerizable compound other than the polymerizable compound (X) (i.e., a polymerizable compound not having an element with an atomic number of 9 or more) (hereinafter, also referred to as a polymerizable compound (X’)).

[0091] The polymerizable compound (X’) may be, for example, a compound having a polymerizable functional group capable of copolymerizing with the polymerizable functional group possessed by the polymerizable compound (X). The polymerizable compound (X’) can be a high specific gravity compound or a low specific gravity compound.

[0092] The polymerizable compound (X') preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group. As the polymerizable compound (X') having a cationically polymerizable functional group, at least one selected from the group consisting of an epoxy compound (for example, a glycidyl ether compound, an alicyclic epoxy compound, and the like), a cationically polymerizable vinyl compound (for example, a vinyl ether compound, and the like), and an oxetane compound is preferable. As the polymerizable compound (X') having a radically polymerizable functional group, a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group is exemplified, and a compound having a (meth)acryloyl group is preferable. As the compound having a (meth)acryloyl group, at least one selected from the group consisting of a (meth)acrylate and a (meth)acrylamide is preferable.

[0093] When the polymerizable compound (X) has a cationically polymerizable functional group, the polymerizable compound (X') preferably has a cationically polymerizable functional group. As the polymerizable compound (X') having a cationically polymerizable functional group, at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a cationically polymerizable vinyl compound is preferable.

[0094] As the epoxy compound, an alicyclic compound having an epoxy group (alicyclic epoxy compound), an aromatic compound having an epoxy group (aromatic epoxy compound), a glycidyl ether compound, and the like are exemplified.

[0095] As the alicyclic epoxy compound, for example, a compound obtained by epoxidizing a compound having at least one cyclic olefin ring (for example, a cyclohexene ring, a cyclopentene ring, a pinene ring, and the like) with a suitable oxidizing agent such as hydrogen peroxide, a peracid, or the like, or a derivative thereof is exemplified. In addition, as the alicyclic epoxy compound, for example, a hydrogenated epoxy compound obtained by hydrogenating an aromatic epoxy compound (for example, a bisphenol A-type epoxy compound, a bisphenol F-type epoxy compound, and the like) is also exemplified.

[0096] As the alicyclic epoxy compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate, (meth)acrylic acid 3,4-epoxycyclohexylalkyl ester (for example, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, and the like), (3,3',4,4'-dihydroxyphenyl)bis cyclohexane, a hydrogenated bisphenol A-type epoxy resin, a hydrogenated bisphenol F-type epoxy resin, and the like are exemplified.

[0097] Among the alicyclic epoxy compounds, an alicyclic epoxy compound having a 1,2-epoxycyclohexane structure is preferable. Among the alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, a compound represented by the following formula (A1-1) is preferable.

[0098] [Chemical Formula 1]

[0099]

[0100] In Formula (A1-1), X represents a single bond or a linking group (a divalent group having one or more atoms).

[0101] The linking group is preferably a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked.

[0102] X is preferably a linking group. As the linking group, a group having an ester bond is preferable. As the compound having a group having an ester bond as the linking group, for example, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate can be given.

[0103] From the viewpoint of further improving the moisture resistance of the cured body and further improving the storage stability of the composition, the molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, further preferably 300 or less, and more preferably 100 to 280. That is, the molecular weight of the alicyclic epoxy compound may be, for example, 100 to 450, 100 to 400, 100 to 300, or 100 to 280.

[0104] In the case where the alicyclic epoxy compound has a molecular weight distribution, the number average molecular weight of the alicyclic epoxy compound is preferably within the above range. Note that, in the present specification, the number average molecular weight represents a value converted to polystyrene, which is measured by gel permeation chromatography (GPC) under the following measurement conditions.

[0105] • Solvent (mobile phase): THF

[0106] • Degassing device: ERC-3310 manufactured by ERMA Inc.

[0107] • Pump: PU-980 manufactured by Japan Spectroscopic Co., Ltd.

[0108] • Flow rate: 1.0 ml / min

[0109] • Automatic sampler: AS-8020 manufactured by Tosoh Bioscience LLC

[0110] • Column oven: L-5030 manufactured by Hitachi, Ltd.

[0111] • Set temperature: 40°C

[0112] • Column configuration: 2 pieces of TSKguard column MP (xL) 6.0 mm ID x 4.0 cm manufactured by Tosoh Bioscience LLC, and 2 pieces of TSK-GEL MULTIPORE HX L-M 7.8 mm ID x 30.0 cm manufactured by Tosoh Bioscience LLC, for a total of 4 pieces

[0113] • Detector: L-3350 by Hitachi Ltd.

[0114] • Data processing: SIC 480 data station

[0115] As the aromatic epoxy compound, any of a monomer, an oligomer, or a polymer can be used, and examples include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, a Novolac Phenol type epoxy resin, a Cresol Novolac type epoxy resin, and a modified product thereof.

[0116] As the aromatic epoxy compound, an aromatic epoxy compound having a bisphenol structure is preferred. Among the aromatic epoxy compounds having a bisphenol structure, a compound represented by the following formula (A2-1) is preferred.

[0117] [Chemical Formula 2]

[0118]

[0119] In formula (A2-1), n represents 0 to 30, R 21 , R 22 , R 23 , and R 24 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. n can be 0.1 or more.

[0120] R 21 , R 22 , R 23 , and R 24 are preferably a hydrogen atom or a methyl group. R 21 , R 22 , R 23 , and R 24 each can be the same or different, and are preferably the same.

[0121] The aromatic epoxy compound having a bisphenol structure is preferably at least one selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.

[0122] From the aspect of further improving the moisture resistance of the cured body, the molecular weight of the aromatic epoxy compound is preferably 100 to 5000, more preferably 150 to 1000, and further preferably 200 to 450. That is, the molecular weight of the aromatic epoxy compound can be, for example, 100 to 5000, 100 to 1000, 100 to 450, 150 to 5000, 150 to 1000, 150 to 450, 200 to 5000, 200 to 1000, or 200 to 450.

[0123] The number average molecular weight of the aromatic epoxy compound is preferably within the above range, with a molecular weight distribution. Note that the number average molecular weight in this specification is a value converted to polystyrene, measured by gel permeation chromatography (GPC) under the above measurement conditions.

[0124] As the glycidyl ether compound, a polyglycidyl ether compound is preferable. As the polyglycidyl ether compound, there is no particular limitation, and examples include dialkylene glycol diglycidyl ethers (e.g., ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like), polyhydric alcohol polyglycidyl ethers (e.g., glycerol diglycidyl ether or triglycidyl ether, or an alkylene oxide adduct thereof, and the like), and polyalkylene glycol diglycidyl ethers (e.g., polyethylene glycol diglycidyl ether or an alkylene oxide adduct thereof, polypropylene glycol diglycidyl ether or an alkylene oxide adduct thereof, and the like). Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

[0125] The cationically polymerizable vinyl compound can be any of a monomer, an oligomer, or a polymer. As the cationically polymerizable vinyl compound, examples include a vinyl ether compound, a vinyl amine compound, and styrene.

[0126] As the vinyl ether compound, there is no particular limitation, and examples include di- or tri-vinyl ether compounds such as ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, and the like; monovinyl ether compounds such as ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether-o-propylene carbonate, dodecyl vinyl ether, and octadecyl vinyl ether; and the like.

[0127] As the oxetane compound, 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., trade name: ARON OXETANE OXT-101, OXT-101, etc.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (ARON OXETANE OXT-101, OXT-121, etc.), 3-ethyl-3-(phenoxy-methyl)oxetane (ARON OXETANE OXT-101, OXT-211, etc.), di(1-ethyl-(3-oxetanyl))methyl ether (ARON OXETANE OXT-101, OXT-221, etc.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (ARON OXETANE OXT-101, OXT-212, etc.), and the like can be given. The oxetane compound refers to a compound having one or more oxetane rings in the molecule.

[0128] When the polymerizable compound (X) has a radical polymerizable functional group, the polymerizable compound (X') preferably has a radical polymerizable functional group. As the polymerizable compound (X') having a radical polymerizable functional group, a compound having at least one radical polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, a vinyl ester group is preferable, and a compound having a (meth)acryloyl group is more preferable. As the compound having a (meth)acryloyl group, at least one selected from the group consisting of a (meth)acrylate and a (meth)acrylamide is further preferable.

[0129] As the (meth)acrylate, for example, monofunctional (meth)acrylates such as ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, ethoxylated o-phenyl phenol acrylate, and the like, polyfunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and the like can be given.

