KR20230090319A - Sealant, cured body, organic electroluminescent display device and manufacturing method of organic electroluminescent display device - Google Patents

Abstract

A sealant comprising a polymerizable compound and a polymerization initiator having elements of groups 13 to 15 of the periodic table and elements of cycles 4 to 6, wherein the polymerizable compound contains a compound having a specific gravity of 1.3 to 4.0.

Description

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

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 light 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 devices are excellent in productivity because they can be easily manufactured by vacuum deposition, solution application, and the like.

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 this 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, the organic EL display device has a problem in that the light emitting property is rapidly deteriorated and the 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 the organic EL display element.

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.

[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

[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 are required.

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 having excellent moisture resistance.

That is, the present invention relates to the following.

<1>

A polymerizable compound and a polymerization initiator having elements of groups 13 to 15 of the periodic table and elements of the 4th to 6th cycles,

A sealant in which the polymerizable compound contains a compound having a specific gravity of 1.3 to 4.0.

<2>

When the sealing agent is cured to obtain a cured product containing the polymer of the polymerizable compound,

The sealing agent according to <1>, wherein the cured body has a specific gravity of 1.35 to 19.0.

<3>

The sealant according to <1> or <2>, wherein the polymerizable compound contains compound (X) having an element having an atomic number of 9 or more.

<4>

The sealing agent according to <3>, wherein the compound (X) contains a halogen group element.

<5>

The sealant according to <4>, wherein the compound (X) contains at least one halogen element selected from the group consisting of elemental fluorine and elemental bromine.

<6>

The sealing agent according to <4> or <5>, wherein the content of the halogen group element in the compound (X) is 10 to 50% by mass with respect to the total amount of elements in the polymerizable compound.

<7>

The sealant according to any one of <1> to <6>, wherein the polymerizable compound contains a crosslinkable compound (Y) having two or more polymerizable functional groups.

<8>

The sealant according to any one of <1> to <7>, 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.

<9>

The sealant according to any one of <1> to <8>, wherein the polymerization initiator is a cationic polymerization initiator.

<10>

The sealant according to any one of <1> to <9>, wherein the polymerization initiator contains an onium salt.

<11>

The sealant according to any one of <1> to <10>, wherein the polymerization initiator has an element of group 13 and periodic table 4 to 6.

<12>

The sealant according to any one of <1> to <11>, wherein the polymerization initiator contains gallium.

<13>

The sealing agent according to any one of <1> to <12>, further comprising an inorganic filler.

<14>

The sealant according to <13>, wherein the inorganic filler has a true specific gravity of 1.5 to 5.0.

<15>

The sealant according to <13> or <14>, wherein the inorganic filler is an electrical insulating inorganic filler.

<16>

The sealant according to any one of <13> 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 <13> to <16>, wherein the content of the inorganic filler is 5 to 500 parts by mass based on 100 parts by mass of the polymerizable compound.

<18>

The sealant according to any one of <1> to <17>, further comprising resin particles.

<19>

The sealing agent according to <18>, 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.

<20>

The sealant according to <18> or <19>, wherein the resin particles have an average particle diameter of 1 μm to 100 μm.

<21>

The sealant according to any one of <18> to <20>, wherein the resin particle has a standard deviation of the particle volume distribution relative to the particle size when expressed as a logarithmic value of 0.25 or less.

<22>

The sealant according to any one of <18> to <21>, 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.

<23>

The sealant according to any one of <1> to <22>, 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.

<24>

When the sealing agent is cured to obtain a cured product containing the polymer of the polymerizable compound,

The sealant according to any one of <1> to <23>, wherein the glass transition temperature of the polymer is 85°C or higher.

<25>

When the sealing agent is cured to obtain a cured product containing the polymer of the polymerizable compound,

The sealing agent according to any one of <1> to <24>, wherein the cured product has a crosslinking density of 1.5×10 ^-3 mol/cm 3 or more.

<26>

When the sealing agent is cured to obtain a cured product containing the polymer of the polymerizable compound,

According to JIS Z0208, the cured product has a water vapor transmission rate of 50 (g/m ² 24h/100 μm) or less measured under conditions of a temperature of 85° C. and a relative humidity of 85% according to any one of <1> to <25>. sealant.

<27>

The sealant according to any one of <1> to <26>, which is a sealant for organic electroluminescence display elements.

<28>

A cured product formed by curing the sealant according to any one of <1> to <27>.

<29>

Including a step of applying and curing the sealant according to any one of <1> to <27> to form a pill,

Method for manufacturing an organic electroluminescent display device having a dam-fill sealing structure.

