WO2021201013A1 - 封止剤、硬化体、有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス表示装置の製造方法 - Google Patents
封止剤、硬化体、有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス表示装置の製造方法 Download PDFInfo
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
Definitions
- the present invention relates to a sealant, a cured product, an organic electroluminescence display device, and a method for manufacturing an organic electroluminescence display device.
- organic electroluminescence (organic EL) display elements and organic thin film solar cell elements have been promoted. Since the organic thin film device can be easily manufactured by vacuum deposition, solution coating, or the like, it is excellent in productivity.
- the organic EL display element is a thin film structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into the organic light emitting material layer from one electrode and holes are injected from the other electrode, so that the electrons and holes are combined in the organic light emitting material layer to perform self-emission. Compared with a liquid crystal display element or the like that requires a backlight, it has the advantages of better visibility, thinner size, and low DC voltage drive.
- an organic EL display element has a problem that when the organic light emitting material layer or the electrode is exposed to the outside air, its light emitting characteristics are rapidly deteriorated and its life is shortened. Therefore, in order to improve the stability and durability of the organic EL display element, a sealing technology that shields the organic light emitting material layer and the electrode from the moisture and oxygen in the atmosphere is indispensable in the organic EL display element. There is.
- Patent Document 1 discloses a method of filling an organic EL display element substrate with a photocurable sealant and irradiating it with light to seal it in a top-emitting organic EL display element or the like.
- Patent Documents 2 to 4 disclose techniques for sealing an organic EL display element to prevent deterioration due to moisture.
- Patent Document 5 contains (A) an epoxy compound, (B) an epoxy resin, and (C) a photocationic polymerization initiator, and has a water content of 1000 ppm or less and a chlorine content of 1000 ppm or less. The composition is disclosed. However, Patent Document 5 does not describe the specific gravity of the polymerizable compound.
- Patent Document 6 discloses a photocurable resin composition containing a cationically polymerizable compound, a photocationic polymerization initiator, and a plate-shaped fine particle inorganic filler having a specific shape.
- the composition described in Patent Document 6 cannot obtain sufficient moisture permeability, and it is difficult to apply it to an organic electroluminescence display element. Further, Patent Document 6 does not describe the specific gravity of the polymerizable compound.
- Patent Document 7 contains a polyfunctional cationically polymerizable compound, an organic layered silicate, and a curing agent.
- the organic layered silicate is dispersed in the polyfunctional cationically polymerizable compound, and the organic layered silicate is dispersed in the polyfunctional cationically polymerizable compound.
- Curable resin compositions are disclosed. However, with the resin composition described in Patent Document 7, sufficient moisture permeability may not be obtained in some cases. Further, Patent Document 7 does not describe the specific gravity of the polymerizable compound.
- Patent Document 8 contains (a) an epoxy compound and (b) a compound having two or more crosslinkable groups reactive with the epoxy compound in a specific ratio, and has a refractive index of 1.6 or more. Moreover, a low moisture permeability epoxy resin composition is disclosed. However, the resin composition described in Patent Document 8 may not have sufficient moisture permeability. Further, Patent Document 8 does not describe the specific gravity of the polymerizable compound.
- Patent Document 9 describes a curable composition containing an organic polymer (A) having a specific reactive silicon group and a polyoxyalkylene polymer (B) having a specific reactive silicon group.
- a curable composition characterized in that the specific gravity of the sex composition is 0.9 or more and 1.3 or less is disclosed.
- Patent Document 9 does not describe reducing the moisture permeability by adjusting the specific gravity of the polymerizable compound.
- Patent Document 10 describes a copolymer obtained by photopolymerizing a composition containing 10 to 70% by weight of a bromine-added bisphenol A type epoxy (meth) acrylate having a specific structure, and has a refractive index of 1.58 or more. , A photocurable resin lens having a specific gravity of 1.5 or less and an Abbe number of 30 or more is disclosed. However, Patent Document 10 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing the organic EL display element.
- Patent Document 11 describes a specific polysiloxane copolymer that is photopolymerized and has a functional acrylic group, and is suitable for restoring a specific gravity greater than about 1.0 and the refractive index of a natural crystalline lens. A polysiloxane copolymer having a refractive index is disclosed. However, Patent Document 11 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing the organic EL display element.
- Patent Document 12 describes an active energy ray-curable compound (A), a photoradical polymerization initiator (C), and / or a photocationic polymerization initiator having one or more ethylenically unsaturated double bonds in one molecule.
- An active energy ray-curable resin composition for balancing motor rotors which comprises (D) and has a specific gravity of 1.4 (25 ° C.) or more and a viscosity of 1,000 poise (25 ° C.) or less. It is disclosed.
- Patent Document 12 does not describe lowering the moisture permeability by adjusting the specific gravity of the polymerizable compound, nor does it describe sealing the organic EL display element.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sealing agent capable of forming a sealing material having excellent moisture resistance and adhesiveness to a glass substrate or the like.
- the present invention also relates to a cured product of the encapsulant, a method for producing an organic electroluminescence display device using the encapsulant, and an organic electroluminescence display device having a sealing material formed from the encapsulant. The purpose is to provide.
- the present invention is as follows.
- the specific gravity of the cured product is 1.35 to 19.0, set to ⁇ 1>.
- the glass transition temperature of the polymer is 85 ° C.
- the encapsulant When the encapsulant is cured to obtain a cured product containing a polymer of the polymerizable compound and the inorganic filler, the cross-linking density of the cured product is 1.5 ⁇ 10 -3 mol / cm 3 or more.
- ⁇ 6> The encapsulant according to ⁇ 5>, wherein the polymerizable compound (X) has a halogen group element.
- ⁇ 7> The encapsulant according to ⁇ 6>, wherein the polymerizable compound (X) has at least one halogen group element selected from the group consisting of a fluorine element and a bromine element.
- ⁇ 8> The encapsulant according to ⁇ 6> or ⁇ 7>, wherein the content of the halogen group element in the polymerizable compound (X) is 10 to 50% by mass with respect to the total element amount of the polymerizable compound. ..
- ⁇ 9> The encapsulant according to any one of ⁇ 1> to ⁇ 8>, wherein the polymerizable compound contains a crosslinkable compound (Y) having two or more polymerizable functional groups.
- Y crosslinkable compound
- the polymerizable compound contains at least one selected from the group consisting of a glycidyl ether compound, an alicyclic epoxy compound, a vinyl ether compound and an oxetane compound. .. ⁇ 11> The encapsulant according to any one of ⁇ 1> to ⁇ 10>, wherein the polymerizable compound has a radically polymerizable functional group.
- ⁇ 12> The encapsulant according to any one of ⁇ 1> to ⁇ 11>, wherein the polymerization initiator is a photopolymerization initiator.
- the polymerization initiator contains an onium salt.
- the polymerization initiator is a radical polymerization initiator.
- ⁇ 15> The sealant according to any one of ⁇ 1> to ⁇ 14>, wherein the true specific gravity of the inorganic filler is 1.5 to 5.0.
- ⁇ 16> The encapsulant according to any one of ⁇ 1> to ⁇ 15>, wherein the inorganic filler contains at least one selected from the group consisting of silica, mica, kaolin, talc and aluminum oxide.
- the inorganic filler contains talc.
- the inorganic filler contains inorganic particles having an average particle diameter of 0.01 to 30 ⁇ m.
- the resin particles contain at least one selected from the group consisting of crosslinked poly (meth) methyl acrylate particles, crosslinked polystyrene particles, and crosslinked poly (meth) methyl acrylate copolymer particles.
- the encapsulant according to. ⁇ 21> The encapsulant according to ⁇ 19> or ⁇ 20>, wherein the average particle size of the resin particles is 1 ⁇ m to 100 ⁇ m.
- ⁇ 22> The encapsulant according to any one of ⁇ 19> to ⁇ 21>, wherein the standard deviation of the particle volume distribution with respect to the particle size when the particle size ( ⁇ m) of the resin particles is displayed logarithmically is 0.25 or less. ..
- ⁇ 23> The sealant according to any one of ⁇ 19> to ⁇ 22>, wherein the content of the resin particles is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- ⁇ 24> The encapsulant according to any one of ⁇ 1> to ⁇ 23>, wherein the content of the polymerization initiator is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- ⁇ 25> The sealant according to any one of ⁇ 1> to ⁇ 24>, wherein the content of the inorganic filler is 5 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- ⁇ 26> The sealant according to any one of ⁇ 1> to ⁇ 25>, wherein the total amount mixture of the polymerizable compound has a viscosity at 80 ° C. of 500 to 30,000 mPa ⁇ s. ⁇ 27>
- the ratio ( ⁇ 2 / ⁇ 1 ) of the viscosity ⁇ 2 at 25 ° C. and 0.1 rpm to the viscosity ⁇ 1 at 25 ° C. and 1 rpm is 1.1 to 10.0, any of ⁇ 1> to ⁇ 27>.
- the sealant described in Crab. ⁇ 29> When the encapsulant is cured to obtain a cured product containing a polymer of the polymerizable compound and the inorganic filler, the mean free volume of the cured product is 1 nm 3 or less, ⁇ 1> to ⁇ 28. > The encapsulant according to any one of. ⁇ 30> When the encapsulant is cured to obtain a cured product containing a polymer of the polymerizable compound and the inorganic filler, the porosity of the cured product is less than 20%, ⁇ 1> to ⁇ 29. > The encapsulant according to any one of.
- the encapsulant When the encapsulant is cured to obtain a cured product containing a polymer of the polymerizable compound and the inorganic filler, the cured product has a temperature of 85 ° C. and a relative humidity of 85% in accordance with JIS Z0208. moisture permeability being measured under the conditions of, and 50 (g / m 2 ⁇ 24h / 100 ⁇ m) or less, ⁇ 1> to sealant according to any one of ⁇ 30>.
- ⁇ 33> The sealant according to any one of ⁇ 1> to ⁇ 32>, which is a sealant for forming a dam.
- ⁇ 34> A cured product obtained by curing the sealant according to any one of ⁇ 1> to ⁇ 33>.
- ⁇ 35> A method for manufacturing an organic electroluminescence display device having a dam-fill sealing structure, which comprises a step of applying and curing the sealing agent according to any one of ⁇ 1> to ⁇ 33> to form a dam.
- ⁇ 36> An organic electroluminescence display device having a dam-fill sealing structure including a dam and a filling agent, wherein the dam contains a cured product of the sealing agent according to any one of ⁇ 1> to ⁇ 33>.
- a sealing agent capable of forming a sealing material having excellent moisture resistance and adhesiveness to a glass substrate or the like. Further, according to the present invention, an organic electroluminescence having a cured product of the encapsulant, a method for producing an organic electroluminescence display device using the encapsulant, and a encapsulant formed from the encapsulant. A display device is provided.
- the composition of the present embodiment contains a polymerizable compound, a polymerization initiator and an inorganic filler.
- the polymerizable compound contains a high specific density compound having a specific density of 1.3 to 4.0.
- the composition of the present embodiment it is possible to form a sealing material having excellent moisture resistance and adhesiveness to a glass substrate or the like. Therefore, the composition of the present embodiment can be suitably used as a sealing agent (preferably a sealing agent for an organic electroluminescence display element). Further, the composition of the present embodiment can be particularly preferably used as a dam-forming sealing agent for forming a dam-fill sealing structure.
- the polymerizable compound can be said to be a compound having a polymerizable functional group.
- the polymerizable compound one type may be used alone, or two or more types may be used in combination.
- the polymerizable compound preferably has at least one selected from the group consisting of cationically polymerizable functional groups and radically polymerizable functional groups.
- the polymerizable compound having a cationically polymerizable functional group is selected from the group consisting of epoxy compounds (for example, glycidyl ether compounds, alicyclic epoxy compounds, etc.), cationically polymerizable vinyl compounds (for example, vinyl ether compounds, etc.) and oxetane compounds. At least one compound is preferred.
- the polymerizable compound having a radically polymerizable functional group a compound having at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, a vinyl ether group and a vinyl ester group is used. Examples thereof include compounds having a (meth) acryloyl group, which are preferred. As the compound having a (meth) acryloyl group, at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide is preferable.
- the high specific density compound has a polymerizable functional group and can be said to be a compound having a specific gravity of 1.3 to 4.0.
- the specific gravity of the high specific density compound is preferably 1.4 or more, more preferably 1.5 or more.
- the specific gravity of the high specific density compound is preferably 3.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less. That is, the specific gravity of the high specific gravity compound is, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0, 1.4 to 3.0, 1.4 to 2.5, 1.4 to 2.0, 1.5 to 4.0, 1.5 to 3.0, 1.5 to 2.5 or 1. It may be 5 to 2.0.