[0130] The polymerizable compound preferably contains a crosslinkable compound (Y) having two or more polymerizable functional groups. The crosslinkable compound (Y) can be a high specific gravity compound or a low specific gravity compound. In addition, the crosslinkable compound (Y) can be the polymerizable compound (X) or the polymerizable compound (X').

[0131] As the crosslinkable compound (Y), a compound having two or more polymerizable functional groups among the above-described polymerizable compounds can be given.

[0132] The proportion of the cross-linkable compound (Y) in the polymerizable compound is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. Thus, there is a tendency that the curability of the composition is further improved, and a cured body having a higher strength can be easily obtained. In addition, the proportion of the cross-linkable compound (Y) in the polymerizable compound is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less. Thus, the adhesion to a glass substrate or the like is further improved, and a sealing material having more excellent reliability can be formed. That is, the proportion of the cross-linkable compound (Y) in the polymerizable compound may be, for example, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 35 to 90% by mass, 35 to 85% by mass, 35 to 80% by mass, 40 to 90% by mass, 40 to 85% by mass, or 40 to 80% by mass.

[0133] From the viewpoint of improving the coatability of the composition of the present embodiment and excellent moldability of the cured body, the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound is preferably 500 mPa s or more, more preferably 700 mPa s or more, and further preferably 1000 mPa s or more. In addition, from the viewpoint of improving the dischargeability at the time of coating of the composition of the present embodiment and a wide range of choices of the molding method, the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound is preferably 30000 mPa s or less, more preferably 25000 mPa s or less, and further preferably 20000 mPa s or less. That is, the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound may be, for example, 500 to 30000 mPa s, 500 to 25000 mPa s, 500 to 20000 mPa s, 700 to 30000 mPa s, 700 to 25000 mPa s, 700 to 20000 mPa s, 1000 to 30000 mPa s, 1000 to 25000 mPa s, or 1000 to 20000 mPa s.

[0134] In the present embodiment, a plurality of the above-described polymerizable compounds can be combined so that the viscosity of the mixture of the entire amount of the polymerizable compound is within the above-described range.

[0135] Note that, in the present specification, the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound indicates a value measured using a cone-plate type viscometer.

[0136] As the polymerization initiator, a photopolymerization initiator is preferred. By using a photopolymerization initiator, the composition of the present embodiment can be cured by irradiation with an energy ray such as ultraviolet light.

[0137] The polymerization initiator may be at least one selected from the group consisting of a cationic polymerization initiator and a free radical polymerization initiator, and preferably at least one selected from the group consisting of a photocationic polymerization initiator and a photoradical polymerization initiator. The use of a cationic polymerization initiator enables polymerization of a polymerizable compound having a cationic polymerizable functional group, and the use of a free radical polymerization initiator enables polymerization of a polymerizable compound having a free radical polymerizable functional group.

[0138] The photocationic polymerization initiator is not particularly limited, and examples thereof include arylsulfonium salt derivatives (e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by Dow Chemical, Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170 and Adeka Optomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd., CPI-100P, CPI-101A, CPI-200K, CPI-210S and LW-S1 manufactured by San-Apro, and Cibacure 1190 manufactured by Double Bond Co., Ltd.), aryliodonium salt derivatives (e.g., Irgacure 250 and RHODIA manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like. RP-2074 manufactured by Japan Co., Ltd.), allene-ion complex derivatives, azide salt derivatives, triazine-based initiators, and other acid generators such as halides.

[0139] Examples of the photocationic polymerization initiator include onium salts represented by formula (B-1).

[0140] [Chemical Formula 3]

[0141]

[0142] [In formula (B-1),

[0143] A represents an element of Group VIA to Group VIIA with a valence of m,

[0144] m represents 1 to 2,

[0145] p represents 0 to 3,

[0146] R represents an organic group bonded to A,

[0147] D represents a divalent group represented by the following formula (B-1-1):

[0148] [Chemical Formula 4]

[0149]

[0150] (In formula (B-1-1), E represents a divalent group, G represents -0-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group (R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms), and a represents 0 to 5. Each of the a G's and the a+1 E's can be the same or different.)

[0151] X - is an onium counterion.

[0152] The onium ion of formula (B-1) is not particularly limited, and examples thereof include 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis〔4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl〕sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenyldi(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl dipara-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl diphenylsulfonium, 2-[(dipara-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, octadecylmethylbenzoylmethylsulfonium, and the like.

[0153] R is an organic group bonded to A. R represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which can have a substituent. As the substituent, for example, at least one selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen can be mentioned.

[0154] The number of R is m + p(m - 1) + 1, and each of them can be the same as or different from each other. In addition, two or more of R can be directly bonded to each other or bonded to each other via -0-, -S-, -SO-, -SO2-, -NH-, -NR'-, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms, or phenylene to form a ring structure containing element A. Here, R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0155] As the aryl group having 6 to 30 carbon atoms, monocyclic aryl groups such as a phenyl group, and fused polycyclic aryl groups such as a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, an anthraquinonyl group, a fluorenyl group, a naphthoquinonyl group, and an anthraquinonyl group can be given.

[0156] The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms can have at least one substituent. As examples of the substituent, the following can be given:

[0157] A straight chain alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, and an octadecyl group;

[0158] A branched alkyl group having 1 to 18 carbon atoms such as an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, and an isohexyl group;

[0159] A cycloalkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;

[0160] A hydroxyl group;

[0161] A straight chain or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a hexyloxy group, a decyloxy group, and a dodecyloxy group;

[0162] A straight chain or branched alkylcarbonyl group having 2 to 18 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, a 2-methylpropionyl group, a heptanoyl group, a 2-methylbutyryl group, a 3-methylbutyryl group, an octanoyl group, a decanoyl group, a dodecanoyl group, and an octadecanoyl group;

[0163] An arylcarbonyl group having 7 to 11 carbon atoms such as a benzoyl group and a naphthoyl group;

[0164] A straight chain or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an octyloxycarbonyl group, a tetradecyloxycarbonyl group, and an octadecyloxycarbonyl group.​

[0165] phenoxycarbonyl, naphthoxycarbonyl, or the like aryl-oxycarbonyl group having 7 to 11 carbon atoms;

[0166] phenylthiocarbonyl, naphthylthiocarbonyl, or the like aryl-thiocarbonyl group having 7 to 11 carbon atoms;

[0167] acetyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, octadecylcarbonyloxy, or the like acyloxy group having 2 to 19 carbon atoms which is linear or branched;

[0168] phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4-(4-methylthiobenzoyl)phenylthio, 4-(2-methylthiobenzoyl)phenylthio, 4-(p-methylbenzoyl)phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, 4-(p-tert-butylbenzoyl)phenylthio, or the like arylthio group having 6 to 20 carbon atoms;

[0169] methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, or the like alkylthio group having 1 to 18 carbon atoms which is linear or branched;

[0170] phenyl, tolyl, dimethylphenyl, naphthyl, or the like aryl group having 6 to 10 carbon atoms;

[0171] thienyl group, furyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidinyl group, pyrazinyl group, indolyl group, benzofuranyl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, acridyl group, phenothiazinyl group, phenoxazinyl group, xanthenyl group, thioxanthyl group, phenoxazinyl group, phenoxazinyl group, benzodihydropyranyl group, isobenzodihydropyranyl group, dibenzothienyl group, xanthonyl group, thioxanthonyl group, diphenylfuranyl group, and the like heterocyclic group having 4 to 20 carbon atoms;

[0172] phenoxy group, naphthoxy group, and the like aryloxy group having 6 to 10 carbon atoms; methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec-butylsulfinyl group, tert-butylsulfinyl group, pentylsulfinyl group, isopentylsulfinyl group, neopentylsulfinyl group, tert-pentylsulfinyl group, octylsulfinyl group, and the like linear or branched alkylsulfinyl group having 1 to 18 carbon atoms;

[0173] phenylsulfinyl group, tolylsulfinyl group, naphthylsulfinyl group, and the like arylsulfinyl group having 6 to 10 carbon atoms;

[0174] methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, pentylsulfonyl group, isopentylsulfonyl group, neopentylsulfonyl group, tert-pentylsulfonyl group, octylsulfonyl group, and the like linear or branched alkylsulfonyl group having 1 to 18 carbon atoms;

[0175] phenylsulfonyl group, tolylsulfonyl (toluenesulfonyl) group, naphthylsulfonyl group, and the like arylsulfonyl group having 6 to 10 carbon atoms;

[0176] alkyleneoxy group represented by the formula (B-1-2) (Q represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5):

[0177] [Chemical Formula 5]

[0178]

[0179] unsubstituted amino group;

[0180] amino group monosubstituted or disubstituted with an alkyl group having 1 to 5 carbon atoms and / or an aryl group having 6 to 10 carbon atoms;

[0181] cyano group;

[0182] nitro group;

[0183] halogen such as fluorine, chlorine, bromine, iodine, and the like.

