WO2019189618A1 - Electronic device-sealed body, sheet-shaped adhesive, adhesive film for sealing electronic device, and method for manufacturing electronic device-sealed body - Google Patents

Electronic device-sealed body, sheet-shaped adhesive, adhesive film for sealing electronic device, and method for manufacturing electronic device-sealed body Download PDF

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Publication number
WO2019189618A1
WO2019189618A1 PCT/JP2019/013695 JP2019013695W WO2019189618A1 WO 2019189618 A1 WO2019189618 A1 WO 2019189618A1 JP 2019013695 W JP2019013695 W JP 2019013695W WO 2019189618 A1 WO2019189618 A1 WO 2019189618A1
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WIPO (PCT)
Prior art keywords
adhesive
electronic device
film
sheet
sealing
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PCT/JP2019/013695
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French (fr)
Japanese (ja)
Inventor
樹 長谷川
健太 西嶋
枝保 前谷
幹広 樫尾
Original Assignee
リンテック株式会社
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Application filed by リンテック株式会社 filed Critical リンテック株式会社
Priority to CN201980023189.7A priority Critical patent/CN111955053B/en
Priority to JP2020511008A priority patent/JP7348165B2/en
Priority to KR1020207023084A priority patent/KR102582788B1/en
Publication of WO2019189618A1 publication Critical patent/WO2019189618A1/en
Priority to JP2021509306A priority patent/JPWO2020196240A1/ja
Priority to CN202080025794.0A priority patent/CN113646399B/en
Priority to PCT/JP2020/012256 priority patent/WO2020196240A1/en
Priority to KR1020217023401A priority patent/KR20210145128A/en
Priority to TW109109397A priority patent/TW202111070A/en

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    • 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
    • C08K5/00—Use of organic ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • 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
    • 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
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to an electronic device encapsulant comprising an electronic device and an adhesive cured material layer that seals between the electronic device and an ultraviolet light impermeable functional film, and a sheet form used for forming the adhesive cured material layer.
  • the present invention relates to an adhesive, an adhesive film for sealing an electronic device having an adhesive layer composed of the functional film and a sheet-like adhesive, and a method for producing an electronic device sealing body.
  • Thermosetting adhesives exist as sealing adhesives for sealing electronic devices such as organic EL elements.
  • damage to an electronic device such as an organic EL element is small even when the adhesive is cured after being bonded to the electronic device.
  • Patent Document 1 describes an adhesive for sealing an electronic device containing a compound having a cyclic ether group and a cationic photopolymerization initiator.
  • Patent Document 1 describes that “a pressure-sensitive adhesive is preferably partially or finally crosslinked only after application to an electronic device” [paragraph (0066)]. Then, such cationic UV curing for crosslinking is premised on that the sealing adhesive is carried on a material that transmits ultraviolet rays, such as PET liner and glass. The present invention is provided with a cured adhesive layer that seals between the functional film and the electronic device on the premise that the member to which the sealing adhesive is bonded is an ultraviolet-opaque functional film.
  • An adhesive containing a compound having a cyclic ether group and a cationic photopolymerization initiator remains adhesive on the adhesive surface even after being irradiated with ultraviolet rays. Therefore, a sheet-like adhesive made of such an adhesive can be attached to an electronic device even after irradiation with ultraviolet rays.
  • the adhesive layer is cured over time after irradiation with ultraviolet rays, and finally, (ultraviolet-impermeable functional film) / (adhesive cured product layer) / (electronic device) It is possible to efficiently obtain an electronic device sealing body having a layer structure of) and having excellent durability.
  • a functional film an electronic device having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less, and an adhesive cured material layer for sealing between the functional film and the electronic device, the adhesive curing
  • the physical layer is a sealed body of an electronic device, which is a cured product of a sheet-like adhesive containing the following components (A) and (B).
  • B) Photocationic polymerization initiator [2] A sheet-like adhesive comprising the following components (A) and (B), wherein the electronic device is sealed according to claim 1: A sheet-like adhesive that is used for manufacturing a stationary body.
  • the sheet-like adhesive has a release film on at least one surface, and soda glass measured under the following condition (i) The sheet adhesive according to [2], wherein the adhesive strength to the plate is 3 N / 25 mm or more.
  • a laminate is prepared by attaching an aluminum-deposited 23 ⁇ m thick polyethylene terephthalate film, and the release film
  • the laminate is irradiated from the release film side with ultraviolet light having a wavelength of 365 nm under the conditions of illuminance: 50 mW / cm 2 and light quantity: 200 mJ / cm 2 , and 3 minutes later, the laminate
  • the release film is peeled off, the exposed sheet-like adhesive layer is opposed to a soda glass plate, and a 2 kg roll is reciprocated once on the laminate to be attached to the glass, and at 50% relative to 23 ° C.
  • B) Photocationic polymerization initiator [6]
  • the adhesive film for sealing an electronic device has a release film on the surface of the adhesive layer on the side where the functional film is not bonded.
  • the adhesive film for sealing an electronic device according to [5] which has an adhesive strength to a soda glass plate measured under the following condition (ii) of 3 N / 25 mm or more.
  • [7] The adhesive film for sealing an electronic device according to [5] or [6], wherein the sheet-like adhesive further contains one or more selected from the group consisting of a modified polyolefin resin and a phenoxy resin.
  • [8] ( ⁇ 1) A step of irradiating the adhesive film for sealing an electronic device according to any one of [5] to [7] from the surface side closer to the adhesive layer than the functional film; ( ⁇ 1) a step of attaching the adhesive film to an electronic device, The manufacturing method of the sealing body of the electronic device which performs ((alpha) 1) process before ((beta) 1) process.
  • ( ⁇ 2) a step of irradiating the sheet-like adhesive containing the following components (A) and (B) with ultraviolet rays; ( ⁇ 2) a step of attaching the sheet-like adhesive to a functional film or an electronic device having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, The manufacturing method of the sealing body of the electronic device which performs the ( ⁇ 2) step before the ( ⁇ 2) step.
  • the present invention even after irradiation with ultraviolet rays, it adheres strongly to an ultraviolet light-impermeable functional film or an electronic device as an adherend, and does not cause peeling at the time of application or after application, The adhesive layer is cured over time, and finally a device sealing body having excellent durability can be obtained.
  • the present invention is classified into 2) an electronic device sealing body, 2) a sheet adhesive, 3) an electronic device sealing adhesive film, and 4) an electronic device sealing body manufacturing method.
  • 2) an electronic device sealing body 2) a sheet adhesive, 3) an electronic device sealing adhesive film, and 4) an electronic device sealing body manufacturing method.
  • the electronic device sealing body of the present invention is a functional film, an electronic device, and an adhesive that seals between the electronic film and a functional film having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less.
  • the adhesive cured material layer is a sheet-like adhesive containing the following components (A) and (B) (hereinafter sometimes referred to as “sheet adhesive of the present invention”). It is a cured product.
  • B Photocationic polymerization initiator
  • FIG. 1 shows a layer configuration example of the electronic device sealing body of the present invention.
  • the electronic device sealing body 10 shown in FIG. 1 is laminated so that the electronic device 3 and the cured adhesive layer 2 face each other so as to cover the surface of the electronic device 3, and the transmittance of ultraviolet light having a wavelength of 365 nm is 60%.
  • the following functional film 1 has a layer structure arranged on the outermost surface.
  • examples of the electronic device to be sealed include an organic EL element such as an organic EL display and organic EL illumination; a liquid crystal element such as a liquid crystal display; an electronic paper; Solar cell elements such as: light emitting diodes and the like.
  • the functional film 1 constituting the electronic device sealing body of the present invention is a film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm.
  • the transmittance of the functional film for ultraviolet rays having a wavelength of 365 nm is preferably 55% or less, more preferably 50% or less, from the viewpoint that the effects of the present invention can be obtained more remarkably.
  • the transmittance of ultraviolet rays having a wavelength of 365 nm of the functional film can be measured by the method described in the examples.
  • the functional film 1 used in the present invention is not particularly limited as long as the transmittance of ultraviolet rays having a wavelength of 365 nm is 60% or less and has a certain function.
  • a conductive layer, a gas barrier film, an antireflection film, a retardation film, a viewing angle improving film, a brightness improving film and the like having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less are included.
  • examples of the gas barrier film include a film having a metal or inorganic compound film, and a film having a metal film is preferable.
  • the metal used include aluminum, zinc, copper and the like. Among these, aluminum is preferable.
  • the thickness of the functional film used in the present invention is not particularly limited, but is usually 5 to 200 ⁇ m, preferably 10 to 100 ⁇ m.
  • the ultraviolet light is still in a sheet form even if the functional film side is irradiated with ultraviolet light after the sheet adhesive is bonded to the electronic device.
  • the amount reaching the adhesive is small, and the sheet-like adhesive cannot be cured.
  • the sheet-like adhesive of the present invention is cured by a photocationic polymerization reaction.
  • the photocationic polymerization reaction has a relatively slow reaction rate compared to a radical polymerization reaction or the like. Therefore, even after the sheet-like adhesive is irradiated with ultraviolet rays, while the curing reaction is in progress, the sheet-like adhesive has sufficient adhesiveness. It adheres strongly to the device and can prevent peeling at the time of application or after application. Further, the adhesive layer is cured with time, and an electronic device sealing body having excellent durability can be finally obtained.
  • the adhesive cured material layer 2 of the electronic device encapsulant of the present invention is composed of a cured product of the sheet adhesive of the present invention, and seals the electronic device to seal the electronic device and the functional film. Plays the role of bonding.
  • the sheet-like adhesive of the present invention is a sheet-like product having adhesiveness, and includes the following components (A) and (B).
  • Sheet adhesive refers to an adhesive formed into a sheet that exhibits non-flowability at room temperature (about 25 ° C).
  • the sheet-like adhesive may be strip-shaped or long (band-shaped).
  • the sheet-like adhesive of the present invention contains a compound having a cyclic ether group as the component (A).
  • a compound having a cyclic ether group it is possible to obtain a cured product of the sheet adhesive that is excellent in the curability and water vapor blocking properties of the sheet adhesive.
  • Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, and a tetrahydropyranyl group.
  • the compound having a cyclic ether group refers to a compound having at least one cyclic ether group in the molecule. Especially, it is preferable that it is a compound which has an oxirane group or an oxetane group from a viewpoint that the hardened
  • an aliphatic epoxy compound (except an alicyclic epoxy compound), an aromatic epoxy compound, an alicyclic epoxy compound etc. are mentioned, for example.
  • aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids; Examples thereof include polyfunctional epoxy compounds such as polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds having a triazine skeleton.
  • Typical examples of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diester.
  • a commercial item can also be used as an aliphatic epoxy compound.
  • Commercially available products include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Call EX-920, Denacol EX-931 (man
  • aromatic epoxy compound examples include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono / polyglycidyl etherified products of alkylene oxide adducts thereof.
  • Representative compounds of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl etherified compounds or epoxy novolac resins obtained by further adding alkylene oxide to these compounds; Mono / polyglycidyl etherified products of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol; Glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol; Examples thereof include glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl est
  • a commercial item can also be used as an aromatic epoxy compound.
  • Commercially available products include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX -1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 (above, manufactured by Nagase ChemteX); Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (above, manufactured by Osaka Gas Chemical Company); HP4032, HP4032D, HP4700 (above, manufactured by DIC); ESN-475V (Nippon Steel & Sumikin Chemical Co., Ltd.); JER (former Epicoat) YX8800 (Mitsubishi Chemical Corporation); Marproof
  • alicyclic epoxy compound a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic structure, or cyclohexene oxide or cyclopentene obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent.
  • cycloalkene oxide compounds such as oxide-containing compounds.
  • Typical examples of these alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methylcyclohexyl.
  • a commercial item can be used as an alicyclic epoxy compound.
  • Examples of commercially available products include YX8000 (manufactured by Mitsubishi Chemical Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (Daicel).
  • Examples of the compound having an oxetane group in the molecule include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1, 2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ) Ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) Bifunctional fats such as butane and 1,6-bis (3-ethy
  • a commercial item can also be used as a compound which has an oxetane group in a molecule
  • Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.); Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toagosei Co., Ltd.); Etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like can be mentioned.
  • a compound that is liquid at 25 ° C. is preferable from the viewpoint that an adhesive excellent in sheet processability (film forming property) and a cured product of adhesive excellent in adhesive strength can be obtained.
  • a cyclic ether group is an oxirane group is preferable.
  • an alicyclic epoxy compound is preferable from the viewpoint of adjusting the properties of the cured product of the adhesive and preventing coloring, and from the viewpoint of improving the reactivity of photocationic polymerization Is preferably a cycloalkene oxide compound.
  • a compound having two or more cyclic ether groups in the molecule such as a polyfunctional epoxy compound and a bifunctional aliphatic oxetane compound, is preferable from the viewpoint of improving the curability of the sheet adhesive.
  • the molecular weight of the compound having a cyclic ether group is usually 100 to 5,000, preferably 200 to 4,000.
  • the cyclic ether equivalent of the compound having a cyclic ether group is preferably 100 g / eq or more and 500 g / eq or less, more preferably 115 g / eq or more and 300 g / eq or less.
  • a sealing material having high adhesive strength and excellent curability can be obtained efficiently.
  • These compounds having a cyclic ether group can be used singly or in combination of two or more.
  • the cyclic ether equivalent in the present invention means a value obtained by dividing the molecular weight by the number of cyclic ether groups.
  • the content of the compound having a cyclic ether group is preferably 20 to 180 parts by mass, more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the binder resin. 140 parts by mass.
  • the content of the component (A) in the sheet-like adhesive of the present invention is 20 to 80% by mass as a solid content (non-volatile content, including a liquid material, the same applies hereinafter) with respect to the entire adhesive. Is more preferable, 25 to 70% by mass is more preferable, and 30 to 65% by mass is particularly preferable.
  • the content of the component (A) in the sheet adhesive of the present invention is in the above range, it becomes easy to adjust the adhesive strength of the sheet adhesive after the ultraviolet irradiation.
  • the sheet adhesive of this invention contains a photocationic polymerization initiator as (B) component. Thereby, it becomes easy to adjust the adhesive force of the sheet-like adhesive after ultraviolet irradiation.
  • the cationic photopolymerization initiator is a compound that generates a cationic species by irradiating active energy rays and initiates the curing reaction of the cationic curable compound. It consists of an anion part.
  • Examples of the cationic photopolymerization initiator include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, and oxonium salt compounds. And bromine salt compounds.
  • a sulfonium salt compound is preferable, and an aromatic sulfonium salt compound having an aromatic group is more preferable. .
  • sulfonium salt compounds include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoro.
  • iodonium salt compounds include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, (triccumyl) iodonium tetrakis (pentafluoro). Phenyl) borate and the like.
  • Examples of the phosphonium salt compound include tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride and the like.
  • ammonium salt compounds include benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide.
  • Antimonate compounds include triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) Phenyl] sulfide bishexafluoroantimonate and diallyliodonium hexafluoroantimonate.
  • photocationic polymerization initiators can be used singly or in combination of two or more.
  • a commercial item can be used as a photocationic polymerization initiator.
  • Commercially available products include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, manufactured by Union Carbide), Irgacure 250, Irgacure 261, Irgacure 264 (above, Ciba Specialty Chemicals) ), SP-150, SP-151, SP-170, Optomer SP-171 (manufactured by ADEKA), CG-24-61 (manufactured by Ciba Specialty Chemicals), DACAT II (manufactured by Daicel), UVAC1590, UVAC1591 (manufactured by Daicel-Cytec), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, CIT-16 2 (above, manufactured by
  • the content of the cationic photopolymerization initiator is usually 0.1 to 10 parts by mass, preferably 0.3 to 8 parts by mass, more preferably 0.5 to 4 parts per 100 parts by mass of the component (A). .5 parts by mass.
  • the sheet-like adhesive of the present invention may contain a component other than the component (A) and the component (B).
  • the components other than the component (A) and the component (B) include a binder resin, a tackifier, a silane coupling agent, and the like.
  • the sheet-like adhesive of the present invention contains a binder resin
  • the composition for forming the sheet-like adhesive is imparted with excellent sheet processability (film forming property), and a sheet-like adhesive having a desired thickness. An agent can be formed efficiently.
  • the binder resin is preferably one or more selected from modified polyolefin resins and phenoxy resins from the viewpoint of excellent compatibility with the component (A).
  • modified polyolefin resins it is possible to maintain low moisture permeability while the polyolefin as the main agent is taken into the cured structure.
  • a phenoxy resin it is possible to keep the elastic modulus of the cured product of the sheet adhesive high, and this is preferable because the reliability of the electronic device sealing body in a high temperature environment is improved.
  • the sheet-like adhesive of the present invention contains a binder resin
  • the content thereof is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass with respect to the whole sheet-like adhesive.
  • the binder resin in such a range, the composition for forming the sheet-like adhesive is imparted with excellent sheet processability (film forming property), and the sheet-like adhesive having a desired thickness is efficiently obtained. Can be formed.
  • the modified polyolefin resin is a polyolefin resin having a functional group introduced, obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.
  • the polyolefin resin refers to a polymer containing repeating units derived from olefinic monomers.
  • the polyolefin resin may be a polymer composed of only one or two or more repeating units derived from an olefin monomer, or may be a copolymer of a repeating unit derived from an olefin monomer and an olefin monomer.
  • polymerize may be sufficient.
  • the olefin monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and even more preferably ethylene or propylene.
  • Examples of other monomers copolymerizable with the olefin monomer include vinyl acetate, (meth) acrylic acid ester, and styrene.
  • (meth) acrylic acid represents acrylic acid or methacrylic acid (the same applies hereinafter).
  • polyolefin resins examples include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and ethylene.
  • VLDPE very low density polyethylene
  • LDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • PP polypropylene
  • ethylene -Propylene copolymer
  • olefin elastomer TPO
  • EVA ethylene-vinyl acetate copolymer
  • ethylene- (meth) acrylic acid copolymer ethylene- (meth) acrylic acid ester copolymer, etc. .
  • the modifier used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule.
  • Functional groups include carboxyl groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups. Thioether group, sulfone group, phosphone group, nitro group, urethane group, alkoxysilyl group, silanol group, halogen atom and the like.
  • a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate group, and an alkoxysilyl group are preferable, and a carboxylic acid anhydride group and an alkoxysilyl group are more preferable.
  • Carboxylic anhydride groups are particularly preferred.
  • the compound having a functional group may have two or more kinds of functional groups in the molecule.
  • modified polyolefin resin examples include acid-modified polyolefin resins and silane-modified polyolefin resins, and acid-modified polyolefin resins are preferable from the viewpoint of obtaining the better effect of the present invention.
  • the acid-modified polyolefin resin refers to a polyolefin resin graft-modified with an acid or acid anhydride.
  • examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride to introduce a carboxyl group or an acid anhydride group (graft modification).
  • Examples of the unsaturated carboxylic acid to be reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid.
  • Unsaturated carboxylic acid anhydrides include maleic anhydride. , Itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like. These can be used alone or in combination of two or more.
  • maleic anhydride is preferred because an adhesive excellent in sheet processability (film forming property) and a cured product of a sheet adhesive excellent in adhesive strength can be easily obtained.
  • the amount of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 0.2 to 1 part by mass.
  • a cured product having an excellent adhesive strength is easily obtained.
  • Admer registered trademark
  • Unistor registered trademark
  • BondyRam manufactured by Mitsui Chemicals
  • BondyRam manufactured by Polyram
  • orevac registered trademark
  • Modic registered trademark
  • Silane-modified polyolefin resin refers to a polyolefin resin graft-modified with an unsaturated silane compound.
  • the silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft copolymerized with a polyolefin resin as a main chain.
  • Examples include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers, and silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene are preferable.
  • vinyl silane compounds include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyloxy silane, vinyl triphenoxy silane, vinyl tribenzyloxy silane, vinyl tri Examples include methylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. These can be used alone or in combination of two or more. In addition, what is necessary is just to employ
  • the amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin. 5 parts by mass.
  • a sheet-like adhesive containing a silane-modified polyolefin-based resin is easy to obtain a cured product having better adhesive strength.
  • silane-modified polyolefin resin examples include Lincron (registered trademark) (manufactured by Mitsubishi Chemical Corporation).
  • Lincron registered trademark
  • low-density polyethylene-based linklon linear low-density polyethylene-based linkron
  • ultra-low-density polyethylene-based linkron examples of commercially available products
  • ethylene-vinyl acetate copolymer-based linkron examples of commercially available products.
  • the modified polyolefin resin can be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the modified polyolefin resin is preferably 10,000 to 300,000, more preferably 20,000 to 150,000.
  • the weight average molecular weight (Mw) of the modified polyolefin resin can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • the phenoxy resin is a polymer whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether.
  • the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A-bisphenol F type phenoxy resin, and bisphenol E type phenoxy resin, depending on the type of main chain skeleton.
  • the phenoxy resin can be obtained by a reaction between a bisphenol or biphenol compound and an epihalohydrin such as epichlorohydrin, or a reaction between a bisphenol or biphenol compound and a liquid epoxy resin.
  • a commercially available product can be used as the phenoxy resin.
  • trade names: PKHC, PKHH, PKHJ (all manufactured by Sakai Chemical Co., Ltd.), trade names: Epicoat 4250, Epicoat 1255HX30, Epicoat 5580BPX40 (all manufactured by Nippon Kayaku Co., Ltd.), trade names: YP-50, YP50S, YP-55, YP-70 (all manufactured by Tohto Kasei Co., Ltd.), trade names: JER 1256, 4250, YX6954BH30, YX7200B35, YL7290BH30 (all manufactured by Mitsubishi Chemical Corporation), and the like.
