KR20220164509A - Sealant, cured body, organic electroluminescent display, and manufacturing method of organic electroluminescent display - Google Patents

Abstract

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

Description

Sealant, cured body, organic electroluminescent display, and manufacturing method of organic electroluminescent display

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

Recently, research on organic optical devices using organic thin film elements such as organic electroluminescence (organic EL) display elements and organic thin film solar cell elements has been conducted. Organic thin-film elements are excellent in productivity because they can be simply manufactured by vacuum deposition or solution application.

An organic EL display element is a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into the organic light emitting material layer from one electrode and holes are injected from the other electrode at the same time, so electrons and holes are combined in the organic light emitting material layer to perform self-luminescence. Compared to a liquid crystal display element or the like that requires a backlight, it has advantages such as better visibility, more thinning possible, and direct current low voltage driving.

However, when the organic light emitting material layer or the electrode is exposed to the outside air, such an organic EL display element has a problem in that its light emitting property is rapidly deteriorated and its lifetime is shortened. Therefore, for the purpose of enhancing the stability and durability of the organic EL display element, a sealing technique for shielding the organic light emitting material layer or the electrode from moisture or oxygen in the atmosphere is indispensable.

For example, Patent Document 1 discloses a method of filling a photocurable sealant between substrates of an organic EL display element in a top emission type organic EL display element and the like, and irradiating light to seal it. In addition, Patent Documents 2 to 4 disclose techniques for preventing deterioration due to moisture by sealing an organic EL display element.

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 1000 ppm or less and a chlorine content of 1000 ppm or less. However, Patent Literature 5 has no description regarding the specific gravity of the polymerizable compound.

Patent Literature 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a photocationic polymerization initiator, and a plate-like particulate inorganic filler having a specific shape. However, in the composition described in Patent Document 6, sufficient moisture permeability was not obtained, and application to organic electroluminescence display elements was difficult. In addition, Patent Document 6 does not describe the specific gravity of the polymerizable compound.

Patent Document 7 contains a polyfunctional cationically polymerizable compound, an organized layered silicate and a curing agent, and the organized layered silicate is dispersed in the polyfunctional cationically polymerizable compound so that the content of the organized layered silicate is equal to the polyfunctional cationically polymerizable compound 100 A curable resin composition for sealing an organic electroluminescent display element having excellent transparency and barrier properties is disclosed, which is 20 to 250 parts by weight, based on parts by weight. There were cases where there was no In addition, Patent Document 7 has no description of the specific gravity of the polymerizable compound.

Patent Document 8 discloses an epoxy resin composition containing (a) an epoxy compound and (b) a compound having two or more reactive crosslinkable groups with the epoxy compound in a specific ratio, and having a refractive index of 1.6 or more, transparency and low moisture permeability. . However, in the resin composition described in Patent Literature 8, sufficient moisture permeability could not be obtained in some cases. In addition, Patent Document 8 does not describe the specific gravity of the polymerizable compound.

Patent Document 9 is a curable composition comprising an organic polymer (A) having a specific reactive silicon group and a polyoxyalkylene-based polymer (B) having a specific reactive silicon group, wherein the specific gravity of the curable composition is 0.9 or more and 1.3 or less. A curable composition is disclosed. However, Patent Document 9 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound.

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

Patent Document 11 discloses a polysiloxane copolymer having a specific gravity greater than about 1.0 and a refractive index suitable for restoring the refractive power of a natural crystalline lens as a specific polysiloxane copolymer having a functional acrylic group by photopolymerization. However, Patent Literature 11 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing of organic EL display elements.

Patent Document 12 includes an active energy ray-curable compound (A) having at least one ethylenically unsaturated double bond in one molecule, a photoradical polymerization initiator (C) and/or a photocationic polymerization initiator (D), and a resin composition Disclosed is an active energy ray-curable resin composition for balancing motor rotors having a specific gravity of 1.4 (25° C.) or more and a viscosity of 1,000 poise (25° C.) or less. However, in Patent Document 12, there is no description about lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, and no description about sealing of the organic EL display element.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2001-357973 [Patent Document 2] Japanese Unexamined Patent Publication No. 10-74583 [Patent Document 3] Japanese Unexamined Patent Publication No. 2001-307873 [Patent Document 4] Japanese Unexamined Patent Publication No. 2009-37812 [Patent Document 5] International Publication No. 2014/017524 [Patent Document 6] Japanese Unexamined Patent Publication No. 2006-291072 [Patent Document 7] International Publication No. 2015/129783 [Patent Document 8] Japanese Unexamined Patent Publication No. 2010-163566 [Patent Document 9] Japanese Unexamined Patent Publication No. 2010-163566 [Patent Document 10] Japanese Unexamined Patent Publication No. 2001-124903 [Patent Document 11] Japanese Unexamined Patent Publication No. 2002-527171 [Patent Document 12] Japanese Unexamined Patent Publication No. 08-109231

[0003] In recent years, the required properties of electronic devices have increased, and sealing materials capable of realizing higher reliability and durability for, for example, organic EL display elements have been demanded.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sealant capable of forming a sealant excellent in moisture resistance and adhesion to a glass substrate or the like. Another object of the present invention is to provide a cured product of the sealant, a method for manufacturing an organic electroluminescence display using the sealant, and an organic electroluminescence display having a sealant formed of the sealant.

That is, the present invention is as follows.

<1>

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

<2>

The sealing agent according to <1>, wherein the specific gravity of the cured product is 1.35 to 19.0 when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler.

<3>

The sealant according to <1> or <2>, wherein the polymer has a glass transition temperature of 85°C or higher when the sealant is cured to obtain a cured product containing the polymer of the polymerizable compound and the inorganic filler.

<4>

Any one of <1> to <3>, wherein the cured product has a crosslinking density of 1.5×10 ^-3 mol/cm 3 or more when the sealant is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler; The sealant described in one.

<5>

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

<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>

The sealant according to <6> or <7>, wherein the content of the halogen group element in the polymerizable compound (X) is 10 to 50% by mass with respect to the total amount of elements in the polymerizable compound.

<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>

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

<11>

The sealant according to any one of <1> to <10>, wherein the polymerizable compound has a radically polymerizable functional group.

<12>

The sealant according to any one of <1> to <11>, wherein the polymerization initiator is a photopolymerization initiator.

<13>

The sealant according to any one of <1> to <12>, wherein the polymerization initiator contains an onium salt.

<14>

The sealant according to any one of <1> to <12>, wherein the polymerization initiator is a radical polymerization initiator.

<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>

The sealant according to any one of <1> to <15>, wherein the inorganic filler contains at least one selected from the group consisting of silica, mica, kaolin, talc, and aluminum oxide.

<17>

The sealant according to any one of <1> to <16>, in which the inorganic filler contains talc.

<18>

The sealant according to any one of <1> to <17>, wherein the inorganic filler contains inorganic particles having an average particle diameter of 0.01 to 30 µm.

<19>

The sealant according to any one of <1> to <18>, further comprising resin particles.

<20>

The sealing agent according to <19>, wherein the resin particles contain at least one selected from the group consisting of crosslinked poly(methyl)acrylate particles, crosslinked polystyrene particles, and crosslinked poly(methyl)acrylate polystyrene copolymer particles.

<21>

The sealant according to <19> or <20>, wherein the resin particles have an average particle diameter of 1 μm to 100 μm.

<22>

The sealant according to any one of <19> to <21>, wherein the resin particle has a standard deviation of particle volume distribution with respect to the particle size when the particle size (μm) is expressed as a logarithm of 0.25 or less.

<23>

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 based on 100 parts by mass of the polymerizable compound.

<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 based on 100 parts by mass of the polymerizable compound.

<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 based on 100 parts by mass of the polymerizable compound.

<26>

The sealant according to any one of <1> to <25>, wherein the viscosity at 80°C of the mixture of the entire amount of the polymerizable compound is 500 to 30000 mPa·s.

<27>

The sealant according to any one of <1> to <26>, wherein the viscosity at 25°C is from 50000 to 1000000 mPa·s.

<28>

The sealing according to any one of <1> to <27>, wherein the ratio of the viscosity η ₂ at 25°C and 0.1 rpm to the viscosity η ₁ at 25°C and 1 rpm (η ₂ /η ₁ ) is 1.1 to 10.0. my.

<29>

The sealing agent according to any one of <1> to <28>, wherein the cured product has an average free volume of 1 nm ³ or less when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler.

<30>

The sealing agent according to any one of <1> to <29>, wherein the cured product has a porosity of less than 20% when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler.

<31>

When the sealant is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler, the cured product has a water vapor transmission rate of 50 (g /m ² ·24h/100 µm) or less, the sealing agent according to any one of <1> to <30>.

<32>

The sealant according to any one of <1> to <31>, which is a sealant for organic electroluminescence display elements.

<33>

The sealant according to any one of <1> to <32>, which is a sealant for forming a dam.