[0184] p in the formula (B-1) represents the number of repeating units of [D-A+R m-1 ] bond, and is preferably an integer of 0 to 3.

[0185] as onium ions [A + ] in the formula (B-1) are preferably sulfonium, iodonium, selenonium, and as representative examples, the following ions can be given.

[0186] As sulfonium ions, the following can be given: triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tri(4-methoxyphenyl)sulfonium, 1-naphthyl diphenylsulfonium, 2-naphthyl diphenylsulfonium, tri(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tri(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl diphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyl di-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyl di-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthrenium, 5-phenylthianthrenium, 5-tolylthianthrenium, 5-(4-ethoxyphenyl)thianthrenium, 5-(2,4,6-trimethylphenyl)thianthrenium, and the like triarylsulfoniums;

[0187] diphenylphenacylsulfonium, diphenyl 4-nitrobenzoylmethylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium, and the like diarylsulfoniums;

[0188] monoarylsulfonium such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetyloxylphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(l-ethoxycarbonyl)ethylsulfonium, phenylmethylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, 4-methoxyphenylmethylbenzoylmethylsulfonium, 4-acetyloxylphenylmethylbenzoylmethylsulfonium, 2-naphthylmethylbenzoylmethylsulfonium, 2-naphthylmethyloctadecylbenzoylmethylsulfonium, 9-anthrylmethylbenzoylmethylsulfonium, and the like;

[0189] trialkylsulfonium such as dimethylbenzoylmethylsulfonium, benzoylmethyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylbenzoylmethylsulfonium, and the like; and the like.

[0190] Among these onium ions, one or more kinds of sulfonium ion and iodonium ion are preferable, and sulfonium ion is more preferable. As the sulfonium ion, one or more kinds selected from the group consisting of triphenylsulfonium, tris-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenyldi(p-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl di-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yl diphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thioxanthium, 5-phenylthioxanthium, diphenylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(l-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, and octadecylmethylbenzoylmethylsulfonium are preferable.

[0191] In formula (B-1), X - is a counter ion. The number thereof is p+1 per 1 molecule. The counter ion is not particularly limited, and examples of the counter ion include halides of boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, alkylsulfonic acid compounds, methylated compounds, and the like. As X - , for example, halogen ions such as F - , Cl - , Br - , I - , OH - , ClO4 - , FSO3 -, ClSO3 - , CH3SO3 - , C6H5SO3 - , CF3SO3 - , HSO4 - , SO4 2- , HCO3 - , CO3 2- , H2PO4 - , HPO4 2- , PO4 3- , PF6 - , PF5OH - , BF4 - , B(C6F5)4 - , B(C6H4CF3)4 - , AlCl4 - ; BiF6 - , SbF6 - , SbF5OH - , AsF6 - , AsF5OH - .

[0192] As the fluoroalkylphosphonium fluoride ion, there can be mentioned a fluoroalkylphosphonium fluoride ion represented by formula (B-1-3) or the like.

[0193] [(Rf) b PF 6-b ] - (B-1-3)

[0194] In formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is an integer of 1 to 5, and is preferably an integer. The b Rf's can be the same or different from each other. The number b of Rf is more preferably 2 to 4, and most preferably 2 to 3. That is, the number b of Rf can be, for example, 1 to 5, 1 to 4, 1 to 3, 2 to 4, or 2 to 3.

[0195] In the fluoroalkyl fluorophosphate ion represented by formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom, and the number of carbon atoms is preferably from 1 to 8, and the number of carbon atoms is further preferably from 1 to 4. As the alkyl group, there are mentioned straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl, and the like; branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl, and the like; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. As specific examples of Rf, there are mentioned CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, (CF3)3C, and the like.

[0196] As specific examples of the preferred fluoroalkyl fluorophosphate anion, there are mentioned [(CF3CF2)2PF4] - , [(CF3CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [(CF3CF2CF2)2PF4] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - , [(CF3CF2CF2CF2)2PF4] - , and [(CF3CF2CF2CF2)3PF3] - and the like.

[0197] As the photocationic polymerization initiator, a substance dissolved in advance in a solvent can be used in order to be easily mixed with the polymerizable compound. As the solvent, there are mentioned, for example, propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, and the like.

[0198] As the photocationic polymerization initiator, at least one selected from the group consisting of triaryl sulfonium salt hexafluoroantimonate represented by formula (B-2) and diphenyl 4-thiophenoxyphenyl sulfonium tris(pentafluoroethyl)trifluorophosphate represented by formula (B-3) is preferred, and the triaryl sulfonium salt hexafluoroantimonate is more preferred.

[0199] [Chemical Formula 6]

[0200]

[0201] [Chemical Formula 7]

[0202]

[0203] As the photoradical polymerization initiator, there are no particular limitations, and examples that can be given include:

[0204] benzophenone and derivatives thereof;

[0205] benzoin and derivatives thereof;

[0206] anthraquinone and derivatives thereof;

[0207] benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzoin dimethyl ketal, and other benzoin-type photopolymerization initiators;

[0208] diethoxyacetophenone, 4-tert-butyltrichloroacetophenone, and other acetophenone-type photopolymerization initiators;

[0209] 2-dimethylaminoethyl benzoate;

[0210] p-dimethylaminoethyl benzoate;

[0211] diphenyl disulfide;

[0212] thioxanthone and derivatives thereof;

[0213] camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride, and other camphorquinone-type photopolymerization initiators;

[0214] 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and other α-aminoalkylphenone-type photopolymerization initiators;

[0215] benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and other acyloxyphosphine oxide-type photopolymerization initiators;

[0216] phenyl-glyoxylic acid-methyl ester;

[0217] oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetyloxy-ethoxy]-ethyl ester;

[0218] Oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester; and the like.

[0219] The content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. Thereby, the curability is further improved. In addition, the content of the polymerization initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. Thereby, the adhesion to a glass substrate or the like is further improved, and a sealing material with more excellent reliability can be formed. That is, the content of the polymerization initiator may, for example, be 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.1 to 5 parts by mass, or 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable compound.

[0220] As the inorganic filler, there can be mentioned, for example, silica particles, glass fillers, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, zinc oxide, and the like oxides, boron nitride, silicon nitride, aluminum nitride, and the like nitrides, silicon carbide, and the like carbides, aluminum hydroxide, magnesium hydroxide, and the like hydroxides, copper, silver, gold, iron, aluminum, nickel, titanium, and the like metals and alloys, diamond, carbon, and the like carbon-based fillers, calcium carbonate, barium sulfate, talc, mica, and the like.

[0221] The inorganic filler can be a material subjected to surface treatment with a fatty acid, a silicone coupling agent, a titanate coupling agent, or the like. One or two or more kinds of inorganic fillers can be used as needed.

[0222] The true specific gravity of the inorganic filler may, for example, be 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more. In addition, the true specific gravity of the inorganic filler may, for example, be 20.0 or less, preferably 8.0 or less, and more preferably 5.0 or less. Note that the true specific gravity of the inorganic filler indicates a value measured in accordance with ASTM D2840. That is, the true specific gravity of the inorganic filler may, for example, be 1.3 to 20.0, 1.3 to 8.0, 1.3 to 5.0, 1.4 to 20.0, 1.4 to 8.0, 1.4 to 5.0, 1.5 to 20.0, 1.5 to 8.0, or 1.5 to 5.0.

[0223] The inorganic filler preferably contains at least one selected from the group consisting of silica, mica, kaolin, talc, and alumina, and more preferably contains talc.

[0224] The inorganic filler can be an inorganic particle having an average particle diameter (hereinafter, sometimes simply referred to as particle diameter or particle size). The average particle diameter of the inorganic particle is preferably 0.005 μm or more, more preferably 0.01 μm or more. In addition, the average particle diameter of the inorganic particle is preferably 50 μm or less, more preferably 30 μm or less. That is, the average particle diameter of the inorganic particle can be, for example, 0.005 to 50 μm, 0.005 to 30 μm, 0.01 to 50 μm, or 0.01 to 30 μm. Note that the average particle diameter of the inorganic particle represents a value measured using a MICROTRAC particle size distribution device by a laser diffraction / scattering method.

