JP7724207B2 - Sealant, cured product, organic electroluminescent display device, and method for manufacturing organic electroluminescent display device - Google Patents

Description

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

In recent years, research has been progressing on organic optical devices using organic thin-film elements, such as organic electroluminescence (organic EL) display elements and organic thin-film solar cell elements. Organic thin-film elements are easy to fabricate using methods such as vacuum deposition and solution coating, making them highly productive.

Organic EL display elements are thin-film structures in which an organic light-emitting material layer is sandwiched between a pair of opposing electrodes. Electrons are injected into this organic light-emitting material layer from one electrode, and holes are injected from the other electrode, causing the electrons and holes to combine within the organic light-emitting material layer, resulting in self-luminescence. Compared to liquid crystal display elements and other devices that require backlighting, organic EL display elements have the advantages of better visibility, thinner construction, and low DC voltage operation.

However, such organic EL display elements have the problem that their light-emitting characteristics rapidly deteriorate and their lifespan shortens when the organic light-emitting material layer or electrodes are exposed to the outside air. Therefore, in order to improve the stability and durability of organic EL display elements, sealing technology that isolates the organic light-emitting material layer and electrodes from moisture and oxygen in the air is essential.

For example, Patent Document 1 discloses a method for sealing top-emitting organic EL display elements by filling the gap between organic EL display element substrates with a photocurable sealant and irradiating it with light. Patent Documents 2 to 4 also disclose techniques for sealing organic EL display elements to prevent deterioration due to moisture.

On the other hand, Patent Document 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 1,000 ppm or less and a chlorine content of 1,000 ppm or less. However, Patent Document 5 does not disclose the specific gravity of the polymerizable compound.

Patent Document 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a photocationic polymerization initiator, and a plate-like inorganic filler particle of a specific shape. However, the composition described in Patent Document 6 does not provide sufficient moisture permeability, making it difficult to apply to organic electroluminescent display elements. Furthermore, Patent Document 6 does not disclose the specific gravity of the polymerizable compound.

Patent Document 7 discloses a curable resin composition for encapsulating organic electroluminescent display elements, which has excellent transparency and barrier properties and is characterized by containing a polyfunctional cationically polymerizable compound, an organo-modified layered silicate, and a curing agent, the organo-modified layered silicate being dispersed in the polyfunctional cationically polymerizable compound, and the content of the organo-modified layered silicate being 20 to 250 parts by weight per 100 parts by weight of the polyfunctional cationically polymerizable compound. However, the resin composition described in Patent Document 7 sometimes fails to provide sufficient moisture permeability. Furthermore, Patent Document 7 does not disclose the specific gravity of the polymerizable compound.

Patent Document 8 discloses a transparent, low-moisture permeability epoxy resin composition having a refractive index of 1.6 or higher, which contains a specific ratio of (a) an epoxy compound and (b) a compound having two or more crosslinkable groups reactive with the epoxy compound. However, the resin composition described in Patent Document 8 sometimes fails to achieve sufficient moisture permeability. Furthermore, Patent Document 8 does not disclose the specific gravity of the polymerizable compound.

Patent Document 9 discloses a curable composition containing an organic polymer (A) having a specific reactive silicon group and a polyoxyalkylene polymer (B) having a specific reactive silicon group, characterized in that the specific gravity of the curable composition is 0.9 or more and 1.3 or less. However, Patent Document 9 does not disclose reducing moisture permeability by adjusting the specific gravity of the polymerizable compound.

Patent Document 10 discloses a photocurable resin lens composed of a copolymer obtained by photopolymerizing a composition containing 10 to 70% by weight of a bromine-added bisphenol A epoxy (meth)acrylate with a specific structure, and having a refractive index of 1.58 or greater, a specific gravity of 1.5 or less, and an Abbe number of 30 or greater. However, Patent Document 10 does not mention lowering moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it mention sealing of organic EL display elements.

Patent Document 11 discloses a specific photopolymerizable polysiloxane copolymer having functional acrylic groups, which has a specific gravity greater than approximately 1.0 and a refractive index suitable for restoring the refractive power of natural crystalline lenses. However, Patent Document 11 does not disclose reducing moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it disclose sealing of organic EL display elements.

Patent Document 12 discloses an active energy ray-curable resin composition for balancing rotors of motors, which comprises an active energy ray-curable compound (A) having one or more ethylenically unsaturated double bonds per molecule, a photoradical polymerization initiator (C), and/or a photocationic polymerization initiator (D), and the resin composition has a specific gravity of 1.4 (25°C) or more and a viscosity of 1,000 poise (25°C) or less. However, Patent Document 12 does not mention lowering moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it mention sealing of organic EL display elements.

Japanese Patent Application Laid-Open No. 2001-357973 Japanese Patent Application Publication No. 10-74583 Japanese Patent Application Laid-Open No. 2001-307873 JP 2009-37812 A International Publication No. 2014/017524 Japanese Patent Application Laid-Open No. 2006-291072 International Publication No. 2015/129783 JP 2010-163566 A JP 2010-163566 A Japanese Patent Application Laid-Open No. 2001-124903 Special Publication No. 2002-527171 Japanese Patent Application Publication No. 08-109231

In recent years, the required characteristics of electronic devices have increased, and there is a demand for encapsulating materials that can achieve higher reliability and durability for organic EL display elements, for example.

The present invention was made in consideration of the above circumstances, and aims to provide a sealant capable of forming a sealant with excellent moisture resistance and adhesion to glass substrates, etc. The present invention also aims to provide a cured product of the sealant, a method for manufacturing an organic electroluminescent display device using the sealant, and an organic electroluminescent display device having a sealant formed from the sealant.

That is, the present invention is as follows.
<1>
A sealant comprising a polymerizable compound, a polymerization initiator, and an inorganic filler, wherein the polymerizable compound contains a compound having a specific gravity of 1.3 to 4.0.
<2>
The sealant according to <1>, wherein when the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler, the cured body has a specific gravity of 1.35 to 19.0.
<3>
<1> or <2>, wherein when the sealant is cured to form a cured product containing a polymer of the polymerizable compound and the inorganic filler, the glass transition temperature of the polymer is 85°C or higher.
＜4＞
The sealant according to any one of <1> to <3>, wherein when the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler, the cured body has a crosslink density of 1.5 × 10 ^-3 mol/cm ³ or more.
<5>
The sealant according to any one of <1> to <4>, wherein the polymerizable compound contains a polymerizable compound (X) having an element with an atomic number of 9 or more.
<6>
The sealant according to <5>, wherein the polymerizable compound (X) contains a halogen element.
＜７＞
The sealant according to <6>, wherein the polymerizable compound (X) contains at least one halogen element selected from the group consisting of a fluorine element and a bromine element.
＜8＞
<6> or <7>, wherein the content of the halogen element in the polymerizable compound (X) is 10 to 50 mass% with respect to the total element amount of the polymerizable compound.
＜９＞
<9> The sealant according to any one of <1> to <8>, wherein the polymerizable compound contains a crosslinkable compound (Y) having two or more polymerizable functional groups.
<10>
<9> The sealant according to any one of <1> to <9>, wherein the polymerizable compound contains at least one compound selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound, and an oxetane compound.
<11>
<10> The sealant according to any one of <1> to <10>, wherein the polymerizable compound has a radically polymerizable functional group.
<12>
<12> The sealant according to any one of <1> to <11>, wherein the polymerization initiator is a photopolymerization initiator.
<13>
<13> The sealant according to any one of <1> to <12>, wherein the polymerization initiator contains an onium salt.
<14>
<13> The sealant according to any one of <1> to <12>, wherein the polymerization initiator is a radical polymerization initiator.
＜15＞
<15> The sealant according to any one of <1> to <14>, wherein the inorganic filler has a true specific gravity of 1.5 to 5.0.
<16>
<16> The sealant according to any one of <1> to <15>, wherein the inorganic filler includes at least one selected from the group consisting of silica, mica, kaolin, talc, and aluminum oxide.
＜17＞
<17> The sealant according to any one of <1> to <16>, wherein the inorganic filler contains talc.
＜18＞
<18> The sealant according to any one of <1> to <17>, wherein the inorganic filler contains inorganic particles having an average particle size of 0.01 to 30 μm.
＜19＞
<19> The sealant according to any one of <1> to <18>, further comprising resin particles.
＜20＞
The sealant according to <19>, wherein the resin particles contain at least one selected from the group consisting of crosslinked polymethyl (meth)acrylate particles, crosslinked polystyrene particles, and crosslinked polymethyl (meth)acrylate polystyrene copolymer particles.
＜21＞
<19> or <20>, wherein the resin particles have an average particle size of 1 μm to 100 μm.
<22>
<22> The sealant according to any one of <19> to <21>, wherein a standard deviation of particle volume distribution with respect to particle diameters when the particle diameters (μm) of the resin particles are expressed in logarithm is 0.25 or less.
＜23＞
<22> The sealant 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.
＜24＞
<24> The sealant 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.
＜25＞
<25> The sealant 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.
<26>
<26> The sealant according to any one of <1> to <25>, wherein the viscosity of the total mixture of the polymerizable compounds at 80°C is 500 to 30,000 mPa·s.
＜27＞
<26> The sealant according to any one of <1> to <26>, which has a viscosity at 25°C of 50,000 to 1,000,000 mPa·s.
＜28＞
The sealant according to any one of <1> to <27>, wherein the ratio (η ₂ /η ₁ ) of the viscosity η ₂ at 25° C. and 0.1 rpm to the viscosity η ₁ at 25° C. and 1 rpm is 1.1 to 10.0.
＜29＞
<29> The sealant according to any one of <1> to <28>, wherein when the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler, the cured body has an average free volume of 1 ^nm3 or less.
＜30＞
<29> The sealant according to any one of <1> to <29>, wherein when the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler, the cured body has a porosity of less than 20%.
＜31＞
The sealant according to any one of <1> to <30>, wherein when the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler, the cured body has a moisture permeability of 50 (g/ ^m2 ·24 h/100 μm) or less, as measured in accordance with JIS Z0208 at a temperature of 85°C and a relative humidity of 85%.
＜32＞
The sealant according to any one of <1> to <31>, which is a sealant for an organic electroluminescence display element.
＜33＞
The sealant according to any one of <1> to <32>, which is a sealant for forming a dam.
＜34＞
<33> A cured product obtained by curing the sealant according to any one of <1> to <33>.
＜35＞
<33> A method for manufacturing an organic electroluminescence display device having a dam-fill sealing structure, the method comprising the steps of applying and curing the sealant according to any one of <1> to <33> to form a dam.
＜36＞
An organic electroluminescence display device having a dam-fill sealing structure including a dam and a fill agent, wherein the dam contains a cured product of the sealant according to any one of <1> to <33>.

