WO2023182493A1 - 樹脂シートおよびその製造方法 - Google Patents

樹脂シートおよびその製造方法 Download PDF

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Publication number
WO2023182493A1
WO2023182493A1 PCT/JP2023/011803 JP2023011803W WO2023182493A1 WO 2023182493 A1 WO2023182493 A1 WO 2023182493A1 JP 2023011803 W JP2023011803 W JP 2023011803W WO 2023182493 A1 WO2023182493 A1 WO 2023182493A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
resin composition
layer
composition layer
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/011803
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
賢 大橋
英治 馬場
真奈美 奥野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ajinomoto Co Inc
Original Assignee
Ajinomoto Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Priority to CN202380029494.3A priority Critical patent/CN118973816A/zh
Priority to JP2024509257A priority patent/JPWO2023182493A1/ja
Priority to KR1020247035582A priority patent/KR20240163738A/ko
Priority to EP23775086.4A priority patent/EP4501627A4/en
Publication of WO2023182493A1 publication Critical patent/WO2023182493A1/ja
Priority to US18/894,796 priority patent/US20250296296A1/en
Anticipated expiration legal-status Critical
Priority to JP2025132433A priority patent/JP2025163236A/ja
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B32B2255/205—Metallic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/00—Properties of the layers or laminate
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/724—Permeability to gases, adsorption
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    • B32B2457/00—Electrical equipment

Definitions

  • the present invention relates to a resin sheet suitable for sealing electronic devices such as organic EL elements, solar cells, and touch panels having conductive substrates, and a method for manufacturing the same.
  • electronic devices In order to protect electronic devices such as organic EL (Electroluminescence) elements, solar cells, and touch panels having conductive substrates from moisture, electronic devices are sealed using a resin sheet having a resin composition layer.
  • organic EL Electrode
  • solar cells In order to protect electronic devices such as organic EL (Electroluminescence) elements, solar cells, and touch panels having conductive substrates from moisture, electronic devices are sealed using a resin sheet having a resin composition layer.
  • a resin sheet is usually composed of a support, a resin composition layer, and a cover film for protecting the resin composition layer (for example, Patent Document 1).
  • Patent Document 2 As a method of increasing the moisture barrier properties of a resin sheet, it is known to blend semi-baked hydrotalcite into the resin composition layer of the resin sheet (for example, Patent Document 2).
  • paragraph [0015] and [0016] of Patent Document 1 describe the use of a plastic film such as polyethylene terephthalate or a plastic film having a barrier layer as a support.
  • paragraph [0018] merely states that "as a cover film for a resin sheet, the same plastic film as the support may be used", which does not imply that a plastic film having a barrier layer is used as a cover film. is not listed.
  • a resin sheet having a resin composition layer containing semi-baked hydrotalcite can achieve high moisture barrier properties due to the semi-baked hydrotalcite, but semi-baked hydrotalcite reversibly absorbs moisture. It has absorption and release properties. Therefore, in a resin sheet having a resin composition layer containing semi-baked hydrotalcite, for example, the semi-baked hydrotalcite absorbs moisture during storage of the resin sheet, and then releases the absorbed moisture to the resin composition layer. do. If an electronic device is sealed with a resin composition layer containing moisture released in this way, the life of the electronic device may be shortened.
  • a resin sheet with a resin composition layer containing calcium oxide can similarly achieve high moisture barrier properties, but since calcium oxide absorbs moisture irreversibly, oxidation occurs during storage of the resin sheet. Calcium absorbs water and loses its water-blocking properties. If an electronic device is sealed with such a resin composition layer, the life of the device may be shortened.
  • Patent Document 3 uses a moisture-proof film as a cover film in addition to using a plastic film having a barrier layer as a support, thereby reducing water absorption of the resin composition layer. Discloses a resin sheet that is suppressed.
  • barrier films with high moisture permeability are generally made by laminating multiple thin inorganic films by vapor deposition on plastic films, adhering metal foils, or multi-layered layers in which inorganic thin films and plastic films are alternately laminated.
  • barrier films with metal foil and barrier films with a multilayer structure often have air bubbles between the layers, but when inspecting the resin composition layer of a resin sheet for foreign substances with an automatic optical visual inspection device (AOI), Since air bubbles are detected as defects, accurate inspection becomes difficult and suitability for AOI evaluation becomes low.
  • AOI automatic optical visual inspection device
  • the present invention was made in view of the above-mentioned circumstances, and its purpose is to be able to suppress warping when forming a resin composition layer, and to provide a highly accurate optical automatic appearance inspection device (AOI).
  • An object of the present invention is to provide a resin sheet that enables foreign matter inspection of a resin composition layer using AOI (AOI).
  • a transparent film is used that has a plastic film as a layer, a barrier layer formed on the plastic film surface, and a release layer formed on the barrier layer surface that is not in contact with the plastic film or the plastic film surface that does not have a barrier layer.
  • a resin sheet having a first film, a resin composition layer, and a second film or glass plate,
  • the resin composition layer is present between the first film and the second film or between the first film and the glass plate
  • the first film is a single-layer plastic film as a base material, a barrier layer formed on the plastic film surface, and a mold release formed on the barrier layer surface that is not in contact with the plastic film or the plastic film surface that does not have a barrier layer.
  • the first film is a transparent film
  • the water vapor transmission rate (hereinafter sometimes abbreviated as “WVTR”) of the first film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less
  • WVTR water vapor transmission rate
  • the release layer of the first film is in contact with the resin composition layer
  • the second film does not have a release layer
  • the water vapor permeability of the second film is less than 0.01 (g/m 2 /24hr)
  • the glass plate does not have a release layer, resin sheet.