<34>

A cured product formed by curing the sealant according to any one of <1> to <33>.

<35>

A method of manufacturing an organic electroluminescent display device having a dam-fill sealing structure, comprising forming a dam by applying and curing the sealant according to any one of <1> to <33>.

<36>

An organic electroluminescent display device having a dam-fill sealing structure including a dam and a filler, wherein the dam includes a hardened body of the sealant according to any one of <1> to <33>.

According to the present invention, a sealing agent capable of forming a sealing material having excellent moisture resistance and adhesion to a glass substrate or the like is provided. In addition, according to the present invention, a cured product of the sealant, a method for manufacturing an organic electroluminescence display device using the sealant, and an organic electroluminescence display device having a sealant formed of the sealant are provided.

Hereinafter, preferred embodiments of the present invention will be described in detail.

The composition of this embodiment contains a polymeric 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.

According to the composition of this embodiment, it is possible to form a sealant excellent in moisture resistance and adhesion to a glass substrate or the like. Therefore, the composition of the present embodiment can be suitably used as a sealant (preferably a sealant for organic electroluminescent display elements). In addition, the composition of the present embodiment can be particularly suitably used as a sealant for forming a dam 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. A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that a polymeric compound has at least 1 sort(s) selected from the group which consists of a cationically polymerizable functional group and a radically polymerizable functional group. Examples of the polymerizable compound having a cationically polymerizable functional group include epoxy compounds (eg, glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (eg, vinyl ether compounds, etc.) and oxetane compounds. At least 1 sort(s) selected from the group which consists of is preferable. Examples of the polymerizable compound having a radically polymerizable functional group include compounds 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, , a compound having a (meth)acryloyl group is preferred. As a compound which has a (meth)acryloyl group, at least 1 sort(s) selected from the group which consists of (meth)acrylate and (meth)acrylamide is preferable.

A compound with a high specific gravity can be said to be a compound having a polymerizable functional group and having a specific gravity of 1.3 to 4.0. The specific gravity of the high specific gravity compound is preferably 1.4 or more, more preferably 1.5 or more. In addition, the specific gravity of the high specific gravity compound is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less. That is, the specific gravity of the high specific gravity compound is, 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 may be sufficient. In addition, the specific gravity of a compound with a high specific gravity shows the value measured based on JISK0061 using a Hubbard type pycnometer.

In this embodiment, the polymerizable compound may further contain a low specific gravity compound having a specific gravity of less than 1.3. A compound with a low specific gravity can be said to be a compound having a polymerizable functional group and having a specific gravity of less than 1.3. The specific gravity of the low specific gravity compound is preferably 0.7 or more, more preferably 0.8 or more, and may be 0.9 or more, 1.0 or more, or 1.1 or more. That is, the specific gravity of the low specific gravity compound may be, for example, 0.7 or more and less than 1.3, 0.8 or more and less than 1.3, 0.9 or more and less than 1.3, 1.0 or more and less than 1.3, or 1.1 or more and less than 1.3. In addition, the specific gravity of a compound with a low specific gravity shows the value measured based on JISK0061 using a Hubbard-type pycnometer.

The ratio of the high specific gravity compound 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, still more preferably is more than 55% by mass. As a result, the above-mentioned effect appears more remarkably. In addition, the ratio of the high specific gravity compound in the polymerizable compound may be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, still more preferably It is preferably 75% by mass or less, still 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% by mass, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 30 to 75% by mass, and 30 to 70% by mass. %, 30 to 65% by mass, 40 to 100% by mass, 40 to 90% by mass, 40 to 85% by mass, 40 to 80% by mass, 40 to 75% by mass, 40 to 70% by mass, 40 to 65% by mass, 45 to 100% by mass, 45 to 90% by mass, 45 to 85% by mass, 45 to 80% by mass, 45 to 75% by mass, 45 to 70% by mass, 45 to 65% by mass, 50 to 100% by mass, 50 to 90% by mass, 50 to 85% by mass, 50 to 80% by mass, 50 to 75% by mass, 50 to 70% by mass, 50 to 65% by mass, 55 to 100% by mass, 55 to 90% by mass, 55 to 85% by mass %, 55-80 mass %, 55-75 mass %, 55-70 mass %, or 55-65 mass % may be sufficient.

The ratio of the low specific gravity compound in the polymerizable compound may be, for example, 0 mass%, preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, still more preferably It is 25 mass % or more, More preferably, it is 30 mass % or more, Especially preferably, it is 35 mass % or more. Further, the ratio of the low specific gravity compound to the polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more. Preferably it is 45 mass % or less. As a result, the above-mentioned effect appears more remarkably.

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

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

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

As for the number of halogen group elements which polymeric compound (X) has in 1 molecule, 1 or more are preferable, 2 or more are more preferable, and 3 or more are still more preferable. The upper limit of the number of halogenated elements that the polymerizable compound (X) has in one molecule is not particularly limited, and may be, for example, 40 or less, preferably 30 or less. That is, the number of halogen group elements that the polymerizable compound (X) has in one molecule 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. As the polymerizable compound (X) having a cationically polymerizable functional group, epoxy compounds (eg, glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (eg, vinyl ether compounds, etc.) and jade At least one selected from the group consisting of cetane compounds is preferred. As the polymerizable compound (X) having a radically polymerizable functional group, a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, and a vinyl ester group. and a compound having a (meth)acryloyl group is preferable. As a compound which has a (meth)acryloyl group, at least 1 sort(s) selected from the group which consists of (meth)acrylate and (meth)acrylamide is preferable.

As the polymerizable compound (X) having a cationically polymerizable functional group, which is one of the specific examples of the polymerizable compound (X), halophenylglycidyl ethers such as bromophenylglycidyl ether and dibromophenylglycidyl ether; Brominated bisphenol A-type epoxy resins, brominated bisphenol F-type novolak-type epoxy resins, brominated phenol novolac-type epoxy resins, and the like are exemplified.

As the polymerizable compound (X) having a radical polymerizable compound, which is one of the specific examples of the polymerizable compound (X), fluorophenyl (meth) acrylate, trifluorophenyl (meth) acrylate, pentafluorophenyl (meth) )Acrylate, chlorophenyl (meth)acrylate, trichlorophenyl (meth)acrylate, pentachlorophenyl (meth)acrylate, bromophenyl (meth)acrylate, tribromophenyl (meth)acrylate, pentachlorophenyl (meth)acrylate Halophenyl (meth)acrylates, such as bromophenyl (meth)acrylate, etc. are mentioned.

As for content of the halogen group element in polymeric compound (X), 10-50 mass % is preferable with respect to the total amount of elements of a polymeric compound. When it is 10% by mass or more, the moisture-proof property of the cured product tends to be further improved, and when it is 50% by mass or less, the curability of the composition tends to be further improved.

The proportion of the polymerizable compound (X) in the polymerizable compound may be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more; More preferably, it is 55 mass % or more. Thereby, there exists a tendency for the moisture-proof property of a hardened|cured body to improve more. The proportion of the polymerizable compound (X) in the polymerizable compound may be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less. , It is still more preferably 75% by mass or less, still more preferably 70% by mass or less, and particularly preferably 65% by mass or less. Thereby, there is a tendency that the adhesion to the glass substrate or the like is further improved and the reliability of the sealing material is further improved. That is, the proportion of the polymerizable compound (X) in the polymerizable compound is, for example, 30 to 100 mass%, 30 to 90 mass%, 30 to 85 mass%, 30 to 80 mass%, 30 to 75 mass%, 30 - 70% by mass, 30 - 65% by mass, 40 - 100% by mass, 40 - 90% by mass, 40 - 85% by mass, 40 - 80% by mass, 40 - 75% by mass, 40 - 70% by mass, 40 - 65 % by mass, 45 to 100% by mass, 45 to 90% by mass, 45 to 85% by mass, 45 to 80% by mass, 45 to 75% by mass, 45 to 70% by mass, 45 to 65% by mass, 50 to 100% by mass %, 50 to 90% by mass, 50 to 85% by mass, 50 to 80% by mass, 50 to 75% by mass, 50 to 70% by mass, 50 to 65% by mass, 55 to 100% by mass, 55 to 90% by mass, 55-85 mass %, 55-80 mass %, 55-75 mass %, 55-70 mass %, or 55-65 mass % may be sufficient.

In the present embodiment, the polymerizable compound is also referred to as a polymerizable compound other than the polymerizable compound (X) (ie, a polymerizable compound having no element having an atomic number of 9 or more) (hereinafter, a polymerizable compound (X')). ) may be additionally included.

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

The polymerizable compound (X') preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group. As the polymerizable compound (X') having a cationically polymerizable functional group, epoxy compounds (eg, glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (eg, vinyl ether compounds, etc.) and At least one selected from the group consisting of oxetane compounds is preferred. As the polymerizable compound (X') having a radically polymerizable functional group, a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, and a vinyl ester group. are mentioned, and the compound which has a (meth)acryloyl group is preferable. As a compound which has a (meth)acryloyl group, at least 1 sort(s) selected from the group which consists of (meth)acrylate and (meth)acrylamide is preferable.

