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

Abstract

A sealant comprising a polymerizable compound, and a polymerization initiator having an element of Groups 13 to 15 and Periods 4 to 6 of the periodic table, the polymerizable compound containing a compound having a specific gravity of 1.3 to 4.0.

Description

Technical Field

[0001] This invention relates to sealants, cured bodies, organic electroluminescent display devices, and methods for manufacturing organic electroluminescent display devices. Background Technology

[0002] In recent years, research on organic optical devices using organic thin-film elements, such as organic electroluminescent (organic EL) display elements and organic thin-film solar cell elements, has been ongoing. Organic thin-film elements can be easily fabricated through vacuum evaporation, solution coating, and other methods, resulting in excellent productivity.

[0003] Organic EL (OLED) display elements are thin-film structures with an organic light-emitting material layer sandwiched between a pair of opposing electrodes. Electrons are injected into the organic light-emitting material layer from one electrode, while holes are injected from the other electrode, thereby combining within the organic light-emitting material layer to produce self-illumination. Compared to liquid crystal display elements and the like, which require a backlight, they have the following advantages: good visual clarity, the ability to be further thinned, and the ability to achieve low-voltage DC drive.

[0004] However, such organic EL display elements have the following problems: when the organic light-emitting material layer and electrodes are exposed to external gases, their light-emitting characteristics deteriorate sharply, and their lifespan is shortened. Therefore, in order to improve the stability and durability of organic EL display elements, sealing technology that isolates the organic light-emitting material layer and electrodes from moisture and oxygen in the atmosphere is indispensable.

[0005] For example, Patent Document 1 discloses a method in which a photocurable sealant is filled between the substrates of an organic EL display element, such as an upper surface light-emitting type organic EL display element, and then sealed by irradiation with light. Furthermore, Patent Documents 2-4 disclose techniques for sealing organic EL display elements to prevent deterioration caused by moisture.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2001-357973

[0009] Patent Document 2: Japanese Patent Application Publication No. 10-74583

[0010] Patent Document 3: Japanese Patent Application Publication No. 2001-307873

[0011] Patent Document 4: Japanese Patent Application Publication No. 2009-37812 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] In recent years, the requirements for electronic devices have increased. For example, there is a demand for sealing materials that can achieve higher reliability and durability for organic EL display elements.

[0014] The present invention was made in view of the above circumstances, and its object is to provide a sealant that can form a sealing material with excellent moisture resistance.

[0015] Methods for solving problems

[0016] That is, the present invention relates to the following.

[0017] <1>

[0018] A sealant comprising a polymerizable compound and a polymerization initiator containing elements of groups 13 to 15 and periods 4 to 6 of the periodic table.

[0019] The aforementioned polymeric compounds contain compounds with a specific gravity of 1.3 to 4.0.

[0020] <2>

[0021] like <1> The sealant, wherein when the aforementioned sealant is cured to form a cured body of a polymer containing the aforementioned polymeric compound,

[0022] The specific gravity of the aforementioned solidified body is 1.35 to 19.0.

[0023] <3>

[0024] like <1> or <2> The sealant, wherein the aforementioned polymeric compound contains a compound (X) having an atomic number of 9 or higher.

[0025] <4>

[0026] like <3> The sealant wherein the aforementioned compound (X) contains a halogen.

[0027] <5>

[0028] like <4> The sealant wherein the aforementioned compound (X) has at least one halogen element selected from the group consisting of fluorine and bromine.

[0029] <6>

[0030] like <4> or <5> The sealant wherein, relative to the total elemental mass of the aforementioned polymeric compound, the content of halogen elements in the aforementioned compound (X) is 10 to 50% by mass.

[0031] <7>

[0032] like <1> ~ <6> The sealant according to any one of the following methods, wherein the aforementioned polymeric compound contains a crosslinking compound (Y) having two or more polymeric functional groups.

[0033] <8>

[0034] like <1> ~ <7> The sealant according to any one of the following methods, wherein the aforementioned polymeric compound contains at least one selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, vinyl ether compounds, and oxetane compounds.

[0035] <9>

[0036] like <1> ~ <8> The sealant according to any one of the following methods, wherein the aforementioned polymerization initiator is a cationic polymerization initiator.

[0037] <10>

[0038] like <1> ~ <9> The sealant according to any one of the above-mentioned polymerization initiators contains an onium salt.

[0039] <11>

[0040] like <1> ~ <10> The sealant according to any one of the following methods, wherein the aforementioned polymerization initiator is an element of Group 13 and Periods 4 to 6 of the periodic table.

[0041] <12>

[0042] like <1> ~ <11> The sealant according to any one of the above-mentioned polymerization initiators has gallium.

[0043] <13>

[0044] like <1> ~ <12> The sealant described in any one of the following methods further comprises an inorganic filler material.

[0045] <14>

[0046] like <13> The sealant wherein the true specific gravity of the aforementioned inorganic filler material is 1.5 to 5.0.

[0047] <15>

[0048] like <13> or <14> The sealant, wherein the aforementioned inorganic filler material is an electrically insulating inorganic filler material.

[0049] <16>

[0050] like <13> ~ <15> The sealant according to any one of the above-mentioned inorganic filler materials contains at least one selected from the group consisting of silica, mica, kaolin, talc and alumina.

[0051] <17>

[0052] like <13> ~ <16> The sealant according to any one of the above, wherein the content of the aforementioned inorganic filler material is 5 to 500 parts by mass relative to 100 parts by mass of the aforementioned polymeric compound.

[0053] <18>

[0054] like <1> ~ <17> The sealant described in any one of the following methods further comprises resin particles.

[0055] <19>

[0056] like <18> The sealant wherein the aforementioned resin particles contain at least one selected from the group consisting of cross-linked poly(methyl methacrylate) particles, cross-linked polystyrene particles, and cross-linked poly(methyl methacrylate) polystyrene copolymer particles.

[0057] <20>

[0058] like <18> or <19> The sealant wherein the average particle size of the aforementioned resin particles is 1 μm to 100 μm.

[0059] <21>

[0060] like <18> ~ <20> The sealant according to any one of the following methods, wherein the standard deviation of the particle volume distribution relative to the particle size when the particle size (μm) of the aforementioned resin particles is expressed logarithmically is 0.25 or less.

[0061] <22>

[0062] like <18> ~ <21> The sealant according to any one of the following methods, wherein the content of the aforementioned resin particles is 0.01 to 5 parts by mass relative to 100 parts by mass of the aforementioned polymeric compound.

[0063] <23>

[0064] like <1> ~ <22> The sealant according to any one of the above, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass relative to 100 parts by mass of the aforementioned polymeric compound.

[0065] <24>

[0066] like <1> ~ <23> The sealant as described in any one of the above statements, wherein when the aforementioned sealant is cured to form a cured polymer containing the aforementioned polymeric compound,

[0067] The glass transition temperature of the aforementioned polymer is above 85°C.

[0068] <25>

[0069] like <1> ~ <24> The sealant as described in any one of the above statements, wherein when the aforementioned sealant is cured to form a cured polymer containing the aforementioned polymeric compound,

[0070] The crosslinking density of the aforementioned cured body is 1.5 × 10⁻⁶. -3 mol / cm 3 above.

[0071] <26>

[0072] like <1> ~ <25> The sealant as described in any one of the above statements, wherein when the aforementioned sealant is cured to form a cured polymer containing the aforementioned polymeric compound,

[0073] The permeability of the aforementioned cured body, measured according to JIS Z0208 at a temperature of 85°C and a relative humidity of 85%, is 50 g / m³. 2 • Below 24h / 100μm.

[0074] <27>

[0075] like <1> ~ <26> The sealant described in any one of the following is a sealant for organic electroluminescent display elements.

[0076] <28>

[0077] A solidified body is a solidified body that ... <1> ~ <27> The sealant described in any one of the above is cured.

[0078] <29>

[0079] A method for manufacturing an organic electroluminescent display device having a cofferdam-filled sealing structure, the method comprising coating... <1> ~ <27> The process of applying any one of the sealants and curing it to form a filler.

[0080] <30>

[0081] A method for manufacturing an organic electroluminescent display device having a cofferdam-filled sealing structure, the method comprising coating... <1> ~ <27> The process of using any one of the sealants to cure and form a cofferdam.

[0082] <31>

[0083] An organic electroluminescent display device having a cofferdam-filling sealing structure with a cofferdam and filler.

[0084] At least one of the aforementioned cofferdam and the aforementioned filling material includes <1> ~ <27> The cured form of the sealant as described in any one of the above.

[0085] Invention Effects

[0086] According to the present invention, a sealant capable of forming a sealing material with excellent moisture resistance can be provided. Detailed Implementation

[0087] The preferred embodiments of the present invention will now be described in detail.

[0088] The composition of this embodiment comprises a polymerizable compound and a polymerization initiator having elements from Groups 13 to 15 and Periods 4 to 6 of the periodic table. In this embodiment, the polymerizable compound contains a compound with a specific gravity of 1.3 to 4.0 (a high specific gravity compound).

[0089] The composition according to this embodiment can form a sealing material with excellent moisture resistance. Therefore, the composition of this embodiment can be suitably used as a sealant (preferably a sealant for organic electroluminescent display elements). In addition, the composition of this embodiment can be particularly suitably used as a sealant for forming a dam or filler sealing structure (a sealant for dam formation or a sealant for filler formation).

[0090] In this embodiment, the polymerizable compound can be defined as a compound having polymerizable functional groups. One polymerizable compound can be used alone, or two or more can be used in combination.

[0091] The polymerizable compound preferably has at least one functional group selected from cationic polymerizable functional groups and radical polymerizable functional groups. As a polymerizable compound having a cationic polymerizable functional group, it is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationic polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. Examples of polymerizable compounds having a radical polymerizable functional group include compounds having at least one radical polymerizable functional group selected from the group consisting of vinyl, (meth)acryloyl, allyl, vinyl ether, and vinyl ester, with compounds having a (meth)acryloyl group being preferred. As a compound having a (meth)acryloyl group, it is preferably at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide.