- the specific gravity of the high specific density compound indicates a value measured according to JIS K0061 using a Herbert type specific gravity bottle.
- the polymerizable compound may further contain a low specific density compound having a specific density of less than 1.3.
- a low specific density compound can be said to be a compound having a polymerizable functional group and having a specific gravity of less than 1.3.
- the specific gravity of the low specific density compound is preferably 0.7 or more, more preferably 0.8 or more, and may be 0.9 or more, 1.0 or more, or 1.1 or more. That is, the specific densities of the low-density compounds are, for example, 0.7 or more and less than 1.3, 0.8 or more and less than 1.3, 0.9 or more and less than 1.3, 1.0 or more and less than 1.3, or 1.1. It may be more than 1.3 and less than 1.3.
- the specific gravity of the low specific density compound indicates a value measured according to JIS K0061 using a Herbert type specific gravity bottle.
- the ratio of the high specific density compound to the polymerizable compound may be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass. % Or more. As a result, the above-mentioned effect is more prominently exhibited.
- the ratio of the high specific gravity compound to the polymerizable compound may be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, still more preferably 75. It is mass% or less, more preferably 70 mass% or less, and particularly preferably 65 mass% or less.
- the ratio of the high specific gravity compound to the polymerizable compound is, for example, 30 to 100% by mass, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 30 to 75% by mass, and 30 to 70% by mass.
- the ratio of the low specific gravity compound to the polymerizable compound may be, for example, 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass. As mentioned above, it is even more preferably 30% by mass or more, and particularly preferably 35% by mass or more.
- the ratio of the low specific density compound to the polymerizable compound may be, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, still more preferably. It is 45% by mass or less. As a result, the above-mentioned effect is more prominently exhibited.
- the ratio of the low specific gravity compound to the polymerizable compound is, for example, 0 to 70% by mass, 0 to 60% by mass, 0 to 55% by mass, 0 to 50% by mass, 0 to 45% by mass, 10 to 70% by mass.
- the polymerizable compound preferably contains a polymerizable compound (X) having an element having an atomic number of 9 or more.
- the polymerizable compound (X) may be a high-density compound or a low-density compound, and is preferably a high-density compound.
- the polymerizable compound (X) preferably has a halogen group element, and more preferably has at least one selected from the group consisting of a fluorine element and a bromine element.
- the number of halogen group elements contained in one molecule of the polymerizable compound (X) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more.
- the number of halogen group elements contained in one molecule of the polymerizable compound (X) is not particularly limited, and may be, for example, 40 or less, preferably 30 or less. That is, the number of halogen group elements contained in one molecule of the polymerizable compound (X) may be, for example, 1 to 40, 1 to 30, 2 to 40, or 2 to 30.
- the polymerizable compound (X) preferably has at least one selected from the group consisting of a cationically polymerizable functional group and a radically polymerizable functional group.
- the polymerizable compound (X) having a cationically polymerizable functional group includes an epoxy compound (for example, a glycidyl ether compound, an alicyclic epoxy compound, etc.), a cationically polymerizable vinyl compound (for example, a vinyl ether compound, etc.) and an oxetane compound. At least one selected from the group is preferred.
- the polymerizable compound (X) having a radically polymerizable functional group at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, a vinyl ether group and a vinyl ester group is used. Examples thereof include compounds having a (meth) acryloyl group, and compounds having a (meth) acryloyl group are preferable.
- the compound having a (meth) acryloyl group at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide is preferable.
- Examples of the polymerizable compound (X) having a cationically polymerizable functional group which is one of the specific examples of the polymerizable compound (X), include halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether, and brominated bisphenol. Examples thereof include A-type epoxy resin, brominated bisphenol F-type novolak type epoxy resin, and brominated phenol novolac type epoxy resin.
- Examples of the polymerizable compound (X) having a radically polymerizable compound which is one of specific examples of the polymerizable compound (X), include fluorophenyl (meth) acrylate, trifluorophenyl (meth) acrylate, and pentafluorophenyl (meth).
- the content of the halogen group element in the polymerizable compound (X) is preferably 10 to 50% by mass with respect to the total element amount of the polymerizable compound. When it is 10% by mass or more, the moisture-proof property of the cured product tends to be further improved, and when it is 50% by mass or less, the curability of the composition tends to be further improved.
- the ratio of the polymerizable compound (X) to the polymerizable compound may be, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably. Is 55% by mass or more. As a result, the moisture resistance of the cured product tends to be further improved.
- the ratio of the polymerizable compound (X) to the polymerizable compound may be, for example, 100% by mass, preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, and further. It is preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% by mass or less.
- the ratio of the polymerizable compound (X) to the polymerizable compound is, for example, 30 to 100% by mass, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 30 to 75% by mass, 30 to 30 to 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.
- the polymerizable compound is also referred to as a polymerizable compound other than the polymerizable compound (X) (that is, a polymerizable compound having no element having an atomic number of 9 or more) (hereinafter, also referred to as a polymerizable compound (X'). ) May be further contained.
- the polymerizable compound (X') may be, for example, a compound having a polymerizable functional group copolymerizable with the polymerizable functional group of the polymerizable compound (X).
- the polymerizable compound (X') may be a high-density compound or a low-density compound.
- the polymerizable compound (X') preferably has at least one selected from the group consisting of cationically polymerizable functional groups and radically polymerizable functional groups.
- the polymerizable compound (X') having a cationically polymerizable functional group includes an epoxy compound (for example, a glycidyl ether compound, an alicyclic epoxy compound, etc.), a cationically polymerizable vinyl compound (for example, a vinyl ether compound, etc.) and an oxetane compound. At least one selected from the group is preferred.
- the polymerizable compound (X') having a radically polymerizable functional group is at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, a vinyl ether group and a vinyl ester group. Examples thereof include a compound having a (meth) acryloyl group, and a compound having a (meth) acryloyl group is preferable.
- the compound having a (meth) acryloyl group at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide is preferable.
- the polymerizable compound (X) When the polymerizable compound (X) has a cationically polymerizable functional group, the polymerizable compound (X') preferably has a cationically polymerizable functional group.
- the polymerizable compound (X') having a cationically polymerizable functional group at least one selected from the group consisting of an epoxy compound, an oxetane compound, and a cationically polymerizable vinyl compound is preferable.
- Examples of the epoxy compound include an alicyclic compound having an epoxy group (alicyclic epoxy compound), an aromatic compound having an epoxy group (aromatic epoxy compound), and a glycidyl ether compound.
- alicyclic epoxy compound for example, a compound having at least one cycloalkene ring (for example, cyclohexene ring, cyclopentene ring, pinen ring, etc.) is used with an appropriate oxidizing agent such as hydrogen peroxide and peracid. Examples thereof include compounds obtained by epoxidation or derivatives thereof. Further, examples of the alicyclic epoxy compound include hydrogenated epoxy compounds obtained by hydrogenating an aromatic epoxy compound (for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, etc.).
- Examples of the alicyclic epoxy compound include 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 3,4-epoxycyclohexylalkyl (meth) acrylate (for example, 3,4-epoxycyclohexylmethyl (meth). ) Acrylic and the like), (3,3', 4,4'-diepoxy) bicyclohexyl, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin and the like.
- an alicyclic epoxy compound having a 1,2-epoxycyclohexane structure is preferable.
- a compound represented by the following formula (A1-1) is preferable.
- X represents a single bond or a linking group (a divalent group having one or more atoms).
- the linking group is preferably a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked.
- X is preferably a linking group.
- a group having an ester bond is preferable.
- Examples of the compound having a group having an ester bond as a linking group include 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
- the molecular weight of the alicyclic epoxy compound is preferably 450 or less, more preferably 400 or less, still more preferably 300 or less, in terms of further improving the moisture resistance of the cured product and further improving the storage stability of the composition. 100 to 280 is more preferable. That is, the molecular weight of the alicyclic epoxy compound may be, for example, 100 to 450, 100 to 400, 100 to 300, or 100 to 280.
- the number average molecular weight of the alicyclic epoxy compound is preferably in the above range.
- the number average molecular weight indicates a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the following measurement conditions.
- any monomer, oligomer or polymer can be used, and a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, and a fluorene type
- a bisphenol A type epoxy resin a bisphenol F type epoxy resin
- a bisphenol S type epoxy resin a bisphenol S type epoxy resin
- a biphenyl type epoxy resin a naphthalene type epoxy resin
- fluorene type examples thereof include epoxy resins, novolak phenol-type epoxy resins, cresol novolak-type epoxy resins, and modified products thereof.
- aromatic epoxy compound an aromatic epoxy compound having a bisphenol structure is preferable.
- aromatic epoxy compounds having a bisphenol structure a compound represented by the following formula (A2-1) is preferable.
- n 0 to 30, and R 21 , R 22 , R 23 and R 24 each independently contain a hydrogen atom or an substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. show. n may be 0.1 or more.
- R 21 , R 22 , R 23 and R 24 are preferably hydrogen atoms or methyl groups.
- R 21 , R 22 , R 23 and R 24 may be the same or different, but are preferably the same.
- the aromatic epoxy compound having a bisphenol structure is preferably at least one selected from the group consisting of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.
- the molecular weight of the aromatic epoxy compound is preferably 100 to 5000, more preferably 150 to 1000, and even more preferably 200 to 450 in that the moisture resistance of the cured product is further improved. That is, the molecular weight of the aromatic epoxy compound may be, for example, 100 to 5000, 100 to 1000, 100 to 450, 150 to 5000, 150 to 1000, 150 to 450, 200 to 5000, 200 to 1000 or 200 to 450. ..
- the number average molecular weight of the aromatic epoxy compound is in the above range.
- the number average molecular weight indicates a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.
- the glycidyl ether compound a polyglycidyl ether compound is preferable.
- the polyglycidyl ether compound is not particularly limited, but is a multivalent alkylene glycol diglycidyl ether (for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.).
- Polyglycidyl ether of alcohol eg di or triglycidyl ether of glycerin or its alkylene oxide adduct
- diglycidyl ether of polyalkylene glycol eg diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or Diglycidyl ether of the alkylene oxide adduct, etc.
- alkylene oxide include ethylene oxide and propylene oxide.
- the cationically polymerizable vinyl compound can be any monomer, oligomer or polymer.
- Examples of the cationically polymerizable vinyl compound include vinyl ether compounds, vinyl amine compounds, and styrene.
- the vinyl ether compound is not particularly limited, but is limited to ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol di.
- Di or trivinyl ether compounds such as vinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, hydroxyethyl monovinyl ether, hydroxynonyl monovinyl ether, trimethylpropantrivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, Monovinyl ether compounds such as cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether o-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, etc.
- the oxetane compound is not particularly limited, but is 3-ethyl-3-hydroxymethyloxetane (trade name: Aron Oxetane OXT-101 manufactured by Toa Synthetic Co., Ltd.), 1,4-bis [(3-ethyl-3-oxetanyl).
- the oxetane compound refers to a compound having one or more oxetane rings in the molecule.
- the polymerizable compound (X') preferably has a radically polymerizable functional group.
- the polymerizable compound (X') having a radically polymerizable functional group is at least one radically polymerizable functional group selected from the group consisting of a vinyl group, a (meth) acryloyl group, an allyl group, a vinyl ether group and a vinyl ester group.
- a compound having (meth) acryloyl group is preferable, and a compound having a (meth) acryloyl group is preferable.
- As the compound having a (meth) acryloyl group at least one selected from the group consisting of (meth) acrylate and (meth) acrylamide is more preferable.
- Examples of the (meth) acrylate include monofunctional (meth) acrylates such as ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, and ethoxylated-o-phenylphenol acrylate, and 1,6-hexanediol.
- Examples thereof include polyfunctional (meth) acrylates such as di (meth) acrylates and 1,12-dodecanediol di (meth) acrylates.
- the polymerizable compound preferably contains a crosslinkable compound (Y) having two or more polymerizable functional groups.
- the crosslinkable compound (Y) may be a high-density compound or a low-density compound. Further, the crosslinkable compound (Y) may be a polymerizable compound (X) or a polymerizable compound (X').
- crosslinkable compound (Y) examples include those having two or more polymerizable functional groups among the above-mentioned polymerizable compounds.
- the ratio of the crosslinkable compound (Y) to the polymerizable compound is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. As a result, the curability of the composition is further improved, and a cured product having higher strength tends to be easily obtained.