<30>

Including a step of forming a dam by applying and curing the sealant according to any one of <1> to <27>;

Method for manufacturing an organic electroluminescent display device having a dam-fill sealing structure.

<31>

It has a dam-fill sealing structure including a dam and a fill,

An organic electroluminescent display device in which at least one of the dam and the fill contains a cured product of the sealant according to any one of <1> to <27>.

According to the present invention, a sealant capable of forming a sealant having excellent moisture resistance is provided.

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

The composition of the present embodiment contains a polymerizable compound and a polymerization initiator having elements of groups 13 to 15 and periodic table 4 to 6. In the present embodiment, the polymerizable compound contains a compound having a specific gravity of 1.3 to 4.0 (high specific gravity compound).

According to the composition of this embodiment, the sealing material excellent in moisture-proof property can be formed. Therefore, the composition of the present embodiment can be suitably used as a sealant (preferably a sealant for organic electroluminescence display elements). In addition, the composition of the present embodiment can be particularly preferably used as a sealant (sealant for dam formation or sealant for fill formation) 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, vinylether 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 may 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 the Herbert type pycnometer. In addition, if the specific gravity is less than 1.3, the above effect cannot be sufficiently obtained. In addition, a polymerizable compound having a specific gravity of 4.0 or more is difficult to obtain and is not economical.

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 low specific gravity compound shows the value measured based on JISK0061 using the Herbert 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 55% by mass or more. As a result, the above-mentioned effect is more remarkably exhibited. 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, 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, 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 mass%, 45 to 90 mass%, 45 to 85 mass%, 45 to 80 mass%, 45 to 75 mass%, 45 to 70 mass%, 45 to 65 mass%, 50 to 100 mass%, 50 to 90% by mass, 50 to 85% by mass, 50 to 80% by mass, 50 to 75% by mass, 50 to 70% by mass, 50 to 65% by mass, 55 to 100% by mass, 55 to 90% by mass, 55 to 85% by mass %, 55 to 80% by mass, 55 to 75% by mass, 55 to 70% by mass, or 55 to 65% by mass 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 25% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more. Further, the ratio of the low specific gravity compound in the polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, even more preferably 50% by mass or less, and even more. Preferably it is 45 mass % or less. Thereby, the said 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, 2 to 30, 3 to 40, or 3 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, aromatic 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. 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 novolac-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 polymerizable 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. , 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 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, 55-85 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 a polymerizable compound other than the polymerizable compound (X) (that is, a polymerizable compound having no element having an atomic number of 9 or more) (hereinafter also referred to as polymerizable compound (X').) may contain more.

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 obtained by epoxidizing a compound having at least one cycloalkene ring (for example, a cyclohexene ring, a cyclopentene ring, a pinene ring, etc.) with an appropriate oxidizing agent such as hydrogen peroxide or peracid. 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 preferred. 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 (molecular weight: 252).

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 from the viewpoint of further improving the moisture resistance of the cured product and the storage stability of the composition, 100 to 280 more preferable That is, the molecular weight of the alicyclic epoxy compound may be 100 to 450, 100 to 400, 100 to 300 or 100 to 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 this specification, the 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: L-5030 manufactured by Hitachi

ㆍSet temperature: 40℃

ㆍColumn configuration: TSK guardcolumn 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

ㆍData 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 (for example, di- or triglycidyl ether of glycerin or its alkylene oxide adduct, etc.), diglycidyl ether of polyalkylene glycol (For example, 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, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol di Di- or trivinyl ether compounds such as vinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane trivinyl ether, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl mono Vinyl ether, 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, octadecyl vinyl ether, etc. are mentioned.

Although it does not specifically limit as an oxetane compound, 3-ethyl-3-hydroxymethyl oxetane (trade name Aaronoxetane 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 proportion of the crosslinkable compound (Y) in 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, It may be 35 to 80% by mass, 40 to 90% by mass, 40 to 85% by mass, or 40 to 80% by mass.

From the viewpoint of improved coatability of the composition of the present embodiment and excellent moldability of a cured product, the viscosity at 80°C of the whole mixture of polymerizable compounds is preferably 500 mPa·s or more, more preferably 700 mPa·s or more, and 1000 mPa · s or more is more preferable. Further, from the viewpoint of improving the ejection properties 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 500 to 30000 mPa s, 500 to 25000 mPa s, 500 to 20000 mPa s, 700 to 30000 mPa s, 700 to 25000 mPa s, 700 to 20000 mPa s , 1000 to 30000 mPa·s, 1000 to 25000 mPa·s, or 1000 to 20000 mPa·s may be sufficient.