[0092] The high-specific-gravity compound can be defined as a compound having polymerizable functional groups and 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. Furthermore, the specific gravity of the high-specific-gravity compound is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. That is, the specific gravity of the high-specific-gravity compound can be, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0, 1.4 to 3.0, 1.4 to 2.5, 1.4 to 2.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5, or 1.5 to 2.0. It should be noted that the specific gravity of the high-specific-gravity compound is expressed as a value measured using a Hubbard-type specific gravity bottle according to JIS K0061. It should be noted that if the specific gravity is less than 1.3, the above-mentioned effects cannot be sufficiently obtained. In addition, polymeric compounds with a specific gravity of 4.0 or higher are difficult to obtain and are uneconomical.

[0093] In this embodiment, the polymerizable compound may further contain a low-specific-gravity compound with a specific gravity of less than 1.3. The low-specific-gravity compound is defined as a compound having polymerizable functional groups and 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 also 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, for example, be 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. It should be noted that the specific gravity of the low-specific-gravity compound is expressed as a value measured using a Hubbard-type specific gravity bottle according to JIS K0061.

[0094] The proportion of the high-gravity compound in the polymerizable compound can be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and even more preferably 55% by mass or more. This allows the aforementioned effects to be achieved more significantly. Furthermore, the proportion of the high-gravity compound in the polymerizable compound can be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less. That is, the proportion of high-gravity compounds in polymerizable compounds can be, for example, 30–100% by mass, 30–90% by mass, 30–85% by mass, 30–80% by mass, 30–75% by mass, 30–70% by mass, 30–65% by mass, 40–100% by mass, 40–90% by mass, 40–85% by mass, 40–80% by mass, 40–75% by mass, 40–70% by mass, 40–65% by mass, 45–100% by mass, and 45–90% by mass. 45–85% by mass, 45–80% by mass, 45–75% by mass, 45–70% by mass, 45–65% by mass, 50–100% by mass, 50–90% by mass, 50–85% by mass, 50–80% by mass, 50–75% by mass, 50–70% by mass, 50–65% by mass, 55–100% by mass, 55–90% by mass, 55–85% by mass, 55–80% by mass, 55–75% by mass, 55–70% by mass, or 55–65% by mass.

[0095] The proportion of the low-gravity compound in the polymerizable compound can be, for example, 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, and particularly preferably 35% by mass or more. Furthermore, the proportion of the low-gravity compound in the polymerizable compound can 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 45% by mass or less. This allows the aforementioned effects to be achieved more significantly.

[0096] That is, the proportion of low-gravity compounds in polymerizable compounds can be, for example, 0–70% by mass, 0–60% by mass, 0–55% by mass, 0–50% by mass, 0–45% by mass, 10–70% by mass, 10–60% by mass, 10–55% by mass, 10–50% by mass, 10–45% by mass, 15–70% by mass, 15–60% by mass, 15–55% by mass, 15–50% by mass, 15–45% by mass, 20–70% by mass, 20– 60% by mass, 20–55% by mass, 20–50% by mass, 20–45% by mass, 25–70% by mass, 25–60% by mass, 25–55% by mass, 25–50% by mass, 25–45% by mass, 30–70% by mass, 30–60% by mass, 30–55% by mass, 30–50% by mass, 30–45% by mass, 35–70% by mass, 35–60% by mass, 35–55% by mass, 35–50% by mass, or 35–45% by mass.

[0097] In this embodiment, the polymerizable compound preferably contains a polymerizable compound (X) having an atomic number of 9 or higher. The polymerizable compound (X) can be a high-density compound or a low-density compound, but is preferably a high-density compound.

[0098] The polymeric compound (X) preferably has a halogen element, and more preferably has at least one element selected from the group consisting of fluorine and bromine.

[0099] The number of halogen elements in one molecule of the polymeric compound (X) is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. There is no particular upper limit to the number of halogen elements in one molecule of the polymeric compound (X), and it can be, for example, 40 or less, preferably 30 or less. That is, the number of halogen elements in one molecule of the polymeric compound (X) can be, for example, 1 to 40, 1 to 30, 2 to 40, 2 to 30, 3 to 40, or 3 to 30.

[0100] The polymerizable compound (X) preferably has at least one functional group selected from cationic polymerizable functional groups and radical polymerizable functional groups. As a polymerizable compound (X) having a cationic polymerizable functional group, it is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, aromatic epoxy compounds, etc.), cationic polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. Examples of polymerizable compounds (X) having a radical polymerizable functional group include compounds having at least one radical polymerizable functional group selected from the group consisting of vinyl, (meth)acryloyl, allyl, vinyl ether, and vinyl ester, with compounds having a (meth)acryloyl group being preferred. As a compound having a (meth)acryloyl group, it is preferably at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide.

[0101] Examples of polymerizable compounds (X) that have cationic polymerizable functional groups include halogenated phenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether, bisphenol A type brominated epoxy resin, bisphenol F type brominated Novolac type epoxy resin, and phenol Novolac type brominated epoxy resin.

[0102] Examples of polymerizable compounds (X) that are free radical polymerizable compounds include fluorophenyl methacrylate, trifluorophenyl methacrylate, pentafluorophenyl methacrylate, chlorophenyl methacrylate, trichlorophenyl methacrylate, pentachlorophenyl methacrylate, bromophenyl methacrylate, tribromophenyl methacrylate, pentabromophenyl methacrylate, and halophenyl methacrylates.

[0103] The content of halogen elements in the polymeric compound (X) is preferably 10 to 50% by mass relative to the total elemental content of the polymeric compound. If it is 10% by mass or more, there is a tendency to further improve the moisture resistance of the cured body; if it is 50% by mass or less, there is a tendency to further improve the curability of the composition.

[0104] The proportion of the polymerizable compound (X) in the polymerizable compound can be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, further preferably 50% by mass or more, and even more preferably 55% by mass or more. This tends to further improve the moisture resistance of the cured body. Furthermore, the proportion of the polymerizable compound (X) in the polymerizable compound can be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less. This tends to further improve adhesion to glass substrates, etc., and further improve the reliability of the sealing material. That is, the proportion of polymerizable compound (X) in the polymerizable compound can be, for example, 30–100% by mass, 30–90% by mass, 30–85% by mass, 30–80% by mass, 30–75% by mass, 30–70% by mass, 30–65% by mass, 40–100% by mass, 40–90% by mass, 40–85% by mass, 40–80% by mass, 40–75% by mass, 40–70% by mass, 40–65% by mass, 45–100% by mass, or 45–90% by mass. 45–85% by mass, 45–80% by mass, 45–75% by mass, 45–70% by mass, 45–65% by mass, 50–100% by mass, 50–90% by mass, 50–85% by mass, 50–80% by mass, 50–75% by mass, 50–70% by mass, 50–65% by mass, 55–100% by mass, 55–90% by mass, 55–85% by mass, 55–80% by mass, 55–75% by mass, 55–70% by mass, or 55–65% by mass.

[0105] In this embodiment, the polymeric compound may also contain polymeric compounds other than polymeric compound (X) (i.e., polymeric compounds that do not have an element with an atomic number of 9 or higher) (hereinafter also referred to as polymeric compound (X')).

[0106] The polymerizable compound (X') can be, for example, a compound having polymerizable functional groups that can copolymerize with the polymerizable functional groups possessed by the polymerizable compound (X). The polymerizable compound (X') can be a high-density compound or a low-density compound.

[0107] The polymerizable compound (X') preferably has at least one functional group selected from cationic polymerizable functional groups and radical polymerizable functional groups. As a polymerizable compound (X') having a cationic polymerizable functional group, it is preferably at least one selected from the group consisting of epoxy compounds (e.g., glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationic polymerizable vinyl compounds (e.g., vinyl ether compounds, etc.), and oxetane compounds. Examples of polymerizable compounds (X') having a radical polymerizable functional group include compounds having at least one radical polymerizable functional group selected from the group consisting of vinyl, (meth)acryloyl, allyl, vinyl ether, and vinyl ester, with compounds having a (meth)acryloyl group being preferred. As a compound having a (meth)acryloyl group, it is preferably at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide.

[0108] When the polymerizable compound (X) has a cationic polymerizable functional group, the polymerizable compound (X') preferably has a cationic polymerizable functional group. As a polymerizable compound (X') having a cationic polymerizable functional group, it is preferably at least one selected from the group consisting of epoxy compounds, oxetane compounds, and cationic polymerizable vinyl compounds.

[0109] Examples of epoxy compounds include alicyclic compounds with epoxy groups (alicyclic epoxy compounds), aromatic compounds with epoxy groups (aromatic epoxy compounds), and glycidyl ether compounds.

[0110] Examples of alicyclic epoxides include compounds or their derivatives obtained by epoxidizing a compound having at least one cyclic olefin ring (e.g., cyclohexene ring, cyclopentene ring, pinene ring, etc.) using a suitable oxidizing agent such as hydrogen peroxide or peroxyacid. Additionally, examples of alicyclic epoxides include hydrogenated epoxides obtained by hydrogenating aromatic epoxides (e.g., bisphenol A type epoxides, bisphenol F type epoxides, etc.).

[0111] Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylalkyl esters of (meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl ester of (meth)acrylate), (3,3',4,4'-diepoxy)bicyclohexane, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin.

[0112] Among alicyclic epoxy compounds, those having a 1,2-epoxycyclohexane structure are preferred. Among alicyclic epoxy compounds having a 1,2-epoxycyclohexane structure, those represented by the following formula (A1-1) are preferred.

[0113] [Chemical Formula 1]

[0114]

[0115] In formula (A1-1), X represents a single bond or a linking group (a divalent group with more than one atom).

[0116] The linking group is preferably a divalent hydrocarbon group, carbonyl group, ether bond, ester bond, carbonate group, amide bond, or a group formed by linking multiple of them.