  • the weight average molecular weight (Mw) of the phenoxy resin is usually 10,000 to 200,000, preferably 20,000 to 100,000, more preferably 30,000 to 80,000. If the weight average molecular weight of the phenoxy resin is too small, the supportability of the sheet-like adhesive tends to be weak and the brittleness tends to be strong. If it is too large, the melt viscosity becomes high and the handleability tends to be poor.
  • a compound having a weight average molecular weight (Mw) of 10,000 or less is defined as the component (A): a compound having a cyclic ether group, A resin having an average molecular weight (Mw) exceeding 10,000 is defined as a phenoxy resin.
  • the weight average molecular weight (Mw) of the phenoxy resin can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • the sheet-like adhesive of the present invention may contain a tackifier in addition to the components (A) and (B) and, if desired, a binder resin. By containing a tackifier, it becomes easy to adjust the storage elastic modulus of a sheet-like adhesive.
  • tackifier examples include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; Terpene resins such as terpene resins, aromatic modified terpene resins, terpene phenol resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; ⁇ -methylstyrene homopolymer resin, ⁇ -methylstyrene / styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, styrene monomer / ⁇ -methylstyrene / aliphatic monomer copolymer system Styrene resins such as resins, styrene monomer monopolymer resins, styrene monomer / aromatic monomer copolymer resins; hydrogenated styren
  • a styrene resin is preferable, and a styrene monomer / aliphatic monomer copolymer resin is more preferable.
  • These tackifiers can be used alone or in combination of two or more.
  • a commercially available product can be used as the tackifier.
  • Commercially available products include terpene resins such as YS resin P, A series, Clearon (registered trademark) P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by PINOVA); Aliphatic petroleum resins such as Quinton (registered trademark) A, B, R, CX series (manufactured by Nippon Zeon); Styrenic resins such as FTR (registered trademark) series (Mitsui Chemicals); Alcon P, M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered trademark) series (manufactured by ExxonMobil Chemical Co., Ltd.), EASTOTAC (registered trademark) series (manufactured by Eastman Chemical Co., Ltd.), ILARV (registered trademark) series (Idemitsu) Alicyclic petroleum resins such as Kosan) Examples include este
  • the weight average molecular weight (Mw) of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000, from the viewpoint of imparting excellent tackiness.
  • the softening point of the tackifier is preferably 50 to 160 ° C., more preferably 60 to 140 ° C., and still more preferably 70 to 130 ° C. from the viewpoint of imparting excellent tackiness.
  • the content thereof is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (A). is there.
  • the sheet-like adhesive of the present invention may contain a silane coupling agent in addition to the components (A) and (B) and, if desired, a binder resin and a tackifier.
  • a silane coupling agent By containing a silane coupling agent, a cured product of a sheet-like adhesive that is superior in adhesive strength is easily obtained.
  • Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri A silane coupling agent having a (meth) acryloyl group such as methoxysilane; Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris (2-methoxyethoxy) silane; Epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-gly
  • the content thereof is preferably 0.01 to 5 parts by mass, more preferably 0.02 with respect to 100 parts by mass of the component (A). ⁇ 3 parts by mass.
  • the sheet adhesive of this invention may further contain components other than the said tackifier and a silane coupling agent in the range which does not inhibit the effect of this invention.
  • components other than the tackifier and the silane coupling agent include an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to determine these content suitably according to the objective.
  • the sheet-like adhesive of the present invention can be formed using an adhesive composition prepared by appropriately mixing and stirring predetermined components according to a conventional method, as will be described later.
  • the sheet-like adhesive of the present invention preferably has a release film on at least one side, and may have a release film on both sides.
  • the sheet-like adhesive of the present invention having a release film on at least one surface represents a state before use, and when using the sheet-like adhesive of the present invention, the release film is usually peeled and removed. Is done. When a sheet-like adhesive has a release film on both sides, a release film having a low peel strength is usually removed first.
  • a resin film can usually be used as the release film.
  • Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane Examples include olefin polymers, aromatic polymers, polyurethane polymers, and the like. Among these, a polyester resin is preferable, and a polyester film is preferable as the resin film.
  • the polyester film a polyethylene terephthalate film that is excellent in heat resistance and ease of handling and has a high ultraviolet transmittance of about 80% at a wavelength of 365 nm is more preferable.
  • the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
  • the thickness of the release film is preferably from 10 to 300 ⁇ m, more preferably from the viewpoint of improving heat resistance, and from the viewpoint of not hindering irradiation of the sheet-like adhesive through ultraviolet rays through the release film.
  • the thickness is 10 to 200 ⁇ m, more preferably 15 to 100 ⁇ m.
  • the transmittance of the release film having a wavelength of 365 nm is as follows: It is preferably 65% or more, and preferably 70% or more.
  • permeability falls remarkably that the wavelength of an ultraviolet-ray is less than 330 nm.
  • the thickness of the sheet adhesive is usually 1 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
  • a sheet-like adhesive having a thickness within the above range is suitably used as a sheet-like sealing material.
  • the thickness of the sheet adhesive can be measured according to JIS K 7130 (1999) using a known thickness meter.
  • the thickness of a sheet-like adhesive is the thickness except the thickness of the peeling film.
  • the sheet-like adhesive of the present invention has adhesive strength even after being irradiated with ultraviolet rays, strongly adheres to an electronic device or a functional film, and does not cause peeling at the time of application or after application. It is. Therefore, it can be suitably used as a sealing material for an electronic device sealing body, in particular, an electronic device sealing body having a functional film that is opaque to ultraviolet rays on the surface.
  • a laminate is prepared by laminating with a polyethylene terephthalate film having a thickness of 23 ⁇ m on which aluminum is vapor-deposited on the opposite surface.
  • the laminate is irradiated with ultraviolet light having a wavelength of 365 nm from the release film side under the conditions of illuminance: 50 mW / cm 2 and light quantity: 200 mJ / cm 2 , and 3 minutes later, the release film is released from the laminate.
  • the exposed sheet-like adhesive layer is opposed to the soda glass plate, and a 2 kg roll is reciprocated once on the laminated body to be attached to the soda glass plate, and the environment at 23 ° C. and 50% relative humidity.
  • the adhesive strength to the soda glass plate after being stored for 24 hours below is preferably 3N / 25mm or more, preferably 5N / 25mm or more There it is more preferable.
  • the adhesive strength to glass is measured by the method described in the examples (180 ° peeling test).
  • the manufacturing method of the sheet adhesive of this invention is not specifically limited. For example, it can be manufactured using a casting method.
  • the method for producing the sheet-like adhesive by the casting method is to apply the adhesive composition to the release layer surface subjected to the release treatment of the release film using a known method, and dry the obtained coating film. A sheet-like adhesive with a release film is obtained.
  • the adhesive composition can be prepared by mixing the components (A) and (B), and other components as desired, by a known method, and stirring.
  • a solvent used for the preparation of the adhesive composition, the viscosity of the adhesive composition can be appropriately adjusted depending on the amount of the solvent used.
  • Solvents include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, mono Halogenated hydrocarbon solvents such as chlorobenzene; Alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; ethyl cellosolve, etc.
  • aliphatic hydrocarbon solvents such as n-hexane and n-heptane
  • aromatic hydrocarbon solvents such as toluene and xylene
  • Cellosolve solvents Cellosolve solvents; ether solvents such as 1,3-dioxolane; and the like. These solvents can be used alone or in combination of two or more. The content of the solvent can be appropriately determined in consideration of coating properties, film thickness, and the like.
  • the release film used for the production of the sheet-like adhesive functions as a support in the production process of the sheet-like adhesive, and as a release film of the above-described sheet-like adhesive until the sheet-like adhesive is used. Function.
  • Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
  • Examples of the method for drying the coating film of the adhesive composition include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
  • the condition for drying the coating film is, for example, 80 to 150 ° C. for 30 seconds to 5 minutes.
  • the adhesive film for sealing an electronic device of the present invention is an adhesive comprising a functional film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, and a sheet-like adhesive containing the component (A) and the component (B). It has a layer.
  • the adhesive film for sealing an electronic device of the present invention is used for sealing an electronic device via the sheet-like adhesive.
  • the adhesive film for sealing an electronic device of the present invention can be obtained, for example, by bonding a functional film and a sheet-like adhesive as described later.
  • the adhesive film for encapsulating an electronic device of the present invention only needs to have at least the functional film and an adhesive layer composed of a sheet-like adhesive, and is composed of only one layer of the adhesive layer. Or even if it is a laminated body of a some adhesive bond layer, it may have another layer other than an adhesive agent.
  • Other layers include a primer layer that improves the adhesion at the interface between the adhesive layer and the functional film, a functional coat layer that is provided on the surface of the functional film that does not have an adhesive layer, a protective film, and a functional film. Examples thereof include an antistatic layer and a stress relaxation layer that can be formed on both sides.
  • the adhesive film for sealing an electronic device of the present invention preferably has a release film on the surface of the adhesive layer on the side where the functional film is not bonded, and the release film is used for the above-described sheet-like adhesive. The thing similar to a thing is preferable.
  • the thickness of the adhesive film for sealing an electronic device of the present invention is usually 6 to 270 ⁇ m.
  • the thickness of the adhesive film for electronic device sealing is a thickness excluding a member that is peeled and removed before use, such as a release film and a protect film.
  • the adhesive film for sealing an electronic device of the present invention has an adhesive force even after being irradiated with ultraviolet rays, strongly adheres to the electronic device, and does not cause peeling at the time of application or after application.
  • it can be suitably used as a sealing material for an electronic device sealing body having a functional film that is opaque to ultraviolet rays on the surface.
  • the adhesive film for sealing an electronic device of the present invention has a release film on the surface of the adhesive layer on the side where the functional film is not attached, a state in which the release film is attached to the adhesive film for device sealing Then, UV light with a wavelength of 365 nm is irradiated from the release film side under the conditions of illuminance: 50 mW / cm 2 and light amount: 200 mJ / cm 2 , and after 3 minutes, the release film is peeled from the adhesive film for sealing an electronic device.
  • the exposed adhesive layer is made to face the soda glass plate, and a 2 kg roll is reciprocated once on the adhesive film for device sealing, so that it is attached to the soda glass plate and placed in an environment of 50% relative humidity at 23 ° C.
  • the adhesive strength to the soda glass plate after being stored for 24 hours is preferably 3N / 25mm or more, and preferably 5N / 25mm or more. It is more preferable.
  • the adhesive strength to glass is measured by the method described in the examples (180 ° peeling test).
  • the electronic device sealing body of the present invention for example, can be produced as follows. Hereinafter, description will be given with reference to the drawings.
  • Manufacturing method 1 The electronic device of the present invention is ( ⁇ 1) a step of irradiating the adhesive film for sealing an electronic device of the present invention with ultraviolet rays from the surface side closer to the adhesive layer than the functional film; ( ⁇ 1) a step of attaching the adhesive film to an electronic device, It can manufacture by performing ((alpha) 1) process before ((beta) 1) process.
  • a sheet-like adhesive 2a is prepared.
  • the sheet-like adhesive 2a can be stored as an adhesive film with a double-sided release film in which release films are laminated on both front and back surfaces.
  • the laminated body 4a shown in FIG. 2 (b) is laminated on one surface side of the obtained sheet-like adhesive 2a by laminating the functional film 1 having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less. Get.
  • the sheet-like adhesive 2a is an adhesive film with a double-sided release film, the release film on one side is peeled off and bonded to the functional film 1. In this case, a laminate having a layer structure of functional film 1 / sheet-like adhesive / release film is obtained.
  • the sheet adhesive 2a is irradiated with ultraviolet rays from the side opposite to the surface on which the functional film 1 of the laminate 4a is laminated, so that the sheet adhesive 2a is photocured. Start the reaction. At this time, the photocuring reaction has started in the sheet-like adhesive, but since the reaction rate of the photocationic polymerization is relatively slow, the curing reaction is not completed. It has adhesive strength (in FIG. 2 (c), sheet-like adhesive 2b).
  • the release film on the sheet-like adhesive It is preferable from the surface of handleability to irradiate ultraviolet rays from the peeling film side without peeling.
  • “having ultraviolet transparency” means a property of transmitting 65% or more, preferably 70% or more of ultraviolet rays having a wavelength of 365 nm (the same applies hereinafter).
  • the ultraviolet light source include light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp.
  • the wavelength range of 190 to 380 nm can be used as the wavelength of the ultraviolet rays to be irradiated.
  • Functional film 1 / sheet adhesive / ultraviolet permeable release film layered laminate release film without peeling the release film side, UV release from the release film side, the release film is a polyethylene terephthalate film
  • the ultraviolet transmittance of the release film is significantly reduced in the region where the wavelength of ultraviolet rays is less than 330 nm.
  • the type, irradiation amount, irradiation time, and the like of the ultraviolet rays can be appropriately determined depending on the component of the sheet adhesive to be irradiated, the content of each component, and the like.
  • the irradiation illuminance is preferably about 20 to 1000 mW / cm 2 and the amount of light is about 50 to 1000 mJ / cm 2 .
  • the irradiation time is usually about 0.1 to 1000 seconds, preferably about 1 to 500 seconds.
  • the target electronic device sealing body 10 can be obtained by bonding the sheet-like adhesive 2 b in a state where the curing reaction is not completed and the electronic device.
  • the time from application of ultraviolet light to bonding to an electronic device is usually 1 minute to 5 hours, and preferably 5 to 60 minutes.
  • the photo-curing reaction proceeds in the sheet-like adhesive even after the electronic device is bonded, and the sheet-like adhesive is completely cured with time. It will be in a state (adhesive hardened material layer 2).
  • the sheet-like adhesive of the present invention has sufficient adhesiveness even after being irradiated with ultraviolet rays as long as the curing reaction does not proceed sufficiently. It adheres strongly to the electronic device that is the body and can prevent peeling at the time of sticking or after sticking. Also, the sheet-like adhesive hardens over time, and finally has excellent durability. An electronic device sealing body can be obtained.
  • the electronic device sealing body of the present invention comprises ( ⁇ 2) a step of irradiating a sheet adhesive containing the following component (A) and component (B) with ultraviolet rays, ( ⁇ 2) a step of attaching the sheet adhesive to a functional film or an electronic device, It can also be produced by performing the ( ⁇ 2) step before the ( ⁇ 2) step.
  • this method is performed as follows. First, the sheet-like adhesive 2a is prepared.
  • the sheet-like adhesive 2a can be stored as an adhesive film with a double-sided release film in which release films are laminated on both front and back sides.
  • the sheet-like adhesive 2a is irradiated with ultraviolet rays to initiate a photocuring reaction of the sheet-like adhesive 2a. In this case, it is preferable to irradiate ultraviolet rays through a peeling film.
  • the photocuring reaction starts in the sheet-like adhesive, but since the reaction rate of the photocationic polymerization is relatively slow, the curing reaction is not completed. It has sufficient adhesive strength.
  • the type of ultraviolet rays, the irradiation conditions of ultraviolet rays, and the like are the same as those described in Production Method 1.
  • the functional film 1 or the electronic device 3 is bonded to one surface side of the sheet-like adhesive 2b to obtain the state shown in FIG.
  • the target electronic device sealing body 10 can be obtained. That is, when the functional film 1 is bonded to one surface side of the sheet-like adhesive 2b, the electronic device 3 is bonded to the surface opposite to the surface where the functional film 1 is bonded. Thereby, the electronic device sealing body 10 can be obtained. Moreover, when the electronic device 3 is bonded to one surface side of the sheet-like adhesive 2b, the functional film 1 is bonded to the surface opposite to the surface where the electronic device 31 is bonded. Thus, the electronic device sealing body 10 can be obtained.
  • the photo-curing reaction proceeds in the layer of the sheet-like adhesive, and the sheet-like adhesive is gradually formed.
  • the adhesive layer is completely cured (adhesive cured product layer 2).
  • the sheet-like adhesive of the present invention has sufficient adhesiveness as long as the curing reaction does not proceed sufficiently even after the adhesive layer is irradiated with ultraviolet rays. Therefore, the adhesive layer strongly adheres to the adherend electronic device, and can be prevented from being peeled off at the time of sticking or after sticking. In particular, an electronic device sealing body with excellent durability can be obtained.
  • the release film is peeled off, the sheet adhesive surface of the exposed adhesive layer is placed on a 1.1 mm thick soda glass plate, and a 2 kg roll is reciprocated once on the surface of the functional film for pressure bonding.
  • a temperature of 23 ° C. and a relative humidity of 50% it is left to stand under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then a 180 ° peeling test is performed at a peeling speed of 300 mm / min. The adhesive strength was measured.
  • Compound having cyclic ether group [component (A)]> (1) Compound (A-1) having a cyclic ether group Hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical, trade name: YX8000, cyclic ether equivalent: 205 g / eq, liquid at 25 ° C.) (2) Compound having a cyclic ether group (A-2) 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [manufactured by Daicel Corporation, trade name: Celoxide 2021P, cyclic ether equivalent: 128 to 145 g / eq, liquid at normal temperature (23 ° C.)]
  • Photocationic polymerization initiator [component (B)]> (1) Photocationic polymerization initiator (B-1) Triarylsulfonium salt [manufactured by San Apro, trade name: CPI-200K, anion: anion having a hexafluorophosphate skeleton] (2) Photocationic polymerization initiator (B-2) Triarylsulfonium salt [manufactured by San Apro, trade name: CPI-100P]
  • Binder resin (C component)]
  • Binder resin (C-1) Acid-modified ⁇ -olefin polymer [Mitsui Chemicals, trade name: Unistor H-200, weight average molecular weight: 52,000]
  • Binder resin (C-2) Phenoxy resin (trade name: YX7200B35, manufactured by Mitsubishi Chemical Corporation)
  • Example 1 Compound (A-1) having a cyclic ether group (50 parts by mass), Compound (A-2) having a cyclic ether group (20 parts by mass), Photocationic polymerization initiator (B-1) 1 part by mass, Photocationic polymerization initiator ( B-2) 1.5 parts, acid-modified ⁇ -olefin polymer (A) 100 parts by mass and silane coupling agent 0.1 part by mass were dissolved in methyl ethyl ketone to obtain an adhesive composition having a solid content concentration of 30%. Prepared.
  • This adhesive composition (1) was obtained by coating the release-treated surface of a release film (trade name: SP-PET752150, thickness 75 ⁇ m, manufactured by Lintec Co., Ltd.) which is a polyethylene terephthalate film subjected to silicone release treatment. The coated film was dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 30 ⁇ m.
  • a polyethylene terephthalate film made by Mitsubishi Shindoh Co., Ltd., product name: metallized film, thickness 23 ⁇ m
  • an adhesive film for sealing an electronic device was obtained in a state having a release film.
  • the transmittance of this functional film at a wavelength of 365 nm was 0%.
  • the adhesive force after ultraviolet irradiation was 12 N / 25 mm.
  • Example 2 The electronic device was encapsulated in the same manner as in Example 1 except that the photocationic polymerization initiator (B-1) was not used and the amount of the photocationic polymerization initiator (B-2) was changed to 3.0 parts by mass. An adhesive film for stopping was obtained. The adhesive strength after UV irradiation was 4 N / 25 mm.
  • Example 3 The electronic device was encapsulated in the same manner as in Example 1 except that the photocationic polymerization initiator (B-1) was not used and the amount of the photocationic polymerization initiator (B-2) was changed to 3.5 parts by mass. An adhesive film for stopping was obtained. The adhesive strength after UV irradiation was 1 N / 25 mm.
  • Example 4 Instead of the raw material (solid content) of the adhesive composition used in Example 1, 120 parts by mass of a compound (A-2) having a cyclic ether group, (2) a photocationic polymerization initiator (B-2) 5 parts by weight, 100 parts by weight of binder resin (C-2), silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM6803) and 0.2 parts by weight were used to prepare an adhesive composition. Otherwise, an adhesive film for sealing an electronic device was obtained in the same manner as in Example 1. The adhesive strength after UV irradiation was 6 N / 25 mm.

Abstract

The present invention pertains to an electronic device-sealed body comprising an electronic device and an adhesive-cured layer that seals between a UV-impermeable functional film and the electronic device; a sheet-shaped adhesive that is used for forming the adhesive-cured layer; an adhesive film for sealing electronic device, the adhesive film having an adhesive layer made of the functional film and the sheet-shaped adhesive; and a method for manufacturing the electronic device-sealed body.

Description

電子デバイス封止体、シート状接着剤、電子デバイス封止用接着フィルム、及び電子デバイス封止体の製造方法Electronic device sealing body, sheet adhesive, electronic device sealing adhesive film, and electronic device sealing body manufacturing method
　本発明は、電子デバイス及び紫外線非透過性の機能性フィルムと電子デバイスの間を封止する接着剤硬化物層を備える電子デバイス封止体、前記接着剤硬化物層の形成に用いられるシート状接着剤、前記機能性フィルムとシート状接着剤とからなる接着剤層を有する電子デバイス封止用接着フィルム、及び電子デバイス封止体の製造方法に関する。 The present invention relates to an electronic device encapsulant comprising an electronic device and an adhesive cured material layer that seals between the electronic device and an ultraviolet light impermeable functional film, and a sheet form used for forming the adhesive cured material layer. The present invention relates to an adhesive, an adhesive film for sealing an electronic device having an adhesive layer composed of the functional film and a sheet-like adhesive, and a method for producing an electronic device sealing body.