  • a resin composition layer is present between the first film and the second film,
  • the first film is a single-layer plastic film as a base material, a barrier layer formed on the plastic film surface, and a mold release formed on the barrier layer surface that is not in contact with the plastic film or the plastic film surface that does not have a barrier layer.
  • the first film is a transparent film,
  • the water vapor permeability of the first film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less,
  • the release layer of the first film is in contact with the resin composition layer, the second film does not have a release layer,
  • the water vapor permeability of the second film is less than 0.01 (g/m 2 /24hr),
  • the resin sheet according to [8], wherein the resin composition layer contains a polyolefin resin contains a polyolefin resin.
  • a manufacturing method comprising the step of laminating the above to a resin composition layer.
  • the first film of the resin sheet according to any one of [1] to [9] is peeled off, the resin composition layer is placed on the electronic device side, and the second film or the glass plate and the resin composition layer are removed.
  • a method for manufacturing an electronic device comprising the steps of laminating the electronic device on the electronic device and sealing the electronic device with a second film or a glass plate and a resin composition layer.
  • a resin sheet precursor comprising a first film, a resin composition layer, and a third film, a resin composition layer is present between the first film and the third film,
  • the first film has a single layer plastic film as a base material, a barrier layer formed on the plastic film surface, and a release layer formed on the barrier layer surface or the plastic film surface,
  • the first film is a transparent film
  • the water vapor permeability of the first film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less
  • the third film has a release layer
  • the water vapor permeability of the third film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less
  • the resin sheet After laminating a certain second film or a glass plate without a release layer to the resin composition layer to obtain a resin sheet having the first film, the resin composition layer, and the second film or glass plate, the resin sheet is The first film is peeled off, the resin composition layer is placed on the electronic device side, the second film or the glass plate and the resin composition layer are laminated on the electronic device, and the second film or the glass plate and the resin composition layer are used as the electronic device.
  • a method for manufacturing an electronic device including the step of sealing.
  • water absorption in the resin composition layer of the resin sheet (particularly water absorption in the resin composition layer containing semi-baked hydrotalcite or calcium oxide) can be suppressed, and optical automatic appearance can be achieved with high precision. It is possible to inspect the resin composition layer of the resin sheet for foreign substances using an inspection device (AOI), and it is possible to suppress warpage when forming the resin composition layer.
  • AOI inspection device
  • the resin sheet of the present invention has a first film, a resin composition layer, a second film or a glass plate, and the resin composition layer is between the first film and the second film or between the first film and the first film.
  • the first film is in contact with a single-layer plastic film as a base material, a barrier layer formed on the plastic film surface (preferably one surface of the plastic film), and the plastic film.
  • the first film is a transparent film, and the first film is a transparent film, and the first film is a transparent film, and the first film is a transparent film, and the first film is a transparent film;
  • the water vapor permeability of the first film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less, the release layer of the first film is in contact with the resin composition layer, and the first film is in contact with the resin composition layer.
  • the second film does not have a release layer, the water vapor permeability of the second film is less than 0.01 (g/m 2 /24hr), and the glass plate does not have a release layer. Note that, according to JIS and the like, those with a thickness of less than 0.25 mm are classified as films, and those with a thickness of more than 0.25 mm are classified as sheets, but the present invention is not limited to such classification.
  • the resin composition layer exists between the first film and the second film or between the first film and the glass plate.
  • the first film is used as a support for forming the resin composition layer. Further, the first film is peeled off to expose the resin composition layer before laminating the resin sheet on an electronic device such as an organic EL element, and also functions as a cover film.
  • the first film has a release layer on the surface that contacts the resin composition layer to facilitate peeling.
  • the second film is incorporated into the electronic device as a barrier film when the electronic device is sealed and is not peeled off, so it does not have a release layer.
  • the resin sheet has a first film, a resin composition layer, and a second film, and the resin composition layer is present between the first film and the second film.
  • the first film includes a single layer plastic film as a base material, a barrier layer formed on the plastic film surface (preferably one surface of the plastic film), and a barrier layer not in contact with the plastic film.
  • a release layer formed on a barrier layer surface or a plastic film surface without a barrier layer (preferably a plastic film surface without a barrier layer) the first film is a transparent film;
  • the water vapor permeability of is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less, and the release layer of the first film is in contact with the resin composition layer.
  • plastic films include polyolefins such as polyethylene and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), cycloolefin polymer (COP), Examples include single-layer plastic films such as polyvinyl chloride.
  • the plastic film is preferably a polyethylene terephthalate film, a cycloolefin polymer film, a polyethylene naphthalate film or a polycarbonate film, more preferably a polyethylene terephthalate film or a cycloolefin polymer film.
  • the thickness of the base material is preferably 10 to 100 ⁇ m, more preferably 15 to 90 ⁇ m, and even more preferably 20 to 80 ⁇ m.
  • the base material By using a transparent single-layer plastic film as the base material (preferably having a total light transmittance as described below), foreign matter inspection ( (defect detection) becomes possible.
  • the base material is a plastic film with two or more layers, an adhesive layer is required between each layer, and many defects and bubbles occur in the base material itself, making it difficult to accurately detect the AOI of the resin composition layer. It disappears.
  • each layer has a different coefficient of linear thermal expansion, so that warping due to the base material is likely to occur during heating.
  • the barrier layer in the first film examples include inorganic films such as silica vapor deposited films, silicon nitride films, and silicon oxide films, and organic/inorganic mixed films containing inorganic substances such as metal oxides and organic substances such as organic resins. .