[0117] X is preferably a linking group. As a linking group, a group having an ester bond is preferred. For example, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarbamate (molecular weight 252) is an example of a compound having an ester bond as a linking group.

[0118] From the perspective of further improving the moisture resistance of the cured body and further improving the storage stability of the composition, the molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, even more preferably 300 or less, and even more preferably 100 to 280. That is, the molecular weight of the alicyclic epoxy compound can be, for example, 100 to 450, 100 to 400, 100 to 300, or 100 to 280.

[0119] When alicyclic epoxides have a specific molecular weight distribution, the number-average molecular weight of the alicyclic epoxide is preferably within the range described above. It should be noted that, in this specification, the number-average molecular weight represents the value converted to polystyrene, obtained using gel permeation chromatography (GPC) under the following determination conditions.

[0120] • Solvent (mobile phase): THF

[0121] • Degassing unit: ERC-3310 manufactured by ERMA

[0122] Pump: PU-980 manufactured by Japan Seiko Co., Ltd.

[0123] • Flow rate: 1.0 ml / min

[0124] • Automatic sampler: TOSOH AS-8020

[0125] • Column oven: Hitachi, Ltd. L-5030

[0126] • Set temperature: 40℃

[0127] • Column composition: 2 TOSOH TSKguardcolumnMP(×L) 6.0mm ID×4.0cm columns and 2 TOSOH TSK-GELMULTIPORE HXL-M 7.8mm ID×30.0cm columns, totaling 4 columns.

[0128] • Detector: RI Hitachi, Ltd. L-3350

[0129] Data processing: SIC480 data station

[0130] As aromatic epoxy compounds, any compound from monomers, oligomers, or polymers can be used, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, Novolac phenol type epoxy resin, cresol Novolac type epoxy resin, and their modified forms.

[0131] As an aromatic epoxy compound, an aromatic epoxy compound having a bisphenol structure is preferred. Among aromatic epoxy compounds having a bisphenol structure, compounds represented by the following formula (A2-1) are preferred.

[0132] [Chemical Formula 2]

[0133]

[0134] In equation (A2-1), n ​​represents 0 to 30, and R 21 R 22 R 23 and R 24 Each can independently represent a hydrogen atom or an alkyl group with 1 to 5 substituted or unsubstituted carbon atoms. n can be 0.1 or more.

[0135] R 21 R 22 R 23 and R 24 Preferably, it contains hydrogen atoms or methyl groups. R 21 R 22 R 23 and R 24 They can be the same or different, but being the same is preferred.

[0136] The aromatic epoxy compound having a bisphenol structure is preferably selected from at least one of the groups consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

[0137] From the perspective of further improving the moisture resistance of the cured body, the molecular weight of the aromatic epoxy compound is preferably 100-5000, more preferably 150-1000, and even more preferably 200-450. That is, the molecular weight of the aromatic epoxy compound can be, for example, 100-5000, 100-1000, 100-450, 150-5000, 150-1000, 150-450, 200-5000, 200-1000, or 200-450.

[0138] When aromatic epoxy compounds have a molecular weight distribution, the number-average molecular weight of the aromatic epoxy compounds is preferably within the above-mentioned range. It should be noted that, in this specification, the number-average molecular weight represents the value converted to polystyrene, obtained by gel permeation chromatography (GPC) under the above-mentioned determination conditions.

[0139] As the glycidyl ether compound, a polyglycidyl ether compound is preferred. There is no particular limitation on the polyglycidyl ether compound; examples include diglycidyl ethers of alkylene glycols (e.g., diglycidyl ethers of ethylene glycol, propylene glycol, and 1,6-hexanediol), polyglycidyl ethers of polyols (e.g., di or triglycidyl ethers of glycerol or its alkylene oxide adducts), and diglycidyl ethers of polyalkylene glycols (e.g., diglycidyl ethers of polyethylene glycol or its alkylene oxide adducts, and diglycidyl ethers of polypropylene glycol or its alkylene oxide adducts). Here, examples of alkylene oxides include ethylene oxide and propylene oxide.

[0140] Cationic polymerizable vinyl compounds can be any compound from monomers, oligomers, or polymers. Examples of cationic polymerizable vinyl compounds include vinyl ether compounds, vinyl amine compounds, and styrene.

[0141] As for vinyl ether compounds, there are no particular limitations, but examples include divinyl glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanediethanol divinyl ether, trimethylolpropane trivinyl ether, etc.; ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanediethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropyl ether-o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, etc.

[0142] As for oxetane compounds, there are no particular limitations, but examples include 3-ethyl-3-hydroxymethyloxetane (manufactured by Toa Synthetic Co., Ltd., trade name ARON OXETANE OXT-101, etc.), 1,4-bis[(3-ethyl-3-oxetane-butyl)methoxymethyl]benzene (ARON OXETANE OXT-121, etc.), 3-ethyl-3-(phenoxymethyl)oxetane (ARON OXETANE OXT-211, etc.), di(1-ethyl-(3-oxetane-butyl))methyl ether (ARON OXETANE OXT-221, etc.), and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (ARON OXETANE OXT-212, etc.). Oxetane compounds are defined as compounds having one or more oxetane rings within their molecules.

[0143] When the polymerizable compound (X) has a free radical polymerizable functional group, the polymerizable compound (X') preferably has a free radical polymerizable functional group. As the polymerizable compound (X') having a free radical polymerizable functional group, it is preferably a compound having at least one free radical polymerizable functional group selected from the group consisting of vinyl, (meth)acryloyl, allyl, vinyl ether, and vinyl ester, and more preferably a compound having a (meth)acryloyl group. As the compound having a (meth)acryloyl group, it is more preferably at least one selected from the group consisting of (meth)acrylate and (meth)acrylamide.

[0144] Examples of (meth)acrylates include, for example, monofunctional (meth)acrylates such as ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, and ethoxylated o-phenylphenol acrylate, and polyfunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate and 1,12-dodecanediol di(meth)acrylate.

[0145] The polymerizable compound preferably contains a crosslinking compound (Y) having two or more polymerizable functional groups. The crosslinking compound (Y) can be a high-density compound or a low-density compound. Furthermore, the crosslinking compound (Y) can be a polymerizable compound (X) or a polymerizable compound (X').

[0146] As a crosslinking compound (Y), examples of the above-mentioned polymeric compounds include crosslinking compounds having two or more polymeric functional groups.

[0147] The proportion of the crosslinking compound (Y) in the polymerizable compound is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. This tends to further improve the curability of the composition and easily obtain a cured body with higher strength. Furthermore, the proportion of the crosslinking compound (Y) in the polymerizable compound is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. This further improves the adhesion to glass substrates, etc., and enables the formation of a sealing material with superior reliability. That is, the proportion of the crosslinking compound (Y) in the polymerizable compound can be, for example, 30–90% by mass, 30–85% by mass, 30–80% by mass, 35–90% by mass, 35–85% by mass, 35–80% by mass, 40–90% by mass, 40–85% by mass, or 40–80% by mass.

[0148] From the viewpoint of improved coatability and excellent moldability of the cured body of the composition of this embodiment, the viscosity of the total amount of the polymeric compound mixture at 80°C is preferably 500 mPa·s or more, more preferably 700 mPa·s or more, and even more preferably 1000 mPa·s or more. Furthermore, from the viewpoint of improved dischargeability during coating and expanded range of molding methods of the composition of this embodiment, the viscosity of the total amount of the polymeric compound mixture at 80°C is preferably 30000 mPa·s or less, more preferably 25000 mPa·s or less, and even more preferably 20000 mPa·s or less. That is, the viscosity of the total amount of the polymerizable compound mixture at 80°C can be 500–30000 mPa·s, 500–25000 mPa·s, 500–20000 mPa·s, 700–30000 mPa·s, 700–25000 mPa·s, 700–20000 mPa·s, 1000–30000 mPa·s, 1000–25000 mPa·s, or 1000–20000 mPa·s.

[0149] In this embodiment, multiple polymeric compounds can be combined such that the viscosity of the total mixture of polymeric compounds is within the above-mentioned range.

[0150] It should be noted that, in this specification, the viscosity of the total amount of the polymeric compound mixture at 80°C is expressed as a value measured using a cone rotor viscometer.

[0151] In this embodiment, the polymerization initiator has elements (M) in Groups 13 to 15 and Periods 4 to 6 of the periodic table. Examples of elements (M) include Ga (gallium), In (indium), Tl (thallium), Ge (germanium), Sn (tin), Pb (lead), As (arsenic), Sb (antimony), and Bi (bismuth).

[0152] In this embodiment, by using a polymerization initiator containing elements (M) from Groups 13 to 15 and Periods 4 to 6 of the periodic table as the polymerization initiator, a cured body with high crosslinking density, excellent moisture resistance, and excellent adhesion to glass substrates and the like can be formed from a polymerizable compound containing a high specific gravity compound.

[0153] In this embodiment, it is believed that by incorporating element (M) into the polymerization initiator, the molecular radius of the active species from the polymerization initiator increases (i.e., the charge density decreases), nucleophilicity decreases, and polymerizability increases. Therefore, it is believed that the crosslinking density of the cured polymeric compound increases, enabling the simultaneous achievement of excellent moisture resistance and adhesion to glass substrates, etc.

[0154] From the viewpoint of achieving the aforementioned effects more significantly, element (M) is preferably one or more elements from Group 13 and Group 15 of the periodic table, more preferably elements from Group 13. Ga (gallium) is a preferred element from Group 13. Sb (antimony) is a preferred element from Group 15.

[0155] The polymerization initiator can be, for example, a photopolymerization initiator. By using a photopolymerization initiator, the composition of this embodiment can be cured by irradiation with energy rays such as ultraviolet light.

[0156] The polymerization initiator is preferably a cationic polymerization initiator. By using a cationic polymerization initiator, polymerization of polymerizable compounds having cationic polymerizable functional groups can be carried out.