The present invention provides a sealant capable of forming a sealant with excellent moisture resistance and adhesion to glass substrates, etc. The present invention also provides a cured product of the sealant, a method for manufacturing an organic electroluminescent display device using the sealant, and an organic electroluminescent display device having a sealant formed from the sealant.

The following describes in detail a preferred embodiment of the present invention.

The composition of this embodiment contains a polymerizable compound, a polymerization initiator, and an inorganic filler. In this embodiment, the polymerizable compound contains a high-specific-gravity compound having a specific gravity of 1.3 to 4.0.

The composition of this embodiment can form a sealant that has excellent moisture resistance and adhesion to glass substrates, etc. Therefore, the composition of this embodiment can be suitably used as a sealant (preferably a sealant for organic electroluminescent display elements). Furthermore, the composition of this embodiment can be particularly suitably used as a dam-forming sealant for forming a dam-fill sealing structure.

In this embodiment, the polymerizable compound can be said to be a compound having a polymerizable functional group. One type of polymerizable compound may be used alone, or two or more types may be used in combination.

The polymerizable compound preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group. The polymerizable compound having a cationically polymerizable functional group is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. The polymerizable compound having a radically polymerizable functional group includes 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, and a vinyl ester group, with a compound having a (meth)acryloyl group being preferred. The compound having a (meth)acryloyl group is preferably at least one selected from the group consisting of (meth)acrylates and (meth)acrylamides.

A high-specific gravity compound can be defined as a compound having a polymerizable functional group and a specific gravity of 1.3 to 4.0. The specific gravity of a high-specific gravity compound is preferably 1.4 or higher, more preferably 1.5 or higher. The specific gravity of a high-specific gravity compound is preferably 3.0 or lower, more preferably 2.5 or lower, and even more preferably 2.0 or lower. That is, the specific gravity of a high-specific gravity compound 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. The specific gravity of a high-specific gravity compound is the value measured using a Herbert-type pycnometer in accordance with JIS K0061.

In this embodiment, the polymerizable compound may further contain a low-gravity compound having a specific gravity of less than 1.3. The low-gravity compound can be defined as a compound having a polymerizable functional group and a specific gravity of less than 1.3. The specific gravity of the low-gravity compound is preferably 0.7 or greater, more preferably 0.8 or greater, and may be 0.9 or greater, 1.0 or greater, or 1.1 or greater. That is, the specific gravity of the low-gravity compound may be, for example, 0.7 or greater but less than 1.3, 0.8 or greater but less than 1.3, 0.9 or greater but less than 1.3, 1.0 or greater but less than 1.3, or 1.1 or greater but less than 1.3. The specific gravity of the low-gravity compound is a value measured using a Herbert-type pycnometer in accordance with JIS K0061.

The proportion of high-specific-gravity compounds in the polymerizable compounds may be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and even more preferably 55% by mass or more. This more significantly enhances the above-mentioned effects. Furthermore, the proportion of high-specific-gravity compounds in the polymerizable compounds may be, for example, 100% by mass, but is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% by mass or less. That is, the ratio of the high specific gravity compound in the polymerizable compound is, for example, 30 to 100 mass%, 30 to 90 mass%, 30 to 85 mass%, 30 to 80 mass%, 30 to 75 mass%, 30 to 70 mass%, 30 to 65 mass%, 40 to 100 mass%, 40 to 90 mass%, 40 to 85 mass%, 40 to 80 mass%, 40 to 75 mass%, 40 to 70 mass%, 40 to 65 mass%, 45 to 100 mass%, 45 to 90 mass%, 45 ...100 mass%, 45 to 90 mass%, 45 to 65 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, 45 to 100 mass%, ~85% by mass, 45-80% by mass, 45-75% by mass, 45-70% by mass, 45-65% by mass, 50-100% by mass, 50-90% by mass, 50-85% by mass, 50-80% by mass, 50-75% by mass, It may be 50-70% by weight, 50-65% by weight, 55-100% by weight, 55-90% by weight, 55-85% by weight, 55-80% by weight, 55-75% by weight, 55-70% by weight or 55-65% by weight.

The proportion of the low-specific-gravity compound in the polymerizable compound may be, for example, 0% by mass, and is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, still more preferably 30% by mass or more, and particularly preferably 35% by mass or more. The proportion of the low-specific-gravity compound in the polymerizable compound may be, for example, 70% by mass or less, and is preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less. This more significantly enhances the above-mentioned effects.
That is, the ratio of the low specific gravity compound in the polymerizable compound is, for example, 0 to 70 mass%, 0 to 60 mass%, 0 to 55 mass%, 0 to 50 mass%, 0 to 45 mass%, 10 to 70 mass%, 10 to 60 mass%, 10 to 55 mass%, 10 to 50 mass%, 10 to 45 mass%, 15 to 70 mass%, 15 to 60 mass%, 15 to 55 mass%, 15 to 50 mass%, 15 to 45 mass%, 20 to 70 mass%, 20 to 60 mass%, 20 to 60 mass%, 20 to 70 mass%, 20 to 60 mass%, 20 to 55 mass%, 20 to 50 mass%, 20 to 45 ...45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, 20 to 45 mass%, Mass%, 20-55 mass%, 20-50 mass%, 20-45 mass%, 25-70 mass%, 25-60 mass%, 25-55 mass%, 25-50 mass%, 25-45 mass%, 30-70 mass%, 3 It may be 0-60% by weight, 30-55% by weight, 30-50% by weight, 30-45% by weight, 35-70% by weight, 35-60% by weight, 35-55% by weight, 35-50% by weight or 35-45% by weight.

In this embodiment, the polymerizable compound preferably contains a polymerizable compound (X) having an element with an atomic number of 9 or greater. The polymerizable compound (X) may be a high-specific-gravity compound or a low-specific-gravity compound, and is preferably a high-specific-gravity compound.

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

The number of halogen group elements contained in one molecule of polymerizable compound (X) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. There is no particular upper limit to the number of halogen group elements contained in one molecule of polymerizable compound (X), and it may be, for example, 40 or less, preferably 30 or less. That is, the number of halogen group elements contained in one molecule of polymerizable compound (X) may be, for example, 1 to 40, 1 to 30, 2 to 40, or 2 to 30.

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. The polymerizable compound (X) having a cationically polymerizable functional group is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. The polymerizable compound (X) having a radically polymerizable functional group includes compounds having at least one radically polymerizable functional group selected from the group consisting of vinyl groups, (meth)acryloyl groups, allyl groups, vinyl ether groups, and vinyl ester groups, with compounds having a (meth)acryloyl group being preferred. The compound having a (meth)acryloyl group is preferably at least one selected from the group consisting of (meth)acrylates and (meth)acrylamides.

Specific examples of polymerizable compounds (X) having a cationically polymerizable functional group include halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether, brominated bisphenol A epoxy resins, brominated bisphenol F novolac epoxy resins, and brominated phenol novolac epoxy resins.

Specific examples of the polymerizable compound (X), namely, the polymerizable compound (X) having a radical polymerizable compound, include halophenyl (meth)acrylates such as fluorophenyl (meth)acrylate, trifluorophenyl (meth)acrylate, pentafluorophenyl (meth)acrylate, chlorophenyl (meth)acrylate, trichlorophenyl (meth)acrylate, pentachlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, and pentabromophenyl (meth)acrylate.

The content of the halogen group element in the polymerizable compound (X) is preferably 10 to 50 mass% based on the total element amount of the polymerizable compound. If it is 10 mass% or more, the moisture resistance of the cured product tends to be further improved, and if it is 50 mass% or less, the curability of the composition tends to be further improved.