　有機ＥＬ素子等の電子デバイスを封止する封止接着剤として、熱硬化性の接着剤が存在する。しかしながら、熱硬化性の接着剤には、デバイスを封止した後に硬化させると熱によるデバイスへのダメージが懸念される。その一方で、電子デバイスに貼り合せる前に硬化させたものでは、初期の感圧接着性が消失してしまうという問題がある。
　一方、紫外線等の活性エネルギー線硬化性の接着剤であれば、電子デバイスに貼り合わせた後に硬化させる場合であっても、有機ＥＬ素子等の電子デバイスへのダメージは小さい。 Thermosetting adhesives exist as sealing adhesives for sealing electronic devices such as organic EL elements. However, there is a concern about damage to the device due to heat when the thermosetting adhesive is cured after sealing the device. On the other hand, in the case where it is cured before being bonded to the electronic device, there is a problem that the initial pressure-sensitive adhesive property is lost.
On the other hand, in the case of an active energy ray-curable adhesive such as ultraviolet rays, damage to an electronic device such as an organic EL element is small even when the adhesive is cured after being bonded to the electronic device.
　特許文献１には、環状エーテル基を有する化合物及び光カチオン重合開始剤を含む電子デバイスの封止用接着剤が記載されている。 Patent Document 1 describes an adhesive for sealing an electronic device containing a compound having a cyclic ether group and a cationic photopolymerization initiator.
特表２０１４－５３４３０９号公報（国際公開２０１３／０５７２６５号）JP-T-2014-534309 (International Publication 2013/057265)
　特許文献１では、「感圧接着剤は、電子的装置への適用後に初めて部分的または最終的に架橋されるのが好ましい」と記載されている〔段落（００６６）〕。そして、このような架橋のためのカチオンＵＶ硬化は、例えば、ＰＥＴライナーやガラスといった紫外線が透過する材料に封止用接着剤が担持された状態で行われることを前提としたものであった。
　本発明は、封止用接着剤が貼り合わされる部材が紫外線非透過性の機能性フィルムであることを前提とし、前記機能性フィルムと電子デバイスの間を封止する接着剤硬化物層を備える電子デバイス封止体、前記接着剤硬化物層の形成材料であるシート状接着剤、前記機能性フィルムとシート状接着剤とからなる接着剤層を有する電子デバイス封止用接着フィルム、並びに、電子デバイス封止体の製造方法を提供することを課題とする。 Patent Document 1 describes that “a pressure-sensitive adhesive is preferably partially or finally crosslinked only after application to an electronic device” [paragraph (0066)]. Then, such cationic UV curing for crosslinking is premised on that the sealing adhesive is carried on a material that transmits ultraviolet rays, such as PET liner and glass.
The present invention is provided with a cured adhesive layer that seals between the functional film and the electronic device on the premise that the member to which the sealing adhesive is bonded is an ultraviolet-opaque functional film. Electronic device sealing body, sheet-like adhesive which is a material for forming the cured adhesive layer, an electronic device sealing adhesive film having an adhesive layer composed of the functional film and the sheet-like adhesive, and an electron It is an object to provide a method for manufacturing a device sealing body.
　環状エーテル基を有する化合物及び光カチオン重合開始剤を含有する接着剤は、紫外線が照射された後であっても接着剤表面の粘着性が残存する。そのため、このような接着剤からなるシート状接着剤は紫外線を照射した後であっても、電子デバイスに貼付することができる。そして、このようなシート状接着剤は、紫外線の照射後経時により接着剤層が硬化し、最終的に、（紫外線非透過性の機能性フィルム）／（接着剤硬化物層）／（電子デバイス）の層構造を有する、耐久性に優れた電子デバイス封止体を効率よく得ることができる。 An adhesive containing a compound having a cyclic ether group and a cationic photopolymerization initiator remains adhesive on the adhesive surface even after being irradiated with ultraviolet rays. Therefore, a sheet-like adhesive made of such an adhesive can be attached to an electronic device even after irradiation with ultraviolet rays. In such a sheet-like adhesive, the adhesive layer is cured over time after irradiation with ultraviolet rays, and finally, (ultraviolet-impermeable functional film) / (adhesive cured product layer) / (electronic device) It is possible to efficiently obtain an electronic device sealing body having a layer structure of) and having excellent durability.
　かくして本発明によれば、下記〔１〕～〔４〕の電子デバイス封止体、〔５〕のシート状接着剤、〔６〕、（７〕の電子デバイス封止用接着フィルム、〔８〕、〔９〕の電子デバイス封止体の製造方法が提供される。 Thus, according to the present invention, the following [1] to [4] electronic device encapsulant, [5] sheet adhesive, [6] and (7) electronic device encapsulating adhesive film, [8] [9] A method for manufacturing an electronic device sealing body is provided.
〔１〕波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム、電子デバイス、及び、前記機能性フィルムと電子デバイスの間を封止する接着剤硬化物層を備え、前記接着剤硬化物層は、下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤の硬化物である、電子デバイスの封止体。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤
〔２〕下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤であって、請求項１に記載の電子デバイスの封止体の製造に用いられるものである、シート状接着剤。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤
〔３〕前記シート状接着剤は、少なくとも一方の面に剥離フィルムを有し、以下の条件（ｉ）で測定されるソーダガラス板に対する粘着力が３Ｎ／２５ｍｍ以上である、〔２〕に記載のシート状接着剤。
（ｉ）前記シート状接着剤の前記剥離フィルムが貼り合わされているのとは逆側の面に、アルミニウムを蒸着した厚さ２３μｍのポリエチレンテレフタレートフィルムと貼り合わせた積層体を作製し、前記剥離フィルムを貼り合わせた状態で、前記剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で前記積層体に照射し、その３分後に、前記積層体から前記剥離フィルムを剥離し、露出したシート状接着剤の層をソーダガラス板に対向させ、前記積層体上で２ｋｇのロールを一往復させることによりガラスに貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後に１８０°引き剥がし試験を実施する。
〔４〕さらに、変性ポリオレフィン樹脂及びフェノキシ樹脂からなる群から選ばれる一種以上を含む、〔２〕又は〔３〕に記載のシート状接着剤。 [1] A functional film, an electronic device having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less, and an adhesive cured material layer for sealing between the functional film and the electronic device, the adhesive curing The physical layer is a sealed body of an electronic device, which is a cured product of a sheet-like adhesive containing the following components (A) and (B).
(A) Compound having a cyclic ether group (B) Photocationic polymerization initiator [2] A sheet-like adhesive comprising the following components (A) and (B), wherein the electronic device is sealed according to claim 1: A sheet-like adhesive that is used for manufacturing a stationary body.
(A) Compound having a cyclic ether group (B) Photocationic polymerization initiator [3] The sheet-like adhesive has a release film on at least one surface, and soda glass measured under the following condition (i) The sheet adhesive according to [2], wherein the adhesive strength to the plate is 3 N / 25 mm or more.
(I) On the opposite side of the sheet-like adhesive from which the release film is attached, a laminate is prepared by attaching an aluminum-deposited 23 μm thick polyethylene terephthalate film, and the release film In the state of bonding, the laminate is irradiated from the release film side with ultraviolet light having a wavelength of 365 nm under the conditions of illuminance: 50 mW / cm 2 and light quantity: 200 mJ / cm 2 , and 3 minutes later, the laminate The release film is peeled off, the exposed sheet-like adhesive layer is opposed to a soda glass plate, and a 2 kg roll is reciprocated once on the laminate to be attached to the glass, and at 50% relative to 23 ° C. After being stored in a humid environment for 24 hours, a 180 ° peel test is performed.
[4] The sheet adhesive according to [2] or [3], further including one or more selected from the group consisting of a modified polyolefin resin and a phenoxy resin.
〔５〕波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルムと、下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤からなる接着剤層を有する、電子デバイス封止用接着フィルム。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤
〔６〕前記電子デバイス封止用接着フィルムは、機能性フィルムが貼り合わされていない側の前記接着剤層の表面に剥離フィルムを有し、以下の条件（ｉｉ）で測定されるソーダガラス板に対する粘着力が３Ｎ／２５ｍｍ以上である、〔５〕に記載の電子デバイス封止用接着フィルム。
（ｉｉ）前記電子デバイス封止用接着フィルムに前記剥離フィルムを貼り合わせた状態で、前記剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で照射し、その３分後に、前記電子デバイス封止用接着剤接着フィルムから前記剥離フィルムを剥離し、露出した接着剤層をソーダガラス板に対向させ、前記電子デバイス封止用接着フィルム上で２ｋｇのロールを一往復させることによりソーダガラス板に貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後に１８０°引き剥がし試験を実施する。
〔７〕さらに、シート状接着剤が、変性ポリオレフィン樹脂及びフェノキシ樹脂からなる群から選ばれる一種以上を含む、〔５〕又は〔６〕に記載の電子デバイス封止用接着フィルム。
〔８〕（α１）上記〔５〕～〔７〕のいずれかの接電子デバイス封止用着性フィルムに対し、機能性フィルムよりも接着剤層に近い表面側から紫外線を照射する工程と、
（β１）前記接着性フィルムを電子デバイスに貼付する工程とを有し、
（β１）工程よりも前に（α１）工程を行う電子デバイスの封止体の製造方法。
〔９〕（α２）下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤に紫外線を照射する工程と、
（β２）前記シート状接着剤を、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム又は電子デバイスに貼付する工程とを有し、
（β２）工程よりも前に（α２）工程を行う電子デバイスの封止体の製造方法。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤 [5] For sealing electronic devices, comprising a functional film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, and an adhesive layer comprising a sheet-like adhesive containing the following components (A) and (B) Adhesive film.
(A) Compound having cyclic ether group (B) Photocationic polymerization initiator [6] The adhesive film for sealing an electronic device has a release film on the surface of the adhesive layer on the side where the functional film is not bonded. The adhesive film for sealing an electronic device according to [5], which has an adhesive strength to a soda glass plate measured under the following condition (ii) of 3 N / 25 mm or more.
(Ii) In the state where the release film is bonded to the adhesive film for sealing an electronic device, ultraviolet rays having a wavelength of 365 nm are applied from the release film side under the conditions of illuminance: 50 mW / cm 2 and light amount: 200 mJ / cm 2 . 3 minutes after irradiation, the release film is peeled off from the adhesive adhesive film for sealing an electronic device, the exposed adhesive layer is opposed to a soda glass plate, and 2 kg on the adhesive film for sealing an electronic device. This roll is attached to a soda glass plate by reciprocating once and stored at 23 ° C. in an environment of 50% relative humidity for 24 hours, and then a 180 ° peeling test is performed.
[7] The adhesive film for sealing an electronic device according to [5] or [6], wherein the sheet-like adhesive further contains one or more selected from the group consisting of a modified polyolefin resin and a phenoxy resin.
[8] (α1) A step of irradiating the adhesive film for sealing an electronic device according to any one of [5] to [7] from the surface side closer to the adhesive layer than the functional film;
(Β1) a step of attaching the adhesive film to an electronic device,
The manufacturing method of the sealing body of the electronic device which performs ((alpha) 1) process before ((beta) 1) process.
[9] (α2) a step of irradiating the sheet-like adhesive containing the following components (A) and (B) with ultraviolet rays;
(Β2) a step of attaching the sheet-like adhesive to a functional film or an electronic device having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm,
The manufacturing method of the sealing body of the electronic device which performs the (α2) step before the (β2) step.
(A) Compound having cyclic ether group (B) Photocationic polymerization initiator
　本発明によれば、紫外線を照射した後においても、紫外線非透過性の機能性フィルムや被着体である電子デバイスに強く接着し、貼付時、あるいは貼付後の剥離を生じることがなく、また、経時的に接着剤層が硬化し、最終的に耐久性に優れたデバイスの封止体を得ることができる。 According to the present invention, even after irradiation with ultraviolet rays, it adheres strongly to an ultraviolet light-impermeable functional film or an electronic device as an adherend, and does not cause peeling at the time of application or after application, The adhesive layer is cured over time, and finally a device sealing body having excellent durability can be obtained.
本発明の電子デバイス封止体の一例を示す図である。It is a figure which shows an example of the electronic device sealing body of this invention. 本発明の電子デバイス封止体の製造方法の概略工程図である。It is a schematic process drawing of the manufacturing method of the electronic device sealing body of this invention. 本発明の電子デバイス封止体の製造方法の概略工程図である。It is a schematic process drawing of the manufacturing method of the electronic device sealing body of this invention.
　以下、本発明を、２）電子デバイス封止体、２）シート状接着剤、３）電子デバイス封止用接着フィルム、及び、４）電子デバイス封止体の製造方法、に項分けして詳細に説明する。 Hereinafter, the present invention is classified into 2) an electronic device sealing body, 2) a sheet adhesive, 3) an electronic device sealing adhesive film, and 4) an electronic device sealing body manufacturing method. Explained.
１）電子デバイス封止体
　本発明の電子デバイス封止体は、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム、電子デバイス及び機能性フィルムと電子デバイスの間を封止する接着剤硬化物層を備え、前記接着剤硬化物層は、下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤（以下、「本発明のシート状接着剤」ということがある。）の硬化物であることを特徴とする。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤 1) Electronic device sealing body The electronic device sealing body of the present invention is a functional film, an electronic device, and an adhesive that seals between the electronic film and a functional film having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less. The adhesive cured material layer is a sheet-like adhesive containing the following components (A) and (B) (hereinafter sometimes referred to as “sheet adhesive of the present invention”). It is a cured product.
(A) Compound having cyclic ether group (B) Photocationic polymerization initiator
　本発明の電子デバイス封止体の層構成例を図１に示す。図１に示す電子デバイス封止体１０は、電子デバイス３の表面を覆うように、電子デバイス３と硬化接着剤層２とが対向するように積層され、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム１が、最表面に配置された層構造を有する。 FIG. 1 shows a layer configuration example of the electronic device sealing body of the present invention. The electronic device sealing body 10 shown in FIG. 1 is laminated so that the electronic device 3 and the cured adhesive layer 2 face each other so as to cover the surface of the electronic device 3, and the transmittance of ultraviolet light having a wavelength of 365 nm is 60%. The following functional film 1 has a layer structure arranged on the outermost surface.
　本発明の電子デバイス封止体において、被封止物である電子デバイスとしては、例えば、有機ＥＬディスプレイ、有機ＥＬ照明等の有機ＥＬ素子；液晶ディスプレイ等の液晶素子；電子ペーパー；有機薄膜太陽電池等の太陽電池素子；発光ダイオード等が挙げられる。 In the electronic device sealing body of the present invention, examples of the electronic device to be sealed include an organic EL element such as an organic EL display and organic EL illumination; a liquid crystal element such as a liquid crystal display; an electronic paper; Solar cell elements such as: light emitting diodes and the like.
〔機能性フィルム〕
　本発明の電子デバイス封止体を構成する機能性フィルム１は、波長３６５ｎｍの紫外線の透過率が６０％以下のフィルムである。機能性フィルムの波長３６５ｎｍの紫外線の透過率は、本発明の効果がより顕著に得られる観点から、５５％以下が好ましく、５０％以下がより好ましい。 [Functional film]
The functional film 1 constituting the electronic device sealing body of the present invention is a film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm. The transmittance of the functional film for ultraviolet rays having a wavelength of 365 nm is preferably 55% or less, more preferably 50% or less, from the viewpoint that the effects of the present invention can be obtained more remarkably.
　機能性フィルムの波長３６５ｎｍの紫外線の透過率は実施例に記載された方法により測定することができる。 The transmittance of ultraviolet rays having a wavelength of 365 nm of the functional film can be measured by the method described in the examples.
　本発明に用いる機能性フィルム１は、波長３６５ｎｍの紫外線の透過率が６０％以下であって、何らかの機能を有するフィルムであれば特に限定されない。例えば、波長３６５ｎｍの紫外線の透過率が６０％以下の、導電層、ガスバリアフィルム、反射防止フィルム、位相差フィルム、視野角向上フィルム、輝度向上フィルム等が挙げられる。これらのうち、例えば、ガスバリアフィルムとしては、金属や無機化合物の膜を有するフィルム等が挙げられ、金属の膜を有するフィルムが好ましい。用いられる金属としては、アルミニウム、亜鉛、銅等が挙げられ、これらの中でも、アルミニウムが好ましい。
　本発明に用いる機能性フィルムの厚みは、特に限定されないが、通常、５～２００μｍ、好ましくは１０～１００μｍである。 The functional film 1 used in the present invention is not particularly limited as long as the transmittance of ultraviolet rays having a wavelength of 365 nm is 60% or less and has a certain function. For example, a conductive layer, a gas barrier film, an antireflection film, a retardation film, a viewing angle improving film, a brightness improving film and the like having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less are included. Among these, examples of the gas barrier film include a film having a metal or inorganic compound film, and a film having a metal film is preferable. Examples of the metal used include aluminum, zinc, copper and the like. Among these, aluminum is preferable.
The thickness of the functional film used in the present invention is not particularly limited, but is usually 5 to 200 μm, preferably 10 to 100 μm.
　波長３６５ｎｍの紫外線の透過率が６０％以下の機能性フィルムを有する場合には、シート状接着剤を電子デバイスに貼り合わせた後に、機能性フィルム側から紫外線を照射しても、紫外線がシート状接着剤に到達する量が少なく、シート状接着剤を硬化させることができない。
　後述するように、本発明のシート状接着剤は、光カチオン重合反応により硬化するものである。光カチオン重合反応は、ラジカル重合反応等に比較して、反応速度が相対的に遅い。従って、シート状接着剤に紫外線を照射した後であっても、硬化反応が進行の途中である間は、シート状接着剤は十分な接着性を有しているので、被着体である電子デバイスに強く接着し、貼付時、あるいは貼付後の剥離を生じることを防止することができる。また、経時的に接着剤層が硬化し、最終的に耐久性に優れた電子デバイスの封止体を得ることができる。 In the case of having a functional film with a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, the ultraviolet light is still in a sheet form even if the functional film side is irradiated with ultraviolet light after the sheet adhesive is bonded to the electronic device. The amount reaching the adhesive is small, and the sheet-like adhesive cannot be cured.
As will be described later, the sheet-like adhesive of the present invention is cured by a photocationic polymerization reaction. The photocationic polymerization reaction has a relatively slow reaction rate compared to a radical polymerization reaction or the like. Therefore, even after the sheet-like adhesive is irradiated with ultraviolet rays, while the curing reaction is in progress, the sheet-like adhesive has sufficient adhesiveness. It adheres strongly to the device and can prevent peeling at the time of application or after application. Further, the adhesive layer is cured with time, and an electronic device sealing body having excellent durability can be finally obtained.
〔接着剤硬化物層〕
　本発明の電子デバイス封止体の接着剤硬化物層２は、本発明のシート状接着剤の硬化物からなるものであり、電子デバイスを封止する封止し、電子デバイスと機能性フィルムを接着する役割を果たす。 [Hardened adhesive layer]
The adhesive cured material layer 2 of the electronic device encapsulant of the present invention is composed of a cured product of the sheet adhesive of the present invention, and seals the electronic device to seal the electronic device and the functional film. Plays the role of bonding.
〔シート状接着剤）
　本発明のシート状接着剤は、接着性を有するシート状物であって、下記（Ａ）成分及び（Ｂ）成分を含むものである。
（Ａ）環状エーテル基を有する化合物
（Ｂ）光カチオン重合開始剤 [Sheet adhesive]
The sheet-like adhesive of the present invention is a sheet-like product having adhesiveness, and includes the following components (A) and (B).
(A) Compound having cyclic ether group (B) Photocationic polymerization initiator
　シート状接着剤とは、常温（２５℃程度）では非流動性を示すシート状に成形された接着剤を言う。本発明において、シート状接着剤は、短冊状のものであっても、長尺状（帯状）のものであってもよい。 «Sheet adhesive refers to an adhesive formed into a sheet that exhibits non-flowability at room temperature (about 25 ° C). In the present invention, the sheet-like adhesive may be strip-shaped or long (band-shaped).
〔（Ａ）成分：環状エーテル基を有する化合物〕
　本発明のシート状接着剤は、（Ａ）成分として、環状エーテル基を有する化合物を含有する。
　環状エーテル基を有する化合物を使用することにより、シート状接着剤の硬化性及び水蒸気遮断性に優れるシート状接着剤の硬化物を得ることができる。 [Component (A): Compound having a cyclic ether group]
The sheet-like adhesive of the present invention contains a compound having a cyclic ether group as the component (A).
By using a compound having a cyclic ether group, it is possible to obtain a cured product of the sheet adhesive that is excellent in the curability and water vapor blocking properties of the sheet adhesive.
　環状エーテル基としては、オキシラン基（エポキシ基）、オキセタン基（オキセタニル基）、テトラヒドロフリル基、テトラヒドロピラニル基等が挙げられる。
　環状エーテル基を有する化合物とは、分子内に少なくとも１個以上の環状エーテル基を有する化合物をいう。なかでも、接着強度により優れた接着剤の硬化物を得ることができるという観点から、オキシラン基又はオキセタン基を有する化合物であることが好ましく、分子内に２個以上のオキシラン基又はオキセタン基を有する化合物が特に好ましい。 Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetane group (oxetanyl group), a tetrahydrofuryl group, and a tetrahydropyranyl group.
The compound having a cyclic ether group refers to a compound having at least one cyclic ether group in the molecule. Especially, it is preferable that it is a compound which has an oxirane group or an oxetane group from a viewpoint that the hardened | cured material of the adhesive agent excellent by adhesive strength can be obtained, and has two or more oxirane groups or oxetane groups in a molecule | numerator. Compounds are particularly preferred.
　分子内にオキシラン基を有する化合物としては、例えば、脂肪族エポキシ化合物（脂環式エポキシ化合物を除く）、芳香族エポキシ化合物、脂環式エポキシ化合物等が挙げられる。
　脂肪族エポキシ化合物としては、脂肪族アルコールのグリシジルエーテル化物、アルキルカルボン酸のグリシジルエステル等の単官能エポキシ化合物；
脂肪族多価アルコール、又はそのアルキレンオキサイド付加物のポリグリシジルエーテル化物、脂肪族長鎖多塩基酸のポリグリシジルエステル、トリアジン骨格を有するエポキシ化合物等の多官能エポキシ化合物が挙げられる。 As a compound which has an oxirane group in a molecule | numerator, an aliphatic epoxy compound (except an alicyclic epoxy compound), an aromatic epoxy compound, an alicyclic epoxy compound etc. are mentioned, for example.