[0225] The content of the inorganic filler can be, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. In addition, the content of the inorganic filler can be, for example, 500 parts by mass or less, 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, further preferably 50 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. That is, the content of the inorganic filler can be, for example, 5 to 500 parts by mass, 5 to 350 parts by mass, 5 to 300 parts by mass, 5 to 200 parts by mass, 5 to 100 parts by mass, 5 to 50 parts by mass, 10 to 500 parts by mass, 10 to 350 parts by mass, 10 to 300 parts by mass, 10 to 200 parts by mass, 10 to 100 parts by mass, 10 to 50 parts by mass, 15 to 500 parts by mass, 15 to 350 parts by mass, 15 to 300 parts by mass, 15 to 200 parts by mass, 15 to 100 parts by mass, or 15 to 50 parts by mass, relative to 100 parts by mass of the polymerizable compound.

[0226] The composition of the present embodiment can further include a photosensitizer. The photosensitizer refers to a compound capable of absorbing energy rays to generate a reaction species (for example, a cation generated from a photocationic polymerization initiator, a radical generated from a photoradical polymerization initiator) with good efficiency from a polymerization initiator.

[0227] The photosensitizer is not particularly limited, and examples thereof include benzophenone derivatives, phenothiazine derivatives, phenylketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, coumarone derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, organoruthenium complexes, and the like. Among these, phenylketone derivatives such as 2-hydroxy-2-methyl-l-phenyl-propan-l-one, anthracene derivatives such as 9,10-dibutoxyanthracene, and more preferably anthracene derivatives are preferable. Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferable. The photosensitizer can be used alone or in combination of two or more.

[0228] In the case where the composition of the present embodiment contains a photosensitizer, the content of the photosensitizer can be, for example, 0.01 parts by mass or more, and can be 0.02 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. In addition, from the viewpoint of storage stability, the content of the photosensitizer can be, for example, 5 parts by mass or less, and preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. That is, the content of the photosensitizer can be, for example, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.02 to 5 parts by mass, or 0.02 to 3 parts by mass, relative to 100 parts by mass of the polymerizable compound.

[0229] The composition of the present embodiment can further contain a silane coupling agent. By incorporating the silane coupling agent, the composition of the present embodiment tends to further improve adhesion and adhesion durability.

[0230] As the silane coupling agent, for example, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, γ-(meth)acryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane, and the like can be given. Among these, one or more selected from the group consisting of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane is preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred. The silane coupling agent can be used alone or in combination of two or more.

[0231] In the case where the composition of the present embodiment contains a silane coupling agent, the content of the silane coupling agent can be, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. In addition, the content of the silane coupling agent can be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. That is, the content of the silane coupling agent can be, for example, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.2 to 10 parts by mass, or 0.2 to 5 parts by mass, relative to 100 parts by mass of the polymerizable compound.

[0232] The composition of the present embodiment can further contain an antioxidant.

[0233] The composition of the present embodiment can further contain resin particles. By incorporating the resin particles, it is easier to form a cured body of a certain thickness. Therefore, the composition incorporating the resin particles is more suitable as a sealant for cofferdam formation.

[0234] As the resin particles, a substance that is not dissolved in the composition and can maintain a shape can be used without particular limitation, and, for example, polyethylene particles, polypropylene particles, crosslinked poly(methyl) methacrylate particles, crosslinked polystyrene particles, crosslinked poly(methyl) methacrylate polystyrene copolymer particles, and the like can be given. The resin particles are preferably at least one selected from the group consisting of crosslinked poly(methyl) methacrylate particles, crosslinked polystyrene particles, and crosslinked poly(methyl) methacrylate polystyrene copolymer particles, and more preferably at least one selected from the group consisting of crosslinked poly(methyl) methacrylate particles and crosslinked polystyrene particles.

[0235] The average particle diameter of the resin particles may be, for example, 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more. In addition, the average particle diameter of the resin particles may be, for example, 200 μm or less, and preferably 100 μm or less. That is, the average particle diameter of the resin particles may be, for example, 0.1 to 200 μm, 0.1 to 100 μm, 1 to 200 μm, 1 to 100 μm, 5 to 200 μm, or 5 to 100 μm. Note that, in the present specification, the average particle diameter of the resin particles represents the average particle diameter on a volume basis as measured using a "laser diffraction type particle size distribution measuring device SALD-2200" manufactured by Shimadzu Corporation.

[0236] The standard deviation of the particle volume distribution with respect to the particle diameter (μm) when the particle diameter is expressed in logarithm is preferably 0.25 or less for the resin particles. Thus, the deviation in the thickness of the cured body caused by the deviation in the particle diameter of the resin particles is suppressed, and the size of the cured body can be controlled with higher accuracy. The standard deviation is more preferably 0.2 or less, and further preferably 0.1 or less. In addition, the standard deviation may be, for example, 0.001 or more, and can be 0.005 or more. That is, the standard deviation may be, for example, 0.001 to 0.25, 0.001 to 0.2, 0.001 to 0.1, 0.005 to 0.25, 0.005 to 0.2, or 0.05 to 0.1.

[0237] In the case where the composition of the present embodiment contains resin particles, the content of the resin particles may be, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the polymerizable compound. In addition, the content of the resin particles may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less, with respect to 100 parts by mass of the polymerizable compound. That is, the content of the resin particles may be, for example, 0 to 10 parts by mass, 0 to 5 parts by mass, 0 to 4 parts by mass, 0 to 3 parts by mass, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 4 parts by mass, 0.01 to 3 parts by mass, 0.02 to 10 parts by mass, 0.02 to 5 parts by mass, 0.02 to 4 parts by mass, 0.02 to 3 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass, with respect to 100 parts by mass of the polymerizable compound.

[0238] The composition of the present embodiment can further contain other components other than those described above. As the other components, known additives used in the field of sealants can be used without particular limitation. As the other components, for example, metal deactivators, fillers, stabilizers, neutralizing agents, lubricants, antibacterial agents, and the like can be exemplified.

[0239] From the perspective of improving the coating properties of the composition and excellent moldability of the cured product, the viscosity of the composition of this embodiment at 25°C can be, for example, 50,000 mPa·s or more, preferably 70,000 mPa·s or more, more preferably 80,000 mPa·s or more, and even more preferably 100,000 mPa·s or more. Furthermore, from the perspective of improving the discharge properties of the composition during coating and widening the range of molding method options, the viscosity of the composition of this embodiment at 25°C can be, for example, 1,000,000 mPa·s or less, preferably 950,000 mPa·s or less, more preferably 900,000 mPa·s or less, and even more preferably 850,000 mPa·s or less. That is, the viscosity of the composition of the present embodiment at 25° C. can be, for example, 50,000 to 1,000,000 mPa·s, 50,000 to 950,000 mPa·s, 50,000 to 900,000 mPa·s, 50,000 to 850,000 mPa·s, 70,000 to 1,000,000 mPa·s, 70,000 to 950,000 mPa·s, 70,000 to 900,000 mPa·s, 70,000 to 850,000 mPa·s, s, 80,000-1,000,000 mPa·s, 80,000-950,000 mPa·s, 80,000-900,000 mPa·s, 80,000-850,000 mPa·s, 100,000-1,000,000 mPa·s, 100,000-950,000 mPa·s, 100,000-900,000 mPa·s, or 100,000-850,000 mPa·s. The viscosity of the composition at 25° C. is a value measured using a cone rotor viscometer.

[0240] In the composition of this embodiment, the type and content of each component can be appropriately adjusted so that the viscosity at 25° C. is within the above-mentioned range.

[0241] The ratio (η2 / η1) of the viscosity η2 at 25°C, 0.1 rpm to the viscosity η1 at 25°C, 1 rpm of the composition of the present embodiment is preferably 1.1 to 10.0. If the ratio (η2 / η1) is 1.1 or more, there is a tendency that the coatability of the composition is further improved and the moldability of the cured body is more excellent. From the viewpoint of making this tendency more remarkable, the ratio (η2 / η1) is preferably 1.15 or more, more preferably 1.2 or more. In addition, if the ratio (η2 / η1) is 10.0 or less, there is a tendency that the dischargeability at the time of coating of the composition is further improved, and from the viewpoint of making this tendency more remarkable, the ratio (η2 / η1) is preferably 9.5 or less, more preferably 9.0 or less. That is, the ratio (η2 / η1) may be, for example, 1.1 to 10.0, 1.1 to 9.5, 1.1 to 9.0, 1.15 to 10.0, 1.15 to 9.5, 1.15 to 9.0, 1.2 to 10.0, 1.2 to 9.5, or 1.2 to 9.0. Note that the viscosity η1 at 25°C, 1 rpm and the viscosity η2 at 25°C, 0.1 rpm of the composition represent values measured using a cone-plate type viscometer.