The proportion of 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, even more preferably 50% by mass or more, and even more preferably 55% by mass or more. This tends to further improve the moisture resistance of the cured product. Furthermore, the proportion of polymerizable compound (X) in the polymerizable compound may be, for example, 100% by mass, but is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% by mass or less. This tends to further improve adhesion to glass substrates and the like, and further improve the reliability of the encapsulant. That is, the proportion of the polymerizable compound (X) in the polymerizable compounds is, for example, 30 to 100 mass%, 30 to 90 mass%, 30 to 85 mass%, 30 to 80 mass%, 30 to 75 mass%, 30 to 70 mass%, 30 to 65 mass%, 40 to 100 mass%, 40 to 90 mass%, 40 to 85 mass%, 40 to 80 mass%, 40 to 75 mass%, 40 to 70 mass%, 40 to 65 mass%, 45 to 100 mass%, 45 to 90 mass%, 45-85% by mass, 45-80% by mass, 45-75% by mass, 45-70% by mass, 45-65% by mass, 50-100% by mass, 50-90% by mass, 50-85% by mass, 50-80% by mass, 50-75% by mass , 50-70% by weight, 50-65% by weight, 55-100% by weight, 55-90% by weight, 55-85% by weight, 55-80% by weight, 55-75% by weight, 55-70% by weight or 55-65% by weight.

In this embodiment, the polymerizable compound may further contain a polymerizable compound other than polymerizable compound (X) (i.e., a polymerizable compound that does not have an element with an atomic number of 9 or higher) (hereinafter also referred to as polymerizable compound (X')).

The polymerizable compound (X') may be, for example, a compound having a polymerizable functional group that is copolymerizable with the polymerizable functional group of the polymerizable compound (X). The polymerizable compound (X') may be a high-specific gravity compound or a low-specific gravity compound.

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. The polymerizable compound (X') having a cationically polymerizable functional group is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. The polymerizable compound (X') having a radically polymerizable functional group includes compounds having at least one radically polymerizable functional group selected from the group consisting of vinyl groups, (meth)acryloyl groups, allyl groups, vinyl ether groups, and vinyl ester groups, with compounds having a (meth)acryloyl group being preferred. The compound having a (meth)acryloyl group is preferably at least one selected from the group consisting of (meth)acrylates and (meth)acrylamides.

When the polymerizable compound (X) has a cationically polymerizable functional group, the polymerizable compound (X') preferably has a cationically polymerizable functional group. The polymerizable compound (X') having a cationically polymerizable functional group is preferably at least one selected from the group consisting of epoxy compounds, oxetane compounds, and cationically polymerizable vinyl compounds.

Examples of epoxy compounds include alicyclic compounds having epoxy groups (alicyclic epoxy compounds), aromatic compounds having epoxy groups (aromatic epoxy compounds), and glycidyl ether compounds.

Examples of alicyclic epoxy compounds include compounds or derivatives thereof obtained by epoxidizing a compound having at least one cycloalkene ring (e.g., a cyclohexene ring, a cyclopentene ring, a pinene ring, etc.) with an appropriate oxidizing agent such as hydrogen peroxide or a peracid. Alicyclic epoxy compounds also include hydrogenated epoxy compounds obtained by hydrogenating aromatic epoxy compounds (e.g., bisphenol A epoxy compounds, bisphenol F epoxy compounds, etc.).

Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl(meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl(meth)acrylate), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A epoxy resin, and hydrogenated bisphenol F epoxy resin.

Among alicyclic epoxy compounds, alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure are preferred. Among alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, compounds represented by the following formula (A1-1) are preferred.

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

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 multiple of these are linked together.

X is preferably a linking group. The linking group is preferably a group having an ester bond. An example of a compound having a group having an ester bond as a linking group is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, even more preferably 300 or less, and even more preferably 100 to 280, in order to further improve the moisture resistance of the cured product and the storage stability of the composition. 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.

When the alicyclic epoxy compound has a molecular weight distribution, the number average molecular weight of the alicyclic epoxy compound is preferably within the above range. In this specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) under the following measurement conditions, expressed in terms of polystyrene.
Solvent (mobile phase): THF
Degassing device: ERMA ERC-3310
Pump: JASCO PU-980
・Flow rate: 1.0ml/min
Autosampler: Tosoh AS-8020
Column oven: Hitachi L-5030
・Set temperature: 40℃
Column configuration: Two TSKguard column MP (xL) 6.0 mm ID x 4.0 cm columns manufactured by Tosoh Corporation, and two TSK-GELMULTIPORE HXL-M 7.8 mm ID x 30.0 cm columns manufactured by Tosoh Corporation, for a total of four columns. Detector: RI L-3350 manufactured by Hitachi, Ltd.
Data processing: SIC480 data station

Aromatic epoxy compounds can be used in the form of monomers, oligomers, or polymers, and examples include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, biphenyl epoxy resins, naphthalene epoxy resins, fluorene epoxy resins, novolac phenol epoxy resins, cresol novolac epoxy resins, and modified versions of these.

Aromatic epoxy compounds having a bisphenol structure are preferred. Among aromatic epoxy compounds having a bisphenol structure, compounds represented by the following formula (A2-1) are preferred.

In formula (A2-1), n represents an integer of 0 to 30, and 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 may be 0.1 or greater.

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 may be the same or different, but are preferably the same.

It is preferable that the aromatic epoxy compound having a bisphenol structure is at least one selected from the group consisting of bisphenol A type epoxy resins and bisphenol F type epoxy resins.

The molecular weight of the aromatic epoxy compound is preferably 100 to 5,000, more preferably 150 to 1,000, and even more preferably 200 to 450, in order to further improve the moisture resistance of the cured product. That is, the molecular weight of the aromatic epoxy compound may be, for example, 100 to 5,000, 100 to 1,000, 100 to 450, 150 to 5,000, 150 to 1,000, 150 to 450, 200 to 5,000, 200 to 1,000, or 200 to 450.

When the aromatic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of the aromatic epoxy compound be within the above range. Note that, in this specification, the number average molecular weight refers to the polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.

Preferred glycidyl ether compounds are polyglycidyl ether compounds. Examples of polyglycidyl ether compounds include, but are not limited to, diglycidyl ethers of alkylene glycols (e.g., diglycidyl ethers of ethylene glycol, diglycidyl ethers of propylene glycol, diglycidyl ethers of 1,6-hexanediol, etc.), polyglycidyl ethers of polyhydric alcohols (e.g., di- or triglycidyl ethers of glycerin or its alkylene oxide adducts, etc.), and diglycidyl ethers of polyalkylene glycols (e.g., diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts, etc.). Examples of alkylene oxides include ethylene oxide and propylene oxide.

Cationically polymerizable vinyl compounds can be used as monomers, oligomers, or polymers. Examples of cationically polymerizable vinyl compounds include vinyl ether compounds, vinylamine compounds, and styrene.

Vinyl ether compounds include, but are not limited to, di- or trivinyl ether compounds such as ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, and trimethylolpropane trivinyl ether; and 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, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

Examples of oxetane compounds include, but are not limited to, 3-ethyl-3-hydroxymethyloxetane (such as Aron Oxetane OXT-101, a trade name of Toagosei Co., Ltd.), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (such as OXT-121), 3-ethyl-3-(phenoxymethyl)oxetane (such as OXT-211), di(1-ethyl-(3-oxetanyl))methyl ether (such as OXT-221), and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (such as OXT-212). An oxetane compound is a compound containing one or more oxetane rings in its molecule.

When the polymerizable compound (X) has a radically polymerizable functional group, the polymerizable compound (X') preferably has a radically polymerizable functional group. The polymerizable compound (X') having a radically polymerizable functional group is preferably 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, and a vinyl ester group, and more preferably a compound having a (meth)acryloyl group. The compound having a (meth)acryloyl group is more preferably at least one selected from the group consisting of (meth)acrylates and (meth)acrylamides.

Examples of (meth)acrylates include monofunctional (meth)acrylates such as ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, and ethoxylated-o-phenylphenol acrylate, and multifunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate and 1,12-dodecanediol di(meth)acrylate.

The polymerizable compound preferably contains a crosslinkable compound (Y) having two or more polymerizable functional groups. The crosslinkable compound (Y) may be a high-specific gravity compound or a low-specific gravity compound. The crosslinkable compound (Y) may also be a polymerizable compound (X) or a polymerizable compound (X').

Examples of the crosslinkable compound (Y) include the polymerizable compounds described above that have two or more polymerizable functional groups.

The proportion of the crosslinkable compound (Y) in the polymerizable compound is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. This improves the curability of the composition and tends to make it easier to obtain a cured product with higher strength. Furthermore, the proportion of the crosslinkable compound (Y) in the polymerizable compound is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. This improves adhesion to glass substrates and the like, allowing for the formation of a more reliable encapsulant. That is, the proportion of the crosslinkable 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.