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

In addition, in this specification, the viscosity at 80 degreeC of the whole amount mixture of a polymeric compound shows the value measured with the conrotor type viscometer.

In this embodiment, the polymerization initiator has elements (M) of groups 13 to 15 of the periodic table and of the 4th to 6th periods. Examples of the element (M) include Ga (gallium), In (indium), Tl (thallium), Ge (germanium), Sn (tin), Pb (lead), As (arsenic), Sb (antimony), Bi ( bismuth).

In the present embodiment, by using a polymerization initiator having elements (M) of groups 13 to 15 of the periodic table and elements (M) of the 4th to 6th cycles as the polymerization initiator, the crosslinking density is obtained from a polymerizable compound containing a compound with a high specific gravity. is high, and a cured product having excellent moisture resistance and adhesion to a glass substrate or the like is formed.

In this embodiment, when the polymerization initiator has the element (M), the molecular radius of the active species derived from the polymerization initiator increases (namely, the charge density decreases), and it is considered that the nucleophilic property decreases and the polymerizability increases. For this reason, it is thought that the crosslinking density of the hardened|cured material of a polymeric compound becomes high, and it is compatible with excellent moisture-proof property and adhesiveness with a glass substrate etc.

The element (M) is preferably one or more elements of group 13 and group 15 of the periodic table, more preferably an element of group 13 of the periodic table, from the viewpoint of obtaining the above effect more remarkably. The element of group 13 of the periodic table is preferably Ga (gallium). The element of group 15 of the periodic table is preferably Sb (antimony).

The polymerization initiator may be, for example, a photopolymerization initiator. By using a photoinitiator, the composition of the present embodiment can be cured by irradiation with energy rays such as ultraviolet rays.

It is preferable that a polymerization initiator is a cationic polymerization initiator. By using a cationic polymerization initiator, polymerization of a polymerizable compound having a cationic polymerizable functional group becomes possible.

The polymerization initiator is preferably an onium salt containing an anion containing element (M) and an onium ion.

The anion containing the element (M) may be, for example, an anion represented by the following formula (M-1).

[In the formula, n ¹ represents an integer, M represents an element (M) having a value of (n ¹ -1), R ¹ represents an alkyl group or an aryl group, and these groups may have substituents. A plurality of R ¹ may be the same as or different from each other.]

For example, when the element (M) is gallium, the anion containing the element (M) may be an anion represented by the following formula (M-2).

[In formula, R ^<1> represents an alkyl group or an aryl group, and these groups may have a substituent. A plurality of R ¹ may be the same as or different from each other.]

The alkyl group of R ¹ may be, for example, an alkyl group of 1 to 18 carbon atoms. The alkyl group of R ¹ may be linear, branched or cyclic.

Examples of the alkyl group for R ¹ include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, iso-pentyl, and t-pentyl. , sec-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, sec-heptyl group, n-octyl group, n-nonyl group, sec-nonyl group, n-decyl group, n-undecyl group , n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, cyclopentyl group, cyclohexyl group, etc. can be heard

The alkyl group of R ¹ may have a substituent. Examples of the substituent that the alkyl group of R ¹ may have include an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (such as NH ₂ group), a hydroxy group, a mercapto group, A cyano group, an isocyano group, etc. are mentioned.

The aryl group of R ¹ may be, for example, an aryl group having 6 to 14 carbon atoms. The aryl group may be any residue except for one hydrogen atom bonded to the aromatic ring of the aromatic compound.

Examples of the aryl group for R ¹ include a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a tolyl group, an indenyl group, a naphthyl group, anthryl group, a fluorenyl group, a pyrenyl group, a phenanthryl group, a mesityl group, and the like. can

The aryl group of R ¹ may have a substituent. Examples of the substituent that the aryl group of R ¹ may have include an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, a halogen atom, an alkyl-substituted amino group, an aryl-substituted amino group, an unsubstituted amino group (such as NH ₂ group), a hydroxy group, and a mercapto group. , cyano group, isocyano group, etc. are mentioned.

R ¹ is preferably an alkyl group having a halogen atom as a substituent or an aryl group having a halogen atom as a substituent, more preferably an alkyl group having a fluorine atom as a substituent or an aryl group having a fluorine atom as a substituent.

As an onium ion, an oxonium ion, an ammonium ion, a phosphonium ion, a sulfonium ion, an iodonium ion etc. are mentioned, for example. From the viewpoint of obtaining the above effect more remarkably, the onium ion is preferably at least one selected from the group consisting of ammonium ion, phosphonium ion, sulfonium ion and iodonium ion, more preferably a sulfonium ion and It is 1 or more types selected from the group which consists of iodonium ions.