[0242] For the composition of the present embodiment, the kind and content of each component can be appropriately adjusted so that the ratio (η2 / η1) is in the above range.

[0243] The liquid specific gravity of the composition of the present embodiment is preferably 1.3 to 4.0. The liquid specific gravity of the composition is preferably 1.4 or more, more preferably 1.5 or more. In addition, the liquid specific gravity of the composition is preferably 3.0 or less, more preferably 2.5 or less, further preferably 2.0 or less. That is, the liquid specific gravity of the composition may be, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0, 1.4 to 3.0, 1.4 to 2.5, 1.4 to 2.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5, or 1.5 to 2.0. Note that the liquid specific gravity of the composition represents a value measured using a 5 mL Gauvitt-type specific gravity bottle in accordance with 8.2.2 of JIS-K-0061.

[0244] For the composition of the present embodiment, the kind and content of each component can be appropriately adjusted so that the liquid specific gravity is in the above range.

[0245] The method for producing the composition of the present embodiment is not particularly limited, and is only required to be a method that can sufficiently mix each component described above. As the mixing method, for example, a stirring method using stirring force accompanying rotation of a propeller, a method using a general disperser such as a planetary stirrer based on rotation and revolution, and the like can be given. From the viewpoint of low cost and stable mixing, the above mixing method is preferred.

[0246] By curing the composition of the present embodiment, a cured body of a polymer including a polymerizable compound and an inorganic filler can be obtained. The cured body has low moisture permeability and can be suitably used as a sealing material, particularly a sealing material for an organic EL display element.

[0247] The composition of the present embodiment can be cured by, for example, irradiation of energy rays. As a light source used in the curing of the composition of the present embodiment, there are no particular limitations, and examples that can be given include a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a xenon quasi-molecular lamp, a xenon flash lamp, a light-emitting diode (hereinafter referred to as an LED), and the like. These light sources are preferred from the viewpoint that irradiation of energy rays corresponding to the reaction wavelength of each photopolymerization initiator can be performed efficiently.

[0248] The emission wavelength and the energy distribution of each of the above light sources are different. Therefore, the above light sources can be appropriately selected depending on the reaction wavelength of the polymerization initiator or the like. In addition, natural light (sunlight) can also be a light source that initiates the reaction.

[0249] Irradiation based on the above light source can be direct irradiation or condensing irradiation using a mirror, an optical fiber, or the like. In addition, irradiation using a low-wavelength cutoff filter, a heat ray cutoff filter, a cold mirror, or the like can also be used.

[0250] At the time of curing of the composition of the present embodiment, a post-heating treatment can be performed after light irradiation in order to promote curing. From the viewpoint of avoiding an influence on the organic EL display element, the temperature of the post-heating is preferably 150°C or lower, and more preferably 100°C or lower. The temperature of the post-heating is preferably 40°C or higher.

[0251] The composition of the present embodiment can also be used as an adhesive. The composition of the present embodiment can be suitably used for, for example, adhesion of a package or the like of an organic EL display element or the like.

[0252] As a method of adhering two members using the composition of the present embodiment, for example, a method including the following steps can be given: a step of applying the composition to the entire surface or a part of a first member; a step of irradiating light on the composition applied to the first member; and a step of adhering the first member to a second member via the composition during a period before the composition irradiated with light is cured. According to such a method, the second member can be adhered to the first member without being exposed to light and heat. Therefore, the above method can be suitably used for adhesion of a back panel to an organic EL display element.

[0253] As a method of manufacturing an organic EL display device using the composition of the present embodiment, for example, a manufacturing method including the following steps can be given: a step of applying the composition on a back panel; a step of irradiating light on the composition applied on the back panel; and a step of bonding the back panel with a substrate on which an organic EL display element is formed via the composition with the light blocked. According to such a method, the organic EL display element can be sealed without being exposed to light and heat.

[0254] In addition, as a method of manufacturing an organic EL display device using the composition of the present embodiment, for example, a manufacturing method including the following steps can be given: a step of applying the composition on a back panel; a step of irradiating light on the composition applied on the back panel; and a step of bonding the back panel with a substrate on which an organic EL display element is formed via the composition with the light blocked. According to such a method, the organic EL display element can be sealed without being exposed to light and heat.

[0255] The specific gravity of the cured body of the composition of the present embodiment (hereinafter, also simply referred to as the cured body of the present embodiment) is, for example, 1.35 or greater. In addition, the specific gravity of the cured body of the present embodiment is, for example, 19.0 or less. Note that the specific gravity of the cured body indicates a value measured according to the JIS K7112B method using water at 23°C as an immersion liquid.

[0256] As for the composition of the present embodiment, the types and contents of the components can be appropriately adjusted in a manner such that the specific gravity of the cured body is within the above range.

[0257] In the cured body of the present embodiment, the glass transition temperature of the polymer of the polymerizable compound can be, for example, 60°C or greater, preferably 70°C or greater, more preferably 80°C or greater, and further preferably 85°C or greater.

[0258] Note that in the present specification, the glass transition temperature (Tg) of the polymer indicates a value calculated from dynamic viscoelastic spectroscopy. In dynamic viscoelastic spectroscopy, the temperature at which the peak top of the tangent of the loss angle (hereinafter, simply referred to as tan δ) is shown when a polymer is subjected to stress and strain at a certain temperature increase rate can be regarded as the glass transition temperature. Note that in a case where even if the temperature is increased from a sufficiently low temperature of about -150°C to a certain temperature (Ta °C), the peak of tan δ does not appear, it can be considered that the glass transition temperature is -150°C or lower or the certain temperature (Ta °C) or higher, but since it is considered that there is no cured body having a glass transition temperature of -150°C or lower, it can be determined that the glass transition temperature is the certain temperature (Ta °C) or higher.

[0259] As for the composition of the present embodiment, the types and contents of the components can be appropriately adjusted in a manner such that the glass transition temperature of the polymer is within the above range.

[0260] The crosslinking density of the cured body of the present embodiment is preferably 1.0 x 10 -3 mol / cm 3 or more, more preferably 2.0 x 10 -3 mol / cm 3 or more. It is considered that, with a high crosslinking density, the number of crosslinking points in the cured body is increased, and thus micro-Brownian motion is suppressed, and the moisture permeability is further reduced. In addition, the crosslinking density of the cured body can be, for example, 1.0 x 10 3 mol / cm -3 or less. Thus, the reliability reduction due to the brittleness of the cured body is further suppressed. That is, the crosslinking density of the cured body can be, for example, 1.0 x 10 3 ~ 1.0 mol / cm -3 , or 2.0 x 10 3 ~ 1.0 mol / cm T+40 .

[0261] Note that, in the present specification, the crosslinking density of the cured body is a value calculated from dynamic viscoelastic spectroscopy. Specifically, a cured body having a thickness of 100 μm is cut into a test piece having a width of 5 mm and a length of 25 mm. Dynamic viscoelasticity measurement is performed on the test piece under conditions of a temperature range of -50°C to 200°C, a temperature increase rate of 2°C / min, and a tensile mode, and the relationship between the temperature and the storage elastic modulus (G') is calculated. The crosslinking density is calculated using the following formula, in which the temperature of Tg + 40°C is set as T (K), the storage elastic modulus (G') at T (K) is set as G' 3 , the gas constant is set as R, and the front factor is set as .

[0262] The crosslinking density

[0263] The types and amounts of the components of the composition of the present embodiment can be appropriately adjusted so that the crosslinking density of the cured body is within the above range.

[0264] The average free volume of the cured body of the present embodiment is preferably 1 nm 3 or less, more preferably 0.5 nm 3 or less, further preferably 0.3 nm 3 or less, more preferably 0.1 nm 3 or less, and still more preferably less than 0.1 nm 3 .

[0265] As a method for calculating the free volume of a polymer, a positron annihilation method is known (see "Polymer", Vol. 42, December issue (1993)). Generally, a positron (e +) and an electron (e - ) in the high molecule. The positron annihilation method is a method of measuring the lifetime (τ3) of an ortho-positronium (o-Ps, radius 0.1 nm, hereinafter also referred to as "o-Ps") that accounts for 3 / 4 of the positronium (Ps) when the o-Ps enters a pore of a high molecule, and thereby calculating the free volume of the high molecule. The lifetime (τ3) of the o-Ps is determined by the probability that the positron (e + ) of the o-Ps overlaps with an electron (e - ) in the wall of the pore when the o-Ps collides with the wall of the pore in the high molecule. The larger the pore of the high molecule, the longer the lifetime (τ3) of the o-Ps. When the pore is regarded as a spherical well potential of infinite height, and it is assumed that there is an electron layer of thickness ΔR on the wall of the pore, a model of the speed of annihilation of the positron (e + ) obtained by calculating the overlap of the electron layer and the wave function of the o-Ps agrees well with the data obtained in actual experiments. Therefore, if the pore diameter R of the high molecule is about 0.16 to 0.8 nm, the following equation (1) holds between the lifetime τ3 of the o-Ps and the pore diameter R.