From the viewpoint of improving the coatability of the composition of this embodiment and achieving excellent moldability of the cured product, the viscosity of the total mixture of polymerizable compounds at 80°C is preferably 500 mPa·s or more, more preferably 700 mPa·s or more, and even more preferably 1000 mPa·s or more. Furthermore, from the viewpoint of improving the dischargeability of the composition of this embodiment during coating and expanding the range of molding methods available, the viscosity of the total mixture of polymerizable compounds at 80°C is preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, and even more preferably 20,000 mPa·s or less. That is, the viscosity of the total mixture of polymerizable compounds at 80°C may be, for example, 500 to 30,000 mPa·s, 500 to 25,000 mPa·s, 500 to 20,000 mPa·s, 700 to 30,000 mPa·s, 700 to 25,000 mPa·s, 700 to 20,000 mPa·s, 1,000 to 30,000 mPa·s, 1,000 to 25,000 mPa·s, or 1,000 to 20,000 mPa·s.

In this embodiment, multiple polymerizable compounds described above may be combined so that the viscosity of the total mixture of polymerizable compounds is within the above range.

In this specification, the viscosity of the total mixture of polymerizable compounds at 80°C indicates the value measured using a cone rotor viscometer.

A photopolymerization initiator is preferred as the polymerization initiator. By using a photopolymerization initiator, the composition of this embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

The polymerization initiator may be at least one selected from the group consisting of cationic polymerization initiators and radical polymerization initiators, and is preferably at least one selected from the group consisting of photocationic polymerization initiators and photoradical polymerization initiators. The use of a cationic polymerization initiator enables the polymerization of polymerizable compounds having cationic polymerizable functional groups, while the use of a radical polymerization initiator enables the polymerization of polymerizable compounds having radical polymerizable functional groups.

The photocationic polymerization initiator is not particularly limited, and examples include arylsulfonium salt derivatives (e.g., Cyracure UVI-6990 and Cyracure UVI-6974 manufactured by The Dow Chemical Company; Adekaoptomer SP-150, Adekaoptomer SP-152, Adekaoptomer SP-170, and Adekaoptomer 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 Cibacur 1190 manufactured by Double Bond Corporation), aryl iodonium salt derivatives (e.g., Irgacure 250 manufactured by Ciba Specialty Chemicals; and RP-2074 manufactured by Rhodia Japan), allene-ion complex derivatives, diazonium salt derivatives, triazine initiators, and acid generators such as other halides.

Examples of the photocationic polymerization initiator include onium salts represented by formula (B-1).
[In formula (B-1),
A represents an element of group VIA to group VIIA with a valence of m,
m represents 1 or 2,
p represents 0 to 3;
R represents an organic group bonded to A;
D is the following formula (B-1-1):
(in formula (B-1-1), E represents a divalent group; G represents -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene or phenylene group having 1 to 3 carbon atoms (R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms); and a represents 0 to 5; a+1 E's and a G's may be the same or different from each other),
X ^- is the counter ion of the onium.

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)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, and 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium. -dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, and octadecylmethylphenacylsulfonium.

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, each of which may have a substituent. Examples of the substituent include at least one selected from the group consisting of alkyl groups, hydroxy groups, alkoxy groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, arylthiocarbonyl groups, acyloxy groups, arylthio groups, alkylthio groups, aryl groups, heterocyclic groups, aryloxy groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, alkyleneoxy groups, amino groups, cyano groups, nitro groups, and halogens.

The number of R is m+p(m-1)+1, and they may be the same or different. Two or more R may be bonded to each other directly or via -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group 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.

Aryl groups having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups, and condensed polycyclic aryl groups such as naphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, chrysenyl groups, naphthacenyl groups, benzanthracenyl groups, anthraquinolyl groups, fluorenyl groups, naphthoquinone groups, and anthraquinone groups.

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

In formula (B-1), p represents the number of repeating units of the [DA ⁺ R _m-1 ] bond, and is preferably an integer of 0 to 3.

The onium ion [A ⁺ ] in formula (B-1) is preferably sulfonium, iodonium, or selenium, and typical examples include the following.

Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxy ... bis(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-chlorophenyl)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)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio] triarylsulfoniums such as thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, 5-tolylthiaanthrenenium, 5-(4-ethoxyphenyl)thiaanthrenenium, and 5-(2,4,6-trimethylphenyl)thiaanthrenenium;
diarylsulfonium such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium;
Monoarylsulfonium compounds such as phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium;
trialkylsulfonium compounds such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium; and the like.

Among these onium ions, one or more of sulfonium ions and iodonium ions are preferred, with sulfonium ions being more preferred. Examples of sulfonium ions include triphenylsulfonium, tri-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)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, and 7-isopropyl-9-oxo-10-thia-9 , 10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenenium, 5-phenylthiaanthrenenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium are preferred.

In formula (B-1), X ⁻ is a counter ion. The number of counter ions per molecule is p+1. The counter ion is not particularly limited, but examples thereof include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds, and methide compounds. Examples of X ⁻ include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; sulfonate ions such as FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ and CF ₃ SO ₃ ⁻ ; sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; carbonate ions such as HCO ₃ ⁻ and CO ₃ ²⁻ ; phosphate ions such as H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ and PO ₄ ³⁻ ; fluorophosphate ions such as PF ₆ ⁻ , PF ₅ OH ⁻ and fluorinated alkyl fluorophosphate ions; BF ₄ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ and B(C ₆ H ₄ CF ₃ ) ₄ ^-, etc.; AlCl ₄ ^- , BiF ₆ ^-, etc. Other examples include fluoroantimonate ions such as SbF ₆ ^- and SbF ₅ OH ^- , and fluoroarsenate ions such as AsF ₆ ^- and AsF ₅ OH ^- .

Examples of the fluorinated alkylfluorophosphate ion include a fluorinated alkylfluorophosphate ion represented by formula (B-1-3) and the like.
[(Rf) _b PF _6-b ] ^- (B-1-3)

In formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is 1 to 5 and is preferably an integer. The b Rfs may be the same or different. The number b of Rfs is more preferably 2 to 4, and most preferably 2 to 3. That is, the number b of Rfs may be, for example, 1 to 5, 1 to 4, 1 to 3, 2 to 4, or 2 to 3.

In the fluorinated alkylfluorophosphate ion represented by formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, and more preferably having 1 to 4 carbon atoms. Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, _{cyclopentyl ,} and cyclohexyl. Specific examples of _{Rf include CF3, CF3CF2, (CF3)2CF , CF3CF2CF2 , CF3CF2CF2CF2 , ( CF3 ) 2CFCF2 , CF3CF2 ( CF3 ) CF} , and ( _CF3 ) _3C .

Specific examples of preferred fluorinated alkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF _{2 ) 2} PF ₄ ] ⁻ , [(CF ₃ ) ₂ CFCF _{2 )} ² PF ₄ ] ⁻ , [(CF _{3 ) 2} CFCF _{2 ) 3 PF 3 ]} ⁻ _, [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- and [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- .

The photocationic polymerization initiator may be dissolved in a solvent in advance to facilitate mixing with the polymerizable compound. Examples of solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.

As the photocationic polymerization initiator, at least one selected from the group consisting of triarylsulfonium salt hexafluoroantimonate represented by formula (B-2) and diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate represented by formula (B-3) is preferred, with triarylsulfonium salt hexafluoroantimonate being more preferred.

The photoradical polymerization initiator is not particularly limited, but may be
Benzophenone and its derivatives;
Benzil and its derivatives;
Anthraquinone and its derivatives;
benzoin-type photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzil dimethyl ketal;
Acetophenone-type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;
2-dimethylaminoethyl benzoate;
p-dimethylaminoethyl benzoate;
Diphenyl disulfide;
Thioxanthone and its derivatives;
camphorquinone-type photopolymerization initiators such as 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, and 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride;
α-aminoalkylphenone photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1;
acylphosphine oxide-type photopolymerization initiators such as benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiethoxyphenylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;
Phenyl-glyoxylic acid-methyl ester;
Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester;
Oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester; and the like.

The content of the polymerization initiator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the polymerizable compound. This further improves curability. Furthermore, the content of the polymerization initiator is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less, per 100 parts by mass of the polymerizable compound. This further improves adhesion to glass substrates and the like, allowing for the formation of a more reliable encapsulant. In other words, the content of the polymerization initiator may be, for example, 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, per 100 parts by mass of the polymerizable compound.

Inorganic fillers include oxides such as silica particles, glass filler, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconia, and zinc oxide; nitrides such as boron nitride, silicon nitride, and aluminum nitride; carbides such as silicon carbide; hydroxides such as aluminum hydroxide and magnesium hydroxide; metals and alloys such as copper, silver, gold, iron, aluminum, nickel, and titanium; carbon-based fillers such as diamond and carbon; calcium carbonate, barium sulfate, talc, and mica.

The inorganic filler may be surface-treated with a fatty acid, a silicone coupling agent, a titanate coupling agent, etc. One or more inorganic fillers may be used as needed.

The true specific gravity of the inorganic filler may be, for example, 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more. The true specific gravity of the inorganic filler may be, for example, 20.0 or less, preferably 8.0 or less, and more preferably 5.0 or less. The true specific gravity of the inorganic filler is the value measured according to ASTM D2840. That is, the true specific gravity of the inorganic filler may be, for example, 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.

The inorganic filler preferably contains at least one selected from the group consisting of silica, mica, kaolin, talc, and aluminum oxide, and more preferably contains talc.