- the ratio of the crosslinkable compound (Y) to the polymerizable compound is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less. As a result, the adhesiveness to the glass substrate or the like is further improved, and a more reliable sealing material can be formed.
- the ratio of the crosslinkable compound (Y) to the polymerizable compound is, for example, 30 to 90% by mass, 30 to 85% by mass, 30 to 80% by mass, 35 to 90% by mass, 35 to 85% by mass, 35 to 35 to It may be 80% by mass, 40 to 90% by mass, 40 to 85% by mass, or 40 to 80% by mass.
- the viscosity of the total amount mixture of the polymerizable compounds at 80 ° C. is preferably 500 mPa ⁇ s or more, and 700 mPa ⁇ s or more. More preferably, 1000 mPa ⁇ s or more is further preferable. Further, from the viewpoint of improving the ejection property of the composition of the present embodiment at the time of coating and expanding the range of choices of molding methods, the viscosity of the total amount mixture of the polymerizable compounds at 80 ° C. is preferably 30,000 mPa ⁇ s or less.
- the viscosities of the total amount mixture of the polymerizable compound at 80 ° C. are, for example, 500 to 30000 mPa ⁇ s, 500 to 25000 mPa ⁇ s, 500 to 20000 mPa ⁇ s, 700 to 30000 mPa ⁇ s, 700 to 25000 mPa ⁇ s, 700 to 20000 mPa. It may be s, 1000 to 30000 mPa ⁇ s, 1000 to 25000 mPa ⁇ s or 1000 to 20000 mPa ⁇ s.
- a plurality of the above-mentioned polymerizable compounds may be combined so that the viscosity of the total amount mixture of the polymerizable compounds is within the above range.
- the viscosity of the total amount mixture of the polymerizable compound at 80 ° C. indicates the value measured by a cone rotor viscometer.
- the polymerization initiator a photopolymerization initiator is preferable.
- the composition of the present embodiment can be cured by irradiation with energy rays such as ultraviolet rays.
- the polymerization initiator may be at least one selected from the group consisting of a cationic polymerization initiator and a radical polymerization initiator, and may be at least one selected from the group consisting of a photocationic polymerization initiator and a photoradical polymerization initiator. Is preferable.
- a cationic polymerization initiator it is possible to polymerize a polymerizable compound having a cationically polymerizable functional group, and by using a radical polymerization initiator, it is possible to polymerize a polymerizable compound having a radically polymerizable functional group. ..
- the photocationic polymerization initiator is not particularly limited, and for example, an aryl sulfonium salt derivative (for example, Cyracure UVI-6990 manufactured by Dow Chemical Co., Ltd., Cyracure UVI-6974, Adecocaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., Adecacaopt).
- an aryl sulfonium salt derivative for example, Cyracure UVI-6990 manufactured by Dow Chemical Co., Ltd., Cyracure UVI-6974, Adecocaoptomer SP-150 manufactured by Asahi Denka Kogyo Co., Ltd., Adecacaopt.
- Examples of the photocationic polymerization initiator include an onium salt represented by the formula (B-1).
- A represents an element having a valence m of Group VIA to Group VIIA.
- m indicates 1 to 2 and p indicates 0 to 3
- R indicates an organic group attached to A
- D is the following formula (B-1-1):
- E represents a divalent group
- G is -O-, -S-, -SO-, -SO 2-, -NH-.
- X - is the counterion of onium.
- the onium ion of the formula (B-1) is not particularly limited, and is, for example, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- ⁇ bis [4- (2).
- R is an organic group bonded to A.
- R is, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. , And these may have substituents.
- substituents examples include an alkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group and an aryl group.
- At least one selected from the group consisting of a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group, and a halogen is mentioned. Be done.
- R is m + p (m-1) + 1, and they may be the same or different from each other. Also, two or more R, directly or -O one another -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH-,
- a ring structure containing the element A may be formed by bonding via an alkylene or phenylene group having 1 to 3 carbon atoms.
- R' is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- aryl group having 6 to 30 carbon atoms examples include a monocyclic aryl group such as a phenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a pyrenyl group, a chrysenyl group, a naphthacenyl group, a benzanthrasenyl group and an anthraquinolyl group.
- a fused polycyclic aryl group such as a fluorenyl group, a naphthoquinone group and an anthraquinone group.
- At least one aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms is at least one kind. It may have a substituent.
- An example of a substituent is Linear alkyl groups with 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecy; Branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; Cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; Hydroxy group; Linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso
- Arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; 2 to 19 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, octadecyloxycarbonyl, etc.
- Phenylthio 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromo Phenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluorophenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2 -Naftilthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl]
- Aryl groups with 6 to 10 carbon atoms such as phenyl, trill, dimethylphenyl, naphthyl; Thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indrill, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thianthenyl, phenoxalinyl Heterocyclic groups having 4 to 20 carbon atoms such as inyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzo
- P in the formula (B-1) represents the number of repeating units of the [DA + R m-1 ] bond, and is preferably an integer of 0 to 3.
- Preferable onium ions [A + ] in the formula (B-1) are sulfonium, iodonium, and selenium, and typical examples include the following.
- sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, and tris (4-fluorophenyl).
- sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, and bis [4- ⁇ bis [4- (2- (2-) Hydroxyethoxy) phenyl] sulfonio ⁇ phenyl] sulfide, bis ⁇ 4- [bis (4-fluorophenyl) sulfonio] phenyl ⁇ sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium , 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium , 4- (4-benzoyl-2-chloroph
- X - is a counterion.
- the number is p + 1 per molecule.
- the counterion is not particularly limited, and examples thereof include halides such as boron compounds, phosphorus compounds, antimony compounds, arsenic compounds, and alkylsulfonic acid compounds, and methide compounds.
- X - include, for example, F -, Cl -, Br -, I - halogen, such as ion; OH -; ClO 4 -; FSO 3 -, ClSO 3 -, CH 3 SO 3 -, C 6 H 5 SO 3 -, CF 3 SO 3 - sulfonate ion such as; HSO 4 -, sulfate ions of SO 4 2- and the like; HCO 3 -, CO 3 carbonate ions of 2-like; H 2 PO 4 -, HPO 4 2, phosphate ions of PO 4 3- and the like; PF 6 -, PF 5 OH -, fluorophosphate ions such as fluorinated alkyl fluorophosphate ion; BF 4 -, B (C 6 F 5) 4 -, B (C 6 H 4 CF 3) 4 - borate ions such as; AlCl 4 -; BiF 6 -, and the like.
- fluoroantimonate
- fluorinated alkylfluorophosphate ion examples include a fluorinated alkylfluorophosphate ion represented by the formula (B-1-3) and the like. [(Rf) b PF 6-b ] - (B-1--3)
- Rf represents an alkyl group substituted with a fluorine atom.
- the number b of Rf is 1 to 5, and is preferably an integer.
- the b Rfs may be the same or different.
- the number b of Rf is more preferably 2 to 4, and most preferably 2 to 3. That is, the number b of Rf may be, for example, 1 to 5, 1 to 4, 1 to 3, 2 to 4 or 2 to 3.
- Rf represents an alkyl group substituted with a fluorine atom, and the preferable carbon number is 1 to 8, and the more preferable carbon number is 1 to 4.
- the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Cycloalkyl group and the like.
- Rf examples include CF 3 , CF 3 CF 2 , (CF 3 ) 2 CF, CF 3 CF 2 CF 2 , CF 3 CF 2 CF 2 CF 2 , (CF 3 ) 2 CFCF 2 , CF 3 CF 2 Examples thereof include (CF 3 ) CF and (CF 3 ) 3 C.
- preferred fluorinated alkylfluorophosphate anions include [(CF 3 CF 2 ) 2 PF 4 ] - , [(CF 3 CF 2 ) 3 PF 3 ] - , [((CF 3 ) 2 CF) 2 PF 4 ] - , [((CF 3 ) 2 CF) 3 PF 3 ] - , [(CF 3 CF 2 CF 2 ) 2 PF 4 ] - , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] - , [((CF 3) 2 CFCF 2) 2 PF 4] -, [((CF 3) 2 CFCF 2) 3 PF 3] -, [(CF 3 CF 2 CF 2 CF 2) 2 PF 4] - and [ (CF 3 CF 2 CF 2 CF 2) 3 PF 3] - , and the like.
- the photocationic polymerization initiator may be previously dissolved in a solvent in order to facilitate mixing with the polymerizable compound.
- a solvent examples include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate.
- Examples of the photocationic polymerization initiator include a triarylsulfonium salt hexafluoroantimonate represented by the formula (B-2) and diphenyl4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) represented by the formula (B-3). At least one selected from the group consisting of trifluorophosphate is preferable, and triarylsulfonium salt hexafluoroantimonate is more preferable.
- the photoradical polymerization initiator is not particularly limited, but Benzophenone and its derivatives; Benzyl and its derivatives; Anthraquinone and its derivatives; Benzoin-type photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; Acetophenone-type photopolymerization initiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone; 2-Dimethylaminoethylbenzoate; p-Dimethylaminoethylbenzoate; Diphenyl disulfide; Thioxanthone and its derivatives; Campharquinone, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,
- the content of the polymerization initiator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the polymerizable compound. This further improves the curability.
- the content of the polymerization initiator is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the polymerizable compound.
- the adhesiveness to the glass substrate or the like is further improved, and a more reliable sealing material can be formed. That is, the content of the polymerization initiator is, for example, 0.01 to 5 parts by mass, 0.01 to 3 parts by mass, 0.1 to 5 parts by mass, or 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymerizable compound. It may be a mass part.
- the inorganic filler examples include oxides such as silica particles, glass filler, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide, zirconia and zinc oxide, and nitrides such as boron nitride, silicon nitride and aluminum nitride. , Carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, gold, iron, aluminum, nickel and titanium, carbon-based materials such as diamond and carbon. Fillers, calcium carbonate, barium sulfate, talc, mica and the like can be mentioned.
- the inorganic filler may be surface-treated with a fatty acid, a silicone coupling agent, a titanate-based coupling agent, or the like.
- a fatty acid e.g., a fatty acid, a silicone coupling agent, a titanate-based coupling agent, or the like.
- the inorganic filler one kind or two or more kinds can be used as needed.
- the true specific gravity of the inorganic filler may be, for example, 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more.
- the true specific gravity of the inorganic filler may be, for example, 20.0 or less, preferably 8.0 or less, and more preferably 5.0 or less.
- the true specific gravity of the inorganic filler indicates a value measured by ASTM D2840. That is, the true specific gravity of the inorganic filler is, for example, 1.3 to 20.0, 1.3 to 8.0, 1.3 to 5.0, 1.4 to 20.0, 1.4 to 8.0. , 1.4 to 5.0, 1.5 to 20.0, 1.5 to 8.0 or 1.5 to 5.0.
- the inorganic filler preferably contains at least one selected from the group consisting of silica, mica, kaolin, talc and aluminum oxide, and more preferably contains talc.
- the inorganic filler may be inorganic particles having an average particle size (hereinafter, may be simply referred to as particle size or particle size).
- the average particle size of the inorganic particles is preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more.
- the average particle size of the inorganic particles is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less. That is, the average particle size of the inorganic particles may be, for example, 0.005 to 50 ⁇ m, 0.005 to 30 ⁇ m, 0.01 to 50 ⁇ m, or 0.01 to 30 ⁇ m.
- the average particle size of the inorganic particles indicates a value measured by a laser diffraction / scattering method using a microtrack particle size distribution device.
- the content of the inorganic filler may be, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 15 parts by mass or more with respect to 100 parts by mass of the polymerizable compound.
- the content of the inorganic filler may be, for example, 500 parts by mass or less, 350 parts by mass or less, preferably 300 parts by mass or less, more preferably 300 parts by mass or less, based on 100 parts by mass of the polymerizable compound. It is 200 parts by mass or less, more preferably 100 parts by mass or less, and even more preferably 50 parts by mass or less.
- the content of the inorganic filler is, for example, 5 to 500 parts by mass, 5 to 350 parts by mass, 5 to 300 parts by mass, 5 to 200 parts by mass, and 5 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- the composition of the present embodiment may further contain a photosensitizer.
- the photosensitizer can absorb energy rays and efficiently generate reactive species (for example, cations generated from a photocationic polymerization initiator and radicals generated from a photoradical polymerization initiator) from a polymerization initiator.