[0266] [Equation 1]

[0267]

[0268] (In the above equation (1), τ3 represents the measured lifetime of the ortho-positronium (o-Ps), R represents the pore diameter of the high molecule, and ΔR represents the thickness of the wall of the pore.)

[0269] That is, by measuring the lifetime (τ3) of the ortho-positronium (o-Ps) using the positron annihilation method, the pore diameter R of the high molecule in the above equation (1) can be calculated. Furthermore, since the pore volume (average free volume) = 4 / 3πR 3 , the average free volume of the high molecule can be calculated from the value of the pore diameter R of the high molecule that is calculated.

[0270] In the composition of the present embodiment, the types and amounts of the components can be appropriately adjusted so that the average free volume of the cured body is in the above range.

[0271] In the cured body of the present embodiment, the pore diameter of the cured body is preferably less than 20%.

[0272] The free volume analyzed by the positron annihilation method represents a region not occupied by the molecular chains of the porous base material and electrolyte formed, and reflects the volume generated in the vicinity of the molecular chains of the base material and electrolyte formed when the molecular chains change. Specifically, the free volume can be calculated by measuring the time from the incidence of a positron to the sample until annihilation, and observing the information about the size, number density, and the like of atomic pores and free volumes from the annihilation lifetime.

[0273] A positron is an antiparticle of an electron, and is a fundamental particle having the same mass as an electron but having an electric charge of the opposite sign. In an amorphous solid such as a polymer, a positron is sometimes paired with an electron, and is referred to as a positronium. When a positronium annihilates, annihilation gamma rays are emitted in two directions. By measuring the time variation of the intensity of the annihilation gamma rays, the lifetime of the positron can be measured.

[0274] A positronium is a para-positronium and a ortho-positronium. The average lifetime of the ortho-positronium is about 140 ns, but is shortened to 1 ns to 5 ns in the case where it undergoes a pick-off process of capturing other electrons in a substance. When an ortho-positronium exists in a free volume space in a solid, the size of the space and the lifetime of the ortho-positronium are in a positive correlation, and by measuring the lifetime based on the annihilation of the pick-off of the ortho-positronium, information about the pore size can be obtained.

[0275] Specifically, the lifetime of the positron is analyzed in three components by a nonlinear least squares method, and from small to large, is set as τ1, τ2, τ3, and the intensities corresponding thereto are set as I1, I2, I3 (I1+I2+I3=100%). Using the above I1, I2, I3 and using the following equation, the porosity of the polymer is defined.

[0276] Porosity (%) = I1 / (I1+I2+I3)

[0277] As for the composition of the present embodiment, the kinds and amounts of the components can be appropriately adjusted in such a manner that the porosity of the polymer is in the above range.

[0278] The moisture permeability of the cured body of the present embodiment, measured at a temperature of 85°C and a relative humidity of 85% according to JIS Z0208, is preferably 60 (g / m 2 ·24h / 100μm) or less, more preferably 55 (g / m 2 ·24h / 100μm) or less, and further preferably 50 (g / m 2• 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m 2 ) 24h / 100μm) or more, 1 to 60 (g / m

[0279] The above describes the preferred embodiments of the present application, but the present application is not limited to the above-described embodiments.

[0280] For example, the present application relates to a method for producing an organic electroluminescent display device having a dam and filler sealing structure, which includes a step of applying the above-described composition and curing to form a dam.

[0281] In addition, the present application also relates to an organic EL display device having a dam and filler sealing structure provided with a dam and a filler, at this time, the dam can contain a cured body of the above-described composition.

[0282] Note that the cofferdam and the filling seal structure can be known cofferdam and filling seal structures, and the filler can be a known filler. In addition, the constitution of the organic EL display device other than the cofferdam and the filling seal structure can be the same as that of a known organic EL display device. The present application can achieve more sufficient moisture permeability than, for example, Patent Literature 5.

[0283] Examples

[0284] Hereinafter, the present application will be described in more detail using examples, but the present application is not limited to these examples. Unless otherwise specified, the examples were tested under conditions of 23°C and a relative humidity of 50 mass%.

[0285] In the examples and comparative examples, the following compounds were used.

[0286] (A) Polymerizable compound - high specific gravity compound (polymerizable compound having a specific gravity of 1.3 to 4.0)

[0287] (A-1) Dibromophenyl glycidyl ether ("BR-250" manufactured by Nippon Kayaku Co., Ltd., content of bromine element: 51 mass%)(maximum atomic number: 35, specific gravity: 1.8, number of polymerizable functional groups in 1 molecule: 1, molecular weight: 308, content of bromine element: 50 mass%)

[0288] (A-2) Brominated cresyl glycidyl ether ("BROC" manufactured by Nippon Kayaku Co., Ltd.)(maximum atomic number: 35, specific gravity: 1.8, number of polymerizable functional groups in 1 molecule: 1, content of bromine element: 50 mass%)

[0289] (A-3) TBBPA epoxy resin ("Epiclon 152" manufactured by DIC Corp.)(maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups in 1 molecule: 2, molecular weight: 972, content of bromine element: 48 mass%)

[0290] (A-4) Brominated bisphenol A type epoxy resin ("SR-T1000" manufactured by Sakamoto Yakuhin Co., Ltd., average molecular weight: 2000)(maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups in 1 molecule: 2)

[0291] (A-5) 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl oxirane ("C6 epoxy" manufactured by DAIKIN Industries, Ltd.)(maximum atomic number: 8, specific gravity: 1.5, number of polymerizable functional groups in 1 molecule: 1, molecular weight: 376)

[0292] (A-6) Pentafluorophenyl acrylate ("Pentafluorophenyl Acrylate" manufactured by Tokyo Chemical Industry Co., Ltd.) (maximum atomic number: 9, specific gravity: 1.5, number of polymerizable functional groups in 1 molecule: 1)

[0293] (A-7) 2,4,6-Tribromophenyl acrylate ("Tribromophenyl Acrylate" manufactured by Tokyo Chemical Industry Co., Ltd.) (maximum atomic number: 35, specific gravity: 2.1, number of polymerizable functional groups in 1 molecule: 1)

[0294] (B) Polymerizable compound - low specific gravity compound (polymerizable compound having a specific gravity of less than 1.3)

[0295] (B-1) 3',4'-Epoxy cyclohexylmethyl-3,4-epoxy cyclohexyl carboxylate ("CELLOXIDE 2021P" manufactured by Daicel Chemical Industries, Ltd.) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in 1 molecule: 2, molecular weight 252)

[0296] (B-2) Bisphenol A type epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, molecular weight 360-390) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in 1 molecule: 2)

[0297] (B-3) Phenol Novolac type epoxy resin ("EPICLON N-775" manufactured by DIC) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in 1 molecule: 2 or more, number average molecular weight 800)

[0298] (B-4) Cyclohexane dimethanol divinyl ether ("CHDVE" manufactured by NIPPON CARBIDE) (maximum atomic number: 8, specific gravity: 0.9, number of polymerizable functional groups in 1 molecule: 1, molecular weight 196)

[0299] (B-5) Polypropylene glycol diglycidyl ether ("EX-946L" manufactured by Nagase Chemtex Corporation) (maximum atomic number: 8, specific gravity: 1.06, number of polymerizable functional groups in 1 molecule: 2)

[0300] (B-6) Lauryl acrylate ("LA" manufactured by Osaka Organic Chemical Industry) (maximum atomic number: 8, specific gravity: 1.1, number of polymerizable functional groups in 1 molecule: 1)

[0301] (B-7) 1,6-Hexanediol dimethacrylate ("HD-N" manufactured by Shin Nakamura Chemical Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.0, number of polymerizable functional groups in 1 molecule: 2)

[0302] (B-8) Tricyclodecane dimethanol dimethacrylate ("DCP" manufactured by Shin-Nakamura Chemical Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.1, number of polymerizable functional groups in 1 molecule: 2)

[0303] (B-9) Hydrogenated product of 1,2-polybutadiene terminal urethane (meth) acrylate ("TEAI-1000" manufactured by JSR Corporation) (maximum atomic number: 8, specific gravity: 1.0, number of polymerizable functional groups in 1 molecule: 2)

[0304] As the (C) polymerization initiator, the following substances were used.