The inorganic filler may be inorganic particles having an average particle size (hereinafter sometimes simply referred to as particle size or particle diameter). The average particle size of the inorganic particles is preferably 0.005 μm or more, more preferably 0.01 μm or more. The average particle size of the inorganic particles is preferably 50 μm or less, more preferably 30 μm or less. That is, the average particle size of the inorganic particles may be, for example, 0.005 to 50 μm, 0.005 to 30 μm, 0.01 to 50 μm, or 0.01 to 30 μm. The average particle size of the inorganic particles is the value measured by laser diffraction/scattering using a Microtrac particle size distribution device.

The content of the inorganic filler may 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, per 100 parts by mass of the polymerizable compound. Furthermore, the content of the inorganic filler may be, for example, 500 parts by mass or less, or may be 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, even more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of the polymerizable compound. That is, the content of the inorganic filler may 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.

The composition of this embodiment may further contain a photosensitizer. A photosensitizer is a compound that can absorb energy rays and efficiently generate reactive species from the polymerization initiator (e.g., cations generated from a photocationic polymerization initiator, or radicals generated from a photoradical polymerization initiator).

The photosensitizer is not particularly limited, and examples include benzophenone derivatives, phenothiazine derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, xanthone derivatives, thioxanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, and organic ruthenium complexes. Among these, phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one and anthracene derivatives such as 9,10-dibutoxyanthracene are preferred, with anthracene derivatives being more preferred. Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferred. The photosensitizers may be used singly or in combination of two or more.

When the composition of this embodiment contains a photosensitizer, the content of the photosensitizer may be, for example, 0.01 parts by mass or more, or 0.02 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. Furthermore, from the viewpoint of storage stability, the content of the photosensitizer may 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 may 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.

The composition of this embodiment may further contain a silane coupling agent. The incorporation of a silane coupling agent tends to further improve the adhesiveness and adhesive durability of the composition of this embodiment.

Examples of silane coupling agents include 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. Among these, one or more selected from the group consisting of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-(meth)acryloxypropyltrimethoxysilane are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred. One type of silane coupling agent may be used alone, or two or more types may be used in combination.

When the composition of this embodiment contains a silane coupling agent, the content of the silane coupling agent may be, for example, 0.1 parts by mass or more, and preferably 0.2 parts by mass or more, per 100 parts by mass of the polymerizable compound. Furthermore, the content of the silane coupling agent may be, for example, 10 parts by mass or less, and preferably 5 parts by mass or less, per 100 parts by mass of the polymerizable compound. That is, the content of the silane coupling agent may 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, per 100 parts by mass of the polymerizable compound.

The composition of this embodiment may further contain an antioxidant.

The composition of this embodiment may further contain resin particles. The inclusion of resin particles makes it easier to form a thick cured body. For this reason, compositions containing resin particles are more suitable as sealants for forming dams.

Any resin particles that do not dissolve in the composition and can maintain their shape can be used without any particular restrictions. Examples include polyethylene particles, polypropylene particles, cross-linked polymethyl(meth)acrylate particles, cross-linked polystyrene particles, and cross-linked polymethyl(meth)acrylate polystyrene copolymer particles. The resin particles are preferably at least one type selected from the group consisting of cross-linked polymethyl(meth)acrylate particles, cross-linked polystyrene particles, and cross-linked polymethyl(meth)acrylate polystyrene copolymer particles, and more preferably at least one type selected from the group consisting of cross-linked polymethyl(meth)acrylate particles and cross-linked polystyrene particles.

The average particle size 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. The average particle size of the resin particles may be, for example, 200 μm or less, preferably 100 μm or less. That is, the average particle size 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. In this specification, the average particle size of the resin particles refers to the volume-based average particle size measured using a Shimadzu SALD-2200 laser diffraction particle size analyzer.

The resin particles preferably have a standard deviation of 0.25 or less in particle volume distribution relative to particle size (μm) expressed logarithmically. This reduces variations in the thickness of the cured body due to variations in the particle size of the resin particles, allowing for more precise control of the dimensions of the cured body. The standard deviation is more preferably 0.2 or less, and even more preferably 0.1 or less. The standard deviation may be, for example, 0.001 or more, or 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.

When the composition of this 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, per 100 parts by mass of the polymerizable compound. Furthermore, 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 even more preferably 3 parts by mass or less, per 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, relative to 100 parts by mass of the polymerizable compound.

The composition of this embodiment may further contain other components in addition to those described above. Known additives used in the sealant field can be used without particular limitation as other components. Examples of other components include metal deactivators, fillers, stabilizers, neutralizers, lubricants, antibacterial agents, etc.

The viscosity of the composition of this embodiment at 25°C may 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, from the viewpoints of improving the coatability of the composition and providing excellent moldability of the cured product. Furthermore, the viscosity of the composition of this embodiment at 25°C may 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, from the viewpoints of improving the dischargeability of the composition when applied and providing a wider range of molding methods. That is, the viscosity of the composition of this embodiment at 25°C is, 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 The viscosity of the composition at 25°C may be 80,000 to 1,000,000 mPa·s, 80,000 to 950,000 mPa·s, 80,000 to 900,000 mPa·s, 80,000 to 850,000 mPa·s, 100,000 to 1,000,000 mPa·s, 100,000 to 950,000 mPa·s, 100,000 to 900,000 mPa·s, or 100,000 to 850,000 mPa·s. The viscosity of the composition at 25°C is a value measured using a cone rotor viscometer.

The type and content of each component of the composition of this embodiment may be appropriately adjusted so that the viscosity at 25°C falls within the above range.

The composition of this embodiment preferably has a ratio (η ₂ /η ₁ ) of the viscosity η ₂ at 25°C and 0.1 rpm to the viscosity η ₁ at 25°C and 1 rpm of 1.1 to 10.0. When the ratio (η ₂ /η ₁ ) is 1.1 or more, the coatability of the composition is further improved, and the moldability of the cured product tends to be more excellent. From the viewpoint of making this tendency more pronounced, the ratio (η ₂ /η ₁ ) is preferably 1.15 or more, and more preferably 1.2 or more. Furthermore, when the ratio (η ₂ /η ₁ ) is 10.0 or less, the dischargeability of the composition during coating tends to be further improved, and from the viewpoint of making this tendency more pronounced, the ratio (η ₂ /η ₁ ) is preferably 9.5 or less, and more preferably 9.0 or less. That is, the ratio (η ₂ /η ₁ ) 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. The viscosity η ₁ of the composition at 25°C and 1 rpm and the viscosity η ₂ of the composition at 25°C and 0.1 rpm are values measured using a cone rotor viscometer.

In the composition of this embodiment, the type and content of each component may be adjusted as appropriate so that the ratio (η ₂ /η ₁ ) falls within the above range.

The liquid density of the composition of this embodiment is preferably 1.3 to 4.0. The liquid density of the composition is preferably 1.4 or higher, more preferably 1.5 or higher. The liquid density of the composition is preferably 3.0 or lower, more preferably 2.5 or lower, and even more preferably 2.0 or lower. That is, the liquid density 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. The liquid density of the composition is the value measured using a 5 mL Gay-Lussac pycnometer in accordance with JIS-K-0061, 8.2.2.

The type and content of each component of the composition of this embodiment may be adjusted appropriately so that the liquid density falls within the above range.

The method for producing the composition of this embodiment is not particularly limited, and any method that thoroughly mixes the above-mentioned components may be used. Examples of mixing methods include a stirring method that utilizes the stirring force associated with propeller rotation, and a method that uses a conventional disperser such as a planetary mixer that revolves around its axis. These mixing methods are preferred because they are low-cost and allow for stable mixing.

By curing the composition of this embodiment, a cured product containing a polymer of the polymerizable compound and an inorganic filler can be obtained. This cured product has low moisture permeability and is suitable for use as a sealant (particularly a sealant for organic EL display elements).

The composition of this embodiment can be cured, for example, by irradiation with energy rays. Light sources used to cure the composition of this embodiment include, but are not limited to, halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, and light-emitting diodes (hereinafter referred to as LEDs). These light sources are preferred because they can efficiently irradiate energy rays corresponding to the reaction wavelength of each photopolymerization initiator.

The above light sources each have different radiation wavelengths and energy distributions. Therefore, the light source should be selected appropriately based on the reaction wavelength of the polymerization initiator. Natural light (sunlight) can also be used as a reaction initiation light source.

Irradiation from the above light source may be direct irradiation or focused irradiation using a reflecting mirror, fiber, etc. Irradiation may also be using a low wavelength cut filter, a heat ray cut filter, a cold mirror, etc.

When curing the composition of this embodiment, a post-heating treatment may be performed after light irradiation to accelerate curing. The post-heating temperature is preferably 150°C or less, and more preferably 100°C or less, to avoid any adverse effects on the organic EL display element. The post-heating temperature is preferably 40°C or more.

The composition of this embodiment can also be used as an adhesive. For example, the composition of this embodiment can be suitably used for bonding packages for organic EL display elements and the like.

A method for bonding two components using the composition of this embodiment includes, for example, the steps of applying the composition to the entire surface or a portion of a first component, irradiating the composition applied to the first component with light, and bonding the first component and the second component via the composition until the irradiated composition cures. This method allows the second component to be bonded to the first component without exposing it to light or heat. Therefore, the method is suitable for use in bonding a back panel to an organic EL display element.