- reactive species for example, cations generated from a photocationic polymerization initiator and radicals generated from a photoradical polymerization initiator
- the photosensitizer is not particularly limited, and for example, benzophenone derivative, phenothiazine derivative, phenylketone derivative, naphthalene derivative, anthracene derivative, phenanthrene derivative, naphthacene derivative, chrysene derivative, perylene derivative, pentacene derivative, aclysine derivative, benzothiazole derivative, Benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, xantone derivative, thioxanthene derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, azine derivative, thiazine derivative, oxazine derivative, indolin derivative, azulene derivative, tri Examples thereof include allylmethane derivatives, phthalocyanine derivatives, spiropirane derivatives, spiroxazine derivatives, thios
- a phenylketone derivative such as 2-hydroxy-2-methyl-1-phenyl-propane-1-one and an anthracene derivative such as 9,10-dibutoxyanthracene are preferable, and anthracene derivative is more preferable.
- anthracene derivative 9,10-dibutoxyanthracene is preferable.
- the photosensitizer one type may be used alone, or two or more types may be used in combination.
- the content of the photosensitizer may be, for example, 0.01 part by mass or more with respect to 100 parts by mass of the polymerizable compound, and 0.02 mass by mass. It may be more than one part.
- the content of the photosensitizer may be, for example, 5 parts by mass or less, preferably 3 parts by mass or less, based on 100 parts by mass of the polymerizable compound from the viewpoint of storage stability. That is, the content of the photosensitizer is, 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 0.02 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound. It may be 3 parts by mass.
- composition of the present embodiment may further contain a silane coupling agent.
- the blending of the silane coupling agent tends to further improve the adhesiveness and adhesive durability of the composition of the present embodiment.
- silane coupling agent examples include ⁇ -chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltricrolsilane, vinyltriethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, and ⁇ - (meth) acryloxipropyl.
- Trimethoxysilane ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -amino Propyltriethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ -ureidopropyltriethoxysilane and the like.
- silane coupling agent may be used alone, or two or more types may be used in combination.
- the content of the silane coupling agent may be, for example, 0.1 part by mass or more, and 0.2 part by mass with respect to 100 parts by mass of the polymerizable compound. More than a part is preferable.
- the content of the silane coupling agent may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the polymerizable compound. That is, the content of the silane coupling agent is, 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 0.2 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound. It may be 5 parts by mass.
- composition of the present embodiment may further contain an antioxidant.
- the composition of the present embodiment may further contain resin particles.
- resin particles By blending the resin particles, it becomes easier to form a thick cured product. Therefore, the composition containing the resin particles is more suitable as a sealing agent for dam formation.
- the resin particles those that can retain their shape without being dissolved in the composition can be used without particular limitation.
- the resin particles are preferably at least one selected from the group consisting of crosslinked poly (meth) methyl acrylate particles, crosslinked polystyrene particles and crosslinked poly (meth) methyl polystyrene copolymer particles, and are preferably crosslinked poly (meth).
- the average particle size of the resin particles may be, for example, 0.1 ⁇ m or more, preferably 1 ⁇ m or more, and more preferably 5 ⁇ m or more.
- the average particle size of the resin particles may be, for example, 200 ⁇ m or less, preferably 100 ⁇ m or less. That is, the average particle size of the resin particles may be, for example, 0.1 to 200 ⁇ m, 0.1 to 100 ⁇ m, 1 to 200 ⁇ m, 1 to 100 ⁇ m, 5 to 200 ⁇ m, or 5 to 100 ⁇ m.
- the average particle size of the resin particles indicates the volume-based average particle size measured by the "laser diffraction type particle size distribution measuring device SALD-2200" manufactured by Shimadzu Corporation.
- the standard deviation of the particle volume distribution with respect to the particle size when the particle size ( ⁇ m) is displayed logarithmically is preferably 0.25 or less.
- the standard deviation is more preferably 0.2 or less, and even more preferably 0.1 or less.
- the standard deviation may be, for example, 0.001 or more, or 0.005 or more. That is, the standard deviation is, for example, 0.001 to 0.25, 0.001 to 0.2, 0.001 to 0.1, 0.005 to 0.25, 0.005 to 0.2, or 0. It may be 05 to 0.1.
- the content of the resin particles may be, for example, 0.01 part by mass or more, preferably 0.02 part by mass or more, based on 100 parts by mass of the polymerizable compound. , More preferably 0.1 parts by mass or more.
- the content of the resin particles may be, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass with respect to 100 parts by mass of the polymerizable compound. It is as follows.
- the content of the resin particles is, for example, 0 to 10 parts by mass, 0 to 5 parts by mass, 0 to 4 parts by mass, 0 to 3 parts by mass, 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.
- Parts, 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 It may be 0.02 to 3 parts by mass, 0.1 to 10 parts by mass, 0.1 to 5 parts by mass, 0.1 to 4 parts by mass, or 0.1 to 3 parts by mass.
- composition of the present embodiment may further contain components other than the above.
- known additives used in the field of encapsulants can be used without particular limitation.
- examples of other components include metal inactivating agents, fillers, stabilizers, neutralizers, lubricants, antibacterial agents and the like.
- the viscosity of the composition of the present embodiment at 25 ° C. may be, for example, 50,000 mPa ⁇ s or more, preferably 70,000 mPa ⁇ s or more, from the viewpoint of improving the coatability of the composition and excellent moldability of the cured product. , More preferably 80,000 mPa ⁇ s or more, still more preferably 100,000 mPa ⁇ s or more. Further, the viscosity of the composition of the present embodiment at 25 ° C. may be, for example, 1000000 mPa ⁇ s or less from the viewpoint of improving the ejection property at the time of coating the composition and expanding the selection of the molding method.
- the viscosity of the composition of the present embodiment at 25 ° C. is, for example, 50,000 to 1000000 mPa ⁇ s, 50,000 to 950000 mPa ⁇ s, 50,000 to 900,000 mPa ⁇ s, 50,000 to 850000 mPa ⁇ s, 70,000 to 1,000,000 mPa ⁇ s, 70,000 to 950000 mPa ⁇ .
- the viscosity of the composition at 25 ° C. indicates a value measured by a cone rotor viscometer.
- the type and content of each component may be appropriately adjusted so that the viscosity at 25 ° C. is within the above range.
- the ratio of the viscosity ⁇ 2 at 25 ° C. and 0.1 rpm ( ⁇ 2 / ⁇ 1 ) to the viscosity ⁇ 1 at 25 ° C. and 1 rpm is preferably 1.1 to 10.0. ..
- the ratio ( ⁇ 2 / ⁇ 1 ) is 1.1 or more, the coatability of the composition is further improved, and the moldability of the cured product tends to be more excellent. From the viewpoint that this tendency becomes more remarkable, the ratio ( ⁇ 2 / ⁇ 1 ) is preferably 1.15 or more, and more preferably 1.2 or more.
- the ratio ( ⁇ 2) / ⁇ 1 ) is preferably 9.5 or less, more preferably 9.0 or less. That is, the ratio ( ⁇ 2 / ⁇ 1 ) is, for example, 1.1 to 10.0, 1.1 to 9.5, 1.1 to 9.0, 1.15 to 10.0, 1.15 to 9. It may be .5, 1.15 to 9.0, 1.2 to 10.0, 1.2 to 9.5 or 1.2 to 9.0.
- the viscosity ⁇ 1 at 25 ° C. and 1 rpm and the viscosity ⁇ 2 at 25 ° C. and 0.1 rpm of the composition indicate values measured by a cone rotor viscometer.
- the type and content of each component may be appropriately adjusted so that the ratio ( ⁇ 2 / ⁇ 1) is within the above range.
- the liquid specific gravity of the composition of this embodiment is preferably 1.3 to 4.0.
- the liquid specific density of the composition is preferably 1.4 or more, more preferably 1.5 or more.
- the liquid specific gravity of the composition is preferably 3.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less. That is, the liquid specific gravity of the composition is, for example, 1.3 to 4.0, 1.3 to 3.0, 1.3 to 2.5, 1.3 to 2.0, 1.4 to 4.0. , 1.4-3.0, 1.4-2.5, 1.4-2.0, 1.5-4.0, 1.5-3.0, 1.5-2.5 or 1 It may be .5-2.0.
- the liquid specific density of the composition is a value measured in accordance with JIS-K-0061 8.2.2 using a 5 mL Gay-Lussac type specific gravity bottle.
- the type and content of each component may be appropriately adjusted so that the liquid specific gravity is within the above range.
- the method for producing the composition of the present embodiment is not particularly limited, and any method may be used as long as the above-mentioned components are sufficiently mixed.
- Examples of the mixing method include a stirring method using the stirring force accompanying the rotation of the propeller, a method using a normal disperser such as a planetary stirrer by rotation and revolution, and the like. These mixing methods are preferable in that stable mixing can be performed at low cost.
- a cured product containing a polymer of a polymerizable compound and an inorganic filler can be obtained.
- the cured product has low moisture permeability and can be suitably used as a sealing material (particularly, a sealing material for an organic EL display element).
- the composition of this embodiment can be cured by, for example, irradiation with energy rays.
- the light source used for curing the composition of the present embodiment is not particularly limited, but is limited to a halogen lamp, a metal halide lamp, a high power metal halide lamp (containing indium and the like), a low pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp. , Xenon lamps, xenon excimer lamps, xenon flash lamps, light-emitting diodes (hereinafter referred to as LEDs) and the like. These light sources are preferable in that they can efficiently irradiate energy rays corresponding to the reaction wavelengths of the respective photopolymerization initiators.
- the above light sources have different radiation wavelengths and energy distributions. Therefore, the light source is appropriately selected depending on the reaction wavelength of the polymerization initiator and the like. Natural light (sunlight) can also be a reaction initiation light source.
- Irradiation by the above light source may be direct irradiation, or may be focused irradiation by a reflecting mirror, fiber, or the like. Further, irradiation using a low wavelength cut filter, a heat ray cut filter, a cold mirror or the like may be used.
- post-heat treatment may be performed to promote curing.
- the temperature of the post-heating is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, from the viewpoint of avoiding the influence on the organic EL display element.
- the post-heating temperature is preferably 40 ° C. or higher.
- composition of this embodiment can also be used as an adhesive.
- the composition of the present embodiment can be suitably used for adhering, for example, a package such as an organic EL display element.
- a step of applying the composition to the entire surface or a part of the first member and a composition applied on the first member are used.
- a method including a step of irradiating the light with light and a step of adhering the first member and the second member via the composition until the composition irradiated with light is cured can be mentioned. ..
- the second member can be adhered onto the first member without being exposed to light and heat. Therefore, the above method can be suitably used for bonding the back plate and the organic EL display element.
- Examples of a method for manufacturing an organic EL display device using the composition of the present embodiment include a step of applying the composition on the back plate and a step of irradiating the composition coated on the back plate with light.
- a manufacturing method including a step of blocking light and adhering a back plate and a substrate on which an organic EL display element is formed via a composition can be mentioned. According to such a method, the organic EL display element can be sealed without being exposed to light and heat.
- a step of applying the composition to one substrate and one substrate and the other substrate via the composition are used.
- a production method including a step of adhering and a step of irradiating the composition between the substrates with light to cure the composition can also be mentioned.
- the specific gravity of the cured product of the composition of the present embodiment (hereinafter, also simply referred to as the cured product of the present embodiment) is, for example, 1.35 or more.
- the specific gravity of the cured product of the present embodiment is, for example, 19.0 or less.
- the specific gravity of the cured product conforms to the JIS K7112 B method and indicates a value measured using water at 23 ° C. as the dipping solution.
- the type and content of each component may be appropriately adjusted so that the specific gravity of the cured product is within the above range.
- the glass transition temperature of the polymer of the polymerizable compound may be, for example, 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 85 ° C. or higher. ..
- the glass transition temperature (Tg) of the polymer indicates a value obtained from the dynamic viscoelastic spectrum.
- stress and strain are applied to the polymer at a constant temperature rise rate, and the temperature showing the peak top of the loss tangent (hereinafter abbreviated as tan ⁇ ) can be defined as the glass transition temperature.
- tan ⁇ the temperature showing the peak top of the loss tangent
- the glass transition temperature is ⁇ 150 ° C. or lower or a certain temperature (Ta ° C.) or higher.
- Ta ° C. since a cured product having a glass transition temperature of ⁇ 150 ° C. or lower cannot be considered, it can be determined that the temperature is above a certain temperature (Ta ° C.).
- the type and content of each component may be appropriately adjusted so that the glass transition temperature of the polymer is within the above range.
- the crosslinked density of the cured product of the present embodiment is preferably 1.0 ⁇ 10 -3 mol / cm 3 or more, and more preferably 2.0 ⁇ 10 -3 mol / cm 3 or more.