Examples of aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl ethers of aliphatic alcohols and glycidyl esters of alkylcarboxylic acids;
Examples thereof include polyfunctional epoxy compounds such as polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and epoxy compounds having a triazine skeleton.
　これらの脂肪族エポキシ化合物の代表的な化合物としては、アリルグリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、Ｃ１２～１３混合アルキルグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、グリセリンのトリグリシジルエーテル、トリメチロールプロパンのトリグリシジルエーテル、ソルビトールのテトラグリシジルエーテル、ジペンタエリスリトールのヘキサグリシジルエーテル、ポリエチレングリコールのジグリシジルエーテル、ポリプロピレングリコールのジグリシジルエーテル、ジシクロペンタジエンジメタノールジグリシジルエーテル等の多価アルコールのグリシジルエーテル、またプロピレングリコール、トリメチロールプロパン、グリセリン等の脂肪族多価アルコールに１種、又は２種以上のアルキレンオキサイドを付加することによって得られるポリエーテルポリオールのポリグリシジルエーテル化物、脂肪族長鎖二塩基酸のジグリシジルエステル；
脂肪族高級アルコールのモノグリシジルエーテルや高級脂肪酸のグリシジルエステル、エポキシ化大豆油、エポキシステアリン酸オクチル、エポキシステアリン酸ブチル、エポキシ化ポリブタジエン；
２，４，６－トリ（グリシジルオキシ）－１，３，５－トリアジン等が挙げられる。 Typical examples of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diester. Glycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, dicyclopentadiene dimethanol Polyglycol glycidyl ether such as diglycidyl ether, propylene glycol, triglyceride Ji trimethylolpropane, one to aliphatic polyhydric alcohols such as glycerin, or two or more polyglycidyl ethers of polyether polyols obtained by adding an alkylene oxide, diglycidyl esters of aliphatic long chain dibasic acid;
Monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene;
Examples include 2,4,6-tri (glycidyloxy) -1,3,5-triazine.
　また、脂肪族エポキシ化合物として、市販品を用いることもできる。市販品としては、デナコールＥＸ－１２１、デナコールＥＸ－１７１、デナコールＥＸ－１９２、デナコールＥＸ－２１１、デナコールＥＸ－２１２、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１、デナコールＥＸ－４１１、デナコールＥＸ－４２１、デナコールＥＸ－５１２、デナコールＥＸ－５２１、デナコールＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－８１０、デナコールＥＸ－８１１、デナコールＥＸ－８５０、デナコールＥＸ－８５１、デナコールＥＸ－８２１、デナコールＥＸ－８３０、デナコールＥＸ－８３２、デナコールＥＸ－８４１、デナコールＥＸ－８６１、デナコールＥＸ－９１１、デナコールＥＸ－９４１、デナコールＥＸ－９２０、デナコールＥＸ－９３１（以上、ナガセケムテックス社製）；
エポライトＭ－１２３０、エポライト４０Ｅ、エポライト１００Ｅ、エポライト２００Ｅ、エポライト４００Ｅ、エポライト７０Ｐ、エポライト２００Ｐ、エポライト４００Ｐ、エポライト１５００ＮＰ、エポライト１６００、エポライト８０ＭＦ、エポライト１００ＭＦ（以上、共栄社化学社製）；
アデカグリシロールＥＤ－５０３、アデカグリシロールＥＤ－５０３Ｇ、アデカグリシロールＥＤ－５０６、アデカグリシロールＥＤ－５２３Ｔ、アデカレジンＥＰ－４０８８Ｓ、アデカレジンＥＰ－４０８８Ｌ、アデカレジンＥＰ－４０８０Ｅ（以上、ＡＤＥＫＡ社製）；
ＴＥＰＩＣ－ＦＬ、ＴＥＰＩＣ－ＰＡＳ、ＴＥＰＩＣ－ＵＣ（以上、日産化学社製）等が挙げられる。 Moreover, a commercial item can also be used as an aliphatic epoxy compound. Commercially available products include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Call EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation);
Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.);
ADEKA GLYCIROL ED-503, ADEKA GLYCIROL ED-503G, ADEKA GLYCIROL ED-506, ADEKA GLYCIROL ED-523T, ADEKA RESIN EP-4088S, ADEKA RESIN EP-4088L, ADEKA RESIN EP-4080E (above, manufactured by ADEKA)
Examples include TEPIC-FL, TEPIC-PAS, and TEPIC-UC (manufactured by Nissan Chemical Co., Ltd.).
　芳香族エポキシ化合物としては、フェノール、クレゾール、ブチルフェノール等の、芳香族環を少なくとも１個以上有する多価フェノール、又はそのアルキレンオキサイド付加物のモノ／ポリグリシジルエーテル化物等が挙げられる。
　これらの芳香族エポキシ化合物の代表的な化合物としては、ビスフェノールＡ、ビスフェノールＦ、又はこれらにさらにアルキレンオキサイドを付加した化合物のグリシジルエーテル化物やエポキシノボラック樹脂；
レゾルシノールやハイドロキノン、カテコール等の２個以上のフェノール性水酸基を有する芳香族化合物のモノ／ポリグリシジルエーテル化物；
フェニルジメタノールやフェニルジエタノール、フェニルジブタノール等のアルコール性水酸基を２個以上有する芳香族化合物のグリシジルエーテル化物；
フタル酸、テレフタル酸、トリメリット酸等の２個以上のカルボン酸を有する多塩基酸芳香族化合物のグリシジルエステル、安息香酸のグリシジルエステル、スチレンオキサイド又はジビニルベンゼンのエポキシ化物等が挙げられる。 Examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono / polyglycidyl etherified products of alkylene oxide adducts thereof.
Representative compounds of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl etherified compounds or epoxy novolac resins obtained by further adding alkylene oxide to these compounds;
Mono / polyglycidyl etherified products of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, catechol;
Glycidyl etherified products of aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol and phenyldibutanol;
Examples thereof include glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, glycidyl esters of benzoic acid, epoxides of styrene oxide or divinylbenzene.
　また、芳香族エポキシ化合物として、市販品を用いることもできる。市販品としては、デナコールＥＸ－１４６、デナコールＥＸ－１４７、デナコールＥＸ－２０１、デナコールＥＸ－２０３、デナコールＥＸ－７１１、デナコールＥＸ－７２１、オンコートＥＸ－１０２０、オンコートＥＸ－１０３０、オンコートＥＸ－１０４０、オンコートＥＸ－１０５０、オンコートＥＸ－１０５１、オンコートＥＸ－１０１０、オンコートＥＸ－１０１１、オンコート１０１２（以上、ナガセケムテックス社製）；
オグソールＰＧ－１００、オグソールＥＧ－２００、オグソールＥＧ－２１０、オグソールＥＧ－２５０（以上、大阪ガスケミカル社製）；
ＨＰ４０３２、ＨＰ４０３２Ｄ、ＨＰ４７００（以上、ＤＩＣ社製）；
ＥＳＮ－４７５Ｖ（以上、新日鉄住金化学社製）；
ＪＥＲ（旧エピコート）ＹＸ８８００（三菱化学社製）；
マープルーフＧ－０１０５ＳＡ、マープルーフＧ－０１３０ＳＰ（以上、日油（株）社製）；
エピクロンＮ－６６５、エピクロンＨＰ－７２００（以上、ＤＩＣ社製）；
ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２Ｓ、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＸＤ－１０００、ＮＣ－３０００、ＥＰＰＮ－５０１Ｈ、ＥＰＰＮ－５０１ＨＹ、ＥＰＰＮ－５０２Ｈ、ＮＣ－７０００Ｌ（以上、日本化薬社製）；
アデカレジンＥＰ－４０００、アデカレジンＥＰ－４００５、アデカレジンＥＰ－４１００、アデカレジンＥＰ－４９０１（以上、ＡＤＥＫＡ社製）；
ＴＥＣＨＭＯＲＥ　ＶＧ－３１０１Ｌ（以上、プリンテック社製）等が挙げられる。 Moreover, a commercial item can also be used as an aromatic epoxy compound. Commercially available products include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX -1040, on-coat EX-1050, on-coat EX-1051, on-coat EX-1010, on-coat EX-1011, on-coat 1012 (above, manufactured by Nagase ChemteX);
Ogsol PG-100, Ogsol EG-200, Ogsol EG-210, Ogsol EG-250 (above, manufactured by Osaka Gas Chemical Company);
HP4032, HP4032D, HP4700 (above, manufactured by DIC);
ESN-475V (Nippon Steel & Sumikin Chemical Co., Ltd.);
JER (former Epicoat) YX8800 (Mitsubishi Chemical Corporation);
Marproof G-0105SA, Marproof G-0130SP (above, manufactured by NOF Corporation);
Epicron N-665, Epicron HP-7200 (above, manufactured by DIC);
EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (above, Nippon Kayaku Co., Ltd.);
Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (above, manufactured by ADEKA);
TECHMORE VG-3101L (manufactured by Printec Co., Ltd.).
　脂環式エポキシ化合物としては、少なくとも１個以上の脂環式構造を有する多価アルコールのポリグリシジルエーテル化物、又はシクロヘキセンやシクロペンテン環含有化合物を酸化剤でエポキシ化することによって得られるシクロヘキセンオキサイドやシクロペンテンオキサイド含有化合物等のシクロアルケンオキサイド化合物が挙げられる。
　これらの脂環式エポキシ化合物の代表的な化合物としては、水素添加ビスフェノールＡジグリシジルエーテル、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、３，４－エポキシ－１－メチルシクロヘキシル－３，４－エポキシ－１－メチルヘキサンカルボキシレート、６－メチル－３，４－エポキシシクロヘキシルメチル－６－メチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－３－メチルシクロヘキシルメチル－３，４－エポキシ－３－メチルシクロヘキサンカルボキシレート、３，４－エポキシ－５－メチルシクロヘキシルメチル－３，４－エポキシ－５－メチルシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、プロパン－２，２－ジイル－ビス（３，４－エポキシシクロヘキサン）、２，２－ビス（３，４－エポキシシクロヘキシル）プロパン、ジシクロペンタジエンジエポキサイド、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、エポキシヘキサヒドロフタル酸ジオクチル、エポキシヘキサヒドロフタル酸ジ－２－エチルヘキシル、１－エポキシエチル－３，４－エポキシシクロヘキサン、１，２－エポキシ－２－エポキシエチルシクロヘキサン、α－ピネンオキシド、リモネンジオキシド等が挙げられる。 As the alicyclic epoxy compound, a polyglycidyl etherified product of a polyhydric alcohol having at least one alicyclic structure, or cyclohexene oxide or cyclopentene obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. And cycloalkene oxide compounds such as oxide-containing compounds.
Typical examples of these alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methylcyclohexyl. -3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl -3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adip 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), propane-2,2-diyl-bis (3,4-epoxycyclohexane), 2,2-bis (3 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3 , 4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide and the like.
　また、脂環式エポキシ化合物として、市販品を用いることができる。市販品としては、ＹＸ８０００（三菱ケミカル社製）、セロキサイド２０２１Ｐ、セロキサイド２０８１、セロキサイド２０００、セロキサイド３０００（ダイセル社製）等が挙げられる。 Moreover, a commercial item can be used as an alicyclic epoxy compound. Examples of commercially available products include YX8000 (manufactured by Mitsubishi Chemical Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2000, Celoxide 3000 (Daicel).
　分子内にオキセタン基を有する化合物としては、３，７－ビス（３－オキセタニル）－５－オキサ－ノナン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，２－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エタン、１，３－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］プロパン、エチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、トリエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、テトラエチレングリコールビス（３－エチル－３－オキセタニルメチル）エーテル、１，４－ビス（３－エチル－３－オキセタニルメトキシ）ブタン、１，６－ビス（３－エチル－３－オキセタニルメトキシ）ヘキサン等の二官能脂肪族オキセタン化合物、３－エチル－３－［（フェノキシ）メチル］オキセタン、３－エチル－３－（ヘキシロキシメチル）オキセタン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、３－エチル－３－（ヒドロキシメチル）オキセタン、３－エチル－３－（クロロメチル）オキセタン等の一官能オキセタン化合物等が挙げられる。 Examples of the compound having an oxetane group in the molecule include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1, 2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ) Ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) Bifunctional fats such as butane and 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane Group oxetane compounds, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl And monofunctional oxetane compounds such as -3- (hydroxymethyl) oxetane and 3-ethyl-3- (chloromethyl) oxetane.
　分子内にオキセタン基を有する化合物としては、市販品を用いることもできる。市販品としては、２－ヒドロキシエチルビニルエーテル、ジエチレングリコールモノビニルエーテル、４－ヒドロキシブチルビニルエーテル（以上、丸善石油化学社製）；
アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＥＸＯＨ、ＰＯＸ、ＯＸＡ、ＯＸＴ－１０１、ＯＸＴ－２１１、ＯＸＴ－２１２（以上、東亞合成社製）；
エタナコールＯＸＢＰ、ＯＸＴＰ（以上、宇部興産社製）等が挙げられる。 A commercial item can also be used as a compound which has an oxetane group in a molecule | numerator. Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.);
Aron Oxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (above, manufactured by Toagosei Co., Ltd.);
Etanacol OXBP, OXTP (manufactured by Ube Industries, Ltd.) and the like can be mentioned.
　これらの中でも、シート加工性（造膜性）により優れた接着剤、及び接着強度により優れた接着剤の硬化物を得ることができるという観点から、２５℃で液状である化合物が好ましい。また、環状エーテル基がオキシラン基であるものが好ましい。環状エーテル基がオキシラン基である化合物（エポキシ化合物）の中でも、接着剤の硬化物の特性を調整し、着色を防ぐ観点から脂環式エポキシ化合物が好ましく、光カチオン重合の反応性の向上の観点からは、シクロアルケンオキサイド化合物が好ましい。 Among these, a compound that is liquid at 25 ° C. is preferable from the viewpoint that an adhesive excellent in sheet processability (film forming property) and a cured product of adhesive excellent in adhesive strength can be obtained. Moreover, what a cyclic ether group is an oxirane group is preferable. Among the compounds in which the cyclic ether group is an oxirane group (epoxy compound), an alicyclic epoxy compound is preferable from the viewpoint of adjusting the properties of the cured product of the adhesive and preventing coloring, and from the viewpoint of improving the reactivity of photocationic polymerization Is preferably a cycloalkene oxide compound.
　また、多官能エポキシ化合物、二官能脂肪族オキセタン化合物のような、分子内に２つ以上の環状エーテル基を有する化合物が、シート状接着剤の硬化性を向上させる観点から好ましい。 Further, a compound having two or more cyclic ether groups in the molecule, such as a polyfunctional epoxy compound and a bifunctional aliphatic oxetane compound, is preferable from the viewpoint of improving the curability of the sheet adhesive.
　環状エーテル基を有する化合物の分子量は、通常、１００～５，０００、好ましくは２００～４，０００である。
　環状エーテル基を有する化合物の環状エーテル当量は、好ましくは１００ｇ／ｅｑ以上５００ｇ／ｅｑ以下、より好ましくは１１５ｇ／ｅｑ以上３００ｇ／ｅｑ以下である。
　シート状接着剤に含まれる環状エーテル基を有する化合物の環状エーテル当量が上記範囲にあることで、接着強度が強く硬化性に優れる封止材を効率よく得ることができる。
　これらの環状エーテル基を有する化合物は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
　本発明における環状エーテル当量とは、分子量を環状エーテル基数で除した値を意味する。 The molecular weight of the compound having a cyclic ether group is usually 100 to 5,000, preferably 200 to 4,000.
The cyclic ether equivalent of the compound having a cyclic ether group is preferably 100 g / eq or more and 500 g / eq or less, more preferably 115 g / eq or more and 300 g / eq or less.
When the cyclic ether equivalent of the compound having a cyclic ether group contained in the sheet-like adhesive is in the above range, a sealing material having high adhesive strength and excellent curability can be obtained efficiently.
These compounds having a cyclic ether group can be used singly or in combination of two or more.
The cyclic ether equivalent in the present invention means a value obtained by dividing the molecular weight by the number of cyclic ether groups.
　本発明のシート状接着剤が後述するバインダー樹脂を含有する場合、環状エーテル基を有する化合物の含有量は、バインダー樹脂１００質量部に対して、好ましくは２０～１８０質量部、より好ましくは４０～１４０質量部である。
　環状エーテル基を有する化合物の含有量を上記範囲とすることで、接着強度により優れる接着剤層の硬化物が得られやすくなる。 When the sheet-like adhesive of the present invention contains a binder resin described later, the content of the compound having a cyclic ether group is preferably 20 to 180 parts by mass, more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the binder resin. 140 parts by mass.
By making content of the compound which has a cyclic ether group into the said range, it becomes easy to obtain the hardened | cured material of the adhesive bond layer which is excellent by adhesive strength.
　本発明のシート状接着剤中の前記（Ａ）成分の含有量は、接着剤全体に対し、固形分（不揮発分であり、液状のものを含む。以下同じ。）として、２０～８０質量％が好ましく、２５～７０質量％がより好ましく、３０～６５質量％が特に好ましい。
　本発明のシート状接着剤の前記（Ａ）成分の含有量が、上記範囲にあることにより、紫外線照射後のシート状接着剤の粘着力を調整することが容易となる。 The content of the component (A) in the sheet-like adhesive of the present invention is 20 to 80% by mass as a solid content (non-volatile content, including a liquid material, the same applies hereinafter) with respect to the entire adhesive. Is more preferable, 25 to 70% by mass is more preferable, and 30 to 65% by mass is particularly preferable.
When the content of the component (A) in the sheet adhesive of the present invention is in the above range, it becomes easy to adjust the adhesive strength of the sheet adhesive after the ultraviolet irradiation.
〔（Ｂ）成分：光カチオン重合開始剤〕
　本発明のシート状接着剤は、（Ｂ）成分として、光カチオン重合開始剤を含有する。これにより、紫外線照射後のシート状接着剤の粘着力を調整することが容易となる。
　光カチオン重合開始剤は、活性エネルギー線が照射されることによってカチオン種を発生して、カチオン硬化性化合物の硬化反応を開始させる化合物であり、活性エネルギー線を吸収するカチオン部と酸の発生源となるアニオン部からなる。 [(B) component: photocationic polymerization initiator]
The sheet adhesive of this invention contains a photocationic polymerization initiator as (B) component. Thereby, it becomes easy to adjust the adhesive force of the sheet-like adhesive after ultraviolet irradiation.
The cationic photopolymerization initiator is a compound that generates a cationic species by irradiating active energy rays and initiates the curing reaction of the cationic curable compound. It consists of an anion part.
　光カチオン重合開始剤としては、例えば、スルホニウム塩系化合物、ヨードニウム塩系化合物、ホスホニウム塩系化合物、アンモニウム塩系化合物、アンチモン酸塩系化合物、ジアゾニウム塩系化合物、セレニウム塩系化合物、オキソニウム塩系化合物、臭素塩系化合物等が挙げられる。これらの中でも、（Ａ）成分との相溶性に優れ、得られる接着剤の保存安定性に優れるという観点から、スルホニウム塩系化合物が好ましく、芳香族基を有する芳香族スルホニウム塩系化合物がより好ましい。 Examples of the cationic photopolymerization initiator include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, and oxonium salt compounds. And bromine salt compounds. Among these, from the viewpoint of excellent compatibility with the component (A) and excellent storage stability of the obtained adhesive, a sulfonium salt compound is preferable, and an aromatic sulfonium salt compound having an aromatic group is more preferable. .
　スルホニウム塩系化合物としては、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、４，４’－ビス［ジフェニルスルホニオ］ジフェニルスルフィド－ビスヘキサフルオロホスフェート、４，４’－ビス［ジ（β－ヒドロキシエトキシ）フェニルスルホニオ］ジフェニルスルフィド－ビスヘキサフルオロアンチモネート、７－［ジ（ｐ－トルイル）スルホニオ］－２－イソプロピルチオキサントンヘキサフルオロホスフェート、７－［ジ（ｐ－トルイル）スルホニオ］－２－イソプロピルチオキサントンヘキサフルオロアンチモネート、７－［ジ（ｐ－トルイル）スルホニオ］－２－イソプロピルテトラキス（ペンタフルオロフェニル）ボレート、フェニルカルボニル－４’－ジフェニルスルホニオ－ジフェニルスルフィド－ヘキサフルオロホスフェート、フェニルカルボニル－４’－ジフェニルスルホニオ－ジフェニルスルフィド－ヘキサフルオロアンチモネート、４－ｔｅｒｔ－ブチルフェニルカルボニル－４’－ジフェニルスルホニオ－ジフェニルスルフィド－ヘキサフルオロホスフェート、４－ｔｅｒｔ－ブチルフェニルカルボニル－４’－ジフェニルスルホニオ－ジフェニルスルフィド－ヘキサフルオロアンチモネート、４－ｔｅｒｔ－ブチルフェニルカルボニル－４’－ジフェニルスルホニオ－ジフェニルスルフィド－テトラキス（ペンタフルオロフェニル）ボレート、チオフェニルジフェニルスルホニウムヘキサフルオロアンチモネート、チオフェニルジフェニルスルホニウムヘキサフルオロホスフェート、４－｛４－（２－クロロベンゾイル）フェニルチオ｝フェニルビス（４－フルオロフェニル）スルホニウムヘキサフルオロアンチモネート、チオフェニルジフェニルスルホニウムヘキサフルオロアンチモネートのハロゲン化物、４，４’，４’’－トリ（β－ヒドロキシエトキシフェニル）スルホニウムヘキサフルオロアンチモネート、４，４’－ビス［ジフェニルスルホニオ］ジフェニルスルフィド－ビスヘキサフルオロアンチモネート、ジフェニル［４－（フェニルチオ）フェニル］スルホニウムトリフルオロトリスペンタフルオロエチルホスファート、トリス［４－（４－アセチルフェニルスルファニル）フェニル］スルホニウムトリス［（トリフルオロメチル）スルホニル］メタニド等が挙げられる。 Examples of the sulfonium salt compounds include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoro. Phosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate, 7 -[Di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopro Rutetrakis (pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl -4'-diphenylsulfonio-diphenyl sulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenyl Sulfonio-diphenylsulfide-tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hexafluo Loantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate halide, 4 , 4 ′, 4 ″ -tri (β-hydroxyethoxyphenyl) sulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, diphenyl [4- (phenylthio) phenyl ] Sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(tri Ruoromechiru) sulfonyl] methanide and the like.