As an oxonium ion, for example,

oxoniums such as trimethyloxonium, diethylmethyloxonium, triethyloxonium, and tetramethylenemethyloxonium;

Pyrilliniums, such as 4-methylpyrilinium, 2,4,6-trimethylpyrilinium, 2,6-di-t-butylpyrrillinium, and 2,6-diphenylpyrrillinium;

chromenium or isochromenium such as 2,4-dimethylchromenium and 1,3-dimethylisochromenium;

etc. can be mentioned.

As an ammonium ion, for example,

pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium;

N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, 1, imidazoliniums such as 2,3,4-tetramethylimidazolinium;

morpholiniums such as tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium and N,N'-dimethylmorpholinium;

piperidiniums such as N,N'-diethylpiperidinium;

pyridiniums such as N-methylpyridinium, N-benzylpyridinium, and N-phenacylpyridinium;

imidazoliums such as N,N'-dimethylimidazolium;

quinolium such as N-methylquinolium, N-benzylquinolium, and N-phenacylquinolium;

isoquinolium such as N-methylisoquinolium;

thiazoniums such as benzylbenzothiazonium and phenacylbenzothiazonium;

acridium such as benzyl acridium and phenacyl acridium;

etc. can be mentioned.

As a phosphonium ion, for example,

tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, tetrakis(4-methoxyphenyl)phosphonium, etc. tetraarylphosphonium;

triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium;

tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium;

etc. can be mentioned.

As a sulfonium ion, for example,

Triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris( 4-fluorophenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenylbis(4-fluoro Phenyl) sulfonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, [4- (4-biphenylylthio) phenyl ]-4-biphenylylphenylsulfonium, [4-(2-thioxanthonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis [4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4 -methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4- Fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- ( 4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-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-(9-oxo-9H-thioxanthen-2-yl)thiophenyl-9-oxo-9H-thioxanthen-2-ylphenylsulfonium, 4-[4-(4-t) -Butylbenzoyl) phenylthio] phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyl Di-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthrenium, 5-phenylthiaantrenium, 5-tolylthionium Triaryl sulfoniums, such as rhenium, 5-(4-ethoxyphenyl) thianthrenium, and 5-(2,4,6-trimethylphenyl) thiaanthrenium;

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

Phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl (2-naphthylmethyl) Methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxy Monoaryl groups such as phenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, and 9-anthracenylmethylphenacylsulfonium phonium;

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

etc. can be mentioned.

As an iodonium ion, for example, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyl oxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium Iodonium ions, such as donium and 4-isobutylphenyl (p-tolyl) iodonium, etc. are mentioned.

You may use a commercial item as a polymerization initiator. As a polymerization initiator of a commercial item, a brand name "CPI-310FG" (triaryl sulfonium tetrakis pentafluorophenyl gallate) etc. are mentioned, for example.

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 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.

The composition of this embodiment may further contain an inorganic filler. The inorganic filler is preferably an electrical insulating inorganic filler.

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 heard

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. 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. In addition, the true specific gravity of the inorganic filler represents a value measured by ASTM D2840.

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

The inorganic filler may be inorganic particles having an average particle size (hereinafter sometimes referred to simply as a particle size or a particle size). 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 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 average particle size represents the cumulative 50% particle size (d50) in the particle size distribution.

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, content of a photosensitizer may be 0.01 mass part or more, for example, 0.02 mass part or more with respect to 100 mass parts of polymeric compounds. 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, when the composition of this embodiment contains a photosensitizer, content of a photosensitizer is 0.01-5 mass parts, 0.01-3 mass parts, and 0.02-5 mass parts with respect to 100 mass parts of polymeric compounds, for example. part or 0.02 to 3 parts by mass may be sufficient.

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)ethyltrimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethyne Toxysilane, γ-ureidopropyl triethoxysilane, etc. are mentioned. do. Among these, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(meth)acryloxypropyl At least one selected from the group consisting of trimethoxysilane is preferred, and γ-glycidoxypropyltrimethoxysilane 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 this embodiment contains a silane coupling agent, content of a silane coupling agent may be 0.1 mass part or more with respect to 100 mass parts of polymeric compounds, for example, 0.2 mass part or more is preferable. 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, when the composition of the present embodiment contains a silane coupling agent, the content of the silane coupling agent is, for example, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.2 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. part or 0.2 to 5 parts by mass may be sufficient.

The composition of this embodiment may further contain antioxidant.