- the crosslink density of the cured product may be, for example, 1.0 mol / cm 3 or less.
- the cross-linking density of the cured product may be, for example, 1.0 ⁇ 10 -3 to 1.0 mol / cm 3 or 2.0 ⁇ 10 -3 to 1.0 mol / cm 3 .
- the crosslink density of the cured product indicates a value obtained from the dynamic viscoelastic spectrum. Specifically, a cured product having a thickness of 100 ⁇ m is cut into a width of 5 mm and a length of 25 mm to obtain a test piece. For this test piece, dynamic viscoelasticity measurement is performed under the conditions of a temperature range of -50 ° C to 200 ° C, a temperature rise rate of 2 ° C / min, and a tensile mode, and the relationship between the temperature and the storage elastic modulus (G') is determined. ..
- Crosslink density G'T + 40 / ⁇ RT
- the type and content of each component may be appropriately adjusted so that the crosslink density of the cured product is within the above range.
- Cured body of the present embodiment preferably has an average free volume of the cured product is 1 nm 3 or less, preferably less than 1 nm 3, more preferably 0.5 nm 3 or less, 0.3 nm 3 or less still more preferably, more preferably at 0.1 nm 3 or less, and still more preferably less than 0.1 nm 3.
- the positron annihilation method is known as a method for determining the free volume of a polymer (see Polymer Vol. 42, December issue (1993)). Generally, when a positron (e + ) is incident on a polymer, the positron combines with an electron (e ⁇ ) to generate positronium (Ps).
- the positron annihilation method is when orthopositronium (o-Ps, radius 0.1 nm, hereinafter also referred to as "o-Ps"), which occupies 3/4 of the positronium (Ps), enters the pores of the polymer. This is a method for obtaining the free volume of a polymer by measuring the lifetime of o-Ps ( ⁇ 3).
- o-Ps lifetime when it collides with the walls of the pores existing in the polymer, o-Ps positron (e +) and electrons in the walls of the pores (e -) is It is determined by the probability of overlapping, and the larger the pores of the polymer, the longer the life of o-Ps ( ⁇ 3 ).
- the vacancy as a spherical well-shaped potential of infinite height and assuming that there is an electron layer with a thickness of ⁇ R on the wall surface of the vacancy, the overlap between this electron layer and the wave function of o-Ps is calculated.
- the model for determining the rate of positron (e +) annihilation obtained fits well with the data obtained in the actual experiment.
- the pore diameter R of the polymer is up to about 0.16 to 0.8 nm, the relationship of the following formula (1) is established between the lifetime ⁇ 3 of o-Ps and the pore diameter R.
- ⁇ 3 indicates the measured lifetime of orthopositronium (o-Ps)
- R indicates the pore diameter of the polymer
- ⁇ R indicates the thickness of the wall surface of the pores.
- the type and content of each component may be appropriately adjusted so that the mean free volume of the cured product is within the above range.
- the cured product of the present embodiment preferably has a pore size of less than 20%.
- the free volume analyzed by the positron annihilation method indicates a region that is not occupied by the molecular chain that forms the porous substrate or electrolyte, and when the molecular chain that forms the substrate or electrolyte changes, the vicinity of the molecular chain. Reflects the volume generated in. Specifically, a method is used in which the time from when a positron is incident on a sample until it disappears is measured, and information on atomic vacancies, the size of free volume, number density, etc. is non-destructively observed from the disappearance lifetime. It is possible to determine the free volume.
- a positron is an antiparticle of an electron, which is an elementary particle having the same mass as an electron but having a charge of the opposite sign.
- positrons may form a pair with an electron and are called positronium.
- positronium disappears, annihilated gamma rays are emitted in two directions. The lifetime of positrons is measured by measuring the time change of the annihilation ⁇ -ray intensity.
- Positronium includes parapositronium and orthopositronium, and the average life of orthopositronium is about 140 ns, but it is shortened to 1 ns to 5 ns when it undergoes a pick-off process that takes away other electrons in the substance.
- orthopositronium is present in the free volume space in a solid, the size of the space and the lifetime of orthopositronium are positively correlated, and the pore size is measured by measuring the lifetime due to the pick-off disappearance of orthopositronium. Information can be obtained.
- the type and content of each component may be appropriately adjusted so that the porosity of the polymer is within the above range.
- a moisture permeability as measured under conditions of a relative humidity of 85% that is 60 (g / m 2 ⁇ 24h / 100 ⁇ m) or less preferably, more preferably 55 (g / m 2 ⁇ 24h / 100 ⁇ m) or less, more preferably 50 (g / m 2 ⁇ 24h / 100 ⁇ m) or less. Due to the low moisture permeability, when used as a sealing material for an organic EL display element, the generation of dark spots due to the arrival of moisture on the organic light emitting material layer can be remarkably suppressed.
- the moisture permeability can also be said to be 100 ⁇ m thick moisture permeability (g / m 2 ) measured by exposing for 24 hours in an environment of 85 ° C. and 85% RH in accordance with JIS Z 0208: 1976. ..
- the moisture permeability for example may be a 0.01 (g / m 2 ⁇ 24h / 100 ⁇ m) or higher, may also be 0.1 (g / m 2 ⁇ 24h / 100 ⁇ m) or higher, 1 (g / m may also be 2 ⁇ 24h / 100 ⁇ m) above, it may be 10 (g / m 2 ⁇ 24h / 100 ⁇ m) above.
- the moisture permeability for example, 0.01 ⁇ 60 (g / m 2 ⁇ 24h / 100 ⁇ m), 0.01 ⁇ 55 (g / m 2 ⁇ 24h / 100 ⁇ m), 0.01 ⁇ 50 (g / m 2 ⁇ 24h / 100 ⁇ m), 0.1 ⁇ 60 (g / m 2 ⁇ 24h / 100 ⁇ m), 0.1 ⁇ 55 (g / m 2 ⁇ 24h / 100 ⁇ m), 0.1 ⁇ 50 (g / m 2 ⁇ 24h / 100 ⁇ m), 1 ⁇ 60 ( g / m 2 ⁇ 24h / 100 ⁇ m), 1 ⁇ 55 (g / m 2 ⁇ 24h / 100 ⁇ m), 1 ⁇ 50 (g / m 2 ⁇ 24h / 100 ⁇ m), 10 ⁇ 60 ( g / m 2 ⁇ 24h / 100 ⁇ m ), 10 ⁇ 55 (g / m 2 ⁇ 24h / 100 ⁇ m), or 10 to
- the present invention may relate to a method for manufacturing an organic electroluminescence display device having a dam fill sealing structure, which comprises a step of applying and curing the above composition to form a dam.
- the present invention may relate to an organic EL display device having a dam-fill sealing structure including a dam and a filling agent, and at this time, the dam may include a cured product of the above-mentioned composition.
- the dumb-fill sealing structure may be a known dam-fill sealing structure, and the filling agent may be a known filling agent. Further, the configuration of the organic EL display device other than the dumb-fill sealing structure may be the same as that of the known organic EL display device. In the present invention, for example, sufficient moisture permeability can be obtained from Patent Document 5.
- A Polymerizable compound-high specific density compound (polymerizable compound with specific gravity of 1.3 to 4.0)
- A-1 Dibromophenylglycidyl ether (“BR-250” manufactured by Nippon Kayaku Co., Ltd., content of bromine element: 51% by mass) (maximum atomic number: 35, specific gravity: 1.8, polymerizable in one molecule Number of functional groups: 1, molecular weight 308, content of bromine element: 50% by mass)
- A-2 Brominated cresyl glycidyl ether (“BROC” manufactured by Nippon Kayaku Co., Ltd.) (maximum atomic number: 35, specific density: 1.8, number of polymerizable functional groups in one molecule: 1, content of bromine element : 50% by mass)
- A-3) TBBPA epoxy resin DI "Epiclon 152"
- C6 Epoxy (Maximum atomic number: 8, specific gravity: 1.5, number of polymerizable functional groups in one molecule: 1, molecular weight 376)
- A-6 Pentafluorophenyl acrylate (“Pentafluorophenyl acrylate” manufactured by Tokyo Chemical Industry Co., Ltd.) (maximum atomic number: 9, specific gravity: 1.5, number of polymerizable functional groups in one molecule: 1)
- A-7) Acrylic acid 2,4,6-tribromophenyl ("Tribromophenyl acrylate” manufactured by Tokyo Chemical Industry Co., Ltd.) (maximum atomic number: 35, specific density: 2.1, number of polymerizable functional groups in one molecule 1)
- B Polymerizable compound-Low specific density compound (polymerizable compound with specific density less than 1.3) (B-1) 3', 4'-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celoxide 2021P" manufactured by Daicel Chemical Co., Ltd.) (maximum atomic number: 8, specific gravity: 1.2, in one molecule Number of polymerizable functional groups: 2, molecular weight 252) (B-2) Bisphenol A type epoxy resin (“jER828” manufactured by Mitsubishi Chemical Corporation, molecular weight 360 to 390) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in one molecule: 2) (B-3) Phenol-novolac type epoxy resin ("EPICLON N-775" manufactured by DIC) (maximum atomic number: 8, specific gravity: 1.2, number of polymerizable functional groups in one molecule: 2 or more, number average molecular weight 800 ) (B-
- C The following was used as the polymerization initiator.
- C-1 Triarylsulfonium salt hexafluoroantimonate ("ADEKA PUTMER SP-170" manufactured by ADEKA, anion species is hexafluoroantimonate)
- C-2 Triarylsulfonium salt (diphenyl4-thiophenoxyphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, "CPI-200K” manufactured by San-Apro, anion species is a phosphorus compound)
- C-4) 1-Hydroxycyclohexylphenyl ketone, "I-184" manufactured by BASF Japan Ltd.)
- GS-210 Spherical crosslinked polystyrene particles (“GS-210” manufactured by Ganz Kasei Co., Ltd.) (average particle size: 20.0 ⁇ m, standard deviation: 0.06 ⁇ m)
- the raw materials of the types shown in Tables 1 to 3 were mixed at the composition ratios shown in Tables 1 to 3 to prepare the encapsulants of Examples and Comparative Examples.
- the unit of composition ratio is parts by mass.
- Tg A sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above photocuring conditions, and the cured product having a thickness of 100 ⁇ m was cut into a width of 5 mm and a length of 25 mm to prepare a test piece.
- This test piece was subjected to dynamic viscoelasticity measurement under the conditions of a temperature range of ⁇ 50 ° C. to 200 ° C., a heating rate of 2 ° C./min, and a tensile mode.
- the temperature at the peak top of tan ⁇ (tangent loss) measured by the above dynamic viscoelasticity measurement was defined as the glass transition temperature (Tg) of the cured product.
- a sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above photocuring conditions, and the cured product having a thickness of 100 ⁇ m was cut into a width of 5 mm and a length of 25 mm to prepare a test piece.
- This test piece was subjected to dynamic viscoelasticity measurement under the conditions of a temperature range of ⁇ 50 ° C. to 200 ° C., a heating rate of 2 ° C./min, and a tensile mode.
- Crosslink density G'T + 40 / ⁇ RT
- Average particle size, standard deviation The standard deviation of the particle volume distribution with respect to the particle size when the inorganic filler, the average particle size of the resin particles (sometimes referred to as the average particle size or the particle size), and the particle size ( ⁇ m) are expressed in logarithm.
- the standard deviation was measured by a laser diffraction type particle size distribution measuring device ("SALD-2200 "manufactured by Shimadzu Corporation).
- [Humidity permeability] A sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above photocuring conditions, and calcium chloride (anhydrous) was used as a hygroscopic agent in accordance with JIS Z0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Material (Cup Method)". The measurement was carried out under the conditions of an atmospheric temperature of 85 ° C. and a relative humidity of 85%. Moisture permeability 50g / (m 2 ⁇ 24hr) or less.
- a sheet-shaped cured product having a thickness of 0.1 mm was prepared under the above photocuring conditions, and a cured product having a thickness of 0.1 mm was cut into a width of 10 mm and a length of 10 mm, and 10 sheets were stacked and fixed as a test sample. ..
- the radiation source was 22 NaCl, and the positron annihilation lifetime and relative intensity were measured under the following conditions.
- Positron radiation source 22 NaCl (intensity 0.6MBq)
- Gamma ray detector barium fluoride scintillator and photomultiplier tube Device resolution: 250 ps Measurement temperature: 25 ° C
- Count number 1,000,000 Sample: Measured by sandwiching a positron radiation source from both sides The average free volume and porosity were calculated from the positron annihilation lifetime measured according to the above measurement conditions.