　ヨードニウム塩系化合物としては、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－ノニルフェニル）ヨードニウムヘキサフルオロホスフェート、（トリクミル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the iodonium salt compounds include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, (triccumyl) iodonium tetrakis (pentafluoro). Phenyl) borate and the like.
　ホスホニウム塩系化合物としては、トリ－ｎ－ブチル（２，５－ジヒドロキシフェニル）ホスホニウムブロマイド、ヘキサデシルトリブチルホスホニウムクロライド等が挙げられる。 Examples of the phosphonium salt compound include tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosphonium chloride and the like.
　アンモニウム塩系化合物としては、ベンジルトリメチルアンモニウムクロライド、フェニルトリブチルアンモニウムクロライド、ベンジルトリメチルアンモニウムブロマイド等が挙げられる。 Examples of ammonium salt compounds include benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide.
　アンチモン酸塩系化合物としては、トリフェニルスルホニウムヘキサフルオロアンチモネート、ｐ－（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロアンチモネート、４－クロルフェニルジフェニルスルホニウムヘキサフルオロアンチモネート、ビス［４－（ジフェニルスルフォニオ）フェニル］スルフィドビスヘキサフルオロアンチモネート及びジアリルヨードニウムヘキサフルオロアンチモネート等が挙げられる。 Antimonate compounds include triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) Phenyl] sulfide bishexafluoroantimonate and diallyliodonium hexafluoroantimonate.
　これらの光カチオン重合開始剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 These photocationic polymerization initiators can be used singly or in combination of two or more.
　また、光カチオン重合開始剤として、市販品を用いることができる。市販品としては、サイラキュアＵＶＩ－６９７０、サイラキュアＵＶＩ－６９７４、サイラキュアＵＶＩ－６９９０、サイラキュアＵＶＩ－９５０（以上、ユニオンカーバイド社製）、イルガキュア２５０、イルガキュア２６１、イルガキュア２６４（以上、チバ・スペシャルティ・ケミカルズ社製）、ＳＰ－１５０、ＳＰ－１５１、ＳＰ－１７０、オプトマーＳＰ－１７１（以上、ＡＤＥＫＡ社製）、ＣＧ－２４－６１（チバ・スペシャルティ・ケミカルズ社製）、ＤＡＩＣＡＴ　ＩＩ（ダイセル社製）、ＵＶＡＣ１５９０、ＵＶＡＣ１５９１（以上、ダイセル・サイテック社製）、ＣＩ－２０６４、ＣＩ－２６３９、ＣＩ－２６２４、ＣＩ－２４８１、ＣＩ－２７３４、ＣＩ－２８５５、ＣＩ－２８２３、ＣＩ－２７５８、ＣＩＴ－１６８２（以上、日本曹達社製）、ＰＩ－２０７４（ローディア社製）、ＦＦＣ５０９（３Ｍ社製）、ＢＢＩ－１０２、ＢＢＩ－１０１、ＢＢＩ－１０３、ＭＰＩ－１０３、ＴＰＳ－１０３、ＭＤＳ－１０３、ＤＴＳ－１０３、ＮＡＴ－１０３、ＮＤＳ－１０３（以上、ミドリ化学社製）、ＣＤ－１０１０、ＣＤ－１０１１、ＣＤ－１０１２（Ｓａｒｔｏｍｅｒ社製）、ＣＰＩ－１００Ｐ、ＣＰＩ－１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－３１０Ｂ（以上、サンアプロ社製）等が挙げられる。 Moreover, a commercial item can be used as a photocationic polymerization initiator. Commercially available products include Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, manufactured by Union Carbide), Irgacure 250, Irgacure 261, Irgacure 264 (above, Ciba Specialty Chemicals) ), SP-150, SP-151, SP-170, Optomer SP-171 (manufactured by ADEKA), CG-24-61 (manufactured by Ciba Specialty Chemicals), DACAT II (manufactured by Daicel), UVAC1590, UVAC1591 (manufactured by Daicel-Cytec), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, CIT-16 2 (above, manufactured by Nippon Soda Co., Ltd.), PI-2074 (manufactured by Rhodia), FFC509 (manufactured by 3M), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (above, manufactured by Midori Chemical), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer), CPI-100P, CPI-101A, CPI-200K, CPI -310B (manufactured by Sun Apro).
　光カチオン重合開始剤の含有量は、前記（Ａ）成分１００質量部に対して、通常、０．１～１０質量部、好ましくは０．３～８質量部、より好ましくは０．５～４．５質量部である。
　光カチオン重合開始剤の含有量を上記範囲とすることで、紫外線照射後のシート状接着剤の粘着力を調整することが容易となる。 The content of the cationic photopolymerization initiator is usually 0.1 to 10 parts by mass, preferably 0.3 to 8 parts by mass, more preferably 0.5 to 4 parts per 100 parts by mass of the component (A). .5 parts by mass.
By making content of a photocationic polymerization initiator into the said range, it becomes easy to adjust the adhesive force of the sheet adhesive after ultraviolet irradiation.
　本発明のシート状接着剤は、前記（Ａ）成分、（Ｂ）成分以外の成分を含有してもよい。前記（Ａ）成分、（Ｂ）成分以外の成分としては、バインダー樹脂、粘着付与剤、及びシランカップリング剤及等が挙げられる。 The sheet-like adhesive of the present invention may contain a component other than the component (A) and the component (B). Examples of the components other than the component (A) and the component (B) include a binder resin, a tackifier, a silane coupling agent, and the like.
〔バインダー樹脂〕
　本発明のシート状接着剤がバインダー樹脂を含有する場合には、シート状接着剤を形成するための組成物に優れたシート加工性（造膜性）を付与し、所望の厚みのシート状接着剤を効率よく形成することができる。 [Binder resin]
When the sheet-like adhesive of the present invention contains a binder resin, the composition for forming the sheet-like adhesive is imparted with excellent sheet processability (film forming property), and a sheet-like adhesive having a desired thickness. An agent can be formed efficiently.
　バインダー樹脂としては、（Ａ）成分との相溶性に優れる観点から、変性ポリオレフィン系樹脂及びフェノキシ樹脂から選ばれる１種又は２種以上が好ましい。
　変性ポリオレフィン系樹脂を用いる場合には、主剤であるポリオレフィンが硬化構造に取り込まれつつ、低い透湿性を維持することが可能となる。また、フェノキシ樹脂を用いる場合には、シート状接着剤の硬化物の弾性率を高く保つことが可能となり、電子デバイス封止体の高温環境下での信頼性が向上するという理由から好ましい。 The binder resin is preferably one or more selected from modified polyolefin resins and phenoxy resins from the viewpoint of excellent compatibility with the component (A).
When the modified polyolefin resin is used, it is possible to maintain low moisture permeability while the polyolefin as the main agent is taken into the cured structure. Further, when a phenoxy resin is used, it is possible to keep the elastic modulus of the cured product of the sheet adhesive high, and this is preferable because the reliability of the electronic device sealing body in a high temperature environment is improved.
　本発明のシート状接着剤が、バインダー樹脂を含有する場合、その含有量は、シート状接着剤全体に対し、３０～８０質量％が好ましく、４０～７０質量％がより好ましい。
　バインダー樹脂をこのような範囲で含有させることにより、シート状接着剤を形成するための組成物に優れたシート加工性（造膜性）を付与し、所望の厚みのシート状接着剤を効率よく形成することができる。 When the sheet-like adhesive of the present invention contains a binder resin, the content thereof is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass with respect to the whole sheet-like adhesive.
By including the binder resin in such a range, the composition for forming the sheet-like adhesive is imparted with excellent sheet processability (film forming property), and the sheet-like adhesive having a desired thickness is efficiently obtained. Can be formed.
（変性ポリオレフィン系樹脂）
　変性ポリオレフィン系樹脂は、前駆体としてのポリオレフィン樹脂に、変性剤を用いて変性処理を施して得られる、官能基が導入されたポリオレフィン樹脂である。 (Modified polyolefin resin)
The modified polyolefin resin is a polyolefin resin having a functional group introduced, obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.
　ポリオレフィン樹脂とは、オレフィン系単量体由来の繰り返し単位を含む重合体をいう。ポリオレフィン樹脂は、オレフィン系単量体由来の繰り返し単位の１種又は２種以上のみからなる重合体であってもよいし、オレフィン系単量体由来の繰り返し単位と、オレフィン系単量体と共重合可能な他の単量体由来の繰り返し単位とからなる重合体であってもよい。 The polyolefin resin refers to a polymer containing repeating units derived from olefinic monomers. The polyolefin resin may be a polymer composed of only one or two or more repeating units derived from an olefin monomer, or may be a copolymer of a repeating unit derived from an olefin monomer and an olefin monomer. The polymer which consists of a repeating unit derived from the other monomer which can superpose | polymerize may be sufficient.
　オレフィン系単量体としては、炭素数２～８のα－オレフィンが好ましく、エチレン、プロピレン、１－ブテン、イソブチレン、又は１－ヘキセンがより好ましく、エチレン又はプロピレンがさらに好ましい。
　オレフィン系単量体と共重合可能な他の単量体としては、酢酸ビニル、（メタ）アクリル酸エステル、スチレン等が挙げられる。ここで、「（メタ）アクリル酸」は、アクリル酸又はメタクリル酸を表す（以下にて同じである）。 The olefin monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and even more preferably ethylene or propylene.
Examples of other monomers copolymerizable with the olefin monomer include vinyl acetate, (meth) acrylic acid ester, and styrene. Here, “(meth) acrylic acid” represents acrylic acid or methacrylic acid (the same applies hereinafter).
　ポリオレフィン樹脂としては、超低密度ポリエチレン（ＶＬＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、ポリプロピレン（ＰＰ）、エチレン－プロピレン共重合体、オレフィン系エラストマー（ＴＰＯ）、エチレン－酢酸ビニル共重合体（ＥＶＡ）、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル共重合体などが挙げられる。 Examples of polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and ethylene. -Propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. .
　ポリオレフィン樹脂の変性処理に用いる変性剤は、分子内に、官能基を有する化合物である。
　官能基としては、カルボキシル基、カルボン酸無水物基、カルボン酸エステル基、水酸基、エポキシ基、アミド基、アンモニウム基、ニトリル基、アミノ基、イミド基、イソシアネート基、アセチル基、チオール基、エーテル基、チオエーテル基、スルホン基、ホスホン基、ニトロ基、ウレタン基、アルコキシシリル基、シラノール基、ハロゲン原子等が挙げられる。これらの中でも、カルボキシル基、カルボン酸無水物基、カルボン酸エステル基、水酸基、アンモニウム基、アミノ基、イミド基、イソシアネート基、アルコキシシリル基が好ましく、カルボン酸無水物基、アルコキシシリル基がより好ましく、カルボン酸無水物基が特に好ましい。
　官能基を有する化合物は、分子内に２種以上の官能基を有していてもよい。 The modifier used for the modification treatment of the polyolefin resin is a compound having a functional group in the molecule.
Functional groups include carboxyl groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, epoxy groups, amide groups, ammonium groups, nitrile groups, amino groups, imide groups, isocyanate groups, acetyl groups, thiol groups, ether groups. Thioether group, sulfone group, phosphone group, nitro group, urethane group, alkoxysilyl group, silanol group, halogen atom and the like. Among these, a carboxyl group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an ammonium group, an amino group, an imide group, an isocyanate group, and an alkoxysilyl group are preferable, and a carboxylic acid anhydride group and an alkoxysilyl group are more preferable. Carboxylic anhydride groups are particularly preferred.
The compound having a functional group may have two or more kinds of functional groups in the molecule.
　変性ポリオレフィン系樹脂としては、酸変性ポリオレフィン系樹脂、シラン変性ポリオレフィン系樹脂が挙げられ、本発明のより優れた効果が得られる観点から、酸変性ポリオレフィン系樹脂が好ましい。 Examples of the modified polyolefin resin include acid-modified polyolefin resins and silane-modified polyolefin resins, and acid-modified polyolefin resins are preferable from the viewpoint of obtaining the better effect of the present invention.
　酸変性ポリオレフィン系樹脂とは、ポリオレフィン樹脂に対して、酸又は酸無水物でグラフト変性したものをいう。例えば、ポリオレフィン樹脂に、不飽和カルボン酸又は不飽和カルボン酸無水物を反応させて、カルボキシル基又は酸無水物基を導入（グラフト変性）したものが挙げられる。 The acid-modified polyolefin resin refers to a polyolefin resin graft-modified with an acid or acid anhydride. Examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride to introduce a carboxyl group or an acid anhydride group (graft modification).
　ポリオレフィン樹脂に反応させる不飽和カルボン酸としては、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グルタコン酸、テトラヒドロフタル酸、アコニット酸等が挙げられる、不飽和カルボン酸無水物としては、無水マレイン酸、無水イタコン酸、無水グルタコン酸、無水シトラコン酸、無水アコニット酸、ノルボルネンジカルボン酸無水物、テトラヒドロフタル酸無水物等が挙げられる。
　これらは、１種を単独で、あるいは２種以上を組み合わせて用いることができる。
　これらの中でも、シート加工性（造膜性）により優れた接着剤、及び接着強度により優れたシート状接着剤の硬化物が得られ易いことから、無水マレイン酸が好ましい。 Examples of the unsaturated carboxylic acid to be reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid. Unsaturated carboxylic acid anhydrides include maleic anhydride. , Itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic anhydride and the like.
These can be used alone or in combination of two or more.
Among these, maleic anhydride is preferred because an adhesive excellent in sheet processability (film forming property) and a cured product of a sheet adhesive excellent in adhesive strength can be easily obtained.
　ポリオレフィン樹脂に反応させる不飽和カルボン酸又は不飽和カルボン酸無水物の量は、ポリオレフィン樹脂１００質量部に対して、好ましくは０．１～５質量部、より好ましくは０．２～３質量部、さらに好ましくは０．２～１質量部である。このようにして得られた酸変性ポリオレフィン系樹脂を含有するシート状接着剤は、接着強度により優れた硬化物が得られ易くなる。 The amount of the unsaturated carboxylic acid or unsaturated carboxylic anhydride to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 0.2 to 1 part by mass. In the sheet adhesive containing the acid-modified polyolefin resin thus obtained, a cured product having an excellent adhesive strength is easily obtained.
　酸変性ポリオレフィン系樹脂としては、市販品を用いることができる。市販品としては、例えば、アドマー（登録商標）（三井化学社製）、ユニストール（登録商標）（三井化学社製）、ＢｏｎｄｙＲａｍ（Ｐｏｌｙｒａｍ社製）、ｏｒｅｖａｃ（登録商標）（ＡＲＫＥＭＡ社製）、モディック（登録商標）（三菱化学社製）等が挙げられる。 Commercially available products can be used as the acid-modified polyolefin resin. Examples of commercially available products include Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistor (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like.
　シラン変性ポリオレフィン系樹脂とは、ポリオレフィン樹脂に対して不飽和シラン化合物でグラフト変性したものをいう。シラン変性ポリオレフィン系樹脂は、主鎖であるポリオレフィン樹脂に側鎖である不飽和シラン化合物がグラフト共重合した構造を有する。例えば、シラン変性ポリエチレン樹脂およびシラン変性エチレン－酢酸ビニル共重合体が挙げられ、シラン変性低密度ポリエチレン、シラン変性超低密度ポリエチレン、シラン変性直鎖状低密度ポリエチレン等のシラン変性ポリエチレン樹脂が好ましい。 “Silane-modified polyolefin resin” refers to a polyolefin resin graft-modified with an unsaturated silane compound. The silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft copolymerized with a polyolefin resin as a main chain. Examples include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers, and silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene are preferable.
　上記ポリオレフィン樹脂に反応させる不飽和シラン化合物としては、ビニルシラン化合物が好ましい。ビニルシラン化合物としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン、ビニルトリペンチロキシシラン、ビニルトリフェノキシシラン、ビニルトリベンジルオキシシラン、ビニルトリメチレンジオキシシラン、ビニルトリエチレンジオキシシラン、ビニルプロピオニルオキシシラン、ビニルトリアセトキシシラン、ビニルトリカルボキシシラン等が挙げられる。
　これらは、１種を単独で、あるいは２種以上を組み合わせて用いることができる。
　なお、不飽和シラン化合物を主鎖であるポリオレフィン樹脂にグラフト重合させる場合の条件は、公知のグラフト重合の常法を採用すればよい。 As the unsaturated silane compound to be reacted with the polyolefin resin, a vinyl silane compound is preferable. Vinyl silane compounds include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyloxy silane, vinyl triphenoxy silane, vinyl tribenzyloxy silane, vinyl tri Examples include methylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane.
These can be used alone or in combination of two or more.
In addition, what is necessary is just to employ | adopt the usual method of a well-known graft polymerization for the conditions in case graft-polymerizing an unsaturated silane compound to the polyolefin resin which is a principal chain.
　ポリオレフィン樹脂に反応させる不飽和シラン化合物の量は、ポリオレフィン樹脂１００質量部に対して、好ましくは０．１～１０質量部、より好ましくは０．３～７質量部、さらに好ましくは０．５～５質量部である。シラン変性ポリオレフィン系樹脂を含有するシート状接着剤は、接着強度により優れた硬化物が得られ易くなる。 The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, and still more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the polyolefin resin. 5 parts by mass. A sheet-like adhesive containing a silane-modified polyolefin-based resin is easy to obtain a cured product having better adhesive strength.
　シラン変性ポリオレフィン系樹脂としては、市販品を用いることができる。市販品としては、例えば、リンクロン（登録商標）（三菱化学社製）等が挙げられる。これらの中でも、低密度ポリエチレン系のリンクロン、直鎖状低密度ポリエチレン系のリンクロン、超低密度ポリエチレン系のリンクロン、およびエチレン－酢酸ビニル共重合体系のリンクロンを好ましく使用することができる。 Commercially available products can be used as the silane-modified polyolefin resin. Examples of commercially available products include Lincron (registered trademark) (manufactured by Mitsubishi Chemical Corporation). Among these, low-density polyethylene-based linklon, linear low-density polyethylene-based linkron, ultra-low-density polyethylene-based linkron, and ethylene-vinyl acetate copolymer-based linkron can be preferably used. .
　変性ポリオレフィン系樹脂は、１種を単独で、あるいは２種以上を組み合わせて用いることができる。 The modified polyolefin resin can be used alone or in combination of two or more.
　変性ポリオレフィン系樹脂の重量平均分子量（Ｍｗ）は、好ましくは１０，０００～３００，０００、より好ましくは、２０，０００～１５０，０００である。
　変性ポリオレフィン系樹脂の重量平均分子量（Ｍｗ）がこのような範囲にあることで、シート状接着剤を形成するための組成物に優れた造膜性を付与しつつ、その特性を調整し易い。
　変性ポリオレフィン系樹脂の重量平均分子量（Ｍｗ）は、テトラヒドロフラン（ＴＨＦ）を溶媒として用いてゲルパーミエーションクロマトグラフィー（ＧＰＣ）を行い、標準ポリスチレン換算値として求めることができる。 The weight average molecular weight (Mw) of the modified polyolefin resin is preferably 10,000 to 300,000, more preferably 20,000 to 150,000.
When the weight average molecular weight (Mw) of the modified polyolefin resin is in such a range, it is easy to adjust the characteristics while imparting excellent film forming properties to the composition for forming the sheet-like adhesive.
The weight average molecular weight (Mw) of the modified polyolefin resin can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
（フェノキシ樹脂）
　フェノキシ樹脂は、主鎖が芳香族ジオールと芳香族ジグリシジルエーテルとの重付加構造である高分子である。
　フェノキシ樹脂としては、主鎖骨格の種類によって、ビスフェノールＡ型フェノキシ樹脂、ビスフェノールＦ型フェノキシ樹脂、ビスフェノールＡ－ビスフェノールＦ型フェノキシ樹脂、ビスフェノールＥ型フェノキシ樹脂等が挙げられる。
　フェノキシ樹脂は、ビスフェノール又はビフェノール化合物とエピクロルヒドリンのようなエピハロヒドリンとの反応や、ビスフェノール又はビフェノール化合物と液状エポキシ樹脂との反応により得ることができる。 (Phenoxy resin)
The phenoxy resin is a polymer whose main chain is a polyaddition structure of an aromatic diol and an aromatic diglycidyl ether.
Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A-bisphenol F type phenoxy resin, and bisphenol E type phenoxy resin, depending on the type of main chain skeleton.
The phenoxy resin can be obtained by a reaction between a bisphenol or biphenol compound and an epihalohydrin such as epichlorohydrin, or a reaction between a bisphenol or biphenol compound and a liquid epoxy resin.