  • inorganic films such as silica vapor deposited films, silicon nitride films, and silicon oxide films
  • organic/inorganic mixed films containing inorganic substances such as metal oxides and organic substances such as organic resins.
  • a plurality of inorganic films can be used. It may have a laminated multilayer structure, or may be composed of an organic substance and an inorganic substance.
  • the total thickness of the barrier layers in the first film is such that the first film is transparent and has a water vapor permeability of 0.01 (g/m 2 /24 hr) or more 1 (g/m 2 /24 hr) Although not particularly limited as long as it is below, it is preferably 0.01 or more and less than 1 ⁇ m, more preferably 0.05 or more and 0.9 ⁇ m, and even more preferably 0.1 or more and 0.8 ⁇ m or less.
  • the barrier layer in the first film is formed by coating an inorganic film such as silicon oxide (silica), aluminum oxide, magnesium oxide, silicon nitride, silicon nitride oxide, SiCN, or amorphous silicon on the surface of the base material (single-layer plastic film) using chemical vapor.
  • phase growth methods e.g. chemical vapor deposition with heat, plasma, ultraviolet light, vacuum heat, vacuum plasma or vacuum ultraviolet light
  • physical vapor deposition methods e.g. vacuum evaporation, sputtering, ion plating, laser It can be manufactured by laminating layers using a deposition method, a molecular beam epitaxy method, etc. (see, for example, Japanese Patent Application Laid-Open No. 2013-108103).
  • it can be formed by applying a coating liquid consisting of an inorganic substance such as a metal oxide and an organic resin to the surface of the base material (single-layer plastic film) and drying it to form an organic/inorganic mixed film (for example, see Japanese Patent No. 4028353).
  • a coating liquid consisting of an inorganic substance such as a metal oxide and an organic resin
  • the release layer can be formed, for example, by applying a release agent to a base material (single-layer plastic film) and drying it.
  • the drying temperature after application of the mold release agent is, for example, 100 to 150° C., and the drying time is, for example, 5 to 120 minutes.
  • the mold release agent examples include silicone mold release agents, alkyd mold release agents, fluorine mold release agents, olefin mold release agents, and the like.
  • the mold release layer is preferably formed from a silicone mold release agent or an alkyd mold release agent.
  • the thickness of the release layer is preferably 0.05 to 1 ⁇ m, more preferably 0.05 to 0.5 ⁇ m, and even more preferably 0.05 to 0.1 ⁇ m.
  • the thickness of the first film is preferably 20 to 100 ⁇ m, more preferably 20 to 90 ⁇ m, and even more preferably 20 to 80 ⁇ m from the viewpoint of suppressing the occurrence of warpage and winding the resin sheet into a roll. .
  • the total light transmittance of the first film is preferably 80% or more, more preferably 82%, in order to enable foreign matter inspection (defect detection) of the resin composition layer with an automatic optical visual inspection device (AOI). % or more, more preferably 85% or more.
  • the total light transmittance can be measured, for example, according to JIS K7361-1 "Testing method for total light transmittance of plastic transparent materials Part 1: Single beam method".
  • the water vapor permeability of the first film is 0.01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less.
  • WVTR is preferably 0.8 (g/m 2 /24hr) or less, more preferably 0.6 (g/m 2 /24hr) or less. It is also preferably 0.05 (g/m 2 /24hr) or more, more preferably 0.1 (g/m 2 /24hr) or more.
  • This WVTR is a value measured by a method described in Examples described later. Further, since the first film is peeled off and discarded before sealing the electronic device, within this range, it is possible to simultaneously suppress water absorption of the resin composition layer during storage and reduce costs.
  • the total thickness of the inorganic film of the film may increase, such as increasing the thickness of the inorganic film or providing more inorganic film layers in a multilayer structure. Because it is larger, warping is more likely to occur.
  • the WVTR By setting the WVTR to 1 (g/m 2 /24 hr) or less, the life of the moisture blocking performance of the resin composition layer can be extended.
  • WVTR exceeds 1 (g/m 2 /24 hr)
  • the hygroscopic filler contained in the resin composition layer absorbs water vapor present in the atmosphere, making it impossible to exhibit the original performance.
  • the first film is used as a support when forming a resin composition layer by coating and drying a resin composition varnish, and is peeled off when sealing an electronic device. That is, the first film is used as a support for coating the resin composition varnish.
  • a highly moisture permeable barrier film is used as a support for varnish coating, it tends to warp when heated, and there is also a risk that the barrier layer will be damaged during coating and the performance for sealing electronic devices will deteriorate. occurs.
  • the second film has a multilayer structure, AOI detects air bubbles in the base material of the laminate structure, and thus the suitability for AOI evaluation of the resin composition layer is low.
  • the barrier layer is a metal foil
  • the resin composition layer cannot be evaluated by AOI because it has no light transmittance.
  • a glass plate is thin, it is brittle, and when it is thick, it is difficult to form it into a roll, making it difficult to apply it to a coating device and difficult to use it as a support for coating.
  • These problems can be solved by using the first film as a support when forming the resin composition. Note that even when the first film is used as a support for forming a resin composition layer, the barrier layer may be damaged, but the first film will eventually be peeled off and will not remain in the electronic device. Therefore, there are no problems with the sealing performance of electronic devices. Furthermore, highly moisture-resistant barrier films and glass plates are disadvantageous in terms of cost when used as layers that are peeled off and discarded.