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

As the resin particles, 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)acrylic acid. Methyl polystyrene copolymer particles etc. are mentioned. 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 At least one or more selected from the group consisting of crosslinked polystyrene particles is more preferred.

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, in this specification, the average particle diameter of resin particles represents the average particle diameter on a volume basis measured by "laser diffraction type particle size distribution analyzer SALD-2200" manufactured by Shimadzu Corporation. The average particle size represents the cumulative 50% particle size (d50) in the particle size distribution.

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 standard deviation may be, for example, 0 to 0.25, 0 to 0.2, 0 to 0.1, 0.001 to 0.25, 0.001 to 0.2, 0.001 to 0.1, 0.005 to 0.25, 0.005 to 0.2, or 0.005 to 0.1.

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 wealth 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, when the composition of the present embodiment contains resin particles, the content of the resin particles is, for example, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 4 parts by mass, based on 100 parts by mass of the polymerizable compound. 0.01 to 3 parts by mass, 0.02 to 10 parts by mass, 0.02 to 5 parts by mass, 0.02 to 4 parts by mass, 0.02 to 3 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 ~ 3 parts by mass may be sufficient.

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.

When the composition of the present embodiment is used as a sealant for forming a dam, the viscosity at 25° C. of the composition of the present embodiment is 50000 mPa s, for example, from the viewpoint of improving the coatability of the composition and excellent moldability of the cured product. It may be more than that, preferably 70000 mPa·s or more, more preferably 80000 mPa·s or more, and still more preferably 100000 mPa·s or more. In addition, the viscosity at 25°C of the composition of the present embodiment may be, for example, 1000000 mPa·s or less, preferably 950000 mPa from the viewpoint of improving the ejection property during coating of the composition and broadening the selection of molding methods. ·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 950000mPa s, 70000 to 900000mPa s, 70000 to 850000mPa s, 80000 to 1000000mPa s, 80000 to 950000mPa s, 80000 to 900000mPa s, 80000 to 850000mPa s, 100 000 to 1000000 mPa s, 100000 to 950000 mPa s , 100000 to 900000 mPa·s, or 100000 to 850000 mPa·s may be sufficient.

When the composition of the present embodiment is used as a sealant for forming a pill, the viscosity at 25°C of the composition of the present embodiment may be, for example, 5 mPa·s or more, preferably from the viewpoint of further improving the coatability of the composition. It is preferably 6 mPa·s or more, more preferably 7 mPa·s or more, and still more preferably 8 mPa·s or more. In addition, the viscosity at 25°C of the composition of the present embodiment may be, for example, 5000 mPa·s or less, preferably 4000 mPa·s or less, more preferably from the viewpoint of further improving the discharge property during application of the composition. 3000 mPa·s or less, more preferably 2000 mPa·s or less. That is, the viscosity at 25°C of the composition of the present embodiment is, for example, 5 to 5000 mPa·s, 5 to 4000 mPa·s, 5 to 3000 mPa·s, 5 to 2000 mPa·s, 6 to 5000 mPa·s, and 6 to 4000 mPa·s. s s, 6 to 3000 mPa s, 6 to 2000 mPa s, 7 to 5000 mPa s, 7 to 4000 mPa s, 7 to 3000 mPa s, 7 to 2000 mPa s, 8 to 5000 mPa s, 8 to 4000 mPa s , 8 to 3000 mPa·s, or 8 to 2000 mPa·s may be sufficient.

The viscosity at 25°C of the composition represents a value measured by a cone rotor 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.

When _the composition of _{the present embodiment is used as a sealant for forming a dam, the composition of the present embodiment has a ratio (η 2 /} It is preferable that _η1 ) is 1.1-10.0. 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 ) is, 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. may be continued

When the composition of the present embodiment is used as a sealant for forming a pill, the composition of the present embodiment preferably has a ratio (η ₂ /η ₁ ) of 0.9 to 1.5. When the ratio (η ₂ /η ₁ ) is 0.9 or more, the coatability of the composition tends to be further improved. In addition, when the ratio (η ₂ /η ₁ ) is 1.5 or less, the ejection property at the time of application of the composition tends to be further improved.

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 represent 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 of the present embodiment 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 of fully mixing each said component is sufficient. As a mixing method, the stirring method using the stirring force accompanying rotation of a propeller, the method using normal dispersers, 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.

A cured body containing a polymer of a polymerizable compound can be obtained by curing the composition of the present embodiment. 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, a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or a xenon lamp , 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. Moreover, irradiation using a low wavelength cut filter, a hot wire cut filter, a cold mirror, or the like may be used.