　フェノキシ樹脂としては、市販品を用いることができる。市販品としては、商品名：ＰＫＨＣ、ＰＫＨＨ，ＰＫＨＪ（いずれも巴化学社製）、商品名：エピコート４２５０、エピコート１２５５ＨＸ３０、エピコート５５８０ＢＰＸ４０（いずれも日本化薬社製）、商品名：ＹＰ－５０、ＹＰ５０Ｓ、ＹＰ－５５、ＹＰ－７０（いずれも東都化成社製）、商品名：ＪＥＲ　１２５６、４２５０、ＹＸ６９５４ＢＨ３０、ＹＸ７２００Ｂ３５、ＹＬ７２９０ＢＨ３０（いずれも三菱ケミカル社製）等が挙げられる。 A commercially available product can be used as the phenoxy resin. As commercial products, trade names: PKHC, PKHH, PKHJ (all manufactured by Sakai Chemical Co., Ltd.), trade names: Epicoat 4250, Epicoat 1255HX30, Epicoat 5580BPX40 (all manufactured by Nippon Kayaku Co., Ltd.), trade names: YP-50, YP50S, YP-55, YP-70 (all manufactured by Tohto Kasei Co., Ltd.), trade names: JER 1256, 4250, YX6954BH30, YX7200B35, YL7290BH30 (all manufactured by Mitsubishi Chemical Corporation), and the like.
　フェノキシ樹脂の重量平均分子量（Ｍｗ）は、通常１０，０００～２００，０００、好ましくは２０，０００～１００，０００、より好ましくは３０，０００～８０，０００である。フェノキシ樹脂の重量平均分子量が小さすぎると、シート状接着剤の支持性が弱くなり、脆弱性が強くなる傾向にあり、大きすぎると、溶融粘度が高くなり、取り扱い性に劣るものとなり易い。
　なお、本明細書においては、フェノキシ樹脂がエポキシ基を有するものである場合、重量平均分子量（Ｍｗ）が１０，０００以下のものを、前記（Ａ）成分：環状エーテル基を有する化合物とし、重量平均分子量（Ｍｗ）が１０，０００超のものを、フェノキシ樹脂とする。　
　フェノキシ樹脂の重量平均分子量（Ｍｗ）は、テトラヒドロフラン（ＴＨＦ）を溶媒として用いてゲルパーミエーションクロマトグラフィー（ＧＰＣ）を行い、標準ポリスチレン換算値として求めることができる。 The weight average molecular weight (Mw) of the phenoxy resin is usually 10,000 to 200,000, preferably 20,000 to 100,000, more preferably 30,000 to 80,000. If the weight average molecular weight of the phenoxy resin is too small, the supportability of the sheet-like adhesive tends to be weak and the brittleness tends to be strong. If it is too large, the melt viscosity becomes high and the handleability tends to be poor.
In the present specification, when the phenoxy resin has an epoxy group, a compound having a weight average molecular weight (Mw) of 10,000 or less is defined as the component (A): a compound having a cyclic ether group, A resin having an average molecular weight (Mw) exceeding 10,000 is defined as a phenoxy resin.
The weight average molecular weight (Mw) of the phenoxy resin can be obtained as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
〔粘着付与剤〕
　本発明のシート状接着剤は、前記（Ａ）成分及び（Ｂ）成分、並びに、所望によりバインダー樹脂に加えて、粘着付与剤を含有していてもよい。粘着付与剤を含有することで、シート状接着剤の貯蔵弾性率を調整しやすくなる。 [Tackifier]
The sheet-like adhesive of the present invention may contain a tackifier in addition to the components (A) and (B) and, if desired, a binder resin. By containing a tackifier, it becomes easy to adjust the storage elastic modulus of a sheet-like adhesive.
　粘着付与剤としては、例えば、ロジン樹脂、ロジンエステル樹脂、ロジン変性フェノール樹脂等のロジン系樹脂；これらロジン系樹脂を水素化した水素化ロジン系樹脂；
テルペン樹脂、芳香族変性テルペン樹脂、テルペンフェノール系樹脂等のテルペン系樹脂；これらテルペン系樹脂を水素化した水素化テルペン系樹脂；
α－メチルスチレン単一重合系樹脂、α－メチルスチレン／スチレン共重合系樹脂、スチレン系モノマー／脂肪族系モノマー共重合系樹脂、スチレン系モノマー／α－メチルスチレン／脂肪族系モノマー共重合系樹脂、スチレン系モノマー単一重合系樹脂、スチレン系モノマー／芳香族系モノマー共重合系樹脂等のスチレン系樹脂；これらスチレン系樹脂を水素化した水素化スチレン系樹脂；
石油ナフサの熱分解で生成するペンテン、イソプレン、ピペリン、１．３－ペンタジエン等のＣ５留分を共重合して得られるＣ５系石油樹脂及びこのＣ５系石油樹脂の水素化石油樹脂；
石油ナフサの熱分解で生成するインデン、ビニルトルエン等のＣ９留分を共重合して得られるＣ９系石油樹脂及びこのＣ９系石油樹脂を水素化石油樹脂；等が挙げられる。これらの中でも、スチレン系樹脂が好ましく、スチレン系モノマー／脂肪族系モノマー共重合系樹脂がより好ましい。
　これらの粘着付与剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 Examples of the tackifier include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins;
Terpene resins such as terpene resins, aromatic modified terpene resins, terpene phenol resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins;
α-methylstyrene homopolymer resin, α-methylstyrene / styrene copolymer resin, styrene monomer / aliphatic monomer copolymer resin, styrene monomer / α-methylstyrene / aliphatic monomer copolymer system Styrene resins such as resins, styrene monomer monopolymer resins, styrene monomer / aromatic monomer copolymer resins; hydrogenated styrene resins obtained by hydrogenating these styrene resins;
A C5 petroleum resin obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1.3-pentadiene produced by thermal decomposition of petroleum naphtha, and a hydrogenated petroleum resin of this C5 petroleum resin;
And C9 petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyltoluene produced by thermal decomposition of petroleum naphtha, and hydrogenated petroleum resins of these C9 petroleum resins. Among these, a styrene resin is preferable, and a styrene monomer / aliphatic monomer copolymer resin is more preferable.
These tackifiers can be used alone or in combination of two or more.
　粘着付与剤は、市販品を用いることができる。市販品としては、ＹＳレジンＰ、Ａシリーズ、クリアロン（登録商標）Ｐシリーズ（ヤスハラケミカル製）、ピコライトＡ、Ｃシリーズ（ＰＩＮＯＶＡ社製）等のテルペン系樹脂；
クイントン（登録商標）Ａ、Ｂ、Ｒ、ＣＸシリーズ（日本ゼオン社製）等の脂肪族系石油樹脂；
ＦＴＲ（登録商標）シリーズ（三井化学社製）等のスチレン系樹脂；
アルコンＰ、Ｍシリーズ（荒川化学社製）、ＥＳＣＯＲＥＺ（登録商標）シリーズ（エクソンモービル・ケミカル社製）、ＥＡＳＴＯＴＡＣ（登録商標）シリーズ（イーストマン・ケミカル社製）、ＩＭＡＲＶ（登録商標）シリーズ（出光興産社製）等の脂環族系石油樹脂；
フォーラルシリーズ（ＰＩＮＯＶＡ社製）、ペンセル（登録商標）Ａシリーズ、エステルガム、スーパー・エステル、パインクリスタル（登録商標）（荒川化学工業社製）等のエステル系樹脂；等が挙げられる。 A commercially available product can be used as the tackifier. Commercially available products include terpene resins such as YS resin P, A series, Clearon (registered trademark) P series (manufactured by Yashara Chemical), picolite A, C series (manufactured by PINOVA);
Aliphatic petroleum resins such as Quinton (registered trademark) A, B, R, CX series (manufactured by Nippon Zeon);
Styrenic resins such as FTR (registered trademark) series (Mitsui Chemicals);
Alcon P, M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered trademark) series (manufactured by ExxonMobil Chemical Co., Ltd.), EASTOTAC (registered trademark) series (manufactured by Eastman Chemical Co., Ltd.), ILARV (registered trademark) series (Idemitsu) Alicyclic petroleum resins such as Kosan)
Examples include ester series resins such as Foral series (manufactured by PINOVA), Pencel (registered trademark) A series, ester gum, super ester, and Pine Crystal (registered trademark) (manufactured by Arakawa Chemical Industries).
　粘着付与剤の重量平均分子量（Ｍｗ）は、優れた粘着性を付与する観点から、好ましくは、１００～１０，０００、より好ましくは５００～５，０００である。
　粘着付与剤の軟化点は、優れた粘着性を付与する観点から、好ましくは、５０～１６０℃、より好ましくは６０～１４０℃、さらに好ましくは７０～１３０℃である。 The weight average molecular weight (Mw) of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000, from the viewpoint of imparting excellent tackiness.
The softening point of the tackifier is preferably 50 to 160 ° C., more preferably 60 to 140 ° C., and still more preferably 70 to 130 ° C. from the viewpoint of imparting excellent tackiness.
　本発明のシート状接着剤が粘着付与剤を含有する場合、その含有量は、前記（Ａ）成分１００質量部に対して、好ましくは１～２００質量部、より好ましくは１０～１５０質量部である。 When the sheet-like adhesive of the present invention contains a tackifier, the content thereof is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the component (A). is there.
〔シランカップリング剤〕
　本発明のシート状接着剤は、前記（Ａ）成分及び（Ｂ）成分、並びに、所望により、バインダー樹脂、粘着付与剤に加えてシランカップリング剤を含有していてもよい。
　シランカップリング剤を含有させることにより、接着強度により優れるシート状接着剤の硬化物が得られやすくなる。
　シランカップリング剤としては、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリメトキシシラン等の（メタ）アクリロイル基を有するシランカップリング剤；
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、トリクロロビニルシラン、ビニルトリス（２－メトキシエトキシ）シラン等のビニル基を有するシランカップリング剤；
２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン等のエポキシ基を有するシランカップリング剤；
ｐ－スチリルトリメトキシシラン、ｐ－スチリルトリエトキシシラン等のスチリル基を有するシランカップリング剤；
Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル・ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩等のアミノ基を有するシランカップリング剤；
３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン等のウレイド基を有するシランカップリング剤；
３－クロロプロピルトリメトキシシラン、３－クロロプロピルトリエトキシシラン等のハロゲン原子を有するシランカップリング剤；
３－メルカプトプロピルメチルジメトキシシラン、３－メルカプトプロピルトリメトキシシラン等のメルカプト基を有するシランカップリング剤；
ビス（トリメトキシシリルプロピル）テトラスルフィド、ビス（トリエトキシシリルプロピル）テトラスルフィド等のスルフィド基を有するシランカップリング剤；
３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシラン等のイソシアネート基を有するシランカップリング剤；
アリルトリクロロシラン、アリルトリエトキシシラン、アリルトリメトキシシラン等のアリル基を有するシランカップリング剤；
３－ヒドキシプロピルトリメトキシシラン、３－ヒドキシプロピルトリエトキシシラン等の水酸基を有するシランカップリング剤；等が挙げられる。
　これらのシランカップリング剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。 〔Silane coupling agent〕
The sheet-like adhesive of the present invention may contain a silane coupling agent in addition to the components (A) and (B) and, if desired, a binder resin and a tackifier.
By containing a silane coupling agent, a cured product of a sheet-like adhesive that is superior in adhesive strength is easily obtained.
Silane coupling agents include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltri A silane coupling agent having a (meth) acryloyl group such as methoxysilane;
Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris (2-methoxyethoxy) silane;
Epoxy groups such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. A silane coupling agent having;
Silane coupling agents having a styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane;
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N A silane coupling agent having an amino group such as hydrochloride of (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane;
Silane coupling agents having a ureido group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
Silane coupling agents having a halogen atom such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane;
Silane coupling agents having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Silane coupling agents having sulfide groups such as bis (trimethoxysilylpropyl) tetrasulfide and bis (triethoxysilylpropyl) tetrasulfide;
Silane coupling agents having an isocyanate group such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane;
Silane coupling agents having an allyl group such as allyltrichlorosilane, allyltriethoxysilane, and allyltrimethoxysilane;
Silane coupling agents having a hydroxyl group such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane;
These silane coupling agents can be used alone or in combination of two or more.
　本発明のシート状接着剤がシランカップリング剤を含有する場合、その含有量は、前記（Ａ）成分１００質量部に対して、好ましくは０．０１～５質量部、より好ましくは０．０２～３質量部である。
　シランカップリング剤の含有量を上記範囲とすることで、接着強度により優れるシート状接着剤の硬化物がより得られやすくなる。 When the sheet adhesive of the present invention contains a silane coupling agent, the content thereof is preferably 0.01 to 5 parts by mass, more preferably 0.02 with respect to 100 parts by mass of the component (A). ~ 3 parts by mass.
By making content of a silane coupling agent into the said range, the hardened | cured material of the sheet-like adhesive agent which is excellent by adhesive strength becomes easier to be obtained.
　また、本発明のシート状接着剤は、本発明の効果を妨げない範囲で、前記粘着付与剤及びシランカップリング剤以外の成分をさらに含有してもよい。
　前記前記粘着付与剤、シランカップリング剤以外の成分としては、帯電防止剤、安定剤、酸化防止剤、可塑剤、滑剤、着色顔料等が挙げられる。これらの含有量は、目的に合わせて適宜決定すればよい。 Moreover, the sheet adhesive of this invention may further contain components other than the said tackifier and a silane coupling agent in the range which does not inhibit the effect of this invention.
Examples of components other than the tackifier and the silane coupling agent include an antistatic agent, a stabilizer, an antioxidant, a plasticizer, a lubricant, and a coloring pigment. What is necessary is just to determine these content suitably according to the objective.
　本発明のシート状接着剤は、後述するように、所定の成分を、常法に従って適宜混合し、攪拌することにより調製した接着剤組成物を用いて形成することができる。 The sheet-like adhesive of the present invention can be formed using an adhesive composition prepared by appropriately mixing and stirring predetermined components according to a conventional method, as will be described later.
（シート状接着剤）
　本発明のシート状接着剤は、外部環境からの保護の観点から、少なくとも一方の面に剥離フィルムを有することが好ましく、両面に剥離フィルムを有していてもよい。 (Sheet adhesive)
From the viewpoint of protection from the external environment, the sheet-like adhesive of the present invention preferably has a release film on at least one side, and may have a release film on both sides.
　なお、少なくとも一方の面に剥離フィルムを有する本発明のシート状接着剤は使用前の状態を表したものであり、本発明のシート状接着剤を使用する際は、通常、剥離フィルムは剥離除去される。シート状接着剤が両面に剥離フィルムを有する場合、通常、剥離力の低い剥離フィルムが先に剥離除去される。 In addition, the sheet-like adhesive of the present invention having a release film on at least one surface represents a state before use, and when using the sheet-like adhesive of the present invention, the release film is usually peeled and removed. Is done. When a sheet-like adhesive has a release film on both sides, a release film having a low peel strength is usually removed first.
　剥離フィルムとしては、通常、樹脂フィルムを利用することができる。
　樹脂フィルムの樹脂成分としては、ポリイミド、ポリアミド、ポリアミドイミド、ポリフェニレンエーテル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリオレフィン、ポリエステル、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルフィド、ポリアリレート、アクリル系樹脂、シクロオレフィン系ポリマー、芳香族系重合体、ポリウレタン系ポリマー等が挙げられる。これらの中でも、ポリエステル樹脂が好ましく、樹脂フィルムとしては、ポリエステルフィルムが好ましい。ポリエステルフィルムとしては、耐熱性や扱いやすさに優れ、紫外線の透過性が波長３６５ｎｍにおいて８０％程度と高い、ポリエチレンテレフタレートフィルムがより好ましい。
　剥離剤としては、シリコーン系樹脂、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂等が挙げられる。
　剥離フィルムの厚みは、耐熱性を向上させる観点や、紫外線を剥離フィルムを透過させてシート状接着剤に照射する場合に、妨げとならないようにする観点から、好ましくは１０～３００μｍ、より好ましくは１０～２００μｍ、さらに好ましくは１５～１００μｍである。本発明のシート状接着剤に、剥離フィルムを透過させて波長３６５ｎｍの紫外線を照射して、光カチオン重合を開始させることを容易とする観点から、剥離フィルムの波長３６５ｎｍの紫外線の透過率は、６５％以上であることが好ましく、７０％以上であることが好ましい。なお、剥離フィルムがポリエチレンテレフタレートフィルムを基材とする場合、紫外線の波長が３３０ｎｍ未満であると、透過性が著しく低下する。 As the release film, a resin film can usually be used.
Resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclohexane Examples include olefin polymers, aromatic polymers, polyurethane polymers, and the like. Among these, a polyester resin is preferable, and a polyester film is preferable as the resin film. As the polyester film, a polyethylene terephthalate film that is excellent in heat resistance and ease of handling and has a high ultraviolet transmittance of about 80% at a wavelength of 365 nm is more preferable.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long chain alkyl resins, alkyd resins, and fluorine resins.
The thickness of the release film is preferably from 10 to 300 μm, more preferably from the viewpoint of improving heat resistance, and from the viewpoint of not hindering irradiation of the sheet-like adhesive through ultraviolet rays through the release film. The thickness is 10 to 200 μm, more preferably 15 to 100 μm. From the viewpoint of facilitating photocationic polymerization by allowing the sheet-like adhesive of the present invention to pass through the release film and irradiate with ultraviolet light having a wavelength of 365 nm, the transmittance of the release film having a wavelength of 365 nm is as follows: It is preferably 65% or more, and preferably 70% or more. In addition, when a peeling film uses a polyethylene terephthalate film as a base material, the transmittance | permeability falls remarkably that the wavelength of an ultraviolet-ray is less than 330 nm.
　シート状接着剤の厚みは、通常、１～５０μｍであり、好ましくは５～３０μｍである。厚みが上記範囲内にあるシート状接着剤は、シート状封止材として好適に用いられる。
　シート状接着剤の厚みは、公知の厚み計を用いて、ＪＩＳ　Ｋ　７１３０（１９９９）に準じて測定することができる。なお、シート状接着剤の厚みは、剥離フィルムの厚みを除いた厚みである。 The thickness of the sheet adhesive is usually 1 to 50 μm, preferably 5 to 30 μm. A sheet-like adhesive having a thickness within the above range is suitably used as a sheet-like sealing material.
The thickness of the sheet adhesive can be measured according to JIS K 7130 (1999) using a known thickness meter. In addition, the thickness of a sheet-like adhesive is the thickness except the thickness of the peeling film.
　本発明のシート状接着剤は紫外線が照射された後であっても、粘着力を有し、電子デバイスや機能性フィルムに強く接着し、貼付時、あるいは貼付後の剥離が生じることがないものである。従って、電子デバイス封止体、特に、表面に紫外線非透過性の機能性フィルムを有する電子デバイス封止体の封止材料として好適に用いることができる。 The sheet-like adhesive of the present invention has adhesive strength even after being irradiated with ultraviolet rays, strongly adheres to an electronic device or a functional film, and does not cause peeling at the time of application or after application. It is. Therefore, it can be suitably used as a sealing material for an electronic device sealing body, in particular, an electronic device sealing body having a functional film that is opaque to ultraviolet rays on the surface.
　本発明のシート状接着剤が少なくとも一方の面に剥離フィルムを有する場合は、その逆側の面に、アルミニウムを蒸着した厚さ２３μｍのポリエチレンテレフタレートフィルムと貼り合わせて積層体を作製し、剥離フィルムを貼り合わせた状態で、剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で積層体に照射し、その３分後に、積層体から剥離フィルムを剥離し、露出したシート状接着剤の層をソーダガラス板に対向させ、積層体上で２ｋｇのロールを一往復させることによりソーダガラス板に貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後のソーダガラス板に対する粘着力が、３Ｎ／２５ｍｍ以上のものであることが好ましく、５Ｎ／２５ｍｍ以上であることがより好ましい。
　ガラスに対する粘着力は、実施例に記載の方法（１８０°引き剥がし試験）により測定されるものである。 When the sheet-like adhesive of the present invention has a release film on at least one surface, a laminate is prepared by laminating with a polyethylene terephthalate film having a thickness of 23 μm on which aluminum is vapor-deposited on the opposite surface. In a state of bonding, the laminate is irradiated with ultraviolet light having a wavelength of 365 nm from the release film side under the conditions of illuminance: 50 mW / cm 2 and light quantity: 200 mJ / cm 2 , and 3 minutes later, the release film is released from the laminate. Is peeled off, the exposed sheet-like adhesive layer is opposed to the soda glass plate, and a 2 kg roll is reciprocated once on the laminated body to be attached to the soda glass plate, and the environment at 23 ° C. and 50% relative humidity. The adhesive strength to the soda glass plate after being stored for 24 hours below is preferably 3N / 25mm or more, preferably 5N / 25mm or more There it is more preferable.
The adhesive strength to glass is measured by the method described in the examples (180 ° peeling test).
（シート状接着剤の製造方法）
　本発明のシート状接着剤の製造方法は、特に限定されない。例えば、キャスト法を用いて製造することができる。 (Method for producing sheet adhesive)
The manufacturing method of the sheet adhesive of this invention is not specifically limited. For example, it can be manufactured using a casting method.
　シート状接着剤をキャスト法により製造する方法は、公知の方法を用いて、接着剤組成物を剥離フィルムの剥離処理された剥離層面に塗工し、得られた塗膜を乾燥することで、剥離フィルム付シート状接着剤を得るものである。 The method for producing the sheet-like adhesive by the casting method is to apply the adhesive composition to the release layer surface subjected to the release treatment of the release film using a known method, and dry the obtained coating film. A sheet-like adhesive with a release film is obtained.