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

Examples of the epoxy compound include an alicyclic compound having an epoxy group (alicyclic epoxy compound), an aromatic compound having an epoxy group (aromatic epoxy compound), and a glycidyl ether compound.

As the alicyclic epoxy compound, for example, a compound having at least one cycloalkene ring (for example, a cyclohexene ring, a cyclopentene ring, a pinene ring, etc.) obtained by epoxidizing a compound having an appropriate oxidizing agent such as hydrogen peroxide or peracid. compounds or derivatives thereof. Moreover, as an alicyclic epoxy compound, the hydrogenation epoxy compound obtained by hydrogenating, for example, an aromatic epoxy compound (for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, etc.) is also mentioned.

As the alicyclic epoxy compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxycyclohexylalkyl (meth)acrylate (for example, 3,4-epoxy Cyclohexylmethyl (meth)acrylate, etc.), (3,3',4,4'-diepoxy)bicyclohexyl, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, etc. are mentioned.

Among the alicyclic epoxy compounds, an alicyclic epoxy compound having a 1,2-epoxycyclohexane structure is preferable. Among the alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, 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 a plurality of these are linked.

X is preferably a linking group. As the linking group, a group having an ester bond is preferable. Examples of the compound having a group having an ester bond as a linking group include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

The molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, still more preferably 300 or less, and 100 to 280 from the viewpoint of further improving the moisture resistance of the cured product and the storage stability of the composition. more preferable That is, the molecular weight of an alicyclic epoxy compound may be 100-450, 100-400, 100-300, or 100-280, for example.

When the alicyclic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of the alicyclic epoxy compound is within the above range. In addition, in this specification, a number average molecular weight represents a value in terms of polystyrene measured by gel permeation chromatography (GPC) under the following measurement conditions.

ㆍSolvent (mobile phase): THF

ㆍDeaerator: ERC-3310 manufactured by ERMA

ㆍPump: PU-980 manufactured by Japan Spectroscopy Co., Ltd.

ㆍFlow Rate: 1.0ml/min

ㆍAutosampler: AS-8020 manufactured by Tosoh Corporation

ㆍColumn oven: Hitachi L-5030

ㆍSet temperature: 4℃

ㆍColumn composition: TSK Guard Column MP(×L) 6.0mmID×4.0cm 2 units manufactured by Tosoh Corporation, and TSK-GELMULTIPORE HXL-M 7.8mmID×30.0cm 2 units manufactured by Tosoh Corporation, total 4 units

ㆍDetector: RI Hitachi L-3350

· Data Processing: SIC480 Data Station

Any of monomers, oligomers or polymers can be used as the aromatic epoxy compound, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, and fluorene type epoxy resins can be used. , novolac phenol type epoxy resins, cresol novolak type epoxy resins, and modified products thereof.

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

In formula (A2-1), n represents 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 more.

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 preferably the same.

It is preferable that the aromatic epoxy compound which has a bisphenol structure is at least 1 sort(s) selected from the group which consists of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.

The molecular weight of the aromatic epoxy compound is preferably from 100 to 5000, more preferably from 150 to 1000, still more preferably from 200 to 450, from the viewpoint that the moisture resistance of the cured product is further improved. That is, the molecular weight of the aromatic epoxy compound may be, for example, 100 to 5000, 100 to 1000, 100 to 450, 150 to 5000, 150 to 1000, 150 to 450, 200 to 5000, 200 to 1000, or 200 to 450.

When an aromatic epoxy compound has a molecular weight distribution, it is preferable that the number average molecular weight of an aromatic epoxy compound is the said range. In the present specification, the number average molecular weight represents a value in terms of polystyrene measured by gel permeation chromatography (GPC) under the above-described measurement conditions.

As the glycidyl ether compound, a polyglycidyl ether compound is preferred. The polyglycidyl ether compound is not particularly limited, but diglycidyl ether of alkylene glycol (eg, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, 1,6-hexanediol diglycidyl ether of polyhydric alcohol, etc.), polyglycidyl ether of polyhydric alcohol (e.g., di- or triglycidyl ether of glycerin or its alkylene oxide adduct, etc.), diglycidyl ether of polyalkylene glycol (eg, diglycidyl ether of polyethylene glycol or an alkylene oxide adduct thereof, diglycidyl ether of polypropylene glycol or an alkylene oxide adduct thereof, etc.). Here, as an alkylene oxide, ethylene oxide, a propylene oxide, etc. are mentioned.

Any of monomers, oligomers or polymers can be used for the cationically polymerizable vinyl compound. A vinyl ether compound, a vinylamine compound, styrene etc. are mentioned as a cationically polymerizable vinyl compound.

Although not particularly limited as the vinyl ether compound, 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 Di or trivinyl, such as glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylolpropane trivinyl ether, etc. Ether compounds, 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 Monovinyl ether compounds, such as propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether, etc. are mentioned.

Although it does not specifically limit as an oxetane compound, 3-ethyl-3-hydroxymethyl oxetane (trade name Aronoxetane OXT-101 manufactured by Toa Synthesis Co., Ltd., etc.), 1,4-bis[(3-ethyl-3- Oxetanyl) methoxymethyl] benzene (same as OXT-121, etc.), 3-ethyl-3- (phenoxymethyl) oxetane (same as OXT-211, etc.), di(1-ethyl-(3-oxetanyl) )) methyl ether (the same OXT-221 etc.), 3-ethyl-3-(2-ethylhexyloxymethyl) oxetane (the same OXT-212 etc.), etc. are mentioned. An oxetane compound refers to a compound having one or more oxetane rings in a molecule.

When the polymerizable compound (X) has a radically polymerizable functional group, the polymerizable compound (X') preferably has a radically polymerizable functional group. As the polymerizable compound (X') having a radically polymerizable functional group, a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth)acryloyl group, an allyl group, a vinyl ether group, and a vinyl ester group. This is preferable, and a compound having a (meth)acryloyl group is preferable. As a compound which has a (meth)acryloyl group, at least 1 sort(s) selected from the group which consists of (meth)acrylate and (meth)acrylamide is more preferable.

Examples of the (meth)acrylate include monofunctional (meth)acrylates such as ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, and ethoxylated o-phenylphenol acrylate, 1 and polyfunctional (meth)acrylates such as 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 compound with a high specific gravity or a compound with a low specific gravity. In addition, the crosslinkable compound (Y) may be a polymerizable compound (X) or a polymerizable compound (X').

Examples of the crosslinkable compound (Y) include those having two or more polymerizable functional groups among the polymerizable compounds described above.

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 still more preferably 40% by mass or more. As a result, the curability of the composition is further improved, and a cured product with higher strength tends to be easily obtained. Moreover, 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, still more preferably 80% by mass or less. As a result, adhesion to a glass substrate or the like is further improved, and a more reliable sealing material can be formed. That is, the ratio of the crosslinkable compound (Y) to the polymerizable compound is, 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 -80 mass %, 40-90 mass %, 40-85 mass %, or 40-80 mass % may be sufficient.

From the viewpoint that the coatability of the composition of the present embodiment is improved and the moldability of the cured body is excellent, the viscosity at 80 ° C. of the total amount of the polymerizable compound is preferably 500 mPa s or more, more preferably 700 mPa s or more, 1000 mPa·s or more is more preferable. Further, from the viewpoint of improving the ejection property during coating of the composition of the present embodiment and broadening the selection of molding methods, the viscosity of the entire mixture of polymerizable compounds at 80°C is preferably 30000 mPa s or less, and 25000 mPa *s or less is more preferable, and 20000 mPa*s or less is still more preferable. That is, the viscosity at 80 ° C. of the total amount of the mixture of polymerizable compounds is, for example, 500 to 30000 mPa s, 500 to 25000 mPa s, 500 to 20000 mPa s, 700 to 30000 mPa s, 700 to 25000 mPa s, 700 ~20000 mPa·s, 1000~30000 mPa·s, 1000~25000 mPa·s, or 1000~20000 mPa·s may be sufficient.

In this embodiment, you may combine plurality of the above-mentioned polymeric compounds so that the viscosity of the whole amount mixture of a polymeric compound may fall into the said range.

In addition, the viscosity at 80 degreeC of the whole amount mixture of polymeric compounds in this specification shows the value measured by the cone rotor type viscometer.

As the polymerization initiator, a photopolymerization initiator is preferable. By using a photoinitiator, the composition of the present 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, preferably at least one selected from the group consisting of photocationic polymerization initiators and photoradical polymerization initiators. By using a cationic polymerization initiator, polymerization of a polymerizable compound having a cationically polymerizable functional group becomes possible, and by using a radical polymerization initiator, polymerization of a polymerizable compound having a radically polymerizable functional group becomes possible.