In curing the composition of the present embodiment, post-heating treatment may be performed after irradiation with light to promote curing. The temperature of the 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. The composition of the present embodiment can be suitably used for adhesion to packages such as organic EL display elements.

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 of 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 light and 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.

In addition, 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 bonding 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 top of the loss tangent (hereinafter abbreviated as tan δ) is indicated can be taken 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 temperature Since it is impossible to think of a cured body at -150°C or less, it can be determined at a certain temperature (Ta°C) or higher.

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 (fragility) of the hardened body is further suppressed.

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. For this test piece, a dynamic viscoelasticity measurement is performed under the conditions of a temperature range of -50°C to 200°C, a heating rate of 2°C/min, and a tension 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 is combined with an electron (e ^- ) to generate positronium (Ps). In the positron annihilation method, 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 pores of the polymer. It is a method of obtaining the free volume of a polymer by measuring the lifetime (τ ₃ ) of o-Ps at the time of release. The lifetime (τ ₃ ) of o-Ps is determined by the overlapping probability of positrons (e ⁺ ) of o-Ps and electrons (e ^- ) in the wall of vacancies when they collide with the walls of vacancies in the polymer. The larger this is, the longer the lifetime (τ ₃ ) of o-Ps is. The rate of annihilation of positrons (e ⁺ ) obtained by considering the void as a spherical well-type potential of infinite height, 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 model for obtaining is in good agreement with the data from the actual experiment. 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), τ ₃ 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, the pore diameter R of the polymer is obtained from the above formula (1) by obtaining the lifetime (τ ₃ ) of orthopositronium (o-Ps) by the positron annihilation method. Also, since 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 cured body of the present embodiment has a pore diameter of 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. do. Specifically, it is free by a method of 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 to find the volume

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 two 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 pickoff extinction of orthopositronium, information of the pore size is obtained. can be obtained.

Specifically, the three-component analysis of the lifetime of a positron is performed by the nonlinear least squares method, and τ ₁ , τ ₂ , τ ₃ are defined 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 ₃ /(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 may have a moisture permeability of 100 (g/m ² 24h/100 μm) or less, measured in accordance with JIS Z0208 at a temperature of 85° C. and a relative humidity of 85%, or 60 (g/m ² 24h). /100 µm) or less, more preferably 55 (g/m ² *24h/100 µm) or less, and even more preferably 50 (g/m ² *24h/100 µm) or less. Due to its low moisture permeability, when used as a sealing material for organic EL display elements, occurrence of dark spots due to the arrival of moisture to the organic light emitting material layer can be remarkably suppressed. In addition, the moisture permeability can also be referred to as the moisture vapor permeability (g/m ² ) at a thickness of 100 μm measured in accordance with JIS Z 0208:1976 by exposure to an environment of 85° C. and 85% RH for 24 hours. The moisture permeability may be, for example, 0.001 (g/m ² 24h/100 μm) or more, 0.01 (g/m ² 24h/100 μm) or more, or 0.03 (g/m ² 24h/100 μm). It may be more than 0.1 (g/m ² ·24h/100 μm) or more. That is, the moisture permeability is, for example, 0 to 100 (g/m ² 24h/100㎛), 0 to 60 (g/m ² 24h/100㎛), 0 to 55 (g/m ² 24h/ 100㎛), 0 ~ 50 (g/m ² 24h/100㎛), 0.001 ~ 100 (g/m ² 24h/100㎛), 0.001 ~ 60 (g/m ² 24h/100㎛), 0.001 ~ 55 (g/m ² 24h/100㎛), 0.001 ~ 50 (g/m ² 24h/100㎛), 0.01 ~ 100 (g/m ² 24h/100㎛), 0.01 ~ 60 (g/m 2 24h/100㎛) m ² 24h/100㎛), 0.01 to 55 (g/m ² 24h/100㎛), 0.01 to 50 (g/m ² 24h/100㎛), 0.03 to 100 (g/m ² 24h/ 100 μm), 0.03 to 60 (g/m ² 24 h/100 μm), 0.03 to 55 (g/m ² 24 h/100 μm), or 0.03 to 50 (g/m ² 24 h/100 μm). do.

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 of 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 also relates to an organic EL display device having a dam-fill sealing structure including a dam and a fill, wherein the dam may contain a cured body of the above-described composition.

Further, the dam/fill sealing structure may be a known dam/fill sealing structure, and the pill may be a known fill. 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.

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 fill by applying and curing the composition described above.

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

In addition, the dam/fill sealing structure may be a known dam/fill sealing structure, and the dam agent for forming the dam may be a known dam agent or may be the composition of the present embodiment. 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.