A method for manufacturing an organic EL display device using the composition of this embodiment includes, for example, the steps of applying the composition to a rear panel, irradiating the composition applied to the rear panel with light, and bonding the rear panel and a substrate on which an organic EL display element is formed via the composition while blocking the light. This method allows the organic EL display element to be sealed without being exposed to light or heat.

In addition, a method for manufacturing an organic EL display device using the composition of this embodiment may include, for example, a manufacturing method including the steps of applying the composition to one substrate, bonding the one substrate to the other substrate via the composition, and irradiating the composition between the substrates with light to harden the composition.

The specific gravity of the cured product of the composition of this embodiment (hereinafter simply referred to as the cured product of this embodiment) is, for example, 1.35 or more. The specific gravity of the cured product of this embodiment is, for example, 19.0 or less. The specific gravity of the cured product is measured in accordance with JIS K7112 Method B using water at 23°C as the immersion liquid.

The composition of this embodiment may have the type and content of each component appropriately adjusted so that the specific gravity of the hardened body falls within the above range.

In the cured product of this embodiment, the glass transition temperature of the polymer of the polymerizable compound may be, for example, 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 85°C or higher.

In this specification, the glass transition temperature (Tg) of a polymer refers to a value determined from a dynamic viscoelasticity spectrum. In a dynamic viscoelasticity spectrum, stress and strain are applied to a polymer at a constant heating rate, and the temperature at which the loss tangent (hereinafter abbreviated as tan δ) peaks can be determined to be the glass transition temperature. If no tan δ peak appears when the polymer is heated from a sufficiently low temperature, such as -150°C, to a certain temperature (Ta°C), the glass transition temperature is considered to be below -150°C or above a certain temperature (Ta°C). However, since a cured product with a glass transition temperature below -150°C is not possible, it can be determined to be above a certain temperature (Ta°C).

The composition of this embodiment may have the type and content of each component appropriately adjusted so that the glass transition temperature of the polymer falls within the above range.

The cured body of this embodiment preferably has a crosslink density of 1.0×10 ⁻³ mol/cm ³ or more, and more preferably 2.0×10 ⁻³ mol/cm ³ or more. This is thought to result in a large number of bonding points in the cured body, which in turn suppresses micro-Brownian motion and further reduces moisture permeability. The crosslink density of the cured body may be, for example, 1.0 mol/cm ³ or less. This further suppresses a decrease in reliability due to the brittleness of the cured body. That is, the crosslink density of the cured body may be, for example, 1.0×10 ⁻³ to 1.0 mol/cm ³ , or 2.0×10 ⁻³ to 1.0 mol/cm ³ .

In this specification, the crosslink density of a cured body refers to a value determined from a dynamic viscoelasticity spectrum. Specifically, a 100 μm thick cured body is cut into a 5 mm wide x 25 mm long test piece. This test piece is subjected to dynamic viscoelasticity measurement under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and tensile mode, and the relationship between temperature and storage modulus (G') is determined. The crosslink density is calculated using the following formula, where T(K) is the temperature at Tg+40°C, G'T ₊₄₀ is the storage modulus (G') at T(K), R is the gas constant, and φ(=1) is the frontal modulus.
Crosslink density (ρ)=G'T ₊₄₀ /φRT

The composition of this embodiment may have the type and content of each component appropriately adjusted so that the crosslink density of the cured product falls within the above range.

The cured product of this embodiment preferably has an average free volume of 1 ^nm3 or less, preferably less than ¹ nm3, more preferably 0.5 ^nm3 or less, even more preferably 0.3 ^nm3 or less, even more preferably 0.1 ^nm3 or less, and even more preferably less than 0.1 ^nm3 .

Positron annihilation is a known method for determining the free volume of polymers (see Polymer, Vol. 42, December issue (1993)). Generally, when a positron (e ⁺ ) is incident on a polymer, the positron combines with an electron (e ^- ) to generate positronium (Ps). Positron annihilation is a method for determining the free volume of a polymer by measuring the lifetime (τ ₃ ) of orthopositronium (o-Ps, radius 0.1 nm, hereinafter also referred to as "o-Ps"), which accounts for three-quarters of the positronium (Ps), when it enters a pore in the polymer. The lifetime (τ ₃ ) of o-Ps is determined by the probability that a positron (e ⁺ ) of o-Ps overlaps with an electron (e ^- ) in the wall of a pore when it collides with the wall of a pore present in the polymer; the larger the pore in the polymer, the longer the lifetime (τ ₃ ) of o-Ps. A model for determining the rate of positron (e + ) annihilation, which is obtained by considering a vacancy as a spherical well potential of infinite height and assuming that there is an electron layer with a thickness ^ΔR on the wall of the vacancy and calculating the overlap between this electron layer and the wave function of o-Ps, fits well with the data obtained from actual experiments. Therefore, if the vacancy diameter R of the polymer is approximately 0.16 to 0.8 nm, the relationship between the lifetime τ ₃ of o-Ps and the vacancy diameter R, as expressed by the following formula (1), holds:
(In the above formula (1), _τ3 represents the measured lifetime of ortho-positronium (o-Ps), R represents the pore diameter of the polymer, and ΔR represents the wall thickness of the pore.)

That is, by determining the lifetime (τ ₃ ) of ortho-positronium (o-Ps) using positron annihilation, the pore diameter R of the polymer in the above formula (1) can be determined. Furthermore, since the pore volume (average free volume) = 4/3πR ³ , the average free volume of the polymer can be calculated from the determined value of the pore diameter R of the polymer.

The composition of this embodiment may have the type and content of each component appropriately adjusted so that the average free volume of the hardened body falls within the above range.

In the hardened body of this embodiment, it is preferable that the pore size of the hardened body is less than 20%.

The free volume analyzed by positron annihilation spectroscopy represents the region not occupied by the molecular chains that make up the porous substrate or electrolyte, and reflects the volume that arises near those molecular chains when the molecular chains that make up the substrate or electrolyte change. Specifically, the time from when a positron is incident on a sample until it annihilates is measured, and the free volume can be determined by non-destructively observing information about the size and number density of atomic vacancies and free volume from its annihilation lifetime.

A positron is the antiparticle of an electron; it is an elementary particle with the same mass as an electron but an opposite charge. In amorphous solids such as polymers, a positron can pair with an electron, forming a pair called a positronium. When a positronium annihilates, annihilation gamma rays are emitted in two directions. The lifetime of a positron can be measured by measuring the change in the intensity of these annihilation gamma rays over time.

Positronium exists in two types: parapositronium and orthopositronium. The average lifetime of orthopositronium is approximately 140 ns, but this is shortened to 1 ns to 5 ns when it undergoes a pick-off process in which it steals electrons from other electrons in the material. When orthopositronium exists in free volume space within a solid, there is a positive correlation between the size of that space and the lifetime of the orthopositronium, and information about the size of the vacancy can be obtained by measuring the lifetime due to orthopositronium pick-off annihilation.

Specifically, the positron lifetime is analyzed into three components using the nonlinear least squares method, and the annihilation lifetimes are designated _τ1 , _τ2 , and _τ3 in ascending order, and the corresponding intensities are designated _I1 , _I2 , and _I3 ( _I1 + _I2 + _I3 = 100%). The porosity of the polymer is defined by the following formula using the above _I1 , _I2 , and _I3 .
Porosity (%) = I ₁ / (I ₁ + I ₂ + I ₃ )

The composition of this embodiment may have the type and content of each component appropriately adjusted so that the porosity of the polymer falls within the above range.

The cured product of this embodiment preferably has a moisture permeability of 60 (g/m2·24h/100μm) or less, more preferably 55 (g/ ^m2 ·24h/100μm) or less, and even more preferably 50 (g/ ^m2 ·24h/100μm) or less, as measured in accordance with JIS Z 0208 at a temperature of ⁸⁵ °C and a relative humidity of 85%. The low moisture permeability significantly prevents the occurrence of dark spots due to moisture reaching the organic light-emitting material layer when used as a sealant for an organic EL display device. The moisture permeability can also be expressed as the moisture permeability (g/m2) at a thickness of 100μm, measured after exposure to an environment of 85°C and 85% RH for 24 hours in accordance with JIS Z 0208: ¹⁹⁷⁶ . The moisture permeability may be, for example, 0.01 (g/ ^m2 ·24h/100μm) or more, 0.1 (g/ ^m2 ·24h/100μm) or more, 1 (g/ ^m2 ·24h/100μm) or more, or 10 (g/ ^m2 ·24h/100μm) or more. That is, the moisture permeability is, for example, 0.01 to 60 (g/m ² ·24h/100μm), 0.01 to 55 (g/m ² ·24h/100μm), 0.01 to 50 (g/m ² ·24h/100μm), 0.1 to 60 (g/m ² ·24h/100μm), 0.1 to 55 (g/m ² ·24h/100μm), 0.1 to 50 (g/m ² ·24h/100μm), 1 to 60 (g/m ² ·24h/100μm), 1 to 55 (g/m ² ·24h/100μm), 1 to 50 (g/m ² ·24h/100μm), 10 to 60 (g/m ² ·24h/100μm), 10 to 55 (g/m ² ·24h/100μm), or 10 to 50 (g/m ² ·24h/100μm).