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

As a photocationic polymerization initiator, the onium salt represented by Formula (B-1) is mentioned, for example.

[In Formula (B-1),

A represents an element of group VIA to group VIA with a valence m,

m represents 1-2,

p represents 0 to 3,

R represents an organic group bonded to A,

D is the following formula (B-1-1):

A divalent group represented by (in the formula (B-1-1), E represents a divalent group, and 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 is 0 to 10 5. A+1 piece of E and a piece of G may be the same or different, respectively), and X- is a counterion of onium.)

The onium ion of formula (B-1) is not particularly limited, and examples thereof include 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, and 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-trilsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di -p-tril)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tril Sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthrenium, diphenylphenacylsulfonium, 4-hydroxyphenylmethyl Benzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, octadecylmethylphenacylsulfonium, etc. are mentioned.

R is an organic group bonded to A; R represents, for example, an aryl group of 6 to 30 carbon atoms, a heterocyclic group of 4 to 30 carbon atoms, an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms, or an alkynyl group of 2 to 30 carbon atoms, these substituents You may have it. Examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, and an aryloxy group. , an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and at least one selected from the group consisting of a halogen.

The number of R's is m+p(m-1)+1, and may be the same as or different from each other. In addition, two or more R are directly or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR'-, -CO-, -COO-, -CONH-, carbon number 1 They may be bonded through three alkylene or phenylene groups 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.

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, chrysenyl groups, naphthacenyl groups, benzanthracenyl groups, anthraquinolyl groups, and flues. Condensed polycyclic aryl groups, such as an orenyl group, a naphthoquinone group, and an anthraquinone group, are mentioned.

The aryl group of 6 to 30 carbon atoms, the heterocyclic group of 4 to 30 carbon atoms, the alkyl group of 1 to 30 carbon atoms, the alkenyl group of 2 to 30 carbon atoms, or the alkynyl group of 2 to 30 carbon atoms may have at least one substituent. Examples of substituents include straight-chain alkyl groups having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and oxadecyl;

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;

Straight-chain or branched carbon atoms of 1 to 18, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy an alkoxy group of;

Straight chain of 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc. or a branched alkylcarbonyl group;

arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl;

methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as 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;

Acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetra straight or branched acyloxy groups having 2 to 19 carbon atoms, such as decylcarbonyloxy and octadecylcarbonyloxy;

Phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4 -Methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[ 4-(phenylthio)phenyl]phenylthio, 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) arylthio groups having 6 to 20 carbon atoms such as phenylthio, 4-(p-ethylbenzoyl)phenylthio, 4-(p-isopropylbenzoyl)phenylthio, and 4-(p-tert-butylbenzoyl)phenylthio;

Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decyl straight-chain or branched alkylthio groups having 1 to 18 carbon atoms such as thio and dodecylthio;

aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, and naphthyl;

thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quina zolinyl, carbazolyl, acridinyl, phenothiadinyl, phenazinyl, xandenyl, thianthrenyl, phenoxazinyl, phenoxathynyl, chromanyl, isochromanyl, dibenzothienyl, xanthenyl , Heterocyclic groups having 4 to 20 carbon atoms such as thioxanthonyl and dibenzofuranyl;

aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; Methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl straight-chain or branched alkyl sulfinyl groups having 1 to 18 carbon atoms such as pinyl and octylsulfinyl;

arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl;

Methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsul straight-chain or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as phonyl, tert-pentylsulfonyl, and octylsulfonyl;

arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl;

Formula (B-1-2):

Alkyleneoxy group represented by (Q represents a hydrogen atom or a methyl group, k represents an integer of 1 to 5);

unsubstituted amino group;

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

cyano group;

nitro group;

Halogens, such as fluorine, chlorine, bromine, and iodine, etc. are mentioned.

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.

Preferable examples of the onium ion [A ⁺ ] in the formula (B-1) are sulfonium, iodonium and selenium, but representative examples include the following.

As the sulfonium ion, triphenylsulfonium, tri-p-trilsulfonium, tri-o-trilsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium Phonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulphonium Phonium, 4-(p-trilthio)phenyldi-p-trilsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis( 4-Fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-trilsulfonium, bis[4-(diphenylsulphate) phonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sul phonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl Phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene -2-yldi-p-trilsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tril) alcohol Fonio] thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-trilsulfonium, 4-[ 4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-trilsulfonium, 4-[4-(benzoylphenylthio)] Phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaantrenium, 5-triylthiaantrenium, 5- (4-ethoxyphenyl) thiaantrenium, 5- (2 , 4,6-trimethylphenyl) triarylsulfoniums such as thiaanthrenium;

diaryl sulfoniums such as diphenylphenacylsulfonium, diphenyl 4-nitrophenacylsulfonium, diphenylbenzylsulfonium, and diphenylmethylsulfonium;

Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naph Tylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium monoarylsulfoniums such as phonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium;

and trialkylsulfoniums such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, and octadecylmethylphenacylsulfonium.

Among these onium ions, one or more of sulfonium ions and iodonium ions is preferred, and sulfonium ions are more preferred. As the sulfonium ion, 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, 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-tol Lylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrenium, 5-phenylthiaantrenium, diphenylphenacyl sulfonium, 4-hydride At least one of hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium and octadecylmethylphenacylsulfonium is preferred.

In formula (B-1), X ^- is a counter ion. Their number is p+1 per molecule. The counterion is not particularly limited, but examples thereof include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds, methide compounds, and the like. Examples of X ⁻ include halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ , and I − ; OH ^- ; ClO ₄ ^- ; sulfonic acid ions such as FSO ₃ ^- , ClSO ₃ ^- , CH ₃ SO ₃ ^- , C ₆ H ₅ SO ₃ ^- , CF ₃ SO ₃ ^- ; sulfuric acid ions such as HSO ₄ ^- and SO ₄ ^2- ; carbonic acid ions such as HCO ₃ ^- and CO ₃ ^2- ; phosphoric acid ions such as H ₂ PO ₄ ^- , HPO ₄ ² - and PO ₄ ^3- ; PF ₆ ^- , PF ₅ OH ^- , fluorophosphate ions such as fluorinated alkyl fluorophosphate ions; boric acid ions such as BF ₄ ^- , B(C ₆ F ₅ ) ⁴ - and B(C ₆ H ₄ CF ₃ ) ₄ ^- ; AlCl ₄ ^- ; BiF ₆ ^- and the like. In addition, fluoroantimonic acid ions such as SbF ₆ ^- and SbF ₅ OH ^- , and fluoroarsenic acid ions such as AsF ₆ ^- and AsF ₅ OH ^- may be mentioned.

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

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

In the formula (B-1-3), Rf represents an alkyl group substituted with a fluorine atom. The number b of Rf is 1 to 5, preferably an integer. The b pieces of Rf may be the same or different, respectively. As for the number b of Rf, 2-4 are more preferable, and 2-3 are the most preferable. That is, the number b of Rf 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, and preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of the alkyl group include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; Furthermore, cycloalkyl groups, such as a cyclopropyl, a cyclobutyl, a cyclopentyl, and a cyclohexyl, etc. are mentioned. Specific examples of Rf include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF , CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, (CF ₃ ) ₃ C, and the like.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ^- and [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- and the like.

The photocationic polymerization initiator may be previously dissolved in solvents in order 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, triarylsulfonium salt hexafluoroantimonate represented by formula (B-2) and diphenyl 4-thiophenoxyphenylsulfonium tris represented by formula (B-3) (pentafluoro At least one selected from the group consisting of ethyl) trifluorophosphate is preferable, and a triarylsulfonium salt hexafluoroantimonate is more preferable.

Although it does not specifically limit as an optical radical polymerization initiator,

benzophenone and its derivatives;

benzyl and its derivatives;

anthraquinones and their derivatives;

benzoin type photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyldimethyl ketal;

acetophenone-type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;

2-dimethylaminoethylbenzoate;

p-dimethylaminoethylbenzoate;

diphenyl disulfide;

thioxanthone and its derivatives;

Camphorquinone, 7,7-dimethyl-2,3-dioxicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxicyclo[2.2.1]heptane-1 -Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl ester, 7,7-dimethyl-2,3-dioxy Campaquinone-type photopolymerization initiators such as sobicyclo[2.2.1]heptane-1-carboxylic acid chloride;

2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone- α-aminoalkylphenone type photopolymerization initiators such as No. 1;

Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6 -acylphosphine oxide type photopolymerization initiators such as 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; etc. can be mentioned.

The content of the polymerization initiator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, with respect to 100 parts by mass of the polymerizable compound. Thereby, curability is further improved. The content of the polymerization initiator is preferably 5 parts by mass or less, and more preferably 3 parts by mass or less with respect to 100 parts by mass of the polymerizable compound. As a result, adhesion to a glass substrate or the like is further improved, and a more reliable sealing material can be formed. That is, 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 with respect to 100 parts by mass of the polymerizable compound.