- Anode ITO, anode film thickness 250 nm -Hole injection layer: Copper phthalocyanine thickness 30 nm -Hole transport layer: N, N'-diphenyl-N, N'-dinaphthylbenzidine ( ⁇ -NPD) 20 nm thick -Light emitting layer: Tris (8-hydroxyquinolinato) aluminum (metal complex material), film thickness of light emitting layer 1000 ⁇ -Electron injection layer: Lithium fluoride 1 nm thick ⁇ Cathode: Aluminum, cathode film thickness 250 nm
- a sealant is applied to a glass substrate in a square shape (side length 20 mm, coating width 0.6 mm, coating height 0.1 mm) in a nitrogen atmosphere with a coating device so that the adhesive thickness is 10 ⁇ m.
- a glass substrate and an organic EL element substrate were bonded to each other via a sealant, and the sealant was cured under the above photocuring conditions to prepare an organic EL element.
- the organic EL element is exposed under the conditions of 85 ° C. and 85% by mass relative humidity for 300 hours, then a voltage of 6 V is applied, and the light emitting state of the organic EL element is visually and microscopically observed, and a dark spot is observed. The diameter of the was measured.
- the diameter of the dark spot is preferably 60 ⁇ m or less, more preferably 40 ⁇ m or less, and most preferably no dark spot.
- Viscosity and thixotropic properties of the composition The viscosity was measured under the conditions of 25 ° C. and 1 rpm with a cone rotor type viscometer (manufactured by Toki Sangyo Co., Ltd., "TV-22 type"). Further, as an evaluation of thixotropic property, the ratio of the viscosity ⁇ 2 at 25 ° C. and 0.1 rpm to the viscosity ⁇ 1 at 25 ° C. and 1 rpm ( ⁇ 2 / ⁇ 1 ) was measured.
- [Applying straightness] Fill a 30 mL light-shielding syringe (trade name "UV block syringe", manufactured by Musashi Engineering Co., Ltd.) with the composition, and use a dispenser (trade name "SHOT mini 1000", manufactured by Musashi Engineering Co., Ltd.).
- the composition was applied to the alkaline glass so that the coating length was 30 mm ⁇ 2 mm, the coating width was 0.6 mm ⁇ 0.2 mm, and the coating height was 0.1 mm ⁇ 0.05 mm.
- the composition was irradiated with light under the condition of an integrated light amount of 2,000 mJ / cm 2 having a wavelength of 365 nm, and then heat-treated in an oven at 100 ° C.
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Abstract
Description
<1>
重合性化合物、重合開始剤及び無機充填材を含み、前記重合性化合物が、比重が1.3~4.0の化合物を含有する、封止剤。
<2>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記硬化体の比重が1.35~19.0となる、<1>に記載の封止剤。
<3>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記重合体のガラス転移温度が85℃以上となる、<1>又は<2>に記載の封止剤。
<4>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記硬化体の架橋密度が1.5×10-3mol/cm3以上となる、<1>~<3>のいずれかに記載の封止剤。
<5>
前記重合性化合物が、原子番号9以上の元素を有する重合性化合物(X)を含有する、<1>~<4>のいずれかに記載の封止剤。
<6>
前記重合性化合物(X)が、ハロゲン族元素を有する、<5>に記載の封止剤。
<7>
前記重合性化合物(X)が、フッ素元素及び臭素元素からなる群より選択される少なくとも一種のハロゲン族元素を有する、<6>に記載の封止剤。
<8>
前記重合性化合物(X)中のハロゲン族元素の含有量が、前記重合性化合物の総元素量に対して、10~50質量%である、<6>又は<7>に記載の封止剤。
<9>
前記重合性化合物が、重合性官能基を2個以上有する架橋性化合物(Y)を含有する、<1>~<8>のいずれかに記載の封止剤。
<10>
前記重合性化合物が、グリシジルエーテル化合物、脂環式エポキシ化合物、ビニルエーテル化合物及びオキセタン化合物からなる群より選択される少なくとも一種を含有する、<1>~<9>のいずれかに記載の封止剤。
<11>
前記重合性化合物が、ラジカル重合性官能基を有する、<1>~<10>のいずれかに記載の封止剤。
<12>
前記重合開始剤が、光重合開始剤である、<1>~<11>のいずれかに記載の封止剤。
<13>
前記重合開始剤が、オニウム塩を含有する、<1>~<12>のいずれかに記載の封止剤。
<14>
前記重合開始剤が、ラジカル重合開始剤である、<1>~<12>のいずれか一項に記載の封止剤。
<15>
前記無機充填材の真比重が、1.5~5.0である、<1>~<14>のいずれかに記載の封止剤。
<16>
前記無機充填材が、シリカ、マイカ、カオリン、タルク及び酸化アルミニウムからなる群より選択される少なくとも1種を含む、<1>~<15>のいずれかに記載の封止剤。
<17>
前記無機充填材が、タルクを含む、<1>~<16>のいずれかに記載の封止剤。
<18>
前記無機充填材が、平均粒子径が0.01~30μmの無機粒子を含む、<1>~<17>のいずれかに記載の封止剤。
<19>
樹脂粒子を更に含む、<1>~<18>のいずれかに記載の封止剤。
<20>
前記樹脂粒子が、架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子、及び、架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子からなる群より選択される少なくとも一種を含有する、<19>に記載の封止剤。
<21>
前記樹脂粒子の平均粒子径が1μm~100μmである、<19>又は<20>に記載の封止剤。
<22>
前記樹脂粒子の粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差が、0.25以下である、<19>~<21>のいずれかに記載の封止剤。
<23>
前記樹脂粒子の含有量が、前記重合性化合物100質量部に対して、0.01~5質量部である、<19>~<22>のいずれかに記載の封止剤。
<24>
前記重合開始剤の含有量が、前記重合性化合物100質量部に対して、0.01~5質量部である、<1>~<23>のいずれかに記載の封止剤。
<25>
前記無機充填材の含有量が、前記重合性化合物100質量部に対して、5~500質量部である、<1>~<24>のいずれかに記載の封止剤。
<26>
前記重合性化合物の全量混合物の80℃における粘度が、500~30000mPa・sである、<1>~<25>のいずれかに記載の封止剤。
<27>
25℃における粘度が、50000~1000000mPa・sである、<1>~<26>のいずれかに記載の封止剤。
<28>
25℃、1rpmにおける粘度η1に対する、25℃、0.1rpmにおける粘度η2の比(η2/η1)が、1.1~10.0である、<1>~<27>のいずれかに記載の封止剤。
<29>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記硬化体の平均自由体積が1nm3以下となる、<1>~<28>のいずれかに記載の封止剤。
<30>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記硬化体の空孔率が20%未満となる、<1>~<29>のいずれかに記載の封止剤。
<31>
前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、前記硬化体の、JIS Z0208に準拠して、温度85℃、相対湿度85%の条件下で測定される透湿度が、50(g/m2・24h/100μm)以下となる、<1>~<30>のいずれかに記載の封止剤。
<32>
有機エレクトロルミネッセンス表示素子用封止剤である、<1>~<31>のいずれかに記載の封止剤。
<33>
ダム形成用封止剤である、<1>~<32>のいずれかに記載の封止剤。
<34>
<1>~<33>のいずれかに記載の封止剤を硬化してなる、硬化体。
<35>
<1>~<33>のいずれかに記載の封止剤を塗布及び硬化して、ダムを形成する工程を含む、ダム・フィル封止構造を有する有機エレクトロルミネッセンス表示装置の製造方法。
<36>
ダム及びフィル剤を備えるダム・フィル封止構造を有し、前記ダムが、<1>~<33>のいずれかに記載の封止剤の硬化体を含む、有機エレクトロルミネッセンス表示装置。
すなわち、重合性化合物に占める低比重化合物の割合は、例えば0~70質量%、0~60質量%、0~55質量%、0~50質量%、0~45質量%、10~70質量%、10~60質量%、10~55質量%、10~50質量%、10~45質量%、15~70質量%、15~60質量%、15~55質量%、15~50質量%、15~45質量%、20~70質量%、20~60質量%、20~55質量%、20~50質量%、20~45質量%、25~70質量%、25~60質量%、25~55質量%、25~50質量%、25~45質量%、30~70質量%、30~60質量%、30~55質量%、30~50質量%、30~45質量%、35~70質量%、35~60質量%、35~55質量%、35~50質量%又は35~45質量%であってよい。
・溶媒(移動相):THF
・脱気装置:ERMA社製ERC-3310
・ポンプ:日本分光社製PU-980
・流速:1.0ml/min
・オートサンプラ:東ソー社製AS-8020
・カラムオーブン:日立製作所製L-5030
・設定温度:40℃
・カラム構成:東ソー社製TSKguardcolumnMP(×L)6.0mmID×4.0cm 2本、及び東ソー社製TSK-GELMULTIPORE HXL-M 7.8mmID×30.0cm 2本、計4本
・検出器:RI 日立製作所製L-3350
・データ処理:SIC480データステーション
AはVIA族~VIIA族の原子価mの元素を示し、
mは1~2を示し、
pは0~3を示し、
RはAに結合している有機基を示し、
Dは下記式(B-1-1):
X-はオニウムの対イオンである。)
メチル、エチル、プロピル、ブチル、ペンチル、オクチル、デシル、ドデシル、テトラデシル、ヘキサデシル、オクダデシル等の炭素数1~18の直鎖アルキル基;
イソプロピル、イソブチル、sec-ブチル、tert-ブチル、イソペンチル、ネオペンチル、tert-ペンチル、イソヘキシル等の炭素数1~18の分岐アルキル基;
シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等の炭素数3~18のシクロアルキル基;
ヒドロキシ基;
メトキシ、エトキシ、プロポキシ、イソプロポキシ、ブトキシ、イソブトキシ、sec-ブトキシ、tert-ブトキシ、ヘキシルオキシ、デシルオキシ、ドデシルオキシ等の炭素数1~18の直鎖又は分岐のアルコキシ基;
アセチル、プロピオニル、ブタノイル、2-メチルプロピオニル、ヘプタノイル、2-メチルブタノイル、3-メチルブタノイル、オクタノイル、デカノイル、ドデカノイル、オクタデカノイル等の炭素数2~18の直鎖又は分岐のアルキルカルボニル基;