[0157] The polymerization initiator is preferably an onium salt containing onium ions and anions containing element (M).

[0158] An anion containing element (M) can be, for example, an anion represented by the following formula (M-1).

[0159] [Chemical Formula 3]

[0160]

[0161] [In the formula, n] 1 M represents an integer, where M represents (n 1 -1) Valence of the element (M), R 1 This indicates an alkyl or aryl group, which may have substituents. Multiple R groups... 1 They can be the same or different.

[0162] For example, if element (M) is gallium, the anion containing element (M) can be the anion represented by the following formula (M-2).

[0163] [Chemical Formula 4]

[0164]

[0165] [In the formula, R] 1 This indicates an alkyl or aryl group, which may have substituents. Multiple R groups... 1 They can be the same or different.

[0166] R 1 The alkyl group can be, for example, an alkyl group having 1 to 18 carbon atoms. R 1 The alkyl group can be in any form, including straight-chain, branched, or cyclic.

[0167] As R 1 Alkyl groups, for example, include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, sec-pentyl, n-hexyl, isohexyl, n-heptyl, sec-heptyl, n-octyl, n-nonyl, sec-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclopentyl, cyclohexyl, etc.

[0168] R 1 The alkyl group may have substituents. As R 1 Alkyl groups may have substituents, for example, alkoxy, aryl, heterocyclic, halogen atom, alkyl-substituted amino, aryl-substituted amino, unsubstituted amino (NH2 group, etc.), hydroxyl, mercapto, cyano, isocyano, etc.

[0169] R 1 The aryl group can be, for example, an aryl group with 6 to 14 carbon atoms. An aryl group is obtained by removing one hydrogen atom from an aromatic compound that is bonded to the aromatic ring.

[0170] As R 1 Aryl groups, for example, include phenyl, biphenyl, terphenyl, tetraphenyl, tolyl, indene, naphthyl, anthracene, fluorenyl, pyrene, phenanthryl, mesitylene, etc.

[0171] R 1 The aryl group can have substituents. As R 1 The aryl group may have substituents, for example, alkyl, alkoxy, aryl, heterocyclic, halogen atom, alkyl-substituted amino, aryl-substituted amino, unsubstituted amino (NH2 group, etc.), hydroxyl, mercapto, cyano, isocyano, etc.

[0172] R 1 Preferably, it is 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.

[0173] Examples of ononium ions include oxyonium ions, ammonium ions, phosphonium ions, sulfonium ions, and iodonium ions. From the viewpoint of obtaining the above-mentioned effects more significantly, the ononium ion is preferably one or more selected from the group consisting of ammonium ions, phosphonium ions, sulfonium ions, and iodonium ions, and more preferably one or more selected from the group consisting of sulfonium ions and iodonium ions.

[0174] Examples of oxonium ions include:

[0175] Trimethyloxonium, diethylmethyloxonium, triethyloxonium, tetramethylenemethyloxonium, and other oxonium compounds;

[0176] Pyranium compounds such as 4-methylpyranium, 2,4,6-trimethylpyranium, 2,6-di-tert-butylpyranium, and 2,6-diphenylpyranium;

[0177] 2,4-Dimethylchromeneonium, 1,3-Dimethylisochromeneonium, and other chromeneonium or isochromeneonium;

[0178] etc.

[0179] Examples of ammonium ions include:

[0180] N,N-Dimethylpyrrolidineonium, N-Ethyl-N-methylpyrrolidineonium, N,N-Diethylpyrrolidineonium, and other pyrrolidineonium;

[0181] N,N'-dimethylimidazoline, N,N'-diethylimidazoline, N-ethyl-N'-methylimidazoline, 1,3,4-trimethylimidazoline, 1,2,3,4-tetramethylimidazoline, and other imidazoline compounds;

[0182] Tetrahydropyrimidinium such as N,N'-dimethyltetrahydropyrimidinium, and morpholinium such as N,N'-dimethylmorpholinium;

[0183] N,N'-Diethylpiperidinium and other piperidinium;

[0184] N-methylpyridinium, N-benzylpyridinium, N-benzoylmethylpyridinium, and other pyridinium compounds;

[0185] N,N'-dimethylimidazolium and other imidazolium;

[0186] Quinolinium such as N-methylquinolinium, N-benzylquinolinium, and N-benzoylmethylquinolinium;

[0187] N-methylisoquinolineonium and other isoquinolineonium;

[0188] Thiazolonium such as benzylbenzothiazolonium and benzoylmethylbenzothiazolonium;

[0189] Acridine-onium, such as benzyl acridine-onium and benzoylmethyl acridine-onium;

[0190] etc.

[0191] Examples of phosphonium ions include:

[0192] Tetraphenylphosphonium, tetra-p-tolylphosphonium, tetra(2-methoxyphenyl)phosphonium, tetra(3-methoxyphenyl)phosphonium, tetra(4-methoxyphenyl)phosphonium and other tetraarylphosphonium;

[0193] Triarylphosphoniums such as triphenylbenzylphosphonium, triphenylbenzoylmethylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium;

[0194] Tetraalkylphosphonium, including triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylbenzoylmethylphosphonium, and tributylbenzoylmethylphosphonium;

[0195] etc.

[0196] Examples of matte ions include:

[0197] 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-fluorophenyl)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio) Phenylenyl di-tolylsulfonium, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium, [4-(2-thioxanthone thio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonyl}phenyl]sulfonium, bis{4-[bis(4-fluorophenyl)sulfonyl]phenyl}sulfonium, bis{4-[bis(4-methylphenyl)sulfonyl]phenyl}sulfonium, bis{4-[bis(4-methoxyphenyl)sulfonyl]phenyl}sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl) 4-(4-benzoyl-2-chlorophenylthio)phenyl diphenylsulfonium, 4-(4-benzoylphenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonium]thioxanthone, 2-[(diphenyl)sulfonium]thioxanthone, 4-(9-oxo-9H-thioxanth-2-yl)thio Triarylsulfonium compounds include phenyl-9-oxo-9H-thioxanth-2-ylphenylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thianthanethium, 5-phenylthianthianthium, 5-tolylthianthianthium, 5-(4-ethoxyphenyl)thianthianthium, and 5-(2,4,6-trimethylphenyl)thianthianthium.

[0198] Diphenylbenzoylmethyl sulfonium, diphenyl-4-nitrobenzylmethyl sulfonium, diphenylbenzyl sulfonium, diphenylmethyl sulfonium, and other diaryl sulfoniums;

[0199] Monoaryl sulfonates include phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl(2-naphthylmethyl)methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenylmethylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, 4-methoxyphenylmethylbenzoylmethylsulfonium, 4-acetylcarbonyloxyphenylmethylbenzoylmethylsulfonium, 2-naphthylmethylbenzoylmethylsulfonium, 2-naphthyloctadecylbenzoylmethylsulfonium, and 9-anthraylmethylbenzoylmethylsulfonium.

[0200] Trialkylsulfonium such as dimethylbenzoylmethylsulfonium, benzoylmethyltetrahydrothiophenonium, dimethylbenzylsulfonium, benzyltetrahydrothiophenonium, and octadecylmethylbenzoylmethylsulfonium;

[0201] etc.

[0202] Examples of iodonium ions include, for example, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0203] Commercially available products can be used as polymerization initiators. Examples of commercially available polymerization initiators include "CPI-310FG" (triarylsulfonium tetra(pentafluorophenyl)gallium salt).

[0204] The content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polymerizable compound. This further improves the curability. Furthermore, the content of the polymerization initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable compound. This further improves the adhesion to glass substrates, etc., enabling the formation of a sealing material with superior reliability. That is, the content of the polymerization initiator can be 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.1 to 5 parts by mass, or 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable compound.

[0205] The composition of this embodiment may further contain an inorganic filler. The inorganic filler is preferably an electrically insulating inorganic filler.

[0206] Examples of inorganic filler materials include silica particles, glass fillers, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, zinc oxide and other oxides, boron nitride, silicon nitride, aluminum nitride and other nitrides, silicon carbide and other carbides, aluminum hydroxide, magnesium hydroxide and other hydroxides, metals and alloys such as copper, silver, gold, iron, aluminum, nickel, titanium and other metals, diamond, carbon and other carbon-based filler materials, calcium carbonate, barium sulfate, talc, mica, etc.

[0207] Inorganic fillers can also be surface-treated using fatty acids, organosilicon coupling agents, titanate coupling agents, etc. One or more inorganic fillers can be used as needed.

[0208] The true specific gravity of the inorganic filler material can be, for example, 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more. Furthermore, the true specific gravity of the inorganic filler material can 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 material can be, for example, 1.3–20.0, 1.3–8.0, 1.3–5.0, 1.4–20.0, 1.4–8.0, 1.4–5.0, 1.5–20.0, 1.5–8.0, or 1.5–5.0. It should be noted that the true specific gravity of the inorganic filler material is expressed as a value measured according to ASTM D2840.

[0209] The inorganic filler material preferably includes at least one selected from the group consisting of silica, mica, kaolin, talc and alumina, and more preferably includes talc.

[0210] The inorganic filler material can be inorganic particles having an average particle size (hereinafter, sometimes simply referred to as particle diameter or particle size). The average particle size of the inorganic particles is preferably 0.005 μm or more, more preferably 0.01 μm or more. Furthermore, the average particle size of the inorganic particles is preferably 50 μm or less, more preferably 30 μm or less. That is, the average particle size of the inorganic particles can be 0.005–50 μm, 0.005–30 μm, 0.01–50 μm, or 0.01–30 μm. It should be noted that the average particle size of the inorganic particles represents the value measured using a MICROTRAC particle size distribution device by laser diffraction and scattering. The average particle size represents the cumulative 50% particle size (d50) in the particle size distribution.