[0305] (C-1) Triaryl sulfonium hexafluoroantimonate salt (Adeka Optomer SP-170 manufactured by Adeka Corporation, anion species is hexafluoroantimonate salt)

[0306] (C-2) Triaryl sulfonium salt (diphenyl 4-thiophenoxy phenyl sulfonium tris (pentafluoroethyl) trifluorophosphate, "CPI-200K" manufactured by San-Apro Corporation, anion species is phosphorus compound)

[0307] (C-3) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide ("TPO" manufactured by BASF JAPAN Ltd.)

[0308] (C-4) 1-Hydroxycyclohexyl phenyl ketone, "I-184" manufactured by BASF JAPAN Ltd.)

[0309] As the (D) photosensitizer, the following substances were used.

[0310] (D-1) 9,10-Dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawaken Co., Ltd.)

[0311] As the (E) silane coupling agent, the following substances were used.

[0312] (E-1) γ-Glycidoxypropyl trimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicone Co., Ltd.)

[0313] As the (F) inorganic filler, the following substances were used.

[0314] (F-1) Microparticulate talc, particle diameter (d50): 4.5 μm, true specific gravity: 2.7 ("#5000PJ" manufactured by Mie Kenki Co., Ltd.)

[0315] (F-2) Microparticulate talc, particle diameter (d50): 15 μm, true specific gravity: 2.7 ("SC" manufactured by Mie Kenki Co., Ltd.)

[0316] (F-3) Microparticulate mica, particle diameter (d50): 3.0 μm, true specific gravity: 2.9 ("A-11" manufactured by Matsuo Sangyo Co., Ltd.)

[0317] (F-4) Microparticulate kaolin, particle diameter (d50): 1.6 μm, true specific gravity: 2.6 ("Kaopolite 1147" manufactured by Hayashibara Biochemical Laboratories Inc.)

[0318] (F-5) Microparticulate silica, particle diameter (d50): 4.2 μm, true specific gravity: 1.9 ("FB-5SDX" manufactured by Denka Co., Ltd.)

[0319] (F-6) Microparticulate alumina, particle diameter (d50): 4.0 μm, true specific gravity: 4.0 ("DAW-03" manufactured by Denka Co., Ltd.)

[0320] (F-7) Microparticulate gold, particle diameter (d50): 4.0 μm, true specific gravity: 19.5 ("TAU-200" manufactured by Tokuriki-do Co., Ltd.)

[0321] As the (G) resin particles, the following substances were used.

[0322] (G-1) GS-210: spherical crosslinked polystyrene particles ("GS-210" manufactured by Ganz Kasei Co., Ltd.) (average particle diameter: 20.0 μm, standard deviation: 0.06 μm)

[0323] The raw materials of the kinds shown in Tables 1 to 3 were mixed at the composition ratios shown in Tables 1 to 3 to prepare the sealants of the Examples and Comparative Examples. The unit of the composition ratio is mass parts.

[0324] [Table 1]

[0325]

[0326] [Table 2]

[0327]

[0328] [Table 3]

[0329]

[0330] Each measurement described below was performed on the sealants of the Examples and Comparative Examples. The results thereof are shown in Tables 1 to 3.

[0331] [Specific gravity of polymerizable compound]

[0332] The measurement was performed in accordance with JIS K0061 using a Hubber-type specific gravity bottle.

[0333] [Specific gravity of liquid]

[0334] Using a 5 mL pycnometer of the Gaukler type, the measurement was performed in accordance with 8.2.2 of JIS-K-0061.

[0335] 〔Light curing conditions〕

[0336] In the evaluation of the curing properties and adhesion of the sealant, the sealant was cured using the following light irradiation conditions. Using a UV curing device (manufactured by FUSION Co., Ltd.) equipped with an electrodeless discharge metal halide lamp, the sealant was light-cured under conditions of a cumulative light quantity of 4,000 mJ / cm2at a wavelength of 365 nm, and then subjected to a post-heating treatment in an oven at 100°C for 60 minutes, to obtain a cured body. 2

[0337] 〔Specific gravity of cured body〕

[0338] A cured body in the form of a sheet having a thickness of 0.1 mm was produced under the aforementioned light curing conditions, and the measurement was performed in accordance with the JIS K7112 B method. As the immersion liquid, water at a temperature of 23°C was used.

[0339] 〔Tg〕

[0340] A cured body in the form of a sheet having a thickness of 0.1 mm was produced under the aforementioned light curing conditions, and a cured body having a thickness of 100 μm was cut into a test piece having a width of 5 mm and a length of 25 mm. Dynamic viscoelasticity measurement was performed on the test piece under conditions of a temperature range of -50°C to 200°C, a temperature increase rate of 2°C / min, and a tensile mode. The temperature at the peak of tan δ (loss tangent) measured by the above dynamic viscoelasticity measurement was taken as the glass transition temperature (Tg) of the cured body.

[0341] 〔Crosslinking density〕

[0342] A cured body in the form of a sheet having a thickness of 0.1 mm was produced under the aforementioned light curing conditions, and a cured body having a thickness of 100 μm was cut into a test piece having a width of 5 mm and a length of 25 mm. Dynamic viscoelasticity measurement was performed on the test piece under conditions of a temperature range of -50°C to 200°C, a temperature increase rate of 2°C / min, and a tensile mode. The crosslinking density was calculated using the following formula. T+40

[0343] Crosslinking density

[0344] 〔Average particle diameter, standard deviation〕

[0345] ​​​The average particle diameter (sometimes also referred to as average particle diameter or particle diameter) of the inorganic filler, the resin particles, and the standard deviation of the particle volume distribution with respect to the particle diameter (pm) when the particle diameter is expressed in logarithm (the above-mentioned "standard deviation") were measured using a laser diffraction type particle size distribution measuring device (SALD-2200 manufactured by Shimadzu Corporation).

[0346] 〔Moisture permeability〕

[0347] A cured body in the form of a sheet having a thickness of 0.1 mm was produced under the aforementioned photocuring conditions, and the moisture permeability was measured in accordance with JIS Z0208 "Moisture Permeability Test Method for Moisture-proof Packaging Materials (Cup Method)", using calcium chloride (anhydrous) as a moisture absorbent, under conditions of an atmospheric temperature of 85°C and a relative humidity of 85%. The moisture permeability was 50 g / (m 2 24 hr) or less is desirable.

[0348] 〔Average free volume and porosity〕

[0349] A cured body in the form of a sheet having a thickness of 0.1 mm was produced under the aforementioned photocuring conditions, and the cured body having a thickness of 0.1 mm was cut into a width of 10 mm x length of 10 mm, and 10 pieces were overlapped and fixed as a test sample.

[0350] The radioactive source was 22 NaCl, and the positron annihilation lifetime and relative intensity were measured under the following conditions.

[0351] Positron radioactive source: 22 NaCl (intensity 0.6 MBq)

[0352] Gamma-ray detector: barium fluoride scintillator and photomultiplier tube

[0353] Resolution of the device: 250 ps

[0354] Measurement temperature: 25°C

[0355] Count: 1,000,000

[0356] Sample: measured with the positron radioactive source sandwiched from both sides

[0357] From the positron annihilation lifetime measured according to the above measurement conditions, the average free volume and porosity were calculated.

[0358] 〔Tensile shear adhesive strength〕

[0359] Two pieces of borosilicate glass test pieces (length 25 mm x width 25 mm x thickness 2.0 mm, TEMPAX (registered trademark) glass) were used, and the adhesive area was made to be 0.5 cm 2The borosilicate glass test piece was bonded with the sealant in a manner such that the bonding thickness became 10 μm, and the sealant was cured under the aforementioned photocuring conditions. After curing, the test piece bonded with the sealant was used to measure the tensile shear adhesive strength (unit: MPa) at a tensile speed of 10 mm / min in an environment of a temperature of 23°C and a relative humidity of 50%.

[0360] [Manufacture of organic EL element substrate]

[0361] A glass substrate (length 25 mm x width 25 mm) having an ITO electrode was cleaned with acetone and isopropyl alcohol. Then, the following compounds were sequentially vapor-deposited in a manner such that thin films were formed, to obtain an organic EL element substrate comprising an anode / hole injection layer / hole transport layer / light-emitting layer / electron injection layer / cathode. The composition of each layer is shown below.