As the inorganic filler, oxides such as silica particles, glass fillers, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconia and zinc oxide, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbonization such as silicon carbide, etc. Logistics, 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, mica etc. can be mentioned.

The inorganic filler may be surface-treated with a fatty acid, a silicone coupling agent, a titanate-based coupling agent, or the like. One type or two or more types of inorganic fillers can 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. In addition, 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. In addition, the true specific gravity of the inorganic filler represents a value measured by 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 includes at least one selected from the group consisting of silica, mica, kaolin, talc and aluminum oxide, and more preferably includes talc.

The inorganic filler may be an inorganic particle having an average particle diameter (hereinafter sometimes referred to simply as a particle diameter or a particle diameter). The average particle diameter of the inorganic particles is preferably 0.005 μm or more, and more preferably 0.01 μm or more. Moreover, 50 micrometers or less are preferable and, as for the average particle diameter of an inorganic particle, 30 micrometers or less are more preferable. That is, the average particle diameter 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. In addition, the average particle diameter of the inorganic particles represents a value measured by a laser diffraction/scattering method 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 with respect to 100 parts by mass of the polymerizable compound. The content of the inorganic filler may be, for example, 500 parts by mass or less, and may be 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, based on 100 parts by mass of the polymerizable compound. More preferably, it is 100 parts by mass or less, and still more preferably 50 parts by mass or less. That is, the content of the inorganic filler is, 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 100 parts by mass, based on 100 parts by mass of the polymerizable compound. -50 parts by mass, 10-500 parts by mass, 10-350 parts by mass, 10-300 parts by mass, 10-200 parts by mass, 10-100 parts by mass, 10-50 parts by mass, 15-500 parts by mass, 15-350 It may be 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.

The composition of this embodiment may further contain a photosensitizer. A photosensitizer refers to a compound capable of efficiently generating reactive species (eg, cations generated from a photocationic polymerization initiator and radicals generated from a photoradical polymerization initiator) from a polymerization initiator by absorbing energy rays.

The photosensitizer is not particularly limited, and examples thereof include benzophenone derivatives, phenothiazine derivatives, phenylketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, and 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, organic A ruthenium complex etc. are mentioned. 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, and anthracene derivatives are more preferred. Among the anthracene derivatives, 9,10-dibutoxyanthracene is preferred. A photosensitizer may be used individually by 1 type, and may be used in combination of 2 or more type.

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 with respect to 100 parts by mass of the polymerizable compound. In addition, the content of the photosensitizer may be, for example, 5 parts by mass or less, and preferably 3 parts by mass or less, with respect to 100 parts by mass of the polymerizable compound from the viewpoint of storage stability. 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 with respect to 100 parts by mass of the polymerizable compound.

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

Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, and γ-(methoxysilane). )Acrylicoxypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ- Mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyl dimethicone Toxysilane, γ-ureidopropyl triethoxysilane, etc. are mentioned. Among these, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-(meth)acryloxypropyl At least one selected from the group consisting of trimethoxysilane is preferred, and γ-glycidoxypropyl trimethoxysilane is more preferred. A silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition of the present embodiment contains a silane coupling agent, the content of the silane coupling agent may be, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, based on 100 parts by mass of the polymerizable compound. 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, based on 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 with respect to 100 parts by mass of the polymerizable compound.

The composition of this embodiment may further contain antioxidant.

The composition of this embodiment may further contain resin particles. Formation of a thick hardened body becomes easier by blending the resin particles. For this reason, a composition containing resin particles is more suitable as a sealant for forming a dam.

Resin particles that do not dissolve in the composition and can maintain their shape can be used without particular limitation, and examples include polyethylene particles, polypropylene particles, crosslinked poly(meth)acrylate particles, crosslinked polystyrene particles, and crosslinked poly(meth)acrylate particles. and methyl acrylate polystyrene copolymer particles. The resin particles are preferably at least one selected from the group consisting of crosslinked poly(meth)acrylate particles, crosslinked polystyrene particles, and crosslinked poly(meth)acrylate polystyrene copolymer particles, and crosslinked poly(meth)acrylate particles and crosslinked poly(meth)acrylate polystyrene particles It is more preferable that it is at least 1 sort(s) selected from the group which consists of polystyrene particles.

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

It is preferable that the resin particles have a standard deviation of the particle volume distribution with respect to the particle size when the particle size (μm) is expressed as a logarithm of 0.25 or less. As a result, variation in the thickness of the cured body caused by variation in particle diameter of the resin particles is suppressed, and the dimensions of the cured body can be controlled with higher precision. The standard deviation is more preferably 0.2 or less, and even more preferably 0.1 or less. In addition, the standard deviation may be, for example, 0.001 or more, or 0.005 or more. That is, the said standard deviation may be 0.001-0.25, 0.001-0.2, 0.001-0.1, 0.005-0.25, 0.005-0.2, or 0.05-0.1, for example.

When the composition of the present embodiment contains resin particles, the content of the resin particles may be, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.1 parts by mass with respect to 100 parts by mass of the polymerizable compound. more than the mass part. 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, still more preferably 3 parts by mass, based on 100 parts by mass of the polymerizable compound. below That is, the content of the resin particles is, 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, or 0.01 parts by mass with respect to 100 parts by mass of the polymerizable compound. 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 It may be part by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass.

The composition of this embodiment may further contain other components other than the above. As other components, known additives used in the sealant field may be used without particular limitation. Examples of other components include metal deactivators, fillers, stabilizers, neutralizers, lubricants, and antibacterial agents.

The viscosity at 25°C of the composition of the present embodiment may be, for example, 50000 mPa·s or more, preferably 70000 mPa·s or more, more preferably from the viewpoint of improving the coatability of the composition and excellent moldability of the cured body. is 80000 mPa·s or more, more preferably 100000 mPa·s or more. In addition, the viscosity of the composition of the present embodiment at 25°C may be, for example, 1,000,000 mPa·s or less, for example, from the viewpoint of improving the discharge property during application of the composition and broadening the selection of molding methods. 950000 mPa·s or less, more preferably 900000 mPa·s or less, still more preferably 850000 mPa·s or less. That is, the viscosity at 25°C of the composition of the present embodiment is, for example, 50000 to 1000000 mPa s, 50000 to 950000 mPa s, 50000 to 900000 mPa s, 50000 to 850000 mPa s, 70000 to 1000000 mPa s, 70000 to 950000 mPa · S, 70000 ~ 900000 MPA · S, 70000 ~ 850000MPA · S, 80000 ~ 10000MPA · S, 80000 ~ 950000MPA · S, 80000 ~ 900000 MPA · S, 80000 ~ 850000MPA · S , 100000 to 900000 mPa·s or 100000 to 850000 mPa·s may be sufficient. In addition, the viscosity at 25 degreeC of a composition shows the value measured with the conrotor type viscometer.

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

The composition of the present embodiment preferably has a ratio (η ₂ /η ₁ ) of viscosity η ₂ at 25°C and 0.1 rpm to 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 excellent. From the standpoint of this tendency being more remarkable, the ratio (η ₂ /η ₁ ) is preferably 1.15 or more, and more preferably 1.2 or more. In addition, when the ratio (η ₂ /η ₁ ) is 10.0 or less, the ejection property at the time of application of the composition tends to be further improved, and from the viewpoint of making this tendency more remarkable, the ratio (η ₂ /η ₁ ) is preferably 9.5 or less. , 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. do. In addition, the viscosity η ₁ of the composition at 25°C and 1 rpm and the viscosity η ₂ at 25°C and 0.1 rpm show values measured by a cone rotor viscometer.

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

As for the liquid specific gravity of the composition of this embodiment, 1.3-4.0 are preferable. The liquid specific gravity of the composition is preferably 1.4 or more, more preferably 1.5 or more. Further, the liquid specific gravity of the composition is preferably 3.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less. That is, the liquid specific gravity of the composition is, 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 may be sufficient. In addition, the liquid specific gravity of a composition shows the value measured based on 8.2.2 of JIS-K-0061 using a 5 mL crab rope type pycnometer.

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the liquid specific gravity falls within the above range.

The manufacturing method of the composition of this embodiment is not specifically limited, Any method in which each component mentioned above is sufficiently mixed is sufficient. As a mixing method, the stirring method using the stirring force accompanying rotation of a propeller, the method using a normal disperser, such as a planetary stirrer by rotation and revolution, etc. are mentioned, for example. These mixing methods are preferable in that stable mixing can be performed at low cost.

By curing the composition of the present embodiment, a cured product containing a polymer of a polymerizable compound and an inorganic filler can be obtained. The cured product has low moisture permeability and can be suitably used as a sealing material (particularly, a sealing material for organic EL display elements).