  • the second film is a film that is incorporated into the electronic device as a barrier film when the electronic device is sealed, does not have a release layer, and has a water vapor permeability of 0.01 (g/m 2 /24hr).
  • the second film may have the same transparency as the first film, or may have no transparency.
  • the WVTR of the second film is more preferably 0.005 (g/m 2 /24hr) or less, further preferably 0.001 (g/m 2 /24hr) or less, particularly preferably 0.0005 ( g/m 2 /24hr) or less.
  • the lower limit of the WVTR of the second film is not particularly limited, preferably a lower value, and most preferably 0 (g/m 2 /24hr). This WVTR is a value measured by a method described in Examples described later.
  • the second film is preferably a film having a base material and a barrier layer.
  • the base material means a portion of the film other than the barrier layer.
  • the base material may be a single layer film or a laminated film.
  • it may have a laminated structure in which plastic films are laminated using an adhesive.
  • adhesive There are no particular limitations on the adhesive, and commercially available adhesives can be used.
  • the base material include polyolefins such as polyethylene and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), cycloolefin polymer (COP), Examples include plastic films such as polyvinyl chloride. Only one type of plastic film may be used, or two or more types may be used.
  • the substrate is preferably a polyethylene terephthalate film, a cycloolefin polymer film, a polyethylene naphthalate film or a polycarbonate film, more preferably a polyethylene terephthalate film or a cycloolefin polymer film.
  • the thickness of the base material (if the base material has a laminated structure, the thickness of the entire base material; if the second film has a multilayer structure of an inorganic film and the base material, the total thickness of the base material part) , preferably 10 to 150 ⁇ m, more preferably 15 to 125 ⁇ m, and still more preferably 20 to 100 ⁇ m.
  • the barrier layer in the second film may be, for example, a metal foil (e.g. aluminum foil, copper foil), an inorganic film such as a silica vapor deposited film, a silicon nitride film, a silicon oxide film, an inorganic material such as a metal oxide, an organic resin, etc. Examples include organic/inorganic mixed films containing organic substances.
  • the barrier layer may be composed of multiple inorganic film layers. Further, the barrier layer may be composed of an organic substance and an inorganic substance.
  • the second film may have a multilayer structure in which inorganic films and base materials are alternately laminated.
  • the inorganic film when the inorganic film is formed by chemical vapor deposition or physical vapor deposition, it is preferable to have a multilayer structure in which the inorganic film and the base material are alternately laminated in order to prevent cracks in the inorganic film.
  • the total thickness of the barrier layer in the second film is preferably 15 ⁇ m or more and 100 ⁇ m or less, more preferably 20 ⁇ m or more and 90 ⁇ m or less, and even more preferably 25 ⁇ m or more and 80 ⁇ m or less. be.
  • the total thickness of the barrier layer in the second film is: It is preferably 1 to 10 ⁇ m, more preferably 1.5 to 8 ⁇ m, and still more preferably 2 to 5 ⁇ m.
  • the second film with a WVTR of less than 0.01 (g/m 2 /24hr), particularly the second film with a WVTR of 0.0005 (g/m 2 /24hr) or less, has silicon oxide (silica) on the surface of the base material. ), aluminum oxide, magnesium oxide, silicon nitride, silicon nitride oxide, SiCN, amorphous silicon, etc., are deposited using chemical vapor deposition methods (for example, chemical vapor deposition using heat, plasma, ultraviolet light, vacuum heat, vacuum plasma, or vacuum ultraviolet light).
  • phase growth method or physical vapor deposition method (e.g., vacuum evaporation method, sputtering method, ion plating method, laser deposition method, molecular beam epitaxy method), etc.
  • physical vapor deposition method e.g., vacuum evaporation method, sputtering method, ion plating method, laser deposition method, molecular beam epitaxy method
  • it can be formed by applying a coating liquid consisting of an inorganic substance such as a metal oxide and an organic resin to the surface of the base material (single-layer plastic film) and drying it to form an organic/inorganic mixed film (for example, see Japanese Patent No. 4028353).
  • a second film with a WVTR of less than 0.01 (g/m 2 /24hr), particularly a second film with a WVTR of 0.0005 (g/m 2 /24hr) or less for example, US foil, aluminum foil, copper
  • a second film with a WVTR of 0.0005 (g/m 2 /24hr) or less for example, US foil, aluminum foil, copper
  • metal foil such as foil
  • a second film manufactured by a method such as laminating a base material and metal foil together via an adhesive are examples.
  • a commercially available product may be used as the second film.
  • Examples include “PET Tsuki AL1N30” manufactured by Toyo Aluminum Co., Ltd., “X-BARRIER” manufactured by Mitsubishi Plastics Co., Ltd., “Belair” manufactured by Reikosha Co., Ltd., and “3EC-III” manufactured by Mitsui Kinzoku Co., Ltd.
  • the thickness of the second film is preferably 10 to 150 ⁇ m, more preferably 15 to 125 ⁇ m, and even more preferably 20 to 100 ⁇ m, from the viewpoint of ease of handling and winding up the resin sheet into a roll.
  • a glass plate can be used instead of the second film. That is, the resin sheet of the present invention has a first film, a resin composition layer, and a glass plate, and the resin composition layer is present between the first film and the glass plate.
  • the glass plate is incorporated into the electronic device as a barrier layer when the electronic device is sealed, and does not have a release layer.
  • the thickness of the glass plate is preferably 10 to 1000 ⁇ m, more preferably 50 to 900 ⁇ m, and still more preferably 100 to 800 ⁇ m. It is preferable that the thickness of the glass plate is within this range because it provides good handling properties.