The above describes a preferred embodiment of the present invention, but the present invention is not limited to the above embodiment.

For example, the present invention may relate to a method for manufacturing an organic electroluminescent display device having a dam-fill sealing structure, which includes a step of applying and curing the above-mentioned composition to form a dam.

The present invention may also relate to an organic EL display device having a dam-fill sealing structure comprising a dam and a fill agent, in which case the dam may contain a cured product of the above-mentioned composition.

The dam-fill sealing structure may be a known dam-fill sealing structure, and the filler may be a known filler. Furthermore, the configuration of the organic EL display device other than the dam-fill sealing structure may be the same as that of known organic EL display devices. The present invention achieves sufficient moisture permeability compared to, for example, Patent Document 5.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, the examples were tested at 23°C and a relative humidity of 50% by weight.

The following compounds were used in the examples and comparative examples.

(A) Polymerizable Compound—High Specific Gravity Compound (Polymerizable Compound with Specific Gravity of 1.3 to 4.0)
(A-1) Dibromophenyl glycidyl ether ("BR-250" manufactured by Nippon Kayaku Co., Ltd., bromine content: 51% by mass) (maximum atomic number: 35, specific gravity: 1.8, number of polymerizable functional groups per molecule: 1, molecular weight: 308, bromine content: 50% by mass)
(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 per molecule: 1, bromine element content: 50% by mass)
(A-3) TBBPA epoxy resin (DIC Corporation "Epicron 152") (maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups per molecule: 2, molecular weight: 972, bromine element content: 48% by mass)
(A-4) Brominated bisphenol A epoxy resin ("SR-T1000" by Sakamoto Pharmaceutical Co., Ltd., average molecular weight 2000) (maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups per molecule: 2)
(A-5) 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxirane (Daikin Industries, Ltd. "C6 Epoxy") (maximum atomic number: 8, specific gravity: 1.5, number of polymerizable functional groups per molecule: 1, molecular weight: 376)
(A-6) Pentafluorophenyl acrylate (Tokyo Chemical Industry Co., Ltd., "Pentafluorophenyl acrylate") (maximum atomic number: 9, specific gravity: 1.5, number of polymerizable functional groups per molecule: 1)
(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 per molecule: 1)

(B) Polymerizable Compound - Low Specific Gravity Compound (Polymerizable Compound with Specific Gravity of Less than 1.3)
(B-1) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celloxide 2021P" manufactured by Daicel Chemical Industries, Ltd.) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups per molecule: 2, molecular weight: 252)
(B-2) Bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, molecular weight 360 to 390) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups per molecule: 2)
(B-3) Phenolic novolac epoxy resin (DIC's "EPICLON N-775") (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups per molecule: 2 or more, number average molecular weight: 800)
(B-4) Cyclohexanedimethanol divinyl ether ("CHDVE" manufactured by Nippon Carbide Corporation) (maximum atomic number: 8, specific gravity: 0.9, number of polymerizable functional groups per molecule: 1, molecular weight: 196)
(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 per molecule: 2)
(B-6) Lauryl acrylate ("LA" manufactured by Osaka Organic Chemicals) (maximum atomic number: 8, specific gravity: 1.1, number of polymerizable functional groups per molecule: 1)
(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 per molecule: 2)
(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 per molecule: 2)
(B-9) Hydrogenated 1,2-polybutadiene terminated with urethane (meth)acrylate ("TEAI-1000" manufactured by Nippon Soda Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.0, number of polymerizable functional groups per molecule: 2)

(C) The following was used as the polymerization initiator.
(C-1) Triarylsulfonium salt hexafluoroantimonate (ADEKA Corporation's "ADEKA Optomer SP-170", anion species is hexafluoroantimonate)
(C-2) Triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, "CPI-200K" manufactured by San-Apro Co., Ltd., anion species is a phosphorus compound)
(C-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("TPO" manufactured by BASF Japan Ltd.)
(C-4) 1-Hydroxycyclohexyl phenyl ketone, "I-184" manufactured by BASF Japan Ltd.

(D) The following was used as a photosensitizer.
(D-1) 9,10-dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Chemical Industries, Ltd.)

(E) The following was used as a silane coupling agent.
(E-1) γ-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicones Co., Ltd.)

(F) The following was used as the inorganic filler.
(F-1) Fine particle talc, particle size (d50): 4.5 μm, true specific gravity: 2.7 ("#5000PJ" manufactured by Matsumura Sangyo Co., Ltd.)
(F-2) Fine particle talc, particle size (d50): 15 μm, true specific gravity: 2.7 ("SC" manufactured by Matsumura Sangyo Co., Ltd.)
(F-3) Fine particle mica, particle size (d50): 3.0 μm, true specific gravity: 2.9 ("A-11" manufactured by Matsuo Sangyo Co., Ltd.)
(F-4) Fine particle kaolin, particle size (d50): 1.6 μm, true specific gravity: 2.6 ("Kaopolite 1147" manufactured by Hayashi Kasei Co., Ltd.)
(F-5) Fine particle silica, particle size (d50): 4.2 μm, true specific gravity: 1.9 ("FB-5SDX" manufactured by Denka Co., Ltd.)
(F-6) Fine particle aluminum oxide, particle size (d50): 4.0 μm, true specific gravity: 4.0 ("DAW-03" manufactured by Denka Co., Ltd.)
(F-7) Fine particle gold, particle size (d50): 4.0 μm, true specific gravity: 19.5 (Tokuriki Honten Co., Ltd. "TAU-200")

The following was used as the (G) resin particles.
(G-1) GS-210: Spherical cross-linked polystyrene particles ("GS-210" manufactured by Ganz Chemical Co., Ltd.) (average particle size: 20.0 μm, standard deviation: 0.06 μm)

The sealants of the examples and comparative examples were prepared by mixing the raw materials shown in Tables 1 to 3 in the composition ratios shown in Tables 1 to 3. The composition ratios are in parts by mass.

The sealants of the examples and comparative examples were subjected to the following measurements. The results are shown in Tables 1 to 3.

[Specific Gravity of Polymerizable Compound]
Measurements were carried out using a Herbert type pycnometer in accordance with JIS K0061.

[Liquid specific gravity]
Measurement was carried out using a 5 mL Gay-Lussac type pycnometer in accordance with 8.2.2 of JIS-K-0061.

[Light curing conditions]
To evaluate the curing properties and adhesiveness of the sealant, the sealant was cured under the following light irradiation conditions: The sealant was photocured using a UV curing device equipped with an electrodeless discharge metal halide lamp (manufactured by Fusion) at a wavelength of 365 nm with an integrated light dose of 4,000 mJ/ ^cm2 , and then post-heated in an oven at 100°C for 60 minutes to obtain a cured product.

[Specific gravity of hardened body]
A 0.1 mm thick sheet-like cured product was prepared under the above photocuring conditions, and the measurement was performed in accordance with JIS K7112 Method B. Water at a temperature of 23°C was used as the immersion liquid.

[Tg]
A 0.1 mm thick sheet-like cured product was prepared under the above photocuring conditions, and a 100 μm thick cured product was cut into a 5 mm wide x 25 mm long test piece. Dynamic viscoelasticity measurements were performed on these test pieces at a temperature range of −50°C to 200°C, a heating rate of 2°C/min, and in tensile mode. The peak top temperature of tan δ (loss tangent) measured in the dynamic viscoelasticity measurement was taken as the glass transition temperature (Tg) of the cured product.

[Crosslink density]
A 0.1 mm thick sheet-like cured product was prepared under the above photocuring conditions, and a 100 μm thick cured product was cut into a 5 mm wide x 25 mm long test piece. This test piece was subjected to dynamic viscoelasticity measurements at a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and tensile mode. The crosslink density was calculated using the following formula, where T(K) is the temperature at Tg+40°C, G'("ElasticModulus" in the table) is G' _T+40 , the gas constant is R, and the frontal modulus is φ (=1).
Crosslink density (ρ)=G'T ₊₄₀ /φRT

[Average particle size, standard deviation]
The average particle diameters (sometimes referred to as average particle diameters or particle diameters) of the inorganic filler and resin particles, and the standard deviations of the particle volume distributions relative to the particle diameters when the particle diameters (μm) are expressed in logarithmic terms (the above-mentioned "standard deviations") were measured using a laser diffraction particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation).

[Moisture permeability]
A 0.1 mm thick sheet of cured material was prepared under the above photocuring conditions, and the moisture permeability was measured in accordance with JIS ^Z0208 "Test method for moisture permeability of moisture-proof packaging materials (cup method)" using calcium chloride (anhydrous) as a moisture absorbent at an ambient temperature of 85°C and a relative humidity of 85%. The moisture permeability is preferably 50 g/(m²·24 hr) or less.

[Average free volume and porosity]
A 0.1 mm thick sheet-like cured product was prepared under the above photocuring conditions, and the 0.1 mm thick cured product was cut into a 10 mm wide x 10 mm long piece. Ten of these pieces were stacked and fixed together to form a test sample.
The radiation source was ²² NaCl, and the positron annihilation lifetime and relative intensity were measured under the following conditions.
Positron source: ²² NaCl (intensity 0.6MBq)
Gamma ray detector: barium fluoride scintillator and photomultiplier tube Instrument resolution: 250 ps
Measurement temperature: 25℃
Count: 1,000,000
Sample: Measurement was performed by sandwiching the positron source from both sides. The average free volume and porosity were calculated from the positron annihilation lifetime measured under the above measurement conditions.