[0211] The content of inorganic filler material relative to 100 parts by mass of the polymeric compound can be, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. Furthermore, the content of inorganic filler material relative to 100 parts by mass of the polymeric compound can be, for example, 500 parts by mass or less, or 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less. That is, relative to 100 parts by mass of the polymeric compound, the content of the inorganic filler material can be, for example, 5-500 parts by mass, 5-350 parts by mass, 5-300 parts by mass, 5-200 parts by mass, 5-100 parts by mass, 5-50 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 parts by mass, 15-300 parts by mass, 15-200 parts by mass, 15-100 parts by mass, or 15-50 parts by mass.

[0212] The composition of this embodiment may further include a photosensitizer. A photosensitizer is a compound that can absorb energy rays, thereby enabling the efficient generation of reactants (e.g., cations generated from photocationic polymerization initiators, radicals generated from photoradical polymerization initiators) from the polymerization initiator.

[0213] Photosensitizers are not particularly limited; examples include benzophenone derivatives, phenothiazine derivatives, phenyl ketone derivatives, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, and tetraphenyl derivatives. Derivatives, perylene derivatives, pentanebenzene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthones derivatives, xanthonone derivatives, thioxanthones derivatives, thioxanthonone derivatives, coumarin derivatives, coumarinone derivatives, anthocyanin derivatives, azazine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, triallylmethane derivatives, phthalocyanine derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, organorruthenium complexes, etc. Among these, phenyl ketone derivatives such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one and anthracene derivatives such as 9,10-dibutoxyanthracene are preferred, and anthracene derivatives are more preferred. Among anthracene derivatives, 9,10-dibutoxyanthracene is preferred. A single photosensitizer or a combination of two or more can be used.

[0214] When the composition of this embodiment contains a photosensitizer, the content of the photosensitizer, relative to 100 parts by mass of the polymeric compound, can be, for example, 0.01 parts by mass or more, or 0.02 parts by mass or more. Furthermore, from the viewpoint of storage stability, the content of the photosensitizer, relative to 100 parts by mass of the polymeric compound, can be, for example, 5 parts by mass or less, preferably 3 parts by mass or less. That is, when the composition of this embodiment contains a photosensitizer, the content of the photosensitizer, relative to 100 parts by mass of the polymeric compound, can be, for example, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.02 to 5 parts by mass, or 0.02 to 3 parts by mass.

[0215] The composition of this embodiment may further include a silane coupling agent. By incorporating a silane coupling agent, the adhesiveness and adhesive durability of the composition of this embodiment tend to be further improved.

[0216] Examples of silane coupling agents include, for example, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane, γ-(meth)acryloyloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and γ-ureidopropyltriethoxysilane. Among these, preferably one or more are selected from the group consisting of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropyltriethoxysilane, and γ-(meth)acryloyloxypropyltrimethoxysilane, more preferably γ-epoxypropoxypropyltrimethoxysilane. A single silane coupling agent may be used alone, or two or more may be used in combination.

[0217] When the composition of this embodiment contains a silane coupling agent, the content of the silane coupling agent relative to 100 parts by mass of the polymerizable compound can be, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more. Furthermore, the content of the silane coupling agent relative to 100 parts by mass of the polymerizable compound can be, for example, 10 parts by mass or less, preferably 5 parts by mass or less. That is, when the composition of this embodiment contains a silane coupling agent, the content of the silane coupling agent relative to 100 parts by mass of the polymerizable compound can be, for example, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.2 to 10 parts by mass, or 0.2 to 5 parts by mass.

[0218] The composition of this embodiment may also contain antioxidants.

[0219] The composition of this embodiment may further contain resin particles. By incorporating resin particles, it is easier to form a cured body with thickness. Therefore, the composition containing resin particles is more suitable as a sealant for dike formation.

[0220] As resin particles, resin particles that are insoluble in the composition and can maintain their shape can be used without particular limitation. Examples include polyethylene particles, polypropylene particles, cross-linked poly(methyl methacrylate) particles, cross-linked polystyrene particles, and cross-linked poly(methyl methacrylate)-polystyrene copolymer particles. Preferably, the resin particles are selected from at least one type chosen from the group consisting of cross-linked poly(methyl methacrylate) particles, cross-linked polystyrene particles, and cross-linked poly(methyl methacrylate)-polystyrene copolymer particles; more preferably, they are selected from at least one type chosen from the group consisting of cross-linked poly(methyl methacrylate) particles and cross-linked polystyrene particles.

[0221] The average particle size of the resin particles can be, for example, 0.1 μm or more, preferably 1 μm or more, and more preferably 5 μm or more. Furthermore, the average particle size of the resin particles can be, for example, 200 μm or less, preferably 100 μm or less. That is, the average particle size of the resin particles can be, for example, 0.1–200 μm, 0.1–100 μm, 1–200 μm, 1–100 μm, 5–200 μm, or 5–100 μm. It should be noted that, in this specification, the average particle size of the resin particles refers to the average particle size based on a volume standard measured using the "laser diffraction particle size distribution measuring device SALD-2200" manufactured by Shimadzu Corporation. The average particle size represents the cumulative 50% particle size (d50) in the particle size distribution.

[0222] Regarding resin particles, the standard deviation of the particle volume distribution relative to the particle size when the particle size (μm) is expressed logarithmically is preferably 0.25 or less. This suppresses deviations in the thickness of the cured body caused by deviations in the particle size, enabling more precise control of the cured body's dimensions. This standard deviation is more preferably 0.2 or less, and even more preferably 0.1 or less. Furthermore, this standard deviation can be, for example, 0.001 or more, or 0.005 or more. That is, the aforementioned standard deviation can be, for example, 0–0.25, 0–0.2, 0–0.1, 0.001–0.25, 0.001–0.2, 0.001–0.1, 0.005–0.25, 0.005–0.2, or 0.005–0.1.

[0223] When the composition of this embodiment contains resin particles, the content of resin particles relative to 100 parts by mass of the polymerizable compound can be, for example, 0.01 parts by mass or more, preferably 0.02 parts by mass or more, and more preferably 0.1 parts by mass or more. Furthermore, relative to 100 parts by mass of the polymerizable compound, the content of resin particles can be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. That is, when the composition of this embodiment contains resin particles, the content of resin particles relative to 100 parts by mass of the polymerizable compound can be, for example, 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, 0.01 to 4 parts by mass, 0.01 to 3 parts by mass, 0.02 to 10 parts by mass, 0.02 to 5 parts by mass, 0.02 to 4 parts by mass, 0.02 to 3 parts by mass, or 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass.

[0224] The composition of this embodiment may also contain other components besides those described above. Known additives used in the field of sealants may be used as other components without particular limitation. Examples of other components include, for instance, metal passivators, fillers, stabilizers, neutralizers, lubricants, and antibacterial agents.

[0225] When the composition of this embodiment is used as a sealant for cofferdam formation, from the viewpoint of improved coatability and excellent moldability of the cured body, the viscosity of the composition at 25°C can be, for example, 50,000 mPa·s or more, preferably 70,000 mPa·s or more, more preferably 80,000 mPa·s or more, and even more preferably 100,000 mPa·s or more. Furthermore, from the viewpoint of improved dischargeability during application and expanded range of molding methods, the viscosity of the composition at 25°C can be, for example, 1,000,000 mPa·s or less, preferably 950,000 mPa·s or less, more preferably 900,000 mPa·s or less, and even more preferably 850,000 mPa·s or less. That is, the viscosity of the composition in this embodiment at 25°C can be, for example, 50,000–1,000,000 mPa·s, 50,000–950,000 mPa·s, 50,000–900,000 mPa·s, 50,000–850,000 mPa·s, 70,000–1,000,000 mPa·s, 70,000–950,000 mPa·s, 70,000–900,000 mPa·s, 70,000–850,000 mPa·s. 0000mPa·s, 80000~1000000mPa·s, 80000~950000mPa·s, 80000~900000mPa·s, 80000~850000mPa ·s, 100000~1000000mPa·s, 100000~950000mPa·s, 100000~900000mPa·s, or 100000~850000mPa·s.

[0226] When the composition of this embodiment is used as a sealant for filling material formation, from the viewpoint of further improving the coatability of the composition, the viscosity of the composition at 25°C can be, for example, 5 mPa·s or more, preferably 6 mPa·s or more, more preferably 7 mPa·s or more, and even more preferably 8 mPa·s or more. Furthermore, from the viewpoint of further improving the expellability of the composition during application, the viscosity of the composition at 25°C can be, for example, 5000 mPa·s or less, preferably 4000 mPa·s or less, more preferably 3000 mPa·s or less, and even more preferably 2000 mPa·s or less. That is, the viscosity of the composition of this embodiment at 25°C can be, for example, 5–5000 mPa·s, 5–4000 mPa·s, 5–3000 mPa·s, 5–2000 mPa·s, 6–5000 mPa·s, 6–4000 mPa·s, 6–3000 mPa·s, 6–2000 mPa·s, 7–5000 mPa·s, 7–4000 mPa·s, 7–3000 mPa·s, 7–2000 mPa·s, 8–5000 mPa·s, 8–4000 mPa·s, 8–3000 mPa·s, or 8–2000 mPa·s.

[0227] The viscosity of the composition at 25°C is expressed as a value measured using a conical rotor viscometer. Regarding the composition of this embodiment, the types and amounts of each component can be appropriately adjusted so that the viscosity at 25°C is within the aforementioned range.

[0228] When the composition of this embodiment is used as a sealant for cofferdam formation, the ratio (η2 / η1) of the viscosity η2 at 25°C and 0.1 rpm to the viscosity η1 at 25°C and 1 rpm is preferably 1.1 to 10.0. If the ratio (η2 / η1) is 1.1 or higher, the coatability of the composition tends to be further improved and the formability of the cured body is more excellent. From the viewpoint that this tendency becomes more significant, the ratio (η2 / η1) is preferably 1.15 or higher, more preferably 1.2 or higher. In addition, if the ratio (η2 / η1) is 10.0 or lower, the dischargeability of the composition during application tends to be further improved. From the viewpoint that this tendency becomes more significant, the ratio (η2 / η1) is preferably 9.5 or lower, more preferably 9.0 or lower. That is, the ratio (η2 / η1) can be, for example, 1.1 to 10.0, 1.1 to 9.5, 1.1 to 9.0, 1.15 to 10.0, 1.15 to 9.5, 1.15 to 9.0, 1.2 to 10.0, 1.2 to 9.5, or 1.2 to 9.0.