  • the thickness of the glass plate is preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less. If the glass plate is too thick to be rolled up, it can be made into sheets.
  • the glass plate (or second film) we will sell, transport, store, etc. as a product form of a resin sheet precursor that uses the third film described below, and before use, peel off the third film and It can also be used as a resin sheet by laminating a plate (or a second film).
  • the water vapor permeability of the glass plate is usually less than 0.01 (g/m 2 /24hr), 0.005 (g/m 2 /24hr) or less, 0.001 (g/m 2 /24hr) or less, It may be 0.0005 (g/m 2 /24hr) or less, or 0 (g/m 2 /24hr).
  • the resin constituting the resin composition layer used in the resin sheet of the present invention is not particularly limited as long as the effects of the present invention are exhibited, and examples include thermoplastic resins (polyolefin resins, etc.), thermosetting resins, etc. Examples include resins (epoxy resins, etc.).
  • the resin composition layer preferably contains a polyolefin resin and/or an epoxy resin, more preferably a polyolefin resin.
  • the polyolefin resin that can be used in the present invention is not particularly limited as long as it has an olefin-derived skeleton.
  • the polyolefin resin described in Patent Document 1 is cited as a known example.
  • the olefin is preferably a monoolefin having one olefinic carbon-carbon double bond and/or a diolefin having two olefinic carbon-carbon double bonds.
  • monoolefins include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutylene (isobutene), 1-pentene, 1-hexene, 1-heptene, and 1-octene, and diolefins include, Preferred examples include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethylbutadiene.
  • the number of olefin-derived skeletons in the polyolefin resin may be one type or two or more types. Only one type of polyolefin resin may be used, or two or more types may be used in combination.
  • the polyolefin resin may be a homopolymer or a copolymer such as a random copolymer or a block copolymer.
  • the copolymer include copolymers of two or more types of olefins, and copolymers of olefins and monomers other than olefins, such as non-conjugated dienes and styrene.
  • preferred copolymers include ethylene-nonconjugated diene copolymer, ethylene-propylene copolymer, ethylene-propylene-nonconjugated diene copolymer, ethylene-butene copolymer, propylene-butene copolymer, and propylene.
  • polyolefin resins examples include isobutylene modified resins described in International Publication No. 2011/62167 and styrene-isobutylene modified resins described in International Publication No. 2013/108731.
  • the polyolefin resin is preferably a polybutene resin or a polypropylene resin.
  • polybutene-based resin refers to a resin in which the main unit (maximum content unit) of all olefin monomer units constituting the polymer is derived from butene
  • polypropylene-based resin refers to a resin that Refers to a resin in which the main unit (maximum content unit) of all the constituent olefin monomer units is derived from propylene.
  • examples of monomers other than butene include styrene, ethylene, propylene, isoprene, and the like.
  • examples of monomers other than propylene include ethylene, butene, isoprene, and the like.
  • Polyolefin resins include polyolefin resins having an acid anhydride group (i.e., carbonyloxycarbonyl group (-CO-O-CO-)) and/or polyolefin resins from the viewpoint of imparting excellent physical properties such as adhesiveness and adhesive resistance to moisture and heat.
  • anhydride group i.e., carbonyloxycarbonyl group (-CO-O-CO-)
  • polyolefin resin having an epoxy group examples include a group derived from succinic anhydride, a group derived from maleic anhydride, and a group derived from glutaric anhydride.
  • the polyolefin resin can have one or more acid anhydride groups.
  • the polyolefin resin having an acid anhydride group can be obtained, for example, by graft-modifying the polyolefin resin with an unsaturated compound having an acid anhydride group under radical reaction conditions. Further, an unsaturated compound having an acid anhydride group may be radically copolymerized with an olefin or the like. Similarly, polyolefin resins having epoxy groups are unsaturated compounds having epoxy groups such as glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether, and polyolefin resins are treated under radical reaction conditions. It can be obtained by graft modification.
  • an unsaturated compound having an epoxy group may be radically copolymerized with an olefin or the like.
  • One type or two or more types of polyolefin resins can be used, and a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group may be used in combination.
  • polystyrene resin having an acid anhydride group a polybutene resin having an acid anhydride group and a polypropylene resin having an acid anhydride group are preferable. Further, as the polyolefin resin having an epoxy group, a polybutene resin having an epoxy group and a polypropylene resin having an epoxy group are preferable.
  • the concentration of acid anhydride groups in the polyolefin resin having acid anhydride groups is preferably 0.05 to 10 mmol/g, more preferably 0.1 to 5 mmol/g.
  • the concentration of acid anhydride groups is obtained from the acid value defined as the number of mg of potassium hydroxide required to neutralize the acid present in 1 g of resin, according to JIS K 2501.
  • the amount of the polyolefin resin having an acid anhydride group in the polyolefin resin is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
  • the concentration of epoxy groups in the polyolefin resin having epoxy groups is preferably 0.05 to 10 mmol/g, more preferably 0.1 to 5 mmol/g.
  • the epoxy group concentration is determined from the epoxy equivalent obtained based on JIS K 7236-1995.
  • the amount of the polyolefin resin having an epoxy group in the polyolefin resin is preferably 0 to 70% by mass, more preferably 10 to 50% by mass.
  • the polyolefin resin preferably contains both a polyolefin resin having an acid anhydride group and a polyolefin resin having an epoxy group, from the viewpoint of imparting excellent physical properties such as sealing performance.