The composition of the present embodiment can be cured by, for example, irradiation with energy rays. Although the light source used for curing the composition of the present embodiment is not particularly limited, halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium or the like), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, and xenon lamps , xenon excimer lamps, xenon flash lamps, light emitting diodes (hereinafter referred to as LEDs), and the like. These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelength of each photopolymerization initiator.

Each of the light sources has a different radiation wavelength or energy distribution. Therefore, the light source is appropriately selected depending on the reaction wavelength of the polymerization initiator and the like. In addition, natural light (sunlight) can also be a reaction initiating light source.

Irradiation by the light source may be direct irradiation or condensed irradiation using a reflector, fiber, or the like. In addition, irradiation using a low wavelength cut filter, a hot wire cut filter, a cold mirror, or the like may be used.

When curing the composition of the present embodiment, post-heat treatment may be performed to promote curing after light irradiation. The temperature of post-heating is preferably 150°C or lower, and more preferably 100°C or lower, from the viewpoint of avoiding the influence on the organic EL display element. The temperature of post-heating is preferably 40°C or higher.

The composition of this embodiment can also be used as an adhesive agent. The composition of this embodiment can be suitably used for adhesion of packages, such as organic EL display elements, for example.

As a method of adhering two members using the composition of the present embodiment, for example, a step of applying the composition to the entire surface or part of the first member, a step of irradiating light to the composition applied on the first member, , a method including a step of adhering the first member and the second member through the composition until the composition irradiated with light is cured. According to this method, the second member can be bonded onto the first member without exposing it to light and heat. For this reason, the method can be suitably used for adhesion between the back plate and the organic EL display element.

As a method for manufacturing an organic EL display device using the composition of the present embodiment, for example, a step of applying the composition on a back plate, a step of irradiating light to the composition applied on the back plate, and blocking the light , a manufacturing method including a step of adhering the back plate and the substrate on which the organic EL display element is formed through the composition. According to this method, the organic EL display element can be sealed without exposing it to light and heat.

Further, as a method of manufacturing an organic EL display device using the composition of the present embodiment, for example, a step of applying the composition to one substrate, a step of adhering one substrate to the other substrate through the composition, and a substrate A manufacturing method including a step of curing the composition by irradiating the liver composition with light is also included.

The specific gravity of the cured body of the composition of the present embodiment (hereinafter, simply referred to as the cured body of the present embodiment) is, for example, 1.35 or more. In addition, the specific gravity of the hardened body of this embodiment is 19.0 or less, for example. In addition, the specific gravity of a hardened body shows the value measured using 23 degreeC water as an immersion liquid based on JIS K7112 B method.

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the specific gravity of the cured product falls within the above range.

In the cured product of the present embodiment, the glass transition temperature of the polymeric compound may be, for example, 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, still more preferably 85°C or higher. . .

In addition, in this specification, the glass transition temperature (Tg) of a polymer shows the value calculated|required from the dynamic-viscoelasticity spectrum. In the dynamic viscoelasticity spectrum, stress and strain are applied to the polymer at a constant heating rate, and the temperature at which the peak peak of the loss tangent (hereinafter abbreviated as tan δ) can be determined as the glass transition temperature. In addition, when the tan δ peak does not appear even when the temperature is raised from a sufficiently low temperature of about -150 ° C to a certain temperature (Ta ° C), the glass transition temperature is considered to be -150 ° C or lower or higher than a certain temperature (Ta ° C), but the glass transition Since a cured body having a temperature of -150°C or lower cannot be considered, it can be judged to be higher than a certain temperature (Ta°C).

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the glass transition temperature of the polymer falls within the above range.

The cured body of the present embodiment preferably has a crosslinking density of 1.0 × 10 ^-3 mol/cm 3 or more, and more preferably 2.0 × 10 ^-3 mol/cm 3 or more. As a result, since there are many bonding points in the cured body, it is thought that the micro Brownian motion is suppressed and the water vapor transmission rate is further reduced. In addition, the crosslinking density of the hardened body may be, for example, 1.0 mol/cm 3 or less. As a result, the decrease in reliability due to brittleness of the hardened body is further suppressed. That is, the crosslinking 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 addition, in this specification, the crosslinking density of a hardened|cured material represents the value calculated|required from the dynamic-viscoelasticity spectrum. Specifically, a cured body having a thickness of 100 μm is cut out into a width of 5 mm × length of 25 mm to obtain a test piece. A dynamic viscoelasticity measurement is performed on this test piece under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and a tensile mode, and the relationship between temperature and storage modulus (G') is determined. For the crosslinking density, the temperature of Tg + 40 ° C is T (K), the storage modulus (G ') at T (K ) is G' _{T + 40} , the gas constant is R, the front coefficient is φ (= 1), It is calculated with the following formula.

Crosslink density (ρ)=G' _T+40 /φRT

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the crosslinking density of the cured product falls within the above range.

The cured body of the present embodiment preferably has an average free volume of 1 nm ³ or less, preferably less than 1 nm ³ , more preferably 0.5 nm ³ or less, still more preferably 0.3 nm ³ or less, and still more preferably 0.1 nm ³ or less. It is preferable, and it is more preferable that it is less than 0.1 nm< ³ >.

As a method for obtaining the free volume of a polymer, a positron annihilation method is known (refer to Polymer 42, December issue (1993)). In general, when a positron (e+) is incident on a polymer, the positron combines with an electron (e-) to generate positronium (Ps). The positron annihilation method is o when orthopositronium (o-Ps, radius 0.1 nm, hereinafter also referred to as “o-Ps”), which accounts for 3/4 of this positronium (Ps), enters the vacancy of a polymer. -This is a method for obtaining the free volume of a polymer by measuring the lifetime (τ ₃ ) of Ps. The lifetime (τ ₃ ) of o-Ps is determined by the overlapping probability of positrons (e ⁺ ) of o-Ps and electrons (e ^- ) in the walls of vacancies when they collide with the walls of vacancies in the polymer. The larger the o-Ps, the longer the life (τ ₃ ). The rate of annihilation of positrons (e+) obtained by considering the void as a spherical well-type potential of infinite height and assuming that there is an electron layer of thickness ΔR on the wall of the void and calculating the superposition of this electron layer and the wave function of o-Ps The obtained model fits well with the experimental data. Therefore, if the pore diameter R of the polymer is about 0.16 to 0.8 nm, the relationship of the following formula (1) is established between the lifetime τ ₃ of o-Ps and the pore diameter R.

(In the above formula (1), τ3 represents the measured lifetime of orthopositronium (o-Ps), R represents the pore diameter of the polymer, and ΔR represents the wall thickness of the pore.)

That is, by using the positron annihilation method to find the lifetime (τ ₃ ) of orthopositronium (o-Ps), the pore diameter R of the polymer in the above formula (1) is obtained. In addition, since the void volume (average free volume) = 4/3πR ³ , the average free volume of the polymer can be calculated from the value of the calculated pore diameter R of the polymer.

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the average free volume of the cured product falls within the above range.

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

The free volume analyzed by the positron annihilation method represents the area not occupied by the molecular chains forming the porous substrate or the electrolyte, and reflects the volume generated in the vicinity of the molecular chains forming the substrate and the electrolyte when the molecular chains are changed. . Specifically, the free volume is obtained by measuring the time from when positrons enter a sample until they disappear, and nondestructively observing information about the size, number density, etc. of atomic vacancies and free volumes from the extinction lifetime. It is possible.

A positron is the antiparticle of an electron, and is a small particle with the same mass as the electron, but with an electric charge of the opposite sign. In amorphous solids such as polymers, positrons sometimes form pairs with electrons, and are referred to as positronium. When positronium annihilates, annihilating γ-rays are emitted in both directions. The lifetime of the positron is measured by measuring the time change of this extinct γ-ray intensity.

There are parapositronium and orthopositronium in positronium, and the average lifetime of orthopositronium is about 140ns, but it is shortened to 1ns to 5ns when it goes through a pick-off process that takes away other electrons in the material. When orthopositronium exists in a free volume space in a solid, the size of the space and the lifetime of orthopositronium are positively correlated, and by measuring the lifetime by pick-off extinction of orthopositronium, information of the pore size is obtained. can be obtained.

Specifically, the three-component analysis of the lifetime of the positron is performed by the nonlinear least squares method, and τ ₁ , τ ₂ , τ ₃ are determined from the smallest extinction lifetime, and the corresponding intensities are I ₁ , I ₂ , I ₃ (I ₁ + I ₂ + I ₃ = 100%). The porosity of the polymer is defined by the following equation using I ₁ , I ₂ , and I ₃ above.

Porosity (%) = I ₁ /(I ₁ + I ₂ + I ₃ )

In the composition of the present embodiment, the type and content of each component may be appropriately adjusted so that the porosity of the polymer falls within the above range.