[0229] When the composition of this embodiment is used as a sealant for filling material formation, the ratio (η2 / η1) of the composition of this embodiment is preferably 0.9 to 1.5. If the ratio (η2 / η1) is 0.9 or more, the coatability of the composition tends to be further improved. In addition, if the ratio (η2 / η1) is 1.5 or less, the expulsion properties of the composition during application tend to be further improved.

[0230] The viscosity η1 of the composition at 25°C and 1 rpm and the viscosity η2 at 25°C and 0.1 rpm represent values ​​measured using a conical rotor viscometer. With respect to the composition of this embodiment, the types and amounts of each component can be appropriately adjusted so that the ratio (η2 / η1) is within the above-mentioned range.

[0231] The liquid specific gravity of the composition in this embodiment is preferably 1.3 to 4.0. The liquid specific gravity of the composition is preferably 1.4 or more, more preferably 1.5 or more. Furthermore, the liquid specific gravity of the composition is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. That is, the liquid specific gravity of the composition in this embodiment can be, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0, 1.4 to 3.0, 1.4 to 2.5, 1.4 to 2.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5, or 1.5 to 2.0. It should be noted that the liquid specific gravity of the composition is the value measured using a 5 mL capped Lürth type specific gravity bottle according to JIS-K-0061 8.2.2.

[0232] Regarding the composition of this embodiment, the types and contents of each component can be appropriately adjusted so that the liquid specific gravity is within the above-mentioned range.

[0233] The method for manufacturing the composition of this embodiment is not particularly limited, as long as the above-described components are thoroughly mixed. Examples of mixing methods include stirring methods utilizing the stirring force accompanying the rotation of a propeller, and methods using conventional dispersers such as planetary mixers based on rotation and revolution. These mixing methods are preferred from the perspective of low cost and stable mixing.

[0234] By curing the composition of this embodiment, a cured polymer containing a polymeric compound can be obtained. This cured polymer has low moisture permeability and can be suitable for use as a sealing material (especially a sealing material for organic EL display elements).

[0235] The composition of this embodiment can be cured by, for example, irradiation with energy rays. There are no particular limitations on the light source used for curing the composition of this embodiment; examples include halogen lamps, metal halide lamps, high-power metal halide lamps (containing indium, etc.), low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, xenon excimer lamps, xenon flash lamps, and light-emitting diodes (hereinafter referred to as LEDs). These light sources are preferred from the viewpoint of efficiently irradiating with energy rays corresponding to the reaction wavelengths of each photopolymerization initiator.

[0236] The aforementioned light sources each have different emission wavelengths and energy distributions. Therefore, these light sources can be appropriately selected based on factors such as the reaction wavelength of the polymerization initiator. Additionally, natural light (sunlight) can also serve as a light source for initiating the reaction.

[0237] Irradiation from the aforementioned light source can be direct irradiation or focused irradiation using reflectors, optical fibers, etc. Alternatively, irradiation can utilize low-wavelength cutoff filters, thermal ray cutoff filters, cold mirrors, etc.

[0238] During the curing of the composition of this embodiment, a post-heating treatment can be performed after light irradiation to promote curing. From the viewpoint of avoiding the influence on the organic EL display element, the post-heating temperature is preferably 150°C or lower, more preferably 100°C or lower. The post-heating temperature is preferably 40°C or higher.

[0239] The composition of this embodiment can also be used as an adhesive. The composition of this embodiment can be suitably used for bonding, for example, packages such as organic EL display elements.

[0240] As a method for bonding two components using the composition of this embodiment, an example method can be described including the following steps: applying the composition to the entire surface or a portion of the first component; irradiating the composition applied to the first component with light; and bonding the first component and the second component together with the composition during the period before the light-irradiated composition cures. According to such a method, the second component can be bonded to the first component without exposure to light and heat. Therefore, the above method can be suitably used for bonding a back panel to an organic EL display element.

[0241] As a method for manufacturing an organic EL display device using the composition of this embodiment, an example manufacturing method may include the following steps: a step of coating a back panel with the composition; a step of irradiating the composition coated on the back panel with light; and a step of blocking the light and bonding the back panel to the substrate on which the organic EL display element is formed by means of the composition. According to such a method, the organic EL display element can be sealed without being exposed to light and heat.

[0242] In addition, as a method for manufacturing an organic EL display device using the composition of this embodiment, a manufacturing method including the following steps can also be cited: a step of coating the composition on a substrate; a step of bonding one substrate to another substrate by means of the composition; and a step of curing the composition by irradiating the composition between the substrates with light.

[0243] The specific gravity of the cured body of the composition in this embodiment (hereinafter also simply referred to as the cured body of this embodiment) is, for example, 1.35 or more. Furthermore, the specific gravity of the cured body in this embodiment is, for example, 19.0 or less. It should be noted that the specific gravity of the cured body is a value measured according to JIS K7112 B method, using water at 23°C as the impregnation liquid.

[0244] Regarding the composition of this embodiment, the types and contents of each component can be appropriately adjusted so that the specific gravity of the cured body is within the above-mentioned range.

[0245] In the cured body of this embodiment, the glass transition temperature of the polymer of the polymeric compound can be, for example, 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, and even more preferably 85°C or higher.

[0246] It should be noted that in this specification, the glass transition temperature (Tg) of the polymer is a value determined based on dynamic viscoelastic spectroscopy. In dynamic viscoelastic spectroscopy, the temperature at which the loss tangent (hereinafter referred to as tanδ) peak is observed when stress and strain are applied to the polymer at a certain heating rate can be taken as the glass transition temperature. It should be noted that if a tanδ peak does not appear even when heated from a sufficiently low temperature of around -150°C to a certain temperature (Ta°C), the glass transition temperature can be considered to be below -150°C or above that temperature (Ta°C). However, since it is assumed that there will be no cured product with a glass transition temperature below -150°C, it can be determined that the glass transition temperature is above that temperature (Ta°C).

[0247] Regarding the composition of this embodiment, the types and contents of each component can be appropriately adjusted so that the glass transition temperature of the polymer is within the above-mentioned range.

[0248] For the cured body of this embodiment, the crosslinking density is preferably 1.0 × 10⁻⁶. -3 mol / cm 3 The above is preferred, and more preferably is 2.0×10 -3 mol / cm 3 The above suggests that the presence of numerous binding sites in the cured body suppresses microscopic Brownian motion, further reducing moisture permeability. Additionally, the crosslinking density of the cured body can, for example, be 1.0 mol / cm³. 3Therefore, the reliability reduction caused by the brittleness of the cured body is further suppressed.

[0249] It should be noted that in this specification, the crosslinking density of the cured body is a value obtained from dynamic viscoelastic spectroscopy. Specifically, a 100 μm thick cured body is cut into test pieces with a width of 5 mm and a length of 25 mm. Dynamic viscoelasticity measurements are performed on these test pieces under the conditions of a temperature range of -50℃ to 200℃, a heating rate of 2℃ / min, and tensile mode, to determine the relationship between temperature and storage modulus (G'). The crosslinking density is defined as T(K) at Tg+40℃ and G' as the storage modulus (G') at T(K). T+40 The gas constant is set to R, and the pre-factor is set to φ (=1), which is calculated using the following formula.

[0250] Crosslinking density (ρ) = G' T+40 / φRT

[0251] Regarding the composition of this embodiment, the types and contents of each component can be appropriately adjusted so that the crosslinking density of the cured body is within the above-mentioned range.

[0252] In the case of the cured body of this embodiment, the mean free volume of the cured body is preferably 1 nm. 3 Below, less than 1nm is preferred. 3 More preferably 0.5nm 3 The following is further preferred to be 0.3nm. 3 The preferred size is 0.1nm. 3 Below, a further preferred size is less than 0.1 nm. 3 .

[0253] One known method for determining the free volume of polymers is the positron annihilation method (see Polymer, Vol. 42, December 1993). Typically, positrons (ep) are annihilated... + When incident on a polymer, positrons and electrons (e) - The positrons combine to form positron-electron atoms (Ps). The so-called positron annihilation method refers to determining the free volume of a polymer by measuring the lifetime (τ3) of the positron-electron dipole atoms (o-Ps, radius 0.1 nm, hereinafter also referred to as "o-Ps") that make up 3 / 4 of the positron-electron atoms (Ps) when they enter the pores of the polymer. The lifetime (τ3) of o-Ps is determined by the number of positrons (electrons) released when the o-Ps collides with the walls of the pores in the polymer. + ) and electrons (e) in the walls of the pores -The probability of overlap determines that the larger the pore size of the polymer, the longer the lifetime (τ3) of o-Ps. Treating the pore as an infinitely high spherical well potential, and assuming an electron layer of thickness ΔR on the pore wall, the positron (ep) is calculated by overlaying this electron layer with the wave function of o-Ps. + The model of annihilation rate matches well with the data from actual experiments. Therefore, if the pore diameter R of the polymer reaches about 0.16 to 0.8 nm, the following equation (1) holds true between the lifetime τ3 of o-Ps and the pore diameter R.

[0254] [Mathematical Expression 1]

[0255]

[0256] (In the above formula (1), τ3 represents the measured lifetime of the positron-pair (o-Ps), R represents the pore diameter of the polymer, and ΔR represents the thickness of the pore wall.)