  • a polyolefin resin can react with an acid anhydride group and an epoxy group by heating to form a crosslinked structure, thereby forming a sealing layer with excellent sealing performance.
  • Formation of the crosslinked structure can be performed after sealing, but if the object to be sealed is sensitive to heat, such as an electronic device, it is sealed using a resin sheet, and the crosslinked structure is formed when manufacturing the resin sheet. It is desirable to form it.
  • the ratio of the polyolefin resin having an acid anhydride group to the polyolefin resin having an epoxy group is not particularly limited as long as an appropriate crosslinked structure can be formed.
  • group is preferably 100:10 to 100:400, more preferably 100:25 to 100:350, particularly preferably 100:40 to 100:300.
  • a polyolefin resin having an epoxy group in the resin composition layer used in the resin sheet of the present invention, a polyolefin resin having a functional group (excluding acid anhydride groups) that can react with an epoxy group is used.
  • the functional group include a hydroxyl group, a phenolic hydroxyl group, an amino group, and a carboxy group.
  • a polyolefin resin having an acid anhydride group when used, a polyolefin resin having an acid anhydride group is used, a polyolefin resin having a functional group (excluding epoxy groups) that can react with the acid anhydride group. may be used.
  • the functional group include a hydroxyl group, a primary or secondary amino group, a thiol group, and an oxetane group.
  • the number average molecular weight of the polyolefin resin is not particularly limited, but from the viewpoint of providing good varnish coating properties of the resin composition and good compatibility with other components in the resin composition, the number average molecular weight is 1,000, 000 or less, more preferably 750,000 or less, even more preferably 500,000 or less, even more preferably 400,000 or less, even more preferably 300,000 or less, particularly preferably 200,000 or less, 150,000 or less The following are most preferred.
  • the number average molecular weight is set to 1,000. It is preferably at least 2,000, more preferably at least 2,000.
  • the number average molecular weight in the present invention is measured by gel permeation chromatography (GPC) method (in terms of polystyrene). Specifically, the number average molecular weight by the GPC method was determined using LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Corporation as a column. It can be measured using toluene or the like as a phase at a column temperature of 40° C., and calculated using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the polyolefin resin in the present invention is preferably amorphous from the viewpoint of suppressing a decrease in fluidity due to thickening of the varnish.
  • amorphous means that the polyolefin resin does not have a clear melting point; for example, when the melting point of the polyolefin resin is measured by DSC (differential scanning calorimetry), no clear peak is observed. things can be used.
  • polypropylene resin As a specific example of the polypropylene resin, "T-YP341” manufactured by Seiko PMC (glycidyl methacrylate modified propylene-butene random copolymer, amount of butene units per 100 mass% total of propylene units and butene units: 29 mass%, Epoxy group concentration: 0.638 mmol/g, number average molecular weight: 155,000), "T-YP279” manufactured by Seiko PMC (maleic anhydride modified propylene-butene random copolymer, total of propylene units and butene units 100 mass Amount of butene units per %: 36% by mass, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 35,000), "T-YP276” manufactured by Seiko PMC (glycidyl methacrylate modified propylene-butene random Copolymer, amount of butene units per 100% by mass of
  • polybutene-based resins include "HV-1900” (polybutene, number average molecular weight: 2,900) manufactured by ENEOS (formerly known as “JXTG Energy”), and "HV-300M” (maleic anhydride) manufactured by Toho Chemical Industry Co., Ltd.
  • Acid-modified liquid polybutene (modified product of "HV-300” (number average molecular weight: 1,400)), number average molecular weight: 2,100, number of carboxy groups constituting acid anhydride groups: 3.2 pieces/1 Molecule, acid value: 43.4 mgKOH/g, acid anhydride group concentration: 0.77 mmol/g), BASF "Opanol B100” (polyisobutylene, viscosity average molecular weight: 1,110,000), BASF " N50SF” (polyisobutylene, viscosity average molecular weight: 400,000).
  • styrene-isobutylene copolymer examples include "SIBSTAR T102” manufactured by Kaneka Corporation (styrene-isobutylene-styrene block copolymer, number average molecular weight: 100,000, styrene content: 30% by mass), manufactured by Seiko PMC Corporation "T-YP757B” (maleic anhydride modified styrene-isobutylene-styrene block copolymer, acid anhydride group concentration: 0.464 mmol/g, number average molecular weight: 100,000), "T-YP766” manufactured by Seiko PMC Co., Ltd.
  • the content of the polyolefin resin in the resin composition layer used in the resin sheet of the present invention is not particularly limited. However, from the viewpoint of sealing performance and handleability of the resin composition layer, the content is preferably 5% by mass or more, more preferably 10% by mass, based on 100% by mass of the nonvolatile content of the resin composition layer. % or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.
  • Epoxy resin The epoxy resin can be used without any restriction as long as it has two or more epoxy groups per molecule on average.
  • the epoxy resin include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, biphenyl epoxy resin, biphenylaralkyl epoxy resin, naphthol epoxy resin, naphthalene epoxy resin, bisphenol F epoxy resin, and phosphorus-containing epoxy resin.
  • Epoxy resins bisphenol S-type epoxy resins, aromatic glycidylamine-type epoxy resins (e.g., tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, diglycidyl-toluidine, diglycidylaniline, etc.), alicyclic epoxy resins, aliphatic Chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having a butadiene structure, diglycidyl ether of bisphenol, diglycidyl ether of naphthalene diol, di-glycidyl ether of naphthalene diol, Examples include glycidyl etherified products, diglycidyl etherified products of alcohols, and alkyl-substituted products, halides, and hydrogenated products of these epoxy resins.