The cured product of the present embodiment preferably has a water vapor transmission rate of 60 (g/m ² ·24h/100 µm) or less, measured under conditions of a temperature of 85°C and a relative humidity of 85% in accordance with JIS Z0208, and a value of 55 (g/m 2 · 24h/100 μm) or less is more preferable, and it is more preferable that it is 50 (g/m 2 24h/100 μm) or less. Due to its low moisture permeability, occurrence of dark spots due to the arrival of moisture to the organic light emitting material layer can be remarkably suppressed when used as a sealing material for organic EL display elements. In addition, the moisture permeability can also be referred to as the moisture permeability (g/m ² ) at a thickness of 100 μm measured by exposing for 24 hours in an environment of 85° C. and 85% RH in accordance with JIS Z 0208:1976. The moisture permeability may be, for example, 0.01 (g/m ² 24h/100 μm) or more, 0.1 (g/m ² 24h/100 μm) or more, or 1 (g/m ² 24h)/100 μm. ) or more, or 10 (g/m 2 24h/100 µm) or more. That is, the moisture permeability is, for example, 0.01 to 60 (g/m ² 24h/100 μm), 0.01 to 55 (g/m ² 24h/100 μm), 0.01 to 50 (g/m ² 24h/100 μm) ), 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) 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), It may be 10 to 55 (g/m ² ·24h/100 μm) or 10 to 50 (g/m ² ·24h/100 μm).

As mentioned above, although the preferable embodiment of this invention was described, this invention is not limited to the said embodiment.

For example, the present invention may also relate to a method for manufacturing an organic light emitting display device having a dam-fill sealing structure including a step of forming a dam by applying and curing the composition.

Further, the present invention may also relate to an organic EL display device having a dam-fill sealing structure including a dam and a filler, and in this case, the dam may contain a cured body of the above-described composition.

The dam/fill sealing structure may be a known dam/fill sealing structure, and the filler may be a known filler material. In addition, the structure other than the dam-fill sealing structure of an organic EL display device may be the same structure as that of a well-known organic EL display device. This invention can obtain sufficient moisture permeability than patent document 5, for example.

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples. The examples were tested at 23°C and 50% by mass relative humidity, unless otherwise noted.

In Examples and Comparative Examples, the following compounds were used.

(A) Polymeric compound - high specific gravity compound (polymerizable compound having specific gravity of 1.3 to 4.0)

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

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

(A-3) TBBPA epoxy resin (DIC company "Epicron 152") (maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups in one molecule: 2, molecular weight 972, content of bromine element: 48% by mass)

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

(A-5) 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxirane (Daikin Kogyo Co., Ltd. "C6 Epoxy") (max. Atomic number: 8, specific gravity: 1.5, number of polymerizable functional groups in one molecule: 1, molecular weight 376)

(A-6) pentafluorophenyl acrylate (“pentafluorophenyl acrylate” manufactured by Tokyo Chemical Industry Co., Ltd.) (maximum atomic number: 9, specific gravity: 1.5, number of polymerizable functional groups in one 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 in one molecule: One)

(B) polymerizable compound - low specific gravity compound (polymerizable compound having specific gravity less than 1.3)

(B-1) 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxide 2021P" manufactured by Daisel Chemical Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.2, 1 Number of polymerizable functional groups in the molecule: 2, molecular weight 252)

(B-2) bisphenol A type 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 in one molecule: 2)

(B-3) Phenol novolak-type epoxy resin (“EPICLON N-775” manufactured by DIC) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in one molecule: 2 or more, number average molecular weight 800)

(B-4) cyclohexane dimethanol divinyl ether ("CHDVE" manufactured by Nippon Carbide Co., Ltd.) (maximum atomic number: 8, specific gravity: 0.9, number of polymerizable functional groups in one molecule: 1, molecular weight 196)

(B-5) Polypropylene glycol diglycidyl ether (“EX-946L” manufactured by Nagase ChemteX Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.06, number of polymerizable functional groups in one molecule: 2)

(B-6) Lauryl acrylate (“LA” manufactured by Osaka Yugi Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.1, number of polymerizable functional groups in one 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 in one 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 in one molecule: 2)

(B-9) Hydrogenated product of 1,2-polybutadiene terminal urethane (meth)acrylate (“TEAI-1000” manufactured by Nippon Sotatsu Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.0, polymerizable functional group in one molecule) Number: 2)

(C) The following was used as a polymerization initiator.

(C-1) triarylsulfonium salt hexafluoroantimonate ("Adeka Optomer SP-170" manufactured by ADEKA, the anion species is hexafluoroantimonate)

(C-2) triarylsulfonium salt (diphenyl 4-thiophenoxyphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, "CPI-200K" manufactured by San Afro Co., Ltd., the anion species is a phosphorus compound)

(C-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("TPO" manufactured by BASF Japan)

(C-4) 1-hydroxycyclohexylphenyl ketone, manufactured by BASF Japan "I-184")

(D) The following was used as a photosensitizer.

(D-1) 9,10-dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Chemical Co., Ltd.)

(E) The following was used as a silane coupling agent.

(E-1) γ-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Silicon Co., Ltd.)

(F) The following was used as an inorganic filler.

(F-1) fine particle talc, particle diameter (d50): 4.5 µm, true specific gravity: 2.7 ("#5000PJ" manufactured by Matsumura Sangyo)

(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 diameter (d50): 4.0 µm, true specific gravity: 19.5 ("TAU-200" manufactured by Tokureki Honten Co., Ltd.)

(G) The following was used as resin particles.

(G-1) GS-210: spherical cross-linked polystyrene particles ("GS-210" manufactured by Gantzukasei Co., Ltd.) (average particle diameter: 20.0 µm, standard deviation: 0.06 µm)

The raw materials of the types shown in Tables 1 to 3 were mixed in the composition ratios shown in Tables 1 to 3 to prepare sealants of Examples and Comparative Examples. The unit of the composition ratio is a mass part.

Each of the following measurements was performed about the sealing agents of Examples and Comparative Examples. The results are shown in Tables 1 to 3.

[Specific gravity of polymerizable compound]

The measurement was performed based on JIS K0061 using a Hubbard type pycnometer.

[liquid specific gravity]

It was measured based on 8.2.2 of JIS-K-0061 using a 5 mL crab rope type pycnometer.

[Photocuring conditions]

When evaluating the cured product properties and adhesiveness of the sealant, the sealant was cured under the following light irradiation conditions. After photo-curing the sealant with a UV curing device (manufactured by Fusion Co., Ltd.) equipped with an electrodeless discharge metal halide lamp under conditions of a 365 nm wavelength and a cumulative light intensity of 4,000 mJ/cm 2 , heat treatment was performed after 60 minutes in an oven at 100 ° C. Thus, a cured product was obtained.

[Specific gravity of cured body]

A sheet-like cured body having a thickness of 0.1 mm was produced under the above photocuring conditions, and measured according to the JIS K7112B method. As an immersion liquid, water at a temperature of 23°C was used.

[Tg]

A sheet-shaped cured body having a thickness of 0.1 mm was prepared under the above photocuring conditions, and a cured body having a thickness of 100 μm was cut out into a width of 5 mm × length of 25 mm to obtain a test piece. Dynamic viscoelasticity was measured for this test piece under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and a tensile mode. The temperature at the top of the peak of tanδ (loss tangent) measured by the dynamic viscoelasticity measurement was taken as the glass transition temperature (Tg) of the cured product.

[Crosslink Density]

A sheet-shaped cured body having a thickness of 0.1 mm was produced under the above photocuring conditions, and a cured body having a thickness of 100 µm was cut out into a width of 5 mm × length of 25 mm to obtain a test piece. Dynamic viscoelasticity was measured for this test piece under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and a tensile mode. The crosslinking density is T(K) at the temperature of Tg+40°C, the storage modulus (G') at T(K) ("elastic modulus" in the table) is G' _T+40 , the gas constant is R, and the front modulus is φ ( = 1) and calculated with the following formula.

Crosslink density (ρ)=G' _T+40 /φRT

[Average particle size, standard deviation]

The average particle diameter of the inorganic filler and resin particles (sometimes referred to as the average particle diameter or particle diameter) and the standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter (μm) is expressed as a logarithm (the above-mentioned “standard deviation”) are It was measured with a laser diffraction type particle size distribution analyzer ("SALD-2200" manufactured by Shimadzu Corporation).

[Permeability]

A sheet-shaped cured body with a thickness of 0.1 mm was produced under the above photocuring conditions, and in accordance with JIS Z0208 "Test method for moisture permeability of moisture-proof packaging materials (cup method)", calcium chloride (anhydrous) was used as a moisture absorbent, and the ambient temperature was 85 ° C. and the relative humidity was 85%. was measured under the condition of As for moisture permeability, 50 g/(m<2>*24hr) or less is preferable.

[Mean free volume and porosity]

A sheet-shaped cured body having a thickness of 0.1 mm was prepared under the above photocuring conditions, and the cured body having a thickness of 0.1 mm was cut out to a width of 10 mm × length of 10 mm, and 10 sheets were overlapped and fixed as a test sample.