ベンゾイル、ナフトイル等の炭素数7~11のアリールカルボニル基;
メトキシカルボニル、エトキシカルボニル、プロポキシカルボニル、イソプロポキシカルボニル、ブトキシカルボニル、イソブトキシカルボニル、sec-ブトキシカルボニル、tert-ブトキシカルボニル、オクチロキシカルボニル、テトラデシルオキシカルボニル、オクタデシロキシカルボニル等の炭素数2~19の直鎖又は分岐のアルコキシカルボニル基;
フェノキシカルボニル、ナフトキシカルボニル等の炭素数7~11のアリールオキシカルボニル基;
フェニルチオカルボニル、ナフトキシチオカルボニル等の炭素数7~11のアリールチオカルボニル基;
アセトキシ、エチルカルボニルオキシ、プロピルカルボニルオキシ、イソプロピルカルボニルオキシ、ブチルカルボニルオキシ、イソブチルカルボニルオキシ、sec-ブチルカルボニルオキシ、tert-ブチルカルボニルオキシ、オクチルカルボニルオキシ、テトラデシルカルボニルオキシ、オクタデシルカルボニルオキシ等の炭素数2~19の直鎖又は分岐のアシロキシ基;
フェニルチオ、2-メチルフェニルチオ、3-メチルフェニルチオ、4-メチルフェニルチオ、2-クロロフェニルチオ、3-クロロフェニルチオ、4-クロロフェニルチオ、2-ブロモフェニルチオ、3-ブロモフェニルチオ、4-ブロモフェニルチオ、2-フルオロフェニルチオ、3-フルオロフェニルチオ、4-フルオロフェニルチオ、2-ヒドロキシフェニルチオ、4-ヒドロキシフェニルチオ、2-メトキシフェニルチオ、4-メトキシフェニルチオ、1-ナフチルチオ、2-ナフチルチオ、4-[4-(フェニルチオ)ベンゾイル]フェニルチオ、4-[4-(フェニルチオ)フェノキシ]フェニルチオ、4-[4-(フェニルチオ)フェニル]フェニルチオ、4-(フェニルチオ)フェニルチオ、4-ベンゾイルフェニルチオ、4-ベンゾイル-2-クロロフェニルチオ、4-ベンゾイル-3-クロロフェニルチオ、4-ベンゾイル-3-メチルチオフェニルチオ、4-ベンゾイル-2-メチルチオフェニルチオ、4-(4-メチルチオベンゾイル)フェニルチオ、4-(2-メチルチオベンゾイル)フェニルチオ、4-(p-メチルベンゾイル)フェニルチオ、4-(p-エチルベンゾイル)フェニルチオ4-(p-イソプロピルベンゾイル)フェニルチオ、4-(p-tert-ブチルベンゾイル)フェニルチオ等の炭素数6~20のアリールチオ基;
メチルチオ、エチルチオ、プロピルチオ、イソプロピルチオ、ブチルチオ、イソブチルチオ、sec-ブチルチオ、tert-ブチルチオ、ペンチルチオ、イソペンチルチオ、ネオペンチルチオ、tert-ペンチルチオ、オクチルチオ、デシルチオ、ドデシルチオ等の炭素数1~18の直鎖又は分岐のアルキルチオ基;
フェニル、トリル、ジメチルフェニル、ナフチル等の炭素数6~10のアリール基;
チエニル、フラニル、ピラニル、ピロリル、オキサゾリル、チアゾリル、ピリジル、ピリミジル、ピラジニル、インドリル、ベンゾフラニル、ベンゾチエニル、キノリル、イソキノリル、キノキサリニル、キナゾリニル、カルバゾリル、アクリジニル、フェノチアジニル、フェナジニル、キサンテニル、チアントレニル、フェノキサジニル、フェノキサチイニル、クロマニル、イソクロマニル、ジベンゾチエニル、キサントニル、チオキサントニル、ジベンゾフラニル等の炭素数4~20の複素環基;
フェノキシ、ナフチルオキシ等の炭素数6~10のアリールオキシ基;メチルスルフィニル、エチルスルフィニル、プロピルスルフィニル、イソプロピルスルフィニル、ブチルスルフィニル、イソブチルスルフィニル、sec-ブチルスルフィニル、tert-ブチルスルフィニル、ペンチルスルフィニル、イソペンチルスルフィニル、ネオペンチルスルフィニル、tert-ペンチルスルフィニル、オクチルスルフィニル等の炭素数1~18の直鎖又は分岐のアルキルスルフィニル基;
フェニルスルフィニル、トリルスルフィニル、ナフチルスルフィニル等の炭素数6~10のアリールスルフィニル基;
メチルスルホニル、エチルスルホニル、プロピルスルホニル、イソプロピルスルホニル、ブチルスルホニル、イソブチルスルホニル、sec-ブチルスルホニル、tert-ブチルスルホニル、ペンチルスルホニル、イソペンチルスルホニル、ネオペンチルスルホニル、tert-ペンチルスルホニル、オクチルスルホニル等の炭素数1~18の直鎖又は分岐のアルキルスルホニル基;
フェニルスルホニル、トリルスルホニル(トシル基)、ナフチルスルホニル等の炭素数の6~10のアリールスルホニル基;
式(B-1-2):
非置換のアミノ基;
炭素数1~5のアルキル及び/又は炭素数6~10のアリールでモノ置換もしくはジ置換されているアミノ基;
シアノ基;
ニトロ基;
フッ素、塩素、臭素、ヨウ素等のハロゲン等が挙げられる。
ジフェニルフェナシルスルホニウム、ジフェニル4-ニトロフェナシルスルホニウム、ジフェニルベンジルスルホニウム、ジフェニルメチルスルホニウム等のジアリールスルホニウム;
フェニルメチルベンジルスルホニウム、4-ヒドロキシフェニルメチルベンジルスルホニウム、4-メトキシフェニルメチルベンジルスルホニウム、4-アセトカルボニルオキシフェニルメチルベンジルスルホニウム、2-ナフチルメチルベンジルスルホニウム、2-ナフチルメチル(1-エトキシカルボニル)エチルスルホニウム、フェニルメチルフェナシルスルホニウム、4-ヒドロキシフェニルメチルフェナシルスルホニウム、4-メトキシフェニルメチルフェナシルスルホニウム、4-アセトカルボニルオキシフェニルメチルフェナシルスルホニウム、2-ナフチルメチルフェナシルスルホニウム、2-ナフチルオクタデシルフェナシルスルホニウム、9-アントラセニルメチルフェナシルスルホニウム等のモノアリールスルホニウム;
ジメチルフェナシルスルホニウム、フェナシルテトラヒドロチオフェニウム、ジメチルベンジルスルホニウム、ベンジルテトラヒドロチオフェニウム、オクタデシルメチルフェナシルスルホニウム等のトリアルキルスルホニウム;等が挙げられる。
[(Rf)bPF6-b]- (B-1-3)
ベンゾフェノン及びその誘導体;
ベンジル及びその誘導体;
アントラキノン及びその誘導体;
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール等のベンゾイン型光重合開始剤;
ジエトキシアセトフェノン、4-tert-ブチルトリクロロアセトフェノン等のアセトフェノン型光重合開始剤;
2-ジメチルアミノエチルベンゾエート;
p-ジメチルアミノエチルベンゾエート;
ジフェニルジスルフィド;
チオキサントン及びその誘導体;
カンファーキノン、7,7-ジメチル-2,3-ジオキソビシクロ[2.2.1]ヘプタン-1-カルボン酸、7,7-ジメチル-2,3-ジオキソビシクロ[2.2.1]ヘプタン-1-カルボキシ-2-ブロモエチルエステル、7,7-ジメチル-2,3-ジオキソビシクロ[2.2.1]ヘプタン-1-カルボキシ-2-メチルエステル、7,7-ジメチル-2,3-ジオキソビシクロ[2.2.1]ヘプタン-1-カルボン酸クロライド等のカンファーキノン型光重合開始剤;
2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1等のα-アミノアルキルフェノン型光重合開始剤;
ベンゾイルジフェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド、ベンゾイルジエトキシホスフィンオキサイド、2,4,6-トリメチルベンゾイルジメトキシフェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイルジエトキシフェニルホスフィンオキサイド、ビス(2,4,6―トリメチルベンゾイル)-フェニルホスフィンオキサイド等のアシルホスフィンオキサイド型光重合開始剤;
フェニル-グリオキシリックアシッド-メチルエステル;
オキシ-フェニル-アセチックアシッド2-[2-オキソ-2-フェニル-アセトキシ-エトキシ]-エチルエステル;
オキシ-フェニル-アセチックアシッド2-[2-ヒドロキシ-エトキシ]-エチルエステル;等が挙げられる。
架橋密度(ρ)=G’T+40/φRT
空孔率(%)=I1/(I1+I2+I3)
(A-1)ジブロモフェニルグリシジルエーテル(日本化薬社製「BR-250」、臭素元素の含有量:51質量%)(最大原子番号:35、比重:1.8、1分子中の重合性官能基数:1、分子量308、臭素元素の含有量:50質量%)
(A-2)臭素化クレジルグリシジルエーテル(日本化薬社製「BROC」)(最大原子番号:35、比重:1.8、1分子中の重合性官能基数:1、臭素元素の含有量:50質量%)
(A-3)TBBPAエポキシ樹脂(DIC社「エピクロン152」)(最大原子番号:35、比重:1.7、1分子中の重合性官能基数:2、分子量972、臭素元素の含有量:48質量%)
(A-4)臭素化ビスフェノールA型エポキシ樹脂(阪本薬品社「SR-T1000」、平均分子量2000)(最大原子番号:35、比重:1.7、1分子中の重合性官能基数:2)
(A-5)2,2,3,3,4,4,5,5,6,6,7,7,7-トリデカフルオロヘプチルオキシラン(ダイキン工業社「C6エポキシ」)(最大原子番号:8、比重:1.5、1分子中の重合性官能基数:1、分子量376)
(A-6)ペンタフルオロフェニルアクリレート(東京化成工業社製「ペンタフルオロフェニルアクリレート」)(最大原子番号:9、比重:1.5、1分子中の重合性官能基数:1)
(A-7)アクリル酸2,4,6-トリブロモフェニル(東京化成工業社製「トリブロモフェニルアクリレート」)(最大原子番号:35、比重:2.1、1分子中の重合性官能基数:1)
(B-1)3’,4’-エポキシシクロヘキシルメチル-3,4-エポキシシクロヘキサンカルボキシレート(ダイセル化学社製「セロキサイド2021P」)(最大原子番号:8、比重:1.2、1分子中の重合性官能基数:2、分子量252)
(B-2)ビスフェノールA型エポキシ樹脂(三菱化学社製「jER828」、分子量360~390)(最大原子番号:8、比重:1.2、1分子中の重合性官能基数:2)
(B-3)フェノ-ルノボラック型エポキシ樹脂(DIC製「EPICLON N-775」)(最大原子番号:8、比重:1.2、1分子中の重合性官能基数:2以上、数平均分子量800)
(B-4)シクロヘキサンジメタノールジビニルエーテル(日本カーバイド社製「CHDVE」)(最大原子番号:8、比重:0.9、1分子中の重合性官能基数:1、分子量196)
(B-5)ポリプロピレングリコールジグリシジルエーテル(ナガセケムテックス社製「EX-946L」)(最大原子番号:8、比重:1.06、1分子中の重合性官能基数:2)
(B-6)ラウリルアクリレート(大阪有機社製「LA」)(最大原子番号:8、比重:1.1、1分子中の重合性官能基数:1)
(B-7)1,6-ヘキサンジオールジメタクリレート(新中村化学社製「HD-N」)(最大原子番号:8、比重:1.0、1分子中の重合性官能基数:2)
(B-8)トリシクロデカンジメタノールジメタクリレート(新中村化学社製「DCP」)(最大原子番号:8、比重:1.1、1分子中の重合性官能基数:2)
(B-9)1,2-ポリブタジエン末端ウレタン(メタ)アクリレートの水素添加物(日本曹達社製「TEAI-1000」)(最大原子番号:8、比重:1.0、1分子中の重合性官能基数:2)
(C-1)トリアリールスルホニウム塩ヘキサフルオロアンチモネート(ADEKA社製「アデカオプトマーSP-170」、アニオン種はヘキサフルオロアンチモネート)
(C-2)トリアリールスルホニウム塩(ジフェニル4-チオフェノキシフェニルスルホニウムトリス(ペンタフルオロエチル)トリフルオロホスフェート、サンアプロ社製「CPI-200K」、アニオン種はリン化合物)
(C-3)2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド(BASFジャパン社製「TPO」)
(C-4)1-ヒドロキシシクロヘキシルフェニルケトン、BASFジャパン社製「I-184」)
(D-1)9,10-ジブトキシアントラセン(川崎化成工業社製「ANTHRACURE UVS-1331」)
(E-1)γ-グリシドキシプロピルトリメトキシシラン(信越シリコーン社製「KBM-403」)
(F-1)微粒子タルク、粒子径(d50):4.5μm、真比重:2.7(松村産業社製「#5000PJ」)
(F-2)微粒子タルク、粒子径(d50):15μm、真比重:2.7(松村産業社製「SC」)
(F-3)微粒子マイカ、粒子径(d50):3.0μm、真比重:2.9(松尾産業社製「A-11」)
(F-4)微粒子カオリン、粒子径(d50):1.6μm、真比重:2.6(林化成社製「Kaopolite 1147」)
(F-5)微粒子シリカ、粒子径(d50):4.2μm、真比重:1.9(デンカ社製「FB-5SDX)
(F-6)微粒子酸化アルミ、粒子径(d50):4.0μm、真比重:4.0(デンカ社製「DAW-03」)
(F-7)微粒子金、粒子径(d50):4.0μm、真比重:19.5(徳力本店社製「TAU-200」)
(G-1)GS-210:球状架橋ポリスチレン粒子(ガンツ化成社製「GS-210」)(平均粒子径:20.0μm、標準偏差:0.06μm)
ハーバート形比重瓶を用い、JIS K0061に準拠して、測定を行った。
5mLゲーリュサック型比重瓶を用い、JIS-K-0061の8.2.2に準拠して測定した。
封止剤の硬化物性及び接着性の評価に際し、下記光照射条件により、封止剤を硬化させた。無電極放電メタルハライドランプ搭載UV硬化装置(フュージョン社製)により、365nmの波長の積算光量4,000mJ/cm2の条件にて、封止剤を光硬化させた後、100℃のオーブン中で、60分間の後加熱処理を実施し、硬化体を得た。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、JIS K7112 B法に準拠して測定した。浸せき液として、温度は23℃の水を使用した。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、厚み100μmの硬化体を幅5mm×長さ25mmに切り出し、試験片とした。この試験片について、温度範囲-50℃~200℃、昇温速度2℃/min、引っ張りモードの条件で、動的粘弾性測定を行った。上記動的粘弾性測定で測定されたtanδ(損失正接)のピークトップの温度を硬化物のガラス転移温度(Tg)とした。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、厚み100μmの硬化体を幅5mm×長さ25mmに切り出し、試験片とした。この試験片について、温度範囲-50℃~200℃、昇温速度2℃/min、引っ張りモードの条件で、動的粘弾性測定を行った。架橋密度は、Tg+40℃の温度をT(K)、T(K)における貯蔵弾性率(G’)(表の「弾性率」)をG’T+40、気体定数をR、フロント係数をφ(=1)として、以下の式で算出した。