  • the number of epoxy resins
  • the epoxy equivalent of the epoxy resin is preferably 50 to 5,000, more preferably 50 to 3,000, still more preferably 80 to 2,000, and even more preferably 100 to 1,000, even more preferably 120 to 1,000, particularly preferably 140 to 300.
  • epoxy equivalent is the number of grams (g/eq) of a resin containing 1 gram equivalent of epoxy groups, and is measured according to the method specified in JIS K 7236. Further, the weight average molecular weight of the epoxy resin is preferably 5,000 or less.
  • the epoxy resin may be either liquid or solid, and both liquid and solid epoxy resins may be used.
  • liquid and solid refer to the state of the epoxy resin at normal temperature (25° C.) and normal pressure (1 atm).
  • the amount of epoxy resin is not particularly limited. When using an epoxy resin, the amount thereof is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 50 to 65% by mass, based on 100% by mass of nonvolatile content of the resin composition layer. .
  • the resin composition layer used in the resin sheet of the present invention may contain a hygroscopic filler.
  • the hygroscopic filler include calcium oxide, hydrotalcite, magnesium oxide, and molecular sieve. Only one type of hygroscopic filler may be used, or two or more types may be used in combination.
  • the content of the hygroscopic filler is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and even more preferably 0 to 20% by mass, based on 100% by mass of the nonvolatile content of the resin composition layer. %.
  • the hygroscopic filler is preferably calcium oxide.
  • Hydrotalcite can be classified into uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite.
  • Uncalcined hydrotalcite is a metal hydroxide having a layered crystal structure, such as natural hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3.4H 2 O), for example, It consists of a basic skeleton layer [Mg 1-X Al X (OH) 2 ] X+ and an intermediate layer [(CO 3 ) X/2 ⁇ mH 2 O] X- .
  • Uncalcined hydrotalcite is a concept that includes hydrotalcite-like compounds such as synthetic hydrotalcite. Examples of hydrotalcite-like compounds include those represented by the following formula (I) and the following formula (II).
  • M 2+ represents a divalent metal ion such as Mg 2+ or Zn 2+
  • M 3+ represents a trivalent metal ion such as Al 3+ or Fe 3+
  • a n- represents CO 3 2 - represents an n-valent anion such as Cl - , NO 3 -, etc., where 0 ⁇ x ⁇ 1, 0 ⁇ m ⁇ 1, and n is a positive number.
  • M 2+ is preferably Mg 2+
  • M 3+ is preferably Al 3+
  • a n- is preferably CO 3 2- .
  • M 2+ represents a divalent metal ion such as Mg 2+ or Zn 2+
  • a n- represents an n-valent anion such as CO 3 2- , Cl - , NO 3 - , etc.
  • x is , is a positive number of 2 or more
  • z is a positive number of 2 or less
  • m is a positive number
  • n is a positive number.
  • M 2+ is preferably Mg 2+ and A n- is preferably CO 3 2- .
  • Semi-fired hydrotalcite is a metal hydroxide obtained by firing unfired hydrotalcite and has a layered crystal structure in which the amount of interlayer water has decreased or disappeared. If explained using a compositional formula, "interlayer water” refers to "H 2 O" described in the compositional formula of the above-mentioned unfired natural hydrotalcite and hydrotalcite-like compound.
  • calcined hydrotalcite is obtained by calcining uncalcined hydrotalcite or semi-calcined hydrotalcite, and refers to a metal oxide having an amorphous structure in which not only interlayer water but also hydroxyl groups have disappeared through condensation and dehydration.
  • Uncalcined hydrotalcite, semi-calcined hydrotalcite and calcined hydrotalcite can be distinguished by their saturated water absorption.
  • the saturated water absorption rate of the semi-calcined hydrotalcite is 1% by mass or more and less than 20% by mass.
  • the saturated water absorption of unfired hydrotalcite is less than 1% by mass, and the saturated water absorption of calcined hydrotalcite is 20% by mass or more.
  • “Saturated water absorption rate” means weighing 1.5 g of a measurement sample (for example, semi-calcined hydrotalcite) on a balance, measuring the initial mass, and then measuring the temperature at atmospheric pressure, 60°C, 90% RH (relative humidity).
  • the mass increase rate with respect to the initial mass when left standing for 200 hours in a small environmental test chamber (SH-222 manufactured by ESPEC) set to Saturated water absorption rate (mass%) 100 ⁇ (mass after moisture absorption - initial mass)/initial mass (i) It can be found by
  • the saturated water absorption rate of the semi-calcined hydrotalcite is preferably 3% by mass or more and less than 20% by mass, more preferably 5% by mass or more and less than 20% by mass.
  • uncalcined hydrotalcite, semi-calcined hydrotalcite, and calcined hydrotalcite can be distinguished by the thermogravimetric reduction rate measured by thermogravimetric analysis.
  • the thermogravimetric reduction rate at 280°C of the semi-calcined hydrotalcite is less than 15% by mass, and the thermogravimetric reduction rate at 380°C is 12% by mass or more.
  • the thermogravimetric loss rate at 280°C of unfired hydrotalcite is 15% by mass or more, and the thermogravimetric loss rate at 380°C of calcined hydrotalcite is less than 12% by mass.
  • thermogravimetric reduction rate 100 x (mass before heating - mass when the predetermined temperature is reached) / mass before heating (ii).
  • unfired hydrotalcite, semi-fired hydrotalcite, and calcined hydrotalcite can be distinguished by peaks and relative intensity ratios measured by powder X-ray diffraction.