　接着剤組成物は、前記（Ａ）成分及び（Ｂ）成分、並びに、所望により他の成分を、公知の方法により混合し、撹拌することにより調製することができる。
　接着剤組成物の調製に溶媒を用いる場合には、溶媒の使用量により、接着剤組成物の粘度を適宜調整することができる。 The adhesive composition can be prepared by mixing the components (A) and (B), and other components as desired, by a known method, and stirring.
When a solvent is used for the preparation of the adhesive composition, the viscosity of the adhesive composition can be appropriately adjusted depending on the amount of the solvent used.
　溶媒としては、ｎ－ヘキサン、ｎ－ヘプタン等の脂肪族炭化水素系溶媒；トルエン、キシレン等の芳香族炭化水素系溶媒；ジクロロメタン、塩化エチレン、クロロホルム、四塩化炭素、１，２－ジクロロエタン、モノクロロベンゼン等のハロゲン化炭化水素系溶媒；
メタノール、エタノール、プロパノール、ブタノール、プロピレングリコールモノメチルエーテル等のアルコール系溶媒；アセトン、メチルエチルケトン、２－ペンタノン、イソホロン、シクロヘキサノン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；エチルセロソルブ等のセロソルブ系溶媒；１，３－ジオキソラン等のエーテル系溶媒；等が挙げられる。
　これらの溶媒は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
　溶媒の含有量は、塗工性や膜厚等を考慮して適宜決定することができる。 Solvents include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, mono Halogenated hydrocarbon solvents such as chlorobenzene;
Alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone; ester solvents such as ethyl acetate and butyl acetate; ethyl cellosolve, etc. Cellosolve solvents; ether solvents such as 1,3-dioxolane; and the like.
These solvents can be used alone or in combination of two or more.
The content of the solvent can be appropriately determined in consideration of coating properties, film thickness, and the like.
　シート状接着剤の製造に用いる剥離フィルムは、シート状接着剤の製造工程においては支持体として機能するとともに、シート状接着剤を使用するまでの間は、上述したシート状接着剤の剥離フィルムとして機能する。 The release film used for the production of the sheet-like adhesive functions as a support in the production process of the sheet-like adhesive, and as a release film of the above-described sheet-like adhesive until the sheet-like adhesive is used. Function.
　前記接着剤組成物を塗工する方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等が挙げられる。 Examples of the method for applying the adhesive composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
　接着剤組成物の塗膜を乾燥する方法としては、熱風乾燥、熱ロール乾燥、赤外線照射等、従来公知の乾燥方法が挙げられる。
　塗膜を乾燥するときの条件としては、例えば、８０～１５０℃で３０秒から５分間である。 Examples of the method for drying the coating film of the adhesive composition include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
The condition for drying the coating film is, for example, 80 to 150 ° C. for 30 seconds to 5 minutes.
〔電子デバイス封止用接着フィルム〕
　本発明の電子デバイス封止用接着フィルムは、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルムと、前記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤からなる接着剤層を有するものである。
　本発明の電子デバイス封止用接着フィルムは、そのシート状接着剤を介して、電子デバイスを封止するために用いられる。
「波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム」、「シート状接着剤」は、上述したものと同様のものが使用できる。本発明の電子デバイス封止用接着フィルムは、例えば、後述するように機能性フィルムとシート状接着剤を貼り合せることにより得ることができる。 [Electronic device sealing adhesive film]
The adhesive film for sealing an electronic device of the present invention is an adhesive comprising a functional film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, and a sheet-like adhesive containing the component (A) and the component (B). It has a layer.
The adhesive film for sealing an electronic device of the present invention is used for sealing an electronic device via the sheet-like adhesive.
As the “functional film whose transmittance of ultraviolet light having a wavelength of 365 nm is 60% or less” and “sheet adhesive”, the same ones as described above can be used. The adhesive film for sealing an electronic device of the present invention can be obtained, for example, by bonding a functional film and a sheet-like adhesive as described later.
　本発明の電子デバイス封止用接着フィルムは、少なくとも、前記機能性フィルムと、シート状接着剤からなる接着剤層を有するものであればよく、前記接着剤層の１層のみからなるものであっても、複数の接着剤層の積層体であっても、接着剤の他に他の層を有するものであってもよい。
　他の層としては、接着剤層と機能性フィルムの界面の接着性を向上させるプライマー層、機能性フィルムの接着剤層を有しない面に設けられる機能性コート層やプロテクトフィルム、機能性フィルムの両面に形成し得る帯電防止層や応力緩和層等が挙げられる。
　また、本発明の電子デバイス封止用接着フィルムに、複数の接着剤層を用いる場合、各接着剤層は、同一の組成からなるものであっても、相異なる組成からなるものであってもよい。
　本発明の電子デバイス封止用接着フィルムは、機能性フィルムが貼り合わされていない側の前記接着剤層の表面に剥離フィルムを有することが好ましく、剥離フィルムとしては、上述したシート状接着剤に用いるものと同様のものが好ましい。 The adhesive film for encapsulating an electronic device of the present invention only needs to have at least the functional film and an adhesive layer composed of a sheet-like adhesive, and is composed of only one layer of the adhesive layer. Or even if it is a laminated body of a some adhesive bond layer, it may have another layer other than an adhesive agent.
Other layers include a primer layer that improves the adhesion at the interface between the adhesive layer and the functional film, a functional coat layer that is provided on the surface of the functional film that does not have an adhesive layer, a protective film, and a functional film. Examples thereof include an antistatic layer and a stress relaxation layer that can be formed on both sides.
Moreover, when using several adhesive bond layers for the adhesive film for electronic device sealing of this invention, even if each adhesive bond layer consists of the same composition, it may consist of a different composition. Good.
The adhesive film for sealing an electronic device of the present invention preferably has a release film on the surface of the adhesive layer on the side where the functional film is not bonded, and the release film is used for the above-described sheet-like adhesive. The thing similar to a thing is preferable.
　本発明の電子デバイス封止用接着フィルムの厚みは、通常６～２７０μｍである。なお、電子デバイス封止用接着フィルムの厚みは、剥離フィルム、プロテクトフィルム等の使用前に剥離除去される部材を除いた厚みである。 The thickness of the adhesive film for sealing an electronic device of the present invention is usually 6 to 270 μm. In addition, the thickness of the adhesive film for electronic device sealing is a thickness excluding a member that is peeled and removed before use, such as a release film and a protect film.
　本発明の電子デバイス封止用接着フィルムは、紫外線が照射された後であっても粘着力を有し、電子デバイスに強く接着し、貼付時、あるいは貼付後の剥離が生じることがないものであり、表面に紫外線非透過性の機能性フィルムを有する電子デバイス封止体の封止材料として好適に用いることができる。 The adhesive film for sealing an electronic device of the present invention has an adhesive force even after being irradiated with ultraviolet rays, strongly adheres to the electronic device, and does not cause peeling at the time of application or after application. In addition, it can be suitably used as a sealing material for an electronic device sealing body having a functional film that is opaque to ultraviolet rays on the surface.
　本発明の電子デバイス封止用接着フィルムが、機能性フィルムが貼り合わされていない側の前記接着剤層の表面に剥離フィルムを有する場合は、デバイス封止用接着フィルムに剥離フィルムを貼り合わせた状態で、剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で照射し、その３分後に、電子デバイス封止用接着フィルムから剥離フィルムを剥離し、露出した接着剤層をソーダガラス板に対向させ、デバイス封止用接着フィルム上で２ｋｇのロールを一往復させることによりソーダガラス板に貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後のソーダガラス板に対する粘着力が、３Ｎ／２５ｍｍ以上のものであることが好ましく、５Ｎ／２５ｍｍ以上であることがより好ましい。
　ガラスに対する粘着力は、実施例に記載の方法（１８０°引き剥がし試験）により測定されるものである。 When the adhesive film for sealing an electronic device of the present invention has a release film on the surface of the adhesive layer on the side where the functional film is not attached, a state in which the release film is attached to the adhesive film for device sealing Then, UV light with a wavelength of 365 nm is irradiated from the release film side under the conditions of illuminance: 50 mW / cm 2 and light amount: 200 mJ / cm 2 , and after 3 minutes, the release film is peeled from the adhesive film for sealing an electronic device. The exposed adhesive layer is made to face the soda glass plate, and a 2 kg roll is reciprocated once on the adhesive film for device sealing, so that it is attached to the soda glass plate and placed in an environment of 50% relative humidity at 23 ° C. The adhesive strength to the soda glass plate after being stored for 24 hours is preferably 3N / 25mm or more, and preferably 5N / 25mm or more. It is more preferable.
The adhesive strength to glass is measured by the method described in the examples (180 ° peeling test).
〔電子デバイス封止体の製造方法〕
　本発明の電子デバイス封止体、例えば、次のようにして製造することができる。
　以下、図を参照しながら説明する。
（製造方法１）
　本発明の電子デバイスは、（α１）本発明の電子デバイス封止用接着フィルムに対し、機能性フィルムよりも接着剤層に近い表面側から紫外線を照射する工程と、
（β１）上記接着性フィルムを電子デバイスに貼付する工程とを有し、
（β１）工程よりも前に（α１）工程を行うことにより製造することができる。 [Method for Manufacturing Electronic Device Sealed Body]
The electronic device sealing body of the present invention, for example, can be produced as follows.
Hereinafter, description will be given with reference to the drawings.
(Manufacturing method 1)
The electronic device of the present invention is (α1) a step of irradiating the adhesive film for sealing an electronic device of the present invention with ultraviolet rays from the surface side closer to the adhesive layer than the functional film;
(Β1) a step of attaching the adhesive film to an electronic device,
It can manufacture by performing ((alpha) 1) process before ((beta) 1) process.
　より具体的には、次のように行う。
　まず、図２（ａ）に示すように、シート状接着剤２ａを用意する。
　この場合、シート状接着剤２ａは、表裏両面に剥離フィルムが積層された両面剥離フィルム付接着フィルムとして、保管することができる。
　次いで、得られたシート状接着剤２ａの一方の面側に、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム１を積層することにより、図２（ｂ）に示す積層体４ａを得る。
　なお、シート状接着剤２ａが、両面剥離フィルム付接着フィルムである場合には、一方の面側の剥離フィルムを剥離して、機能性フィルム１と貼り合せる。この場合、機能性フィルム１／シート状接着剤／剥離フィルムの層構成を有する積層体が得られる。 More specifically, it is performed as follows.
First, as shown in FIG. 2A, a sheet-like adhesive 2a is prepared.
In this case, the sheet-like adhesive 2a can be stored as an adhesive film with a double-sided release film in which release films are laminated on both front and back surfaces.
Next, the laminated body 4a shown in FIG. 2 (b) is laminated on one surface side of the obtained sheet-like adhesive 2a by laminating the functional film 1 having a transmittance of ultraviolet light having a wavelength of 365 nm of 60% or less. Get.
In addition, when the sheet-like adhesive 2a is an adhesive film with a double-sided release film, the release film on one side is peeled off and bonded to the functional film 1. In this case, a laminate having a layer structure of functional film 1 / sheet-like adhesive / release film is obtained.
　次いで、図２（ｃ）に示すように、積層体４ａの機能性フィルム１が積層されている面と反対側から、シート状接着剤に紫外線を照射して、シート状接着剤２ａの光硬化反応を開始させる。このとき、シート状接着剤中では光硬化反応が開始しているが、光カチオン重合の反応速度は比較的緩やかであるため、硬化反応が完結しておらず、シート状接着剤は、十分な接着力を有している（図２（ｃ）中、シート状接着剤２ｂ）。 Next, as shown in FIG. 2 (c), the sheet adhesive 2a is irradiated with ultraviolet rays from the side opposite to the surface on which the functional film 1 of the laminate 4a is laminated, so that the sheet adhesive 2a is photocured. Start the reaction. At this time, the photocuring reaction has started in the sheet-like adhesive, but since the reaction rate of the photocationic polymerization is relatively slow, the curing reaction is not completed. It has adhesive strength (in FIG. 2 (c), sheet-like adhesive 2b).
　なお、機能性フィルム１／シート状接着剤／剥離フィルムの層構成を有する積層体を用いる場合であって、剥離フィルムが紫外線透過性のものである場合には、シート状接着剤上の剥離フィルムを剥離することなく、剥離フィルム側から紫外線を照射することが、取り扱い性の面から好ましい。
　ここで、「紫外線透過性を有する」とは、波長３６５ｎｍの紫外線の６５％以上、好ましくは７０％以上を透過させる性質をいう（以下にて同じ）。 In addition, when using the laminated body which has a layer structure of functional film 1 / sheet-like adhesive / release film, and the release film is UV transmissive, the release film on the sheet-like adhesive It is preferable from the surface of handleability to irradiate ultraviolet rays from the peeling film side without peeling.
Here, “having ultraviolet transparency” means a property of transmitting 65% or more, preferably 70% or more of ultraviolet rays having a wavelength of 365 nm (the same applies hereinafter).
　紫外線源の具体例としては、例えば、超高圧水銀灯、高圧水銀灯、低圧水銀灯、カーボンアーク灯、ブラックライト蛍光灯、メタルハライドランプ灯等の光源が挙げられる。また、照射する紫外線の波長としては、１９０～３８０ｎｍの波長域を使用することができる。機能性フィルム１／シート状接着剤／紫外線透過性の剥離フィルムの層構成を有する積層体の剥離フィルムを剥離することなく、剥離フィルム側から紫外線を照射する場合において、剥離フィルムがポリエチレンテレフタレートフィルムを基材とするものであると、紫外線の波長が３３０ｎｍ未満の領域において、剥離フィルムの紫外線の透過性が著しく低下してしまう。そのため、３３０～３８０ｎｍの波長域の紫外線を照射することが好ましい。
　紫外線の種類や照射量、照射時間等は、照射するシート状接着剤の構成成分や各構成成分の含有量などにより、適宜決定することができる。
　照射照度は、２０～１０００ｍＷ／ｃｍ２、光量５０～１０００ｍＪ／ｃｍ２程度が好ましい。
　また、照射時間は、通常、０．１～１０００秒、好ましくは１～５００秒程度である。 Specific examples of the ultraviolet light source include light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp. Further, the wavelength range of 190 to 380 nm can be used as the wavelength of the ultraviolet rays to be irradiated. Functional film 1 / sheet adhesive / ultraviolet permeable release film layered laminate release film without peeling the release film side, UV release from the release film side, the release film is a polyethylene terephthalate film When the substrate is used, the ultraviolet transmittance of the release film is significantly reduced in the region where the wavelength of ultraviolet rays is less than 330 nm. Therefore, it is preferable to irradiate ultraviolet rays having a wavelength range of 330 to 380 nm.
The type, irradiation amount, irradiation time, and the like of the ultraviolet rays can be appropriately determined depending on the component of the sheet adhesive to be irradiated, the content of each component, and the like.
The irradiation illuminance is preferably about 20 to 1000 mW / cm 2 and the amount of light is about 50 to 1000 mJ / cm 2 .
The irradiation time is usually about 0.1 to 1000 seconds, preferably about 1 to 500 seconds.
　その後、図２（ｄ）に示すように、硬化反応が完結していない状態のシート状接着剤２ｂと電子デバイスを貼り合せることにより、目的とする電子デバイス封止体１０を得ることができる。
　紫外線を照射した後、電子デバイスに貼り合せるまでの時間は、紫外線が照射されたシート状接着剤が、硬化反応が完結していない状態であって、十分な接着力を有している間であればよい。
　紫外線を照射した後、電子デバイスに貼り合せるまでの時間は、特に限定されないが、通常、１分～５時間であり、５～６０分であることが好ましい。 Thereafter, as shown in FIG. 2D, the target electronic device sealing body 10 can be obtained by bonding the sheet-like adhesive 2 b in a state where the curing reaction is not completed and the electronic device.
After irradiating with ultraviolet rays, the time until bonding to the electronic device is in a state in which the sheet-like adhesive irradiated with ultraviolet rays is in a state where the curing reaction has not been completed and has sufficient adhesive force. I just need it.
There is no particular limitation on the time from application of ultraviolet light to bonding to an electronic device, but it is usually 1 minute to 5 hours, and preferably 5 to 60 minutes.
　硬化反応が完結していない状態のシート状接着剤２ｂは電子デバイスを貼り合わせた後においても、シート状接着剤中では光硬化反応は進行し、経時的にシート状接着剤は完全に硬化した状態（接着剤硬化物層２）となる。
　このように、本発明のシート状接着剤は、紫外線が照射された後であっても、硬化反応が十分に進行していない間であれば、十分な接着性を有しているので、被着体である電子デバイスに強く接着し、貼付時、あるいは貼付後の剥離を生じることを防止することができ、また、経時的にシート状接着剤が硬化し、最終的に耐久性に優れた電子デバイス封止体を得ることができる。 In the sheet-like adhesive 2b in a state where the curing reaction is not completed, the photo-curing reaction proceeds in the sheet-like adhesive even after the electronic device is bonded, and the sheet-like adhesive is completely cured with time. It will be in a state (adhesive hardened material layer 2).
As described above, the sheet-like adhesive of the present invention has sufficient adhesiveness even after being irradiated with ultraviolet rays as long as the curing reaction does not proceed sufficiently. It adheres strongly to the electronic device that is the body and can prevent peeling at the time of sticking or after sticking. Also, the sheet-like adhesive hardens over time, and finally has excellent durability. An electronic device sealing body can be obtained.
　（製造方法２）
　また、本発明の電子デバイス封止体は、（α２）下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤に紫外線を照射する工程と、
（β２）前記シート状接着剤を、機能性フィルム又は電子デバイスに貼付する工程とを有し、
（β２）工程よりも前に（α２）工程を行うことにより製造することもできる。 (Manufacturing method 2)
Moreover, the electronic device sealing body of the present invention comprises (α2) a step of irradiating a sheet adhesive containing the following component (A) and component (B) with ultraviolet rays,
(Β2) a step of attaching the sheet adhesive to a functional film or an electronic device,
It can also be produced by performing the (α2) step before the (β2) step.
　この方法は、具体的には次のように行う。
　まず、シート状接着剤２ａを用意する。シート状接着剤２ａは、表裏両面に剥離フィルムが積層された両面剥離フィルム付接着フィルムとして保管することができる。
　次いで、図３（ａ）に示すように、シート状接着剤２ａに紫外線を照射して、シート状接着剤２ａの光硬化反応を開始させる。この場合、紫外線を剥離フィルム越しに照射することが好ましい。 Specifically, this method is performed as follows.
First, the sheet-like adhesive 2a is prepared. The sheet-like adhesive 2a can be stored as an adhesive film with a double-sided release film in which release films are laminated on both front and back sides.
Next, as shown in FIG. 3A, the sheet-like adhesive 2a is irradiated with ultraviolet rays to initiate a photocuring reaction of the sheet-like adhesive 2a. In this case, it is preferable to irradiate ultraviolet rays through a peeling film.
　紫外線が照射されると、シート状接着剤中では光硬化反応が開始するが、光カチオン重合の反応速度は比較的緩やかであるため、硬化反応が完結しておらず、シート状接着剤は、十分な接着力を有している。
　紫外線の種類、紫外線の照射条件等は、製造方法１で述べたものと同様である。 When ultraviolet light is irradiated, the photocuring reaction starts in the sheet-like adhesive, but since the reaction rate of the photocationic polymerization is relatively slow, the curing reaction is not completed. It has sufficient adhesive strength.
The type of ultraviolet rays, the irradiation conditions of ultraviolet rays, and the like are the same as those described in Production Method 1.
次いで、シート状接着剤２ｂの一方の面側に、機能性フィルム１又は電子デバイス３を貼り合せることにより、図３（ｂ）に示す状態を得る。 Next, the functional film 1 or the electronic device 3 is bonded to one surface side of the sheet-like adhesive 2b to obtain the state shown in FIG.
その後、図３（ｃ）に示すように、硬化反応が完結していない状態のシート状接着剤２ｂの、機能性フィルム１又は電子デバイス３が貼り合されている面と反対側の面と、電子デバイス３又機能性フィルム１を重ね合わせることにより、目的とする電子デバイス封止体１０を得ることができる。すなわち、シート状接着剤２ｂの一方の面側に機能性フィルム１が貼り合されている場合には、機能性フィルム１が貼り合されている面と反対側の面に電子デバイス３を貼り合せることで、電子デバイス封止体１０を得ることができる。また、シート状接着剤２ｂの一方の面側に電子デバイス３が貼り合されている場合には、電子デバイス３１が貼り合されている面と反対側の面に機能性フィルム１を貼り合せることで、電子デバイス封止体１０を得ることができる。 Thereafter, as shown in FIG. 3 (c), the surface of the sheet-like adhesive 2b in a state where the curing reaction is not completed, on the side opposite to the surface on which the functional film 1 or the electronic device 3 is bonded, By superimposing the electronic device 3 or the functional film 1, the target electronic device sealing body 10 can be obtained. That is, when the functional film 1 is bonded to one surface side of the sheet-like adhesive 2b, the electronic device 3 is bonded to the surface opposite to the surface where the functional film 1 is bonded. Thereby, the electronic device sealing body 10 can be obtained. Moreover, when the electronic device 3 is bonded to one surface side of the sheet-like adhesive 2b, the functional film 1 is bonded to the surface opposite to the surface where the electronic device 31 is bonded. Thus, the electronic device sealing body 10 can be obtained.