[Tensile shear adhesive strength]
Two borosilicate glass test pieces (25 mm long x 25 mm wide x 2.0 mm thick, Tempax (registered trademark) glass) were bonded to each other with a sealant to a bonding area of 0.5 cm ² and a bonding thickness of 10 μm, and the sealant was cured under the above-mentioned photocuring conditions. After curing, the tensile shear bond strength (unit: MPa) of the test pieces bonded with the sealant was measured at a temperature of 23°C and a relative humidity of 50% at a pulling rate of 10 mm/min.

[Fabrication of Organic EL Element Substrate]
A glass substrate (25 mm long x 25 mm wide) with an ITO electrode was washed with acetone and isopropanol. The following compounds were then sequentially deposited by vacuum deposition to form thin films, yielding an organic EL device substrate consisting of an anode, a hole injection layer, a hole transport layer, an emitting layer, an electron injection layer, and a cathode. The composition of each layer is as follows:
Anode: ITO, anode film thickness 250 nm
Hole injection layer: copper phthalocyanine, thickness 30 nm
Hole transport layer: N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD) thickness 20 nm
Light-emitting layer: tris(8-hydroxyquinolinato)aluminum (metal complex material), light-emitting layer thickness 1000 Å
Electron injection layer: lithium fluoride, thickness 1 nm
Cathode: Aluminum, cathode film thickness 250 nm

[Fabrication of Organic EL Device]
The sealant was applied to a glass substrate in a rectangular shape (side length 20 mm, application width 0.6 mm, application height 0.1 mm) using a coating device under a nitrogen atmosphere, and the glass substrate and the organic EL element substrate were bonded together via the sealant so that the adhesive thickness was 10 μm. The sealant was then cured under the photocuring conditions described above, thereby producing an organic EL element.

[Evaluation of Organic EL]
〔initial〕
A voltage of 6 V was applied to the organic EL element immediately after fabrication, and the light-emitting state of the organic EL element was observed visually and under a microscope, and the diameter of the dark spot was measured.

[After high temperature and humidity test]
The organic EL element immediately after fabrication was exposed to conditions of 85°C and a relative humidity of 85% by mass for 300 hours, and then a voltage of 6 V was applied thereto, and the light-emitting state of the organic EL element was observed visually and with a microscope, and the diameter of the dark spot was measured.

The diameter of the dark spots is preferably 60 μm or less, more preferably 40 μm or less, and most preferably there are no dark spots.

Next, the types of 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 composition ratios are in parts by mass.

The sealants of the examples and comparative examples were subjected to the above and following measurements. The results are shown in Tables 4 to 6.

[Viscosity and thixotropy of the composition]
The viscosity was measured at 25°C and 1 rpm using a cone rotor viscometer (TV-22 model, manufactured by Toki Sangyo Co., Ltd.) and the ratio (η ₂ /η ₁ ) of the viscosity η ₂ at 25°C and 0.1 rpm to the viscosity η ₁ at 25°C and 1 rpm was measured to evaluate the thixotropy.

[Straight application]
The composition was filled into a 30 mL light-blocking syringe (trade name "UV Block Syringe," manufactured by Musashi Engineering Co., Ltd.), and applied to alkali-free glass using a dispenser (trade name "SHOT mini 1000," manufactured by Musashi Engineering Co., Ltd.) to a coating length of 30 mm ± 2 mm, a coating width of 0.6 mm ± 0.2 mm, and a coating height of 0.1 mm ± 0.05 mm. The composition was irradiated with light at a wavelength of 365 nm with an integrated light dose of 2,000 mJ/ ^cm2 , and then post-heated in an oven at 100°C for 60 minutes to obtain a cured product. The coating straightness was evaluated according to the following criteria.
Evaluation criteria AA: The coating width of the cured product is 0.4 mm or more, and the average standard deviation of the coating width is less than 0.040 mm.
A: The coating width of the cured product is 0.4 mm or more, and the average standard deviation of the coating width is 0.040 mm to 0.100 mm.
C: The coating width of the cured product is 0.4 mm or more, and the average standard deviation of the coating width is 0.100 mm or more.

[Specific Gravity of Polymerizable Compound]
Measurements were carried out using a Herbert type pycnometer in accordance with JIS K0061.

[Specific gravity of hardened body]
A 0.1 mm thick sheet-like cured product was prepared under the above photocuring conditions, and the measurement was performed in accordance with JIS K7112 Method B. Water at a temperature of 23°C was used as the immersion liquid.

Claims (33)

The polymerizable compound includes a polymerization initiator and an inorganic filler.
30% by mass or more and 90% by mass or less of the polymerizable compound is a polymerizable compound (X) having a specific gravity of 1.3 to 4.0 and containing a bromine element,
A sealant having a liquid specific gravity of 1.3 to 4.0 . When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to claim 1, wherein the specific gravity of the cured product is 1.35 to 19.0. When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to claim 1 or 2, wherein the polymer has a glass transition temperature of 85°C or higher. When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to any one of claims 1 to 3, wherein the cured product has a crosslink density of 1.5 x 10 ^-3 mol/cm ³ or more. The sealant according to any one of claims 1 to 4, 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. The sealant according to any one of claims 1 to 5, wherein the polymerizable compound contains a crosslinkable compound (Y) having two or more polymerizable functional groups. The sealant according to any one of claims 1 to 6, wherein the polymerizable compound contains at least one compound selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, vinyl ether compounds, and oxetane compounds. The sealant according to any one of claims 1 to 7, wherein the polymerizable compound has a radically polymerizable functional group. The sealant according to any one of claims 1 to 8, wherein the polymerization initiator is a photopolymerization initiator. The sealant according to any one of claims 1 to 9, wherein the polymerization initiator contains an onium salt. The sealant according to any one of claims 1 to 10, wherein the polymerization initiator is a radical polymerization initiator. The sealant according to any one of claims 1 to 11, wherein the true specific gravity of the inorganic filler is 1.5 to 5.0. The sealant according to any one of claims 1 to 12, wherein the inorganic filler comprises at least one selected from the group consisting of silica, mica, kaolin, talc, and aluminum oxide. The sealant according to any one of claims 1 to 13, wherein the inorganic filler comprises talc. The sealant according to any one of claims 1 to 14, wherein the inorganic filler contains inorganic particles having an average particle size of 0.01 to 30 μm. The sealant according to any one of claims 1 to 15, further comprising resin particles. The sealant according to claim 16, wherein the resin particles contain at least one selected from the group consisting of cross-linked polymethyl(meth)acrylate particles, cross-linked polystyrene particles, and cross-linked polymethyl(meth)acrylate polystyrene copolymer particles. The sealant according to claim 16 or 17, wherein the resin particles have an average particle size of 1 μm to 100 μm. The sealant according to any one of claims 16 to 18, wherein the standard deviation of the particle volume distribution relative to the particle diameter (μm) of the resin particles expressed in logarithm is 0.25 or less. The sealant according to any one of claims 16 to 19, wherein the content of the resin particles is 0.01 to 5 parts by mass per 100 parts by mass of the polymerizable compound. The sealant according to any one of claims 1 to 20, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass per 100 parts by mass of the polymerizable compound. The sealant according to any one of claims 1 to 21, wherein the content of the inorganic filler is 5 to 500 parts by mass per 100 parts by mass of the polymerizable compound. The sealant according to any one of claims 1 to 22, wherein the viscosity of the total mixture of polymerizable compounds at 80°C is 500 to 30,000 mPa·s. The sealant according to any one of claims 1 to 23, having a viscosity at 25°C of 50,000 to 1,000,000 mPa·s. The sealant according to any one of claims 1 to 24, wherein the ratio (η ₂ /η ₁ ) of the viscosity η ₂ at 25°C and 0.1 rpm to the viscosity η ₁ at 25°C and 1 rpm is 1.1 to 10.0. When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to any one of claims 1 to 25, wherein the cured product has an average free volume of 1 ^nm3 or less. When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to any one of claims 1 to 26, wherein the cured product has a porosity of less than 20%. When the sealant is cured to form a cured body containing a polymer of the polymerizable compound and the inorganic filler,
The sealant according to any one of claims 1 to 27, wherein the moisture permeability of the cured product measured in accordance with JIS Z0208 at a temperature of 85°C and a relative humidity of 85% is 50 (g/ ^m2 ·24h/100μm) or less. The sealant according to any one of claims 1 to 28, which is a sealant for an organic electroluminescence display element. The sealant according to any one of claims 1 to 29, which is a sealant for forming a dam. A cured body obtained by curing the sealant described in any one of claims 1 to 30. Applying and curing the sealant according to any one of claims 1 to 30 to form a dam.
A method for manufacturing an organic electroluminescent display device having a dam-fill sealing structure. a dam-fill sealing structure including a dam and a fill agent;
An organic electroluminescence display device, wherein the dam comprises a cured product of the sealant according to any one of claims 1 to 30.