According to the present invention, a sealant capable of forming a sealant excellent in 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 light emitting display device using the sealant, and an organic light emitting display device having a sealant formed of the sealant are provided.

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

[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) polymerizable 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.) (maximum atomic number: 35, specific gravity: 1.8, number of polymerizable functional groups in one molecule: 1)

(A-2) TBBPA (tetrabromobisphenol A) epoxy resin (DIC Corporation "Epicron 152") (maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups in one molecule: 2)

(A-3) Brominated bisphenol A type epoxy resin ("SR-T1000" manufactured by Sakamoto Pharmaceutical Co., Ltd.) (maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups in one molecule: 2)

(A-4) 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxirane (Daikin Corporation "C6 Epoxy") (maximum atom Number: 9, specific gravity: 1.5, number of polymerizable functional groups in one molecule: 1)

(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 Daicel Chemical Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.2, 1 molecule) Number of polymerizable functional groups in: 2)

(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 novolac 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)

(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)

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

(C-1) Triarylsulfonium-tetrakispentafluorophenylgallate ("CPI-310FG" manufactured by San-Apro Corporation, described as "CPI-310FG" in the tables.)

(C-2) triarylsulfonium salt hexafluoroantimonate (“ADEKA Optomer SP-170” manufactured by ADEKA, anion species is hexafluoroantimonate)

(C-3) Aryliodonium-hexafluorophosphate ("Irgacure 250" manufactured by BASF, described as "Irgacure 250" in the tables.)

(C-4) Arylsulfonium-hexafluorophosphate (“Irgacure 270” manufactured by BASF, described as “Irgacure 270” in the tables.)

(C-5) Triphenylsulfonium tetrafluoroborate (“Triphenylsulfonium tetrafluoroborate” manufactured by Tokyo Chemical Industry Co., Ltd., described as “BF4” in the tables.)

(C-6) Tri-p-tolylsulfonium trifluoromethanesulfonate (“Tri-p-tolylsulfonium trifluoromethanesulfonate” manufactured by Tokyo Chemical Industry Co., Ltd., described as “CF ₃ SO ₃ ” in the tables) .)

(D) The following was used as a photosensitizer.

(D-1) 9,10-dibutoxyanthracene ("ANTHRACURE UVS-1331" manufactured by Kawasaki Chemical Industry 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 size (d50): 4.5 µm, true specific gravity: 2.7 ("#5000PJ" manufactured by Matsumura Sangyo Co., Ltd.)

(F-2) Fine particle silica, particle diameter (d50): 4.2 µm, true specific gravity: 1.9 ("FB-5SDX" manufactured by Denka 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 Table 1 or Table 2 were mixed in the composition ratio shown in Table 1 or Table 2 to prepare sealants of Examples and Comparative Examples. The unit of the composition ratio is a mass part.

For the sealing agents (or components in the sealing agent) of Examples and Comparative Examples, the following measurements were performed. The results are shown in Table 1 or Table 2.

[Specific gravity of polymerizable compound]

The measurement was performed based on JIS K0061 using a Herbert 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]

In evaluating the curability and adhesion of the sealant, the sealant was cured under the following light irradiation conditions. After photo-curing the sealant under conditions of a cumulative light intensity of 4,000 mJ/cm 2 at a wavelength of 365 nm with a UV curing device (manufactured by Fusion Co.) equipped with an electrodeless discharge metal halide lamp, post-heating treatment was performed in an oven at 100 ° C. for 60 minutes. This was carried out to obtain a cured product.

[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, elastic modulus at Tg+40°C (storage modulus)]

A sheet-like 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. The dynamic viscoelasticity of this test piece was measured 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 storage modulus was measured. The temperature of the peak top 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-like 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. About this test piece, the dynamic viscoelasticity was measured under the conditions of the temperature range -50 degreeC - 200 degreeC, the heating rate of 2 degreeC/min, and tension mode. The crosslinking density is T(K) at 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 coefficient is φ ( = 1) and calculated with the following formula.

Crosslink density (ρ)=G' _T+40 /φRT

[Average particle diameter, 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 relative 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).

[Tensile shear adhesive strength]

Using two borosilicate glass test pieces (length 25 mm × width 25 mm × thickness 2.0 mm, Tempex (registered trademark) glass), the bonding area was 0.5 cm ² and the bonding thickness was 10 μm. The borosilicate glass test pieces were bonded through a sealant, , The sealant was cured under the above 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.

[Vapor permeability]

A sheet-like 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.