[0362] • Anode: ITO, film thickness of anode 250 nm

[0363] • Hole injection layer: copper phthalocyanine, thickness 30 nm

[0364] • Hole transport layer: N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD), thickness 20 nm

[0365] • Light-emitting layer: tris(8-hydroxyquinoline)aluminum (metal complex-based material), film thickness of light-emitting layer

[0366] • Electron injection layer: lithium fluoride, thickness 1 nm

[0367] • Cathode: aluminum, film thickness of cathode 250 nm

[0368] [Manufacture of organic EL element]

[0369] A sealant was applied to a glass substrate in a quadrangle (side length 20 mm, application width 0.6 mm, application height 0.1 mm) using an application device under a nitrogen atmosphere, and the glass substrate and the organic EL element substrate were bonded with the sealant in a manner such that the bonding thickness became 10 μm, and the sealant was cured under the aforementioned photocuring conditions, to manufacture an organic EL element.

[0370] [Organic EL evaluation]

[0371] [Initial]

[0372] A voltage of 6 V was applied to the just-manufactured organic EL element, and the light-emitting state of the organic EL element was observed by visual observation and microscopy, to measure the diameter of dark spots.

[0373] [After high-temperature high-humidity test]

[0374] After the organic EL element immediately after production was exposed to 85°C, 85%RH for 300 hours, a voltage of 6V was applied, and the light emission state of the organic EL element was observed by visual inspection and microscopy, and the diameter of the dark spot was measured.

[0375] Note that it is desirable that the diameter of the dark spot be 60 μm or less, more desirable that it be 40 μm or less, and most desirable that there be no dark spot.

[0376] Next, the raw materials shown in Tables 4 to 6 were mixed in the composition ratios shown in Tables 4 to 6 to prepare the sealants of the Examples and Comparative Examples. The unit of the composition ratio is parts by mass.

[0377] [Table 4]

[0378]

[0379] [Table 5]

[0380]

[0381] [Table 6]

[0382]

[0383] For the sealants of the Examples and Comparative Examples, each of the above-described measurements and each of the following measurements was performed. The results are shown in Tables 4 to 6.

[0384] 〔Viscosity and thixotropy of composition〕

[0385] The viscosity under the conditions of 25°C and 1 rpm was measured using a cone- and-plate viscometer (TV-22, available from Tokimec, Inc.). In addition, as an evaluation of thixotropy, the ratio of the viscosity η2 at 25°C and 0.1 rpm to the viscosity η1 at 25°C and 1 rpm (η2 / η1) was measured.

[0386] 〔Coating straightness〕

[0387] The composition was filled in a 30 mL light-shielding syringe (trade name "UV BLOCK SYRINGE", available from Musashi Engineering Co., Ltd.), and a dispenser (trade name "SHOT mini 1000", available from Musashi Engineering Co., Ltd.) was used to coat the composition on an alkali-free glass in such a manner that the coating length would be 30 mm ± 2 mm, the coating width would be 0.6 mm ± 0.2 mm, and the coating height would be 0.1 mm ± 0.05 mm. The coating was performed under the conditions of a cumulative light amount of 2,000 mJ / cm2at 365 nm and a coating speed of 30 mm / sec. 2The composition was subjected to light irradiation under the above conditions, and after a post-heating treatment in an oven at 100°C for 60 minutes, a cured body was obtained. The coatability was evaluated according to the following criteria.

[0388] Evaluation Criteria

[0389] AA: The coatability of the cured body was 0.4 mm or more, and the average standard deviation of the coatability was less than 0.040 mm.

[0390] A: The coatability of the cured body was 0.4 mm or more, and the average standard deviation of the coatability was 0.040 mm to 0.100 mm.

[0391] C: The coatability of the cured body was 0.4 mm or more, and the average standard deviation of the coatability was 0.100 mm or more.

[0392] Specific Gravity of Polymerizable Compound

[0393] The specific gravity was measured according to JIS K0061 using a Hubber-type specific gravity bottle.

[0394] Specific Gravity of Cured Body

[0395] A cured body in the form of a sheet having a thickness of 0.1 mm was produced according to the above photocuring conditions, and was measured according to the JIS K7112 B method. As the immersion liquid, water having a temperature of 23°C was used.

Claims

1. A sealant comprising a polymerizable compound, a polymerization initiator, and an inorganic filler material, the polymerizable compound contains a polymerizable compound (X) having a bromine element with a specific gravity of 1.3 to 4.0, the proportion of the polymerizable compound (X) in the polymerizable compound is 30 to 90 mass%.

2. The sealant of claim 1, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the specific gravity of the cured body is 1.35 to 19.

0.

3. The sealant of claim 1 or 2, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the glass transition temperature of the polymer is 85°C or higher.

4. The sealant of claim 1 or 2, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, The crosslinking density of the cured body is 1.5 x 10 -3 mol / cm 3 or more.

5. The sealant of claim 1 or 2, wherein, the content of the halogen element in the polymerizable compound (X) is 10 to 50 mass% relative to the total amount of elements of the polymerizable compound.

6. The sealant of claim 1 or 2, wherein, the polymerizable compound contains a cross-linkable compound (Y) having two or more polymerizable functional groups.

7. The sealant of claim 1 or 2, wherein, the polymerizable compound contains at least one selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound, and an oxetane compound.

8. The sealant of claim 1 or 2, wherein, the polymerizable compound has a radical polymerizable functional group.

9. The sealant of claim 1 or 2, wherein, the polymerization initiator is a photopolymerization initiator.

10. The encapsulant of claims 1 or 2, wherein, the polymerization initiator contains an onium salt.

11. The sealant of claim 1 or 2, wherein, the polymerization initiator is a radical polymerization initiator.

12. The sealant of claim 1 or 2, wherein, the true specific gravity of the inorganic filler material is 1.5 to 5.

0.

13. The sealant of claim 1 or 2, wherein, the inorganic filler material contains at least one selected from the group consisting of silicon dioxide, mica, kaolin, talc, and alumina.

14. The sealant of claims 1 or 2, wherein, the inorganic filler material contains talc.

15. The encapsulant of claim 1 or 2, wherein, the inorganic filler material contains inorganic particles with an average particle diameter of 0.01 to 30 μm.

16. The sealant according to claim 1 or 2, further comprising resin particles.

17. The sealant of claim 16, wherein, the resin particles contain at least one selected from the group consisting of cross-linked poly(methyl) methacrylate particles, cross-linked polystyrene particles, and cross-linked poly(methyl) methacrylate polystyrene copolymer particles.

18. The encapsulant of claim 16, wherein, the average particle diameter of the resin particles is 1 μm to 100 μm.

19. The encapsulant of claim 16, wherein, the standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter (μm) of the resin particles is expressed in logarithm is 0.25 or less.

20. The encapsulant of claim 16, wherein, the content of the resin particles is 0.01 to 5 parts by mass relative to 100 parts by mass of the polymerizable compound.

21. The encapsulant of claims 1 or 2, wherein, the content of the polymerization initiator is 0.01 to 5 parts by mass relative to 100 parts by mass of the polymerizable compound.

22. The encapsulant of claims 1 or 2, wherein, the content of the inorganic filler material is 5 to 500 parts by mass relative to 100 parts by mass of the polymerizable compound.

23. The encapsulant of claims 1 or 2, wherein, the viscosity at 80°C of the total amount of the polymerizable compound mixture is 500 to 30,000 mPa-s.

24. The sealant according to claim 1 or 2, having a viscosity at 25°C of 50,000 to 1,000,000 mPa-s.

25. The encapsulant of claims 1 or 2, wherein, the ratio (η2 / η1) of the viscosity η2 at 25°C, 0.1 rpm to the viscosity η1 at 25°C, 1 rpm is 1.1 to 10.

0.

26. The encapsulant of claims 1 or 2, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, The average free volume of the cured body is 1 nm 3 The following.

27. The encapsulant of claims 1 or 2, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, the porosity of the cured body is less than 20%.

28. The encapsulant of claims 1 or 2, wherein, when the sealant is cured to produce a cured body containing a polymer of the polymerizable compound and the inorganic filler material, The moisture permeability of the cured body, measured according to JIS Z0208 under conditions of a temperature of 85°C and a relative humidity of 85%, is 50 (g / m 2 24h / 100μm or less.

29. The sealant according to claim 1 or 2, which is a sealant for an organic electroluminescent display element.

30. The sealant according to claim 1 or 2, which is a sealant for cofferdam formation.

31. A cured body, which is obtained by curing the sealant according to any one of claims 1 to 30.

32. A method for producing an organic electroluminescent display device, which comprises a step of forming a cofferdam by applying and curing the sealant according to any one of claims 1 to 30, the organic electroluminescent display device has a cofferdam-filling seal structure.

33. An organic electroluminescent display device, which has a cofferdam-filling seal structure provided with a cofferdam and a filler, the cofferdam contains a cured body of the sealant according to any one of claims 1 to 30.

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