架橋密度(ρ)=G’T+40/φRT
無機充填材、樹脂粒子の平均粒子径(平均粒径又は粒径という場合もある)、及び、粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差(上述の「標準偏差」)は、レーザー回折式粒度分布測定装置(島津製作所製「SALD-2200」)により測定した。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、JIS Z0208「防湿包装材料の透湿度試験方法(カップ法)」に準じ、吸湿剤として塩化カルシウム(無水)を用い、雰囲気温度85℃、相対湿度85%の条件で測定した。透湿度は50g/(m2・24hr)以下が好ましい。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、厚み0.1mmの硬化体を幅10mm×長さ10mmに切り出し、10枚重ねて固定したものを試験サンプルとした。
線源を22NaClとして、下記の条件にて陽電子消滅寿命と相対強度を測定した。
陽電子線源:22NaCl(強度0.6MBq)
ガンマ線検出器:フッ化バリウムシンチレーター及び光電子倍増管
装置分解能:250ps
測定温度:25℃
カウント数:1,000,000
試料:陽電子線源を両側から挟み込んで測定
上記測定条件に沿って測定された陽電子消滅寿命から、平均自由体積及び空孔率を算出した。
ホウ珪酸ガラス試験片(縦25mm×横25mm×厚2.0mm、テンパックス(登録商標)ガラス)を2枚用い、接着面積0.5cm2、接着厚み10μmとなるように、封止剤を介してホウ珪酸ガラス試験片を接着し、前記光硬化条件にて封止剤を硬化させた。硬化後、封止剤で接合した試験片を用い、引張剪断接着強さ(単位:MPa)を、温度23℃、相対湿度50%の環境下で、引張速度10mm/分で測定した。
ITO電極付きガラス基板(縦25mm×横25mm)をアセトン及びイソプロパノールを用いて洗浄した。その後、真空蒸着法にて以下の化合物を薄膜となるように順次蒸着し、陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極からなる有機EL素子基板を得た。各層の構成は以下の通りである。
・陽極:ITO、陽極の膜厚250nm
・正孔注入層:銅フタロシアニン 厚さ30nm
・正孔輸送層:N,N’-ジフェニル-N,N’-ジナフチルベンジジン(α-NPD) 厚さ20nm
・発光層:トリス(8-ヒドロキシキノリナト)アルミニウム(金属錯体系材料)、発光層の膜厚1000Å
・電子注入層:フッ化リチウム 厚さ1nm
・陰極:アルミニウム、陰極の膜厚250nm
窒素雰囲気下にて塗工装置にてガラス基板に、封止剤を四角状(辺長20mm、塗布幅0.6mm、塗布高さ0.1mm)に塗布し、接着厚み10μmとなるように、封止剤を介してガラス基板と有機EL素子基板とを貼り合わせ、前記光硬化条件にて封止剤を硬化させ、有機EL素子を作製した。
〔初期〕
作製した直後の有機EL素子に6Vの電圧を印加し、有機EL素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。
作製した直後の有機EL素子を、85℃、相対湿度85質量%の条件下に300時間暴露した後、6Vの電圧を印加し、有機EL素子の発光状態を目視と顕微鏡で観察し、ダークスポットの直径を測定した。
コーンローター式粘度計(東機産業社製、「TV-22型」)により、25℃、1rpmの条件における粘度を測定した。また、チキソ性の評価として、25℃、1rpmにおける粘度η1に対する、25℃、0.1rpmにおける粘度η2の比(η2/η1)を測定した。
30mLの遮光性シリンジ(商品名「UVブロックシリンジ」、武蔵エンジニアリング(株)製)に組成物を充填し、ディスペンサー(商品名「SHOT mini 1000」、武蔵エンジニアリング(株)製)を用いて、無アルカリガラスに塗布長さ30mm±2mm、塗布幅0.6mm±0.2mm、塗布高さ0.1mm±0.05mmになるように組成物を塗布した。組成物を365nmの波長の積算光量2,000mJ/cm2の条件にて、光照射した後に、100℃のオーブン中で60分間の後加熱処理を実施し、硬化体を得た。塗布直進性は、下記基準で評価した。
評価基準
AA:硬化体の塗布幅が0.4mm以上であり、塗布幅の平均標準偏差が0.040mm未満である。
A:硬化体の塗布幅が0.4mm以上であり、塗布幅の平均標準偏差が0.040mm~0.100mmである。
C:硬化体の塗布幅が0.4mm以上であり、塗布幅の平均標準偏差が0.100mm以上である。
ハーバート形比重瓶を用い、JIS K0061に準拠して、測定を行った。
厚さ0.1mmのシート状の硬化体を前記光硬化条件にて作製し、JIS K7112 B法に準拠して測定した。浸せき液として、温度は23℃の水を使用した。
Claims (36)
- 重合性化合物、重合開始剤及び無機充填材を含み、
前記重合性化合物が、比重が1.3~4.0の化合物を含有する、封止剤。 - 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記硬化体の比重が1.35~19.0となる、請求項1に記載の封止剤。 - 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記重合体のガラス転移温度が85℃以上となる、請求項1又は2に記載の封止剤。 - 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記硬化体の架橋密度が1.5×10-3mol/cm3以上となる、請求項1~3のいずれか一項に記載の封止剤。 - 前記重合性化合物が、原子番号9以上の元素を有する重合性化合物(X)を含有する、請求項1~4のいずれか一項に記載の封止剤。
- 前記重合性化合物(X)が、ハロゲン族元素を有する、請求項5に記載の封止剤。
- 前記重合性化合物(X)が、フッ素元素及び臭素元素からなる群より選択される少なくとも一種のハロゲン族元素を有する、請求項6に記載の封止剤。
- 前記重合性化合物(X)中のハロゲン族元素の含有量が、前記重合性化合物の総元素量に対して、10~50質量%である、請求項6又は7に記載の封止剤。
- 前記重合性化合物が、重合性官能基を2個以上有する架橋性化合物(Y)を含有する、請求項1~8のいずれか一項に記載の封止剤。
- 前記重合性化合物が、グリシジルエーテル化合物、脂環式エポキシ化合物、ビニルエーテル化合物及びオキセタン化合物からなる群より選択される少なくとも一種を含有する、請求項1~9のいずれか一項に記載の封止剤。
- 前記重合性化合物が、ラジカル重合性官能基を有する、請求項1~10のいずれか一項に記載の封止剤。
- 前記重合開始剤が、光重合開始剤である、請求項1~11のいずれか一項に記載の封止剤。
- 前記重合開始剤が、オニウム塩を含有する、請求項1~12のいずれか一項に記載の封止剤。
- 前記重合開始剤が、ラジカル重合開始剤である、請求項1~12のいずれか一項に記載の封止剤。
- 前記無機充填材の真比重が、1.5~5.0である、請求項1~14のいずれか一項に記載の封止剤。
- 前記無機充填材が、シリカ、マイカ、カオリン、タルク及び酸化アルミニウムからなる群より選択される少なくとも1種を含む、請求項1~15のいずれか一項に記載の封止剤。
- 前記無機充填材が、タルクを含む、請求項1~16のいずれか一項に記載の封止剤。
- 前記無機充填材が、平均粒子径が0.01~30μmの無機粒子を含む、請求項1~17のいずれか一項に記載の封止剤。
- 樹脂粒子を更に含む、請求項1~18のいずれか一項に記載の封止剤。
- 前記樹脂粒子が、架橋ポリ(メタ)アクリル酸メチル粒子、架橋ポリスチレン粒子、及び、架橋ポリ(メタ)アクリル酸メチルポリスチレン共重合体粒子からなる群より選択される少なくとも一種を含有する、請求項19に記載の封止剤。
- 前記樹脂粒子の平均粒子径が1μm~100μmである、請求項19又は20に記載の封止剤。
- 前記樹脂粒子の粒径(μm)を対数で表示したときの粒径に対する粒子体積分布の標準偏差が、0.25以下である、請求項19~21のいずれか一項に記載の封止剤。
- 前記樹脂粒子の含有量が、前記重合性化合物100質量部に対して、0.01~5質量部である、請求項19~22のいずれか一項に記載の封止剤。
- 前記重合開始剤の含有量が、前記重合性化合物100質量部に対して、0.01~5質量部である、請求項1~23のいずれか一項に記載の封止剤。
- 前記無機充填材の含有量が、前記重合性化合物100質量部に対して、5~500質量部である、請求項1~24のいずれか一項に記載の封止剤。
- 前記重合性化合物の全量混合物の80℃における粘度が、500~30000mPa・sである、請求項1~25のいずれか一項に記載の封止剤。
- 25℃における粘度が、50000~1000000mPa・sである、請求項1~26のいずれか一項に記載の封止剤。
- 25℃、1rpmにおける粘度η1に対する、25℃、0.1rpmにおける粘度η2の比(η2/η1)が、1.1~10.0である、請求項1~27のいずれか一項に記載の封止剤。
- 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記硬化体の平均自由体積が1nm3以下となる、請求項1~28のいずれか一項に記載の封止剤。 - 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記硬化体の空孔率が20%未満となる、請求項1~29のいずれか一項に記載の封止剤。 - 前記封止剤を硬化して、前記重合性化合物の重合体及び前記無機充填材を含有する硬化体としたとき、
前記硬化体の、JIS Z0208に準拠して、温度85℃、相対湿度85%の条件下で測定される透湿度が、50(g/m2・24h/100μm)以下となる、請求項1~30のいずれか一項に記載の封止剤。 - 有機エレクトロルミネッセンス表示素子用封止剤である、請求項1~31のいずれか一項に記載の封止剤。
- ダム形成用封止剤である、請求項1~32のいずれか一項に記載の封止剤。
- 請求項1~33のいずれか一項に記載の封止剤を硬化してなる、硬化体。
- 請求項1~33のいずれか一項に記載の封止剤を塗布及び硬化して、ダムを形成する工程を含む、
ダム・フィル封止構造を有する有機エレクトロルミネッセンス表示装置の製造方法。 - ダム及びフィル剤を備えるダム・フィル封止構造を有し、
前記ダムが、請求項1~33のいずれか一項に記載の封止剤の硬化体を含む、有機エレクトロルミネッセンス表示装置。
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| WO2022210785A1 (ja) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | 組成物、硬化体及び有機el表示装置 |
| WO2025173628A1 (ja) * | 2024-02-15 | 2025-08-21 | デンカ株式会社 | 組成物、硬化体、表示装置および太陽電池 |
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| JPWO2022085599A1 (ja) * | 2020-10-20 | 2022-04-28 | ||
| WO2022085599A1 (ja) * | 2020-10-20 | 2022-04-28 | デンカ株式会社 | 封止剤、硬化体、有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス表示装置の製造方法 |
| JP7523568B2 (ja) | 2020-10-20 | 2024-07-26 | デンカ株式会社 | 封止剤、硬化体、有機エレクトロルミネッセンス表示装置、及び、有機エレクトロルミネッセンス表示装置の製造方法 |
| WO2022210785A1 (ja) * | 2021-03-31 | 2022-10-06 | デンカ株式会社 | 組成物、硬化体及び有機el表示装置 |
| WO2025173628A1 (ja) * | 2024-02-15 | 2025-08-21 | デンカ株式会社 | 組成物、硬化体、表示装置および太陽電池 |
| JP2025125432A (ja) * | 2024-02-15 | 2025-08-27 | デンカ株式会社 | 組成物、硬化体、表示装置および太陽電池 |
Also Published As
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| JP7724207B2 (ja) | 2025-08-15 |
| TW202142666A (zh) | 2021-11-16 |
| JPWO2021201013A1 (ja) | 2021-10-07 |
| CN115336389A (zh) | 2022-11-11 |
| CN115336389B (zh) | 2025-10-24 |
| KR20220164509A (ko) | 2022-12-13 |
| TWI869579B (zh) | 2025-01-11 |
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