[Production of organic EL element substrate]

A glass substrate (length 25 mm × width 25 mm) having an ITO electrode was washed using acetone and isopropanol. Thereafter, the following compounds were sequentially deposited into thin films by vacuum deposition to obtain an organic EL device substrate composed of anode/hole injection layer/hole transport layer/light emitting layer/electron injection layer/cathode. The composition 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 1000Å

ㆍElectron injection layer: lithium fluoride thickness 1nm

ㆍCathode: Aluminum, cathode film thickness 250nm

[Production of organic EL element]

Under a nitrogen atmosphere, a sealant is applied to the glass substrate in a rectangular shape (side length: 20 mm, coating width: 0.6 mm, coating height: 0.1 mm) with a coating device, and the glass substrate and the organic EL element are passed through the sealant so that the adhesive thickness is 10 μm. The substrates were bonded, and the sealant was cured under the above photocuring conditions to manufacture an organic EL device.

[Evaluation of organic EL]

〔Early〕

A voltage of 6 V was applied to the organic EL element immediately after fabrication, 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, and the diameter of the dark spot was determined. was measured.

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.

Claims (31)

A sealant comprising a polymerizable compound and a polymerization initiator having an element belonging to groups 13 to 15 of the periodic table and from cycles 4 to 6, wherein the polymerizable compound contains a compound having a specific gravity of 1.3 to 4.0. The sealant according to claim 1, wherein when the sealant is cured into a cured product containing the polymer of the polymerizable compound, the specific gravity of the cured product is 1.35 to 19.0. The sealant according to claim 1 or 2, wherein the polymerizable compound contains compound (X) having an element having an atomic number of 9 or higher. The sealant according to claim 3, wherein the compound (X) contains a halogen group element. The sealant according to claim 4, wherein the 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 4 or 5, wherein the content of the halogen group element in the 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 6, 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 7, 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 8, wherein the polymerization initiator is a cationic polymerization initiator. The sealant according to any one of claims 1 to 9, wherein the polymerization initiator contains an onium salt. The sealant according to any one of claims 1 to 10, wherein the polymerization initiator is group 13 of the periodic table and contains an element of the 4th to 6th period. The sealing agent according to any one of claims 1 to 11, wherein the polymerization initiator has gallium. The sealant according to any one of claims 1 to 12, further comprising an inorganic filler. The sealant according to claim 13, wherein the inorganic filler has a true specific gravity of 1.5 to 5.0. The sealant according to claim 13 or 14, wherein the inorganic filler is an electrically insulating inorganic filler. The sealant according to any one of claims 13 to 15, wherein the inorganic filler contains at least one selected from the group consisting of silica, mica, kaolin, talc and aluminum oxide. The sealing agent according to any one of claims 13 to 16, 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 sealant according to any one of claims 1 to 17, further comprising resin particles. The sealant according to claim 18, 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)acrylate polystyrene copolymer particles. The sealant according to claim 18 or 19, wherein the resin particles have an average particle diameter of 1 μm to 100 μm. The sealant according to any one of claims 18 to 20, wherein the standard deviation of the particle volume distribution with respect to the particle diameter when the particle diameter (μm) of the resin particles is expressed as a logarithm is 0.25 or less. The sealing agent according to any one of claims 18 to 21, 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. The sealant according to any one of claims 1 to 22, 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 23, wherein when the sealant is cured into a cured product containing a polymer of the polymerizable compound, the glass transition temperature of the polymer is 85°C or higher. The sealant according to any one of claims 1 to 24, wherein when the sealant is cured into a cured product containing the polymer of the polymerizable compound, the cured product has a crosslink density of 1.5×10 ^-3 mol/cm ^{3 or} more. . The method according to any one of claims 1 to 25, wherein when the sealing agent is cured to obtain a cured product containing the polymer of the polymerizable compound, the cured product is subjected to conditions of a temperature of 85°C and a relative humidity of 85% in accordance with JIS Z0208. A sealant having a water vapor transmission rate of 50 (g/m ² ·24h/100 μm) or less measured under The sealant according to any one of claims 1 to 26, which is a sealant for organic electroluminescence display elements. A cured product formed by curing the sealant according to any one of claims 1 to 27. A method of manufacturing an organic electroluminescent display device having a dam-fill sealing structure, comprising a step of forming a fill by applying and curing the sealant according to any one of claims 1 to 27. A method of manufacturing an organic light emitting display device having a dam-fill sealing structure, comprising forming a dam by applying and curing the sealant according to any one of claims 1 to 27. It has a dam-fill sealing structure including a dam and a fill,
At least one of the dam and the fill includes an organic electroluminescent display device comprising a cured body of the sealant according to any one of claims 1 to 27.