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

Positron source: ²² NaCl (strength 0.6 MBq)

Gamma ray detectors: barium fluoride scintillators and photomultipliers

Device resolution: 250 ps

Measurement temperature: 25℃

Counts: 1,000,000

Sample: Measured by inserting a positron source from both sides

Average free volume and porosity were calculated from the positron annihilation lifetime measured according to the above measurement conditions.

[Tensile shear adhesive strength]

Two borosilicate glass test pieces (length 25 mm × width 25 mm × thickness 2.0 mm, Tempex (registered trademark) glass) are used, and the borosilicate glass test pieces are bonded through a sealant so that the bonding area is 0.5 cm ² and the bonding thickness is 10 μm. And, the sealant was cured under the photocuring conditions. After curing, the tensile shear adhesive strength (unit: MPa) was measured at a tensile speed of 10 mm/min in an environment of a temperature of 23°C and a relative humidity of 50% using the test piece bonded with the sealant.

[Production of organic EL device substrate]

A glass substrate with an ITO electrode (25 mm long x 25 mm wide) was washed with acetone and isopropanol. Thereafter, the following compounds were sequentially deposited into thin films by vacuum evaporation to obtain an organic EL element substrate composed of anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode. The configuration of each layer is as follows.

ㆍAnode: ITO, anode film thickness 250nm

ㆍHole injection layer: copper phthalocyanine thickness 30nm

ㆍHole transport layer: N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD) thickness 20nm

ㆍEmitting layer: Tris(8-hydroxyquinolinate) aluminum (metal complex material), thickness of the light emitting layer is 1000 Å

ㆍElectron injection layer: lithium fluoride thickness 1nm

ㆍCathode: Aluminum, cathode film thickness 250nm

[Production of organic EL element]

The sealant is applied to the glass substrate in a square shape (side length: 20 mm, coating width: 0.6 mm, coating height: 0.1 mm) with a coating device under a nitrogen atmosphere, and the glass substrate and the organic EL element are interposed with the sealant so that the adhesive thickness is 10 μm. An organic EL device was fabricated by bonding the substrates and curing the encapsulant under the photocuring conditions.

[Evaluation of organic EL]

〔Early〕

A voltage of 6 V was applied to the organic EL element immediately after fabrication, and the light emission state of the organic EL element was observed with the naked eye and a microscope, and the diameter of the dark spot was measured.

[After high temperature and high humidity test]

After exposing the organic EL element immediately after fabrication for 300 hours under conditions of 85°C and 85% by mass relative humidity, a voltage of 6 V was applied, and the light emission state of the organic EL element was observed with the naked eye and a microscope to measure the diameter of the dark spot. did

Further, the diameter of the dark spot is preferably 60 μm or less, more preferably 40 μm or less, and most preferably no dark spot.

Next, the raw materials of the types shown in Tables 4 to 6 were mixed in the composition ratios shown in Tables 4 to 6 to prepare sealants of Examples and Comparative Examples. The unit of composition ratio is a mass part.

The above measurements and the following measurements were performed on the sealing agents of Examples and Comparative Examples. The results are shown in Tables 4 to 6.

[Viscosity and thixotropic properties of the composition]

The viscosity on condition of 25 degreeC and 1 rpm was measured with the cone rotor type viscometer ("TV-22 type|mold" by Toki Sangyo Co., Ltd.). Further, as evaluation of thixotropic properties, 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.

[Coating straightness]

A 30 mL light-shielding syringe (trade name "UV Block Syringe", manufactured by Musashi Engineering Co., Ltd.) was filled with the composition, and applied to alkali-free glass using a dispenser (trade name "SHOT mini 1000", manufactured by Musashi Engineering Co., Ltd.) The composition was applied so that the length was 30 mm ± 2 mm, the coating width was 0.6 mm ± 0.2 mm, and the coating height was 0.1 mm ± 0.05 mm. After light-irradiating the composition under conditions of a cumulative light quantity of 2,000 mJ/cm 2 with a wavelength of 365 nm, post-heating treatment was performed in an oven at 100° C. for 60 minutes to obtain a cured product. Coating straightness was evaluated according to the following criteria.

Evaluation standard

AA: The coating width of the cured body 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 body 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 body 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]

The measurement was performed based on JIS K0061 using a Hubbard type pycnometer.

[Specific gravity of cured body]

A sheet-shaped cured body having a thickness of 0.1 mm was produced under the above photocuring conditions, and measured according to the JIS K7112B method. As an immersion liquid, water at a temperature of 23°C was used.

Claims (36)

containing a polymerizable compound, a polymerization initiator and an inorganic filler;
A sealant containing a compound wherein the polymerizable compound has a specific gravity of 1.3 to 4.0. The method according to claim 1, when the sealing agent is cured to form a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant having a specific gravity of the cured body of 1.35 to 19.0. The method according to claim 1, when the sealing agent is cured to form a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant in which the glass transition temperature of the polymer is 85° C. or higher. The method according to any one of claims 1 to 3, when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant having a crosslinking density of the cured body of 1.5 × 10 ^{-3 mol/cm3} or more. The sealant according to any one of claims 1 to 4, wherein the polymerizable compound contains a polymerizable compound (X) having an element having an atomic number of 9 or higher. The sealant according to claim 5, wherein the polymerizable compound (X) contains a halogen group element. The sealant according to claim 6, wherein the polymerizable compound (X) contains at least one halogen group element selected from the group consisting of elemental fluorine and elemental bromine. The sealing agent according to claim 6 or 7, wherein the content of the halogen group element in the polymerizable compound (X) is 10 to 50% by mass with respect to the total amount of elements in the polymerizable compound. The sealant according to any one of claims 1 to 8, 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 9, wherein the polymerizable compound contains at least one 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 10, wherein the polymerizable compound has a radically polymerizable functional group. The sealant according to any one of claims 1 to 11, wherein the polymerization initiator is a photopolymerization initiator. The sealant according to any one of claims 1 to 12, wherein the polymerization initiator contains an onium salt. The sealant according to any one of claims 1 to 12, wherein the polymerization initiator is a radical polymerization initiator. The sealant according to any one of claims 1 to 14, wherein the inorganic filler has a true specific gravity of 1.5 to 5.0. The sealant according to any one of claims 1 to 15, wherein the inorganic filler contains 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 16, wherein the inorganic filler contains talc. The sealing agent according to any one of claims 1 to 17, wherein the inorganic filler contains inorganic particles having an average particle diameter of 0.01 to 30 µm. The sealant according to any one of claims 1 to 18, further comprising resin particles. The sealant according to claim 19, wherein the resin particles contain at least one selected from the group consisting of crosslinked poly(meth)acrylate particles, crosslinked polystyrene particles, and crosslinked poly(meth)methylacrylatepolystyrene copolymer particles. The sealant according to claim 19 or 20, wherein the resin particles have an average particle diameter of 1 μm to 100 μm. The sealant according to any one of claims 19 to 21, wherein a standard deviation of particle volume distribution with respect to the particle size when the particle size (μm) of the resin particles is expressed as a logarithm is 0.25 or less. The sealing agent according to any one of claims 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. The sealing agent according to any one of claims 1 to 23, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass based on 100 parts by mass of the polymerizable compound. The sealant according to any one of claims 1 to 24, wherein the content of the inorganic filler is 5 to 500 parts by mass based on 100 parts by mass of the polymerizable compound. The sealing agent according to any one of claims 1 to 25, wherein the viscosity at 80 ° C. of the mixture of the total amount of the polymerizable compound is 500 to 30000 mPa·s. The sealing agent according to any one of claims 1 to 26, which has a viscosity of 50000 to 1000000 mPa·s at 25°C. The sealant according to any one of claims 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 from 1.1 to 10.0. The method according to any one of claims 1 to 28, when the sealing agent is cured to form a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant in which the cured body has an average free volume of 1 nm ³ or less. The method according to any one of claims 1 to 29, when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant in which the porosity of the cured body is less than 20%. The method according to any one of claims 1 to 30, when the sealing agent is cured into a cured product containing the polymer of the polymerizable compound and the inorganic filler,
A sealant having a water vapor permeability of 50 (g/m ² ·24h/100 µm) or less as measured under conditions of a temperature of 85°C and a relative humidity of 85% in accordance with JIS Z0208 of the cured product. The sealant according to any one of claims 1 to 31, which is a sealant for organic electroluminescence display elements. The sealant according to any one of claims 1 to 32, which is a sealant for forming a dam. A cured product obtained by curing the sealant according to any one of claims 1 to 33. A step of forming a dam by applying and curing the sealant according to any one of claims 1 to 33,
Method for manufacturing an organic electroluminescent display device having a dam-fill sealing structure. It has a dam and fill sealing structure including a dam and a fill agent,
An organic electroluminescent display device in which the dam includes a cured product of the sealant according to any one of claims 1 to 33.