[0257] That is, by using the positron annihilation method to determine the lifetime (τ3) of the positron-pair (o-Ps), the pore diameter R of the polymer can be calculated from the above equation (1). Furthermore, since the pore volume (mean free volume) = 4 / 3πR 3 Therefore, the mean free volume of the polymer can be calculated based on the obtained value of the pore diameter R.

[0258] Regarding the composition of this embodiment, the types and contents of each component can be appropriately adjusted so that the average free volume of the cured body is within the above-mentioned range.

[0259] In the case of the cured body of this embodiment, the pore diameter of the cured body is preferably less than 20%.

[0260] The free volume analyzed using positron annihilation represents the region not occupied by molecular chains forming porous substrates and electrolytes, reflecting the volume generated near these molecular chains when they change. Specifically, the free volume can be determined by measuring the time from positron incident on the sample until annihilation, and non-destructively observing information related to atomic porosity, free volume size, number density, etc., based on the annihilation lifetime.

[0261] A positron is the antiparticle of the electron, a fundamental particle with the same mass but opposite charge. In amorphous solids such as polymers, positrons sometimes pair with electrons, forming positronic elements. When a positronic element annihilates, it releases annihilation gamma rays in two directions. By measuring the time-varying intensity of these annihilation gamma rays, the lifetime of the positron can be determined.

[0262] Positrons include parapositrons and positron-p ...

[0263] Specifically, the lifetime of positrons is analyzed using a three-component nonlinear least squares method. The self-annihilation lifetimes, from smallest to largest, are denoted as τ1, τ2, and τ3, and their corresponding intensities are denoted as I1, I2, and I3 (I1 + I2 + I3 = 100%). Using the above I1, I2, and I3 and the following formula, the porosity of the polymer is defined.

[0264] Porosity (%) = I3 / (I1+I2+I3)

[0265] Regarding the composition of this embodiment, the type and content of each component can be appropriately adjusted so that the porosity of the polymer is within the above-mentioned range.

[0266] Regarding the cured body of this embodiment, the water permeability measured according to JIS Z0208 at a temperature of 85°C and a relative humidity of 85% is 100 g / m³. 2 • 24h / 100μm or less, preferably 60 (g / m 2 • 24h / 100μm or less, more preferably 55 (g / m 2 • 24h / 100μm or less, more preferably 50 (g / m 2 • 24h / 100μm or less. By achieving low moisture permeability, when used as a sealing material for organic EL display elements, the generation of dark spots caused by moisture reaching the organic light-emitting material layer can be significantly suppressed. It should be noted that the above-mentioned moisture permeability can also be described as the moisture permeability (g / m³) of a 100μm thickness measured according to JIS Z 0208:1976 after exposure at 85°C and 85%RH for 24 hours. 2 The aforementioned water permeability can be, for example, 0.001 g / m³. 2 • 24h / 100μm or higher, or 0.01g / m 2 • 24h / 100μm or higher, or 0.03 (g / m 2 • 24h / 100μm or higher, or 0.1g / m 2 • 24h / 100μm or higher. That is, the above-mentioned permeability can be, for example, 0 to 100 (g / m²). 2·24h / 100μm), 0~60 (g / m 2 ·24h / 100μm), 0~55 (g / m 2 ·24h / 100μm), 0~50 (g / m 2 ·24h / 100μm), 0.001~100(g / m 2 ·24h / 100μm), 0.001~60(g / m 2 ·24h / 100μm), 0.001~55(g / m 2 ·24h / 100μm), 0.001~50(g / m 2 ·24h / 100μm), 0.01~100(g / m 2 •24h / 100μm), 0.01~60 (g / m 2 • 24h / 100μm), 0.01~55 (g / m 2 • 24h / 100μm), 0.01~50 (g / m 2 ·24h / 100μm), 0.03~100(g / m 2 •24h / 100μm), 0.03~60 (g / m 2 •24h / 100μm), 0.03~55 (g / m 2 • 24h / 100μm), or 0.03~50 (g / m 2 •24h / 100μm).

[0267] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0268] For example, the present invention may relate to a method for manufacturing an organic electroluminescent display device having a dike-filled sealing structure, the method comprising a step of coating the above-described composition and curing it to form a dike.

[0269] Alternatively, the present invention may relate to an organic EL display device having a cofferdam-filled sealing structure with a cofferdam and a filler, wherein the cofferdam may comprise a cured form of the above-described composition.

[0270] It should be noted that the cofferdam and filling sealing structure can be a known cofferdam and filling sealing structure, and the filler can be a known filler. Furthermore, the components of the OLED display device other than the cofferdam and filling sealing structure can be the same as those of known OLED display devices.

[0271] The present invention may relate to a method for manufacturing an organic electroluminescent display device having a dike-fill sealing structure, the manufacturing method comprising a step of coating the above-described composition and curing it to form a filler.

[0272] Alternatively, the present invention may relate to an organic EL display device having a cofferdam-fill sealing structure with a cofferdam and a filler, wherein the filler may comprise a cured form of the above-described composition.

[0273] It should be noted that the cofferdam / filling sealing structure can be a known cofferdam / filling sealing structure, and the cofferdam agent used to form the cofferdam can be a known cofferdam agent or the composition of this embodiment. Furthermore, the components of the organic EL display device other than the cofferdam / filling sealing structure can be the same as those of known organic EL display devices.

[0274] This invention provides a sealant capable of forming a sealing material with excellent moisture resistance and adhesion to glass substrates, etc. Furthermore, according to this invention, a cured form of the sealant, a method for manufacturing an organic electroluminescent display device using the sealant, and an organic electroluminescent display device having a sealing material formed from the sealant are provided.

[0275] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0276] Example

[0277] The present invention will now be described in more detail using examples, but the invention is not limited to these examples. Unless otherwise specified, the examples were conducted at 23°C and 50% by mass relative humidity.

[0278] The following compounds were used in the examples and comparative examples.

[0279] (A) Polymerizable compounds - high specific gravity compounds (polymerizable compounds with a specific gravity of 1.3 to 4.0)

[0280] (A-1) Dibromophenyl glycidyl ether (BR-250 manufactured by Nippon Kayaku Co., Ltd.) (Maximum atomic number: 35, specific gravity: 1.8, number of polymerizable functional groups per molecule: 1)

[0281] (A-2) TBBPA (Tetrabromobisphenol A) epoxy resin (DIC Company "Epiclon 152") (Maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups per molecule: 2)

[0282] (A-3) Brominated bisphenol A type epoxy resin (Sakamoto Pharmaceutical Co., Ltd. "SR-T1000") (Maximum atomic number: 35, specific gravity: 1.7, number of polymerizable functional groups per molecule: 2)

[0283] (A-4)2,2,3,3,4,4,5,5,6,6,7,7,7-Tetrafluoroheptylethylene oxide (DAIKIN Industries "C6Epoxy") (Maximum atomic number: 9, specific gravity: 1.5, number of polymerizable functional groups per molecule: 1)

[0284] (B) Polymerizable compounds - low specific gravity compounds (polymerizable compounds with a specific gravity less than 1.3)

[0285] (B-1) 3',4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (Daicel Chemicals, “Celloxide 2021P”) (Maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups per molecule: 2)

[0286] (B-2) Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation "jER828", molecular weight 360-390) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups per molecule: 2)

[0287] (B-3) Phenol Novolac type epoxy resin (DIC "EPICLON N-775") (Maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in 1 molecule: 2 or more)

[0288] (B-4) Cyclohexanediethanol divinyl ether (NIPPON CARBIDE "CHDVE") (Maximum atomic number: 8, specific gravity: 0.9, number of polymerizable functional groups per molecule: 1)

[0289] The following substance is used as the polymerization initiator for (C).

[0290] (C-1) Triarylsulfonium tetra(pentafluorophenyl)gallium salt (San-Apro Corporation, "CPI-310FG", listed as "CPI-310FG" in the table).

[0291] (C-2) Triarylsulfonium hexafluoroantimonate (ADEKA OPTOMER SP-170, anionic species is hexafluoroantimonate)

[0292] (C-3) Aryliodonium-hexafluorophosphate (BASF "Irgacure 250", listed as "Irgacure 250" in the table).

[0293] (C-4) Arylsulfonium hexafluorophosphate (BASF manufacturer, "Irgacure 270", listed as "Irgacure 270" in the table).

[0294] (C-5) Triphenylsulfonium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd., listed as "BF4" in the table).

[0295] (C-6) Tri-tolylsulfonium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd., listed as "CF3SO3" in the table).

[0296] The following substance is used as (D) photosensitizer.

[0297] (D-1)9,10-Dibutoxyanthracene (ANTHRACURE UVS-1331, manufactured by Kawasaki Chemical Industry Co., Ltd.)

[0298] The following substances are used as (E) silane coupling agents.

[0299] (E-1)γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Silicone, “KBM-403”)

[0300] The following substances are used as (F) inorganic filler materials.

[0301] (F-1) Microparticle talc, particle size (d50): 4.5 μm, true specific gravity: 2.7 (Made by Matsumura Sangyo Co., Ltd., "#5000PJ")

[0302] (F-2) Particulate silica, particle size (d50): 4.2 μm, true specific gravity: 1.9 (manufactured by Denka Co., Ltd., "FB-5SDX")

[0303] The following substances are used as (G) resin particles.

[0304] (G-1)GS-210: Spherical cross-linked polystyrene particles (manufactured by Ganz Chemical Co., Ltd. as "GS-210") (average particle size: 20.0 μm, standard deviation: 0.06 μm)

[0305] The raw materials of the types shown in Table 1 or Table 2 were mixed in the composition ratios shown in Table 1 or Table 2 to prepare the sealants of the examples and comparative examples. The unit of composition ratio is parts by mass.

[0306] [Table 1]

[0307]

[0308] [Table 2]

[0309]

[0310] The sealants (or components thereof) of the examples and comparative examples were subjected to the following measurements. The results are shown in Table 1 or Table 2.

[0311] [Specific gravity of polymeric compounds]

[0312] The determination was performed using a Hubbard-shaped specific gravity bottle in accordance with JIS K0061.