　硬化反応が完結していないシート状接着剤２ｂと、機能性フィルム１又は電子デバイス３を貼り合わせた後においても、シート状接着剤の層中で光硬化反応は進行し、経時的にシート状接着剤の層は完全に硬化した状態（接着剤硬化物層２）となる。
　このように、本発明のシート状接着剤は、その接着剤層に紫外線を照射した後であっても、硬化反応が十分に進行していない間であれば、接着剤層は十分な接着性を有しているので、被着体である電子デバイスに強く接着し、貼付時、あるいは貼付後の剥離を生じることを防止することができ、また、経時的に接着剤層が硬化し、最終的に耐久性に優れた電子デバイス封止体を得ることができる。 Even after the sheet-like adhesive 2b in which the curing reaction is not completed and the functional film 1 or the electronic device 3 are bonded together, the photo-curing reaction proceeds in the layer of the sheet-like adhesive, and the sheet-like adhesive is gradually formed. The adhesive layer is completely cured (adhesive cured product layer 2).
As described above, the sheet-like adhesive of the present invention has sufficient adhesiveness as long as the curing reaction does not proceed sufficiently even after the adhesive layer is irradiated with ultraviolet rays. Therefore, the adhesive layer strongly adheres to the adherend electronic device, and can be prevented from being peeled off at the time of sticking or after sticking. In particular, an electronic device sealing body with excellent durability can be obtained.
　以下、実施例を挙げて本発明を更に詳細に説明する。但し、本発明は、以下の実施例になんら限定されるものではない。
　各例中の部及び％は、特に断りのない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Unless otherwise indicated, the part and% in each example are based on mass.
　［機能性フィルムの波長３６５ｎｍの紫外線の透過率］
　機能性フィルムの波長３６５ｎｍの紫外線の透過率は、紫外可視光透過率測定装置（島津製作所社製、ＵＶ－３６００）を用いて測定した。 [Transmission of functional film with ultraviolet ray of wavelength 365 nm]
The transmittance of ultraviolet rays having a wavelength of 365 nm of the functional film was measured using an ultraviolet-visible light transmittance measuring apparatus (manufactured by Shimadzu Corporation, UV-3600).
　［紫外線照射後の接着剤層の粘着力測定］
　実施例および比較例で得られた、剥離フィルム付電子デバイス封止用接着フィルムから、剥離フィルムを剥がさずに、幅２５ｍｍに裁断して試料を得た。２３℃、５０％環境下で、剥離フィルム側から、照度５０ｍＷ／ｃｍ２、積算光量２００ｍＪ／ｃｍ２で、波長３６５ｎｍの紫外線を照射した。紫外線の照射は、アイグラフィックス社製、高圧水銀ランプを使用して行った。また、光量計は、アイグラフィックス社製「ＵＶＰＦ－Ａ１」を使用した。
　３分経過後に、剥離フィルムを剥がし、露出した接着剤層のシート状接着剤面を厚さ１．１ｍｍのソーダガラス板に重ねて、機能性フィルムの表面上で２ｋｇロールを一往復させて圧着させた。電子デバイス封止用接着フィルムをソーダガラス板に圧着させてから２４時間、温度２３℃、相対湿度５０％の条件下に静置し、その後３００ｍｍ／分の剥離速度で１８０°引き剥がし試験を行い、粘着力を測定した。 [Measurement of adhesive strength of adhesive layer after UV irradiation]
From the adhesive film for sealing an electronic device with a release film obtained in Examples and Comparative Examples, a sample was obtained by cutting to a width of 25 mm without peeling off the release film. Under an environment of 23 ° C. and 50%, an ultraviolet ray having a wavelength of 365 nm was irradiated from the release film side with an illuminance of 50 mW / cm 2 and an integrated light amount of 200 mJ / cm 2 . Irradiation with ultraviolet rays was performed using a high-pressure mercury lamp manufactured by Eye Graphics. In addition, “UVPF-A1” manufactured by Eye Graphics Co., Ltd. was used as the light meter.
After 3 minutes, the release film is peeled off, the sheet adhesive surface of the exposed adhesive layer is placed on a 1.1 mm thick soda glass plate, and a 2 kg roll is reciprocated once on the surface of the functional film for pressure bonding. I let you. 24 hours after pressure-bonding the adhesive film for sealing an electronic device to a soda glass plate, it is left to stand under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then a 180 ° peeling test is performed at a peeling speed of 300 mm / min. The adhesive strength was measured.
　以下の実施例及び比較例においては、環状エーテル基を有する化合物〔（Ａ）成分〕、光カチオン重合開始剤〔（Ｂ）成分〕、バインダー樹脂〔（Ｃ）成分〕、粘着付与剤、及びシランカップリング剤として、以下のものを用いた。 In the following Examples and Comparative Examples, a compound having a cyclic ether group [(A) component], a photocationic polymerization initiator [(B) component], a binder resin [(C) component], a tackifier, and a silane The following were used as coupling agents.
＜環状エーテル基を有する化合物〔（Ａ）成分〕＞
（１）環状エーテル基を有する化合物（Ａ－１）
　水添ビスフェノールＡ型エポキシ樹脂〔三菱ケミカル社製、商品名：ＹＸ８０００、環状エーテル当量：２０５ｇ／ｅｑ、２５℃で液状〕
（２）環状エーテル基を有する化合物（Ａ－２）
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〔株式会社ダイセル製、商品名：セロキサイド２０２１Ｐ、環状エーテル当量：１２８～１４５ｇ／ｅｑ、常温（２３℃）で液状物〕 <Compound having cyclic ether group [component (A)]>
(1) Compound (A-1) having a cyclic ether group
Hydrogenated bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical, trade name: YX8000, cyclic ether equivalent: 205 g / eq, liquid at 25 ° C.)
(2) Compound having a cyclic ether group (A-2)
3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate [manufactured by Daicel Corporation, trade name: Celoxide 2021P, cyclic ether equivalent: 128 to 145 g / eq, liquid at normal temperature (23 ° C.)]
＜光カチオン重合開始剤〔（Ｂ）成分〕＞
（１）光カチオン重合開始剤（Ｂ－１）
　トリアリールスルホニウム塩〔サンアプロ社製、商品名：ＣＰＩ－２００Ｋ、アニオン：ヘキサフルオロホスフェート骨格を有するアニオン〕
（２）光カチオン重合開始剤（Ｂ－２）
トリアリールスルホニウム塩〔サンアプロ社製、商品名：ＣＰＩ－１００Ｐ〕 <Photocationic polymerization initiator [component (B)]>
(1) Photocationic polymerization initiator (B-1)
Triarylsulfonium salt [manufactured by San Apro, trade name: CPI-200K, anion: anion having a hexafluorophosphate skeleton]
(2) Photocationic polymerization initiator (B-2)
Triarylsulfonium salt [manufactured by San Apro, trade name: CPI-100P]
＜バインダー樹脂〔（Ｃ成分）〕
（１）バインダー樹脂（Ｃ－１）
　酸変性α－オレフィン重合体〔三井化学社製、商品名：ユニストールＨ－２００、重量平均分子量：５２，０００〕
（２）バインダー樹脂（Ｃ－２）
フェノキシ樹脂（三菱ケミカル社製、商品名：ＹＸ７２００Ｂ３５） <Binder resin [(C component)]
(1) Binder resin (C-1)
Acid-modified α-olefin polymer [Mitsui Chemicals, trade name: Unistor H-200, weight average molecular weight: 52,000]
(2) Binder resin (C-2)
Phenoxy resin (trade name: YX7200B35, manufactured by Mitsubishi Chemical Corporation)
［実施例１］
　環状エーテル基を有する化合物（Ａ－１）５０質量部、環状エーテル基を有する化合物（Ａ－２）２０質量部、光カチオン重合開始剤（Ｂ－１）１質量部、光カチオン重合開始剤（Ｂ－２）を１．５部、酸変性α－オレフィン重合体（Ａ）１００質量部、シランカップリング剤０．１質量部をメチルエチルケトンに溶解し、固形分濃度３０％の接着剤組成物を調製した。
　この接着剤組成物（１）を、シリコーン剥離処理されたポリエチレンテレフタレートフィルムである剥離フィルム（リンテック社製、商品名：ＳＰ－ＰＥＴ７５２１５０、厚さ７５μｍ）の剥離処理面上に塗工し、得られた塗膜を１００℃で２分間乾燥し、厚みが３０μｍの接着剤層を形成した。
　その接着剤層の上に、機能性フィルムとして、金属アルミニウムを蒸着したポリエチレンテレフタレートフィルム（三菱伸銅社製、商品名：メタライズドフィルム、厚さ２３μｍ）を、金属アルミニウムが蒸着されていない面側にして貼り合わせ、剥離フィルムを有する状態で電子デバイス封止用接着フィルムを得た。この機能性フィルムの波長３６５ｎｍにおける透過率は０％であった。また、紫外線照射後の粘着力は１２Ｎ／２５ｍｍであった。 [Example 1]
Compound (A-1) having a cyclic ether group (50 parts by mass), Compound (A-2) having a cyclic ether group (20 parts by mass), Photocationic polymerization initiator (B-1) 1 part by mass, Photocationic polymerization initiator ( B-2) 1.5 parts, acid-modified α-olefin polymer (A) 100 parts by mass and silane coupling agent 0.1 part by mass were dissolved in methyl ethyl ketone to obtain an adhesive composition having a solid content concentration of 30%. Prepared.
This adhesive composition (1) was obtained by coating the release-treated surface of a release film (trade name: SP-PET752150, thickness 75 μm, manufactured by Lintec Co., Ltd.) which is a polyethylene terephthalate film subjected to silicone release treatment. The coated film was dried at 100 ° C. for 2 minutes to form an adhesive layer having a thickness of 30 μm.
On the adhesive layer, as a functional film, a polyethylene terephthalate film (made by Mitsubishi Shindoh Co., Ltd., product name: metallized film, thickness 23 μm) on which metal aluminum is vapor-deposited is placed on the side where metal aluminum is not vapor-deposited. Then, an adhesive film for sealing an electronic device was obtained in a state having a release film. The transmittance of this functional film at a wavelength of 365 nm was 0%. Moreover, the adhesive force after ultraviolet irradiation was 12 N / 25 mm.
［実施例２］
光カチオン重合開始剤（Ｂ－１）を使用せず、光カチオン重合開始剤（Ｂ－２）の配合量を３．０質量部に変更した以外は、実施例１と同様にして電子デバイス封止用接着フィルムを得た。紫外線照射後の粘着力は４Ｎ／２５ｍｍであった。 [Example 2]
The electronic device was encapsulated in the same manner as in Example 1 except that the photocationic polymerization initiator (B-1) was not used and the amount of the photocationic polymerization initiator (B-2) was changed to 3.0 parts by mass. An adhesive film for stopping was obtained. The adhesive strength after UV irradiation was 4 N / 25 mm.
［実施例３］
　光カチオン重合開始剤（Ｂ－１）を使用せず、光カチオン重合開始剤（Ｂ－２）の配合量を３．５質量部に変更した以外は、実施例１と同様にして電子デバイス封止用接着フィルムを得た。紫外線照射後の粘着力は１Ｎ／２５ｍｍであった。 [Example 3]
The electronic device was encapsulated in the same manner as in Example 1 except that the photocationic polymerization initiator (B-1) was not used and the amount of the photocationic polymerization initiator (B-2) was changed to 3.5 parts by mass. An adhesive film for stopping was obtained. The adhesive strength after UV irradiation was 1 N / 25 mm.
［実施例４］
　実施例１で使用した接着剤組成物の原材料（固形分）に代えて、環状エーテル基を有する化合物（Ａ－２）１２０質量部、（２）光カチオン重合開始剤（Ｂ－２）２．５質量部、バインダー樹脂（Ｃ－２）１００質量部、シランカップリング剤（信越化学工業社性、商品名：ＫＢＭ６８０３）を、０．２質量部を使用して接着剤組成物を調製したこと以外は実施例１と同様にして、電子デバイス封止用接着フィルムを得た。紫外線照射後の粘着力は６Ｎ／２５ｍｍであった。 [Example 4]
Instead of the raw material (solid content) of the adhesive composition used in Example 1, 120 parts by mass of a compound (A-2) having a cyclic ether group, (2) a photocationic polymerization initiator (B-2) 5 parts by weight, 100 parts by weight of binder resin (C-2), silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM6803) and 0.2 parts by weight were used to prepare an adhesive composition. Otherwise, an adhesive film for sealing an electronic device was obtained in the same manner as in Example 1. The adhesive strength after UV irradiation was 6 N / 25 mm.
１・・・機能性フィルム
２ａ・・・シート状接着剤
２ｂ・・・硬化反応が完結していないシート状接着剤
２・・・接着剤硬化物層
３・・・電子デバイス
４ａ・・・積層体
１０・・・電子デバイス封止体 DESCRIPTION OF SYMBOLS 1 ... Functional film 2a ... Sheet-like adhesive 2b ... Sheet-like adhesive 2 in which hardening reaction is not completed ... Adhesive hardened material layer 3 ... Electronic device 4a ... Lamination | stacking Body 10 ... Electronic device sealing body

Claims (9)

  1. 　波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム、電子デバイス、及び、前記機能性フィルムと電子デバイスの間を封止する接着剤硬化物層を備え、前記接着剤硬化物層は、下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤の硬化物である、電子デバイスの封止体。
    （Ａ）環状エーテル基を有する化合物
    （Ｂ）光カチオン重合開始剤     A functional film, an electronic device, and a cured adhesive layer that seals between the functional film and the electronic device, wherein the transmittance of ultraviolet light having a wavelength of 365 nm is 60% or less; The sealing body of an electronic device which is the hardened | cured material of the sheet-like adhesive agent containing the following (A) component and (B) component.
    (A) Compound having cyclic ether group (B) Photocationic polymerization initiator
  2. 　下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤であって、請求項１に記載の電子デバイスの封止体の製造に用いられるものである、シート状接着剤。
    （Ａ）環状エーテル基を有する化合物
    （Ｂ）光カチオン重合開始剤     A sheet-like adhesive comprising the following component (A) and component (B), which is used for producing an electronic device encapsulant according to claim 1.
    (A) Compound having cyclic ether group (B) Photocationic polymerization initiator
  3. 　前記シート状接着剤は、少なくとも一方の面に剥離フィルムを有し、以下の条件（ｉ）で測定されるソーダガラス板に対する粘着力が３Ｎ／２５ｍｍ以上である、請求項２に記載のシート状接着剤。
    （ｉ）前記シート状接着剤の前記剥離フィルムが貼り合わされているのとは逆側の面に、アルミニウムを蒸着した厚さ２３μｍのポリエチレンテレフタレートフィルムと貼り合わせた積層体を作製し、前記剥離フィルムを貼り合わせた状態で、前記剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で前記積層体に照射し、その３分後に、前記積層体から前記剥離フィルムを剥離し、露出したシート状接着剤の層をソーダガラス板に対向させ、前記積層体上で２ｋｇのロールを一往復させることによりソーダガラス板に貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後に１８０°引き剥がし試験を実施する。     The sheet-like adhesive according to claim 2, wherein the sheet-like adhesive has a release film on at least one surface, and has an adhesive strength to a soda glass plate measured under the following condition (i) of 3 N / 25 mm or more. adhesive.
    (I) On the opposite side of the sheet-like adhesive from which the release film is attached, a laminate is prepared by attaching an aluminum-deposited 23 μm thick polyethylene terephthalate film, and the release film In the state of bonding, the laminate is irradiated from the release film side with ultraviolet light having a wavelength of 365 nm under the conditions of illuminance: 50 mW / cm 2 and light quantity: 200 mJ / cm 2 , and 3 minutes later, the laminate The release film is peeled off, the exposed sheet-like adhesive layer is made to face the soda glass plate, and a 2 kg roll is reciprocated once on the laminated body to be stuck to the soda glass plate, and the film is applied at 23 ° C. at 50 ° C. After being stored for 24 hours in an environment of% relative humidity, a 180 ° peel test is performed.
  4. 　さらに、変性ポリオレフィン樹脂及びフェノキシ樹脂からなる群から選ばれる一種以上を含む、請求項２又は３に記載のシート状接着剤。 Furthermore, the sheet adhesive of Claim 2 or 3 containing 1 or more types chosen from the group which consists of a modified polyolefin resin and a phenoxy resin.
  5. 　波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルムと、下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤からなる接着剤層を有する、電子デバイス封止用接着フィルム。
    （Ａ）環状エーテル基を有する化合物
    （Ｂ）光カチオン重合開始剤     An adhesive film for encapsulating an electronic device, comprising a functional film having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm, and an adhesive layer comprising a sheet-like adhesive containing the following components (A) and (B).
    (A) Compound having cyclic ether group (B) Photocationic polymerization initiator
  6. 前記電子デバイス封止用接着フィルムは、機能性フィルムが貼り合わされていない側の前記接着剤層の表面に剥離フィルムを有し、以下の条件（ｉｉ）で測定されるソーダガラス板に対する粘着力が３Ｎ／２５ｍｍ以上である、請求項５に記載の電子デバイス封止用接着フィルム。
    （ｉｉ）前記電子デバイス封止用接着フィルムに前記剥離フィルムを貼り合わせた状態で、前記剥離フィルム側から、波長３６５ｎｍの紫外線を、照度：５０ｍＷ／ｃｍ２、光量：２００ｍＪ／ｃｍ２の条件で照射し、その３分後に、前記電子デバイス封止用接着剤接着フィルムから前記剥離フィルムを剥離し、露出した接着剤層をソーダガラス板に対向させ、前記電子デバイス封止用接着フィルム上で２ｋｇのロールを一往復させることによりソーダガラス板に貼付して、２３℃で５０％相対湿度の環境下に２４時間保管された後に１８０°引き剥がし試験を実施する。     The adhesive film for sealing an electronic device has a release film on the surface of the adhesive layer on the side where the functional film is not bonded, and has an adhesive force to a soda glass plate measured under the following condition (ii). The adhesive film for electronic device sealing of Claim 5 which is 3 N / 25mm or more.
    (Ii) In the state where the release film is bonded to the adhesive film for sealing an electronic device, ultraviolet rays having a wavelength of 365 nm are applied from the release film side under the conditions of illuminance: 50 mW / cm 2 and light amount: 200 mJ / cm 2 . 3 minutes after irradiation, the release film is peeled off from the adhesive adhesive film for sealing an electronic device, the exposed adhesive layer is opposed to a soda glass plate, and 2 kg on the adhesive film for sealing an electronic device. This roll is attached to a soda glass plate by reciprocating once and stored at 23 ° C. in an environment of 50% relative humidity for 24 hours, and then a 180 ° peeling test is performed.
  7. 　さらに、シート状接着剤が、変性ポリオレフィン樹脂及びフェノキシ樹脂からなる群から選ばれる一種以上を含む、請求項５又は６に記載の電子デバイス封止用接着フィルム。 Furthermore, the adhesive film for electronic device sealing of Claim 5 or 6 in which a sheet-like adhesive contains 1 or more types chosen from the group which consists of a modified polyolefin resin and a phenoxy resin.
  8. （α１）上記５～７のいずれかの接電子デバイス封止用着性フィルムに対し、機能性フィルムよりも接着剤層に近い表面側から紫外線を照射する工程と、
    （β１）上記接着性フィルムを電子デバイスに貼付する工程とを有し、
    （β１）工程よりも前に（α１）工程を行う電子デバイスの封止体の製造方法。     (Α1) A step of irradiating the adhesive film for sealing an electronic device according to any one of 5 to 7 with ultraviolet rays from the surface side closer to the adhesive layer than the functional film;
    (Β1) a step of attaching the adhesive film to an electronic device,
    The manufacturing method of the sealing body of the electronic device which performs ((alpha) 1) process before ((beta) 1) process.
  9. （α２）下記（Ａ）成分及び（Ｂ）成分を含むシート状接着剤に紫外線を照射する工程と、
    （β２）前記シート状接着剤を、波長３６５ｎｍの紫外線の透過率が６０％以下である機能性フィルム又は電子デバイスに貼付する工程とを有し、
    （β２）工程よりも前に（α２）工程を行う電子デバイスの封止体の製造方法。
    （Ａ）環状エーテル基を有する化合物
    （Ｂ）光カチオン重合開始剤     (Α2) a step of irradiating the sheet-like adhesive containing the following components (A) and (B) with ultraviolet rays;
    (Β2) a step of attaching the sheet-like adhesive to a functional film or an electronic device having a transmittance of 60% or less of ultraviolet light having a wavelength of 365 nm,
    The manufacturing method of the sealing body of the electronic device which performs the (α2) step before the (β2) step.
    (A) Compound having cyclic ether group (B) Photocationic polymerization initiator
PCT/JP2019/013695 2018-03-28 2019-03-28 Electronic device-sealed body, sheet-shaped adhesive, adhesive film for sealing electronic device, and method for manufacturing electronic device-sealed body WO2019189618A1 (en)

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JP2020511008A JP7348165B2 (en) 2018-03-28 2019-03-28 Electronic device encapsulation, sheet adhesive, adhesive film for electronic device encapsulation, and manufacturing method of electronic device encapsulation
KR1020207023084A KR102582788B1 (en) 2018-03-28 2019-03-28 Electronic device encapsulation, sheet-like adhesive, adhesive film for electronic device encapsulation, and manufacturing method of electronic device encapsulation
JP2021509306A JPWO2020196240A1 (en) 2019-03-28 2020-03-19
CN202080025794.0A CN113646399B (en) 2019-03-28 2020-03-19 Sheet-like adhesive, sealing sheet, electronic device sealing body, and method for manufacturing electronic device sealing body
PCT/JP2020/012256 WO2020196240A1 (en) 2019-03-28 2020-03-19 Sheet-like adhesive agent, sealing sheet, electronic device sealed body, and method for manufacturing electronic device sealed body
KR1020217023401A KR20210145128A (en) 2019-03-28 2020-03-19 A sheet-like adhesive, a sealing sheet, the sealing body of an electronic device, and the manufacturing method of the sealing body of an electronic device
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