[0313] [Liquid Specific Gravity]

[0314] The determination was performed using a 5 mL cap Lüthner specific gravity bottle, in accordance with section 8.2.2 of JIS-K-0061.

[0315] [Light curing conditions]

[0316] When evaluating the curing and adhesion properties of the sealant, the sealant was cured under the following light irradiation conditions: A UV curing apparatus (manufactured by FUSION Corporation) equipped with an electrodeless discharge metal halide lamp was used, with a cumulative light intensity of 4,000 mJ / cm² at a wavelength of 365 nm. 2 Under certain conditions, the sealant is light-cured, and then post-heat treatment is carried out in an oven at 100°C for 60 minutes to obtain the cured body.

[0317] [Specific gravity of the cured body]

[0318] A sheet-like cured body with a thickness of 0.1 mm was prepared under the aforementioned light curing conditions, and its thickness was measured according to JIS K7112 B method. Water at a temperature of 23°C was used as the impregnation solution.

[0319] [Elastic modulus at Tg and Tg+40℃ (storage elastic modulus)]

[0320] A 0.1 mm thick sheet of cured material was prepared under the aforementioned photocuring conditions. A 100 μm thick cured material was then cut into test pieces measuring 5 mm wide and 25 mm long. Dynamic viscoelasticity was measured on these test pieces under tensile conditions within a temperature range of -50 °C to 200 °C and a heating rate of 2 °C / min. The storage modulus was determined by this measurement. The temperature of the peak of tanδ (loss tangent) obtained from the dynamic viscoelasticity measurement was taken as the glass transition temperature (Tg) of the cured material.

[0321] [Cross-linking density]

[0322] A 0.1 mm thick sheet of cured material was prepared under the aforementioned photocuring conditions. A 100 μm thick cured material was then cut into test pieces measuring 5 mm wide and 25 mm long. Dynamic viscoelasticity was measured on these test pieces under the following conditions: a temperature range of -50℃ to 200℃, a heating rate of 2℃ / min, and a tensile mode. The crosslinking density was defined as T(K) at Tg+40℃, and the storage modulus (G') at T(K) (referred to as "elastic modulus" in the table) was defined as G'. T+40 The gas constant is set as R, and the coefficient is set as φ (=1). The following formula is used to calculate the gas constant.

[0323] Crosslinking density (ρ) = G' T+40 / φRT

[0324] [Average particle size, standard deviation]

[0325] The average particle size (sometimes referred to as average particle size or particle size) of inorganic filler materials and resin particles, and the standard deviation of particle volume distribution relative to particle size when particle size (μm) is expressed logarithmically (the “standard deviation” mentioned above) are measured using a laser diffraction particle size distribution measuring device (Shimadzu Corporation “SALD-2200”).

[0326] [Tensile shear bond strength]

[0327] Two borosilicate glass test pieces (25mm x 25mm x 2.0mm, TEMPAX (registered trademark) glass) were used, with an adhesion area of ​​0.5cm². 2 Borosilicate glass test pieces were bonded together with a sealant to a thickness of 10 μm, and the sealant was cured under the aforementioned light-curing conditions. After curing, the tensile shear bond strength (unit: MPa) was measured using the sealant-bonded test pieces at a temperature of 23°C and a relative humidity of 50% at a tensile speed of 10 mm / min.

[0328] [Humidity permeability]

[0329] A 0.1 mm thick sheet-like cured body was prepared under the aforementioned light-curing conditions. Following JIS Z0208 "Test Method for Moisture Permeability of Moisture-proof Packaging Materials (Cup Method)," anhydrous calcium chloride was used as the desiccant, and the test was conducted at an ambient temperature of 85°C and a relative humidity of 85%. The preferred moisture permeability was 50 g / (m³). 2 • Less than 24 hours.

[0330] Fabrication of organic EL (Elastic Optical Component) substrates

[0331] The glass substrate (25mm x 25mm) with ITO electrodes was cleaned using acetone and isopropanol. Then, the following compounds were sequentially deposited as thin films using vacuum evaporation to obtain an organic EL device substrate comprising an anode / hole injection layer / hole transport layer / light-emitting layer / electron injection layer / cathode. The structure of each layer is described below.

[0332] • Anode: ITO, anode film thickness 250nm

[0333] Hole injection layer: copper phthalocyanine, 30nm thick

[0334] Hole transport layer: N,N'-diphenyl-N,N'-dinaphthylbenzidine (α-NPD), 20 nm thick

[0335] • Light-emitting layer: Tri(8-hydroxyquinoline)aluminum (metal complex material), film thickness of the light-emitting layer

[0336] • Electron injection layer: Lithium fluoride, 1 nm thick

[0337] • Cathode: Aluminum, cathode film thickness 250nm

[0338] [Fabrication of Organic EL Components]

[0339] Under a nitrogen atmosphere, a coating device is used to apply a sealant in a quadrilateral shape (side length 20 mm, coating width 0.6 mm, coating height 0.1 mm) onto a glass substrate. The sealant is applied to achieve a bonding thickness of 10 μm, thereby bonding the glass substrate and the organic EL element substrate together. The sealant is then cured under the aforementioned photocuring conditions to fabricate the organic EL element.

[0340] [Organic EL Evaluation]

[0341] [Initial stage]

[0342] A 6V voltage was applied to the freshly fabricated organic EL element, and the luminescence state of the organic EL element was observed visually and under a microscope to determine the diameter of the dark spot.

[0343] [After high temperature and high humidity test]

[0344] After exposing the freshly fabricated organic EL element to 85°C and 85% relative humidity for 300 hours, a voltage of 6V was applied, and the luminescence state of the organic EL element was observed visually and under a microscope, and the diameter of the dark spot was measured.

[0345] It should be noted that a dark spot diameter of less than 60 μm is ideal, less than 40 μm is even more ideal, and no dark spots are the most ideal.

Claims

1. A sealant comprising a polymerizable compound and a gallium-containing cationic polymerization initiator. The polymerizable compound contains a compound (X) with a specific gravity of 1.3 to 4.0, wherein the compound (X) has at least one halogen element selected from the group consisting of fluorine and bromine, and has a cationic polymerizable functional group. The cationic polymerization initiator is an onium salt containing onium ions and gallium-containing anions.

2. The sealant as claimed in claim 1, wherein, When the sealant is cured to form a cured polymer containing the polymeric compound, The specific gravity of the cured body is 1.35 to 19.

0.

3. The sealant as described in claim 1 or 2, wherein, The content of halogens in the compound (X) is 10 to 50 by mass relative to the total elemental mass of the polymeric compound.

4. The sealant as described in claim 1 or 2, wherein, The polymeric compound contains a crosslinked compound (Y) having two or more polymeric functional groups.

5. The sealant as described in claim 1 or 2, wherein, The polymeric compound contains at least one selected from the group consisting of glycidyl ether compounds, alicyclic epoxy compounds, vinyl ether compounds, and oxetane compounds.

6. The sealant as claimed in claim 1 or 2, further comprising an inorganic filler material.

7. The sealant as claimed in claim 6, wherein, The true specific gravity of the inorganic filler material is 1.5 to 5.

0.

8. The sealant as claimed in claim 6, wherein, The inorganic filler material is an electrically insulating inorganic filler material.

9. The sealant as claimed in claim 6, wherein, The inorganic filler material contains at least one selected from the group consisting of silica, mica, kaolin, talc and alumina.

10. The sealant of claim 6, wherein, The content of the inorganic filler material is 5 to 500 parts by mass relative to 100 parts by mass of the polymeric compound.

11. The sealant as claimed in claim 1 or 2, further comprising resin particles.

12. The sealant of claim 11, wherein, The resin particles contain at least one selected from the group consisting of cross-linked poly(methyl methacrylate) particles, cross-linked polystyrene particles, and cross-linked poly(methyl methacrylate) polystyrene copolymer particles.

13. The sealant of claim 11, wherein, The average particle size of the resin particles is 1 μm to 100 μm.

14. The sealant of claim 11, wherein, The standard deviation of the particle volume distribution relative to the particle size when the particle size is expressed logarithmically is less than 0.25, and the unit of particle size is μm.

15. The sealant of claim 11, wherein, The content of the resin particles is 0.01 to 5 parts by mass relative to 100 parts by mass of the polymeric compound.

16. The sealant as claimed in claim 1 or 2, wherein, The content of the polymerization initiator is 0.01 to 5 parts by mass relative to 100 parts by mass of the polymerizable compound.

17. The sealant as claimed in claim 1 or 2, wherein, When the sealant is cured to form a cured polymer containing the polymeric compound, The glass transition temperature of the polymer is above 85°C.

18. The sealant as claimed in claim 1 or 2, wherein, When the sealant is cured to form a cured polymer containing the polymeric compound, The crosslinking density of the cured body is 1.5 × 10⁻⁶. -3 mol / cm 3 above.

19. The sealant as claimed in claim 1 or 2, wherein, When the sealant is cured to form a cured polymer containing the polymeric compound, The permeability of the cured body, measured according to JIS Z0208 at 85°C and 85% relative humidity, is 50 g / m³. 2 • Below 24h / 100μm.

20. The sealant as described in claim 1 or 2, wherein it is a sealant for organic electroluminescent display elements.

21. A cured body, which is formed by curing the sealant according to any one of claims 1 to 20.

22. A method for manufacturing an organic electroluminescent display device having a sealed structure comprising a cofferdam and a filler, the method comprising the steps of applying a sealant according to any one of claims 1 to 20 and curing it to form a filler.

23. A method for manufacturing an organic electroluminescent display device having a sealed structure comprising a dam and a filler, the method comprising the steps of applying a sealant according to any one of claims 1 to 20 and curing it to form a dam.

24. An organic electroluminescent display device having a sealed structure with a dike and filler. At least one of the cofferdam and the filling material comprises a cured form of the sealant according to any one of claims 1 to 20.

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