  • Semi-calcined hydrotalcite shows a split peak in the vicinity of 2 ⁇ of 8 to 18 degrees in powder X-ray diffraction, or a peak with a shoulder due to the synthesis of the two peaks, and a peak that appears on the lower angle side or a peak with a shoulder.
  • uncalcined hydrotalcite has only one peak around 8 to 18 degrees, or the relative intensity ratio of the diffraction intensity of the peak or shoulder appearing on the low angle side and the peak or shoulder appearing on the high angle side is the same as above. Out of range. Calcined hydrotalcite does not have a characteristic peak in the region of 8° to 18° and has a characteristic peak at 43°.
  • Powder X-ray diffraction measurements were performed using a powder X-ray diffractometer (manufactured by PANalytical, Empyrean) using an anticathode CuK ⁇ (1.5405 ⁇ ), voltage: 45 V, current: 40 mA, sampling width: 0. 0260°, scanning speed: 0.0657°/s, and measurement diffraction angle range (2 ⁇ ): 5.0131 to 79.9711°.
  • peak search use the peak search function of the software attached to the diffraction device, and use the following methods: "Minimum significance: 0.50, minimum peak tip: 0.01°, maximum peak tip: 1.00°, peak base width: 2 .00°, Method: Minimum value of second-order differential".
  • the BET specific surface area of the semi-calcined hydrotalcite is preferably 1 to 250 m 2 /g, more preferably 5 to 200 m 2 /g. These BET specific surface areas can be calculated using the BET multi-point method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM Model 1210 manufactured by Mountech).
  • the particle size of the semi-fired hydrotalcite is preferably 1 to 1,000 nm, more preferably 10 to 800 nm. These particle diameters are the median diameters of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).
  • the semi-fired hydrotalcite one that has been surface treated with a surface treatment agent can be used.
  • a surface treatment agent used for surface treatment for example, higher fatty acids, alkylsilanes, silane coupling agents, etc. can be used, and higher fatty acids and alkylsilanes are particularly preferred.
  • One type or two or more types of surface treatment agents can be used.
  • a commercially available semi-calcined hydrotalcite can be used.
  • Commercially available products include, for example, "DHT-4C” and “DHT-4A-2” manufactured by Kyowa Chemical Industry Co., Ltd.
  • Calcium oxide products can be used.
  • Commercially available products include, for example, “QC-X” manufactured by Inoue Lime Industry Co., Ltd.; “Moistop #10” manufactured by Sankyo Seifun Co., Ltd.; “HAL-G”, “HAL-J”, and “HAL-F” manufactured by Yoshizawa Lime Industry Co., Ltd. “; “CaO Nano Powder” manufactured by Filgen.
  • a mixture containing calcium oxide may be used as a hygroscopic filler.
  • a mixture includes, for example, calcined dolomite (a mixture containing calcium oxide and magnesium oxide).
  • Calcined dolomite can be obtained from Yoshizawa Lime Industries Co., Ltd., for example.
  • the particle size of calcium oxide and the particle size of the mixture containing calcium oxide are determined in order to prevent calcium oxide, etc. from damaging electronic devices during the sealing process, and In order to increase the interfacial bonding strength between calcium oxide etc. and the resin, the thickness is preferably 0.03 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and still more preferably 0.1 to 3 ⁇ m.
  • These particle diameters are the median diameters of the particle size distribution when the particle size distribution is created on a volume basis by laser diffraction scattering particle size distribution measurement (JIS Z 8825).
  • Calcium oxide is a hygroscopic inorganic particle that is essential for exhibiting high moisture barrier properties. Calcium oxide, unlike semi-calcined hydrotalcite, irreversibly absorbs moisture, so once it absorbs moisture, its moisture absorption performance decreases. Therefore, it is necessary to form a resin composition layer at high temperature and in a short time.
  • the base material is a first film that is a plastic film with two or more layers, each layer has a different linear thermal expansion coefficient, so that the base material warps more significantly under high temperature exposure.
  • the resin composition layer used in the resin sheet of the present invention may further contain a tackifier.
  • a tackifier also called a tackifier, is a component that imparts tackiness to the composition.
  • Tackifiers are not particularly limited, and include terpene resins, modified terpene resins (hydrogenated terpene resins, terpene-phenol copolymer resins, aromatic modified terpene resins, etc.), coumaron resins, indene resins, petroleum resins (fatty preferred are petroleum resins from the group petroleum group, hydrogenated alicyclic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene petroleum resins, and their hydrides, etc. used.
  • terpene resins include YS Resin PX and YS Resin PXN (both manufactured by Yasuhara Chemical Co., Ltd.), and examples of aromatic modified terpene resins include YS Resin TO and TR series (both manufactured by Yasuhara Chemical Co., Ltd.).
  • terpene resins include Clearon P, Clearon M, and Clearon K series (all manufactured by Yasuhara Chemical Co., Ltd.), and examples of terpene-phenol copolymer resins include YS Polystar 2000, Polystar U, Polystar T, Polystar S, and Mighty Ace G (all manufactured by Yasuhara Chemical Co., Ltd.).
  • Hydrogenated alicyclic petroleum resins include Escorez 5300 series and 5600 series (both manufactured by ExxonMobil), and aromatic petroleum resins include ENDEX155 (manufactured by Eastman).
  • Examples of the aliphatic aromatic copolymer petroleum resin include Quintone D100 (manufactured by Nippon Zeon Co., Ltd.), and examples of the alicyclic petroleum resin include Quintone 1325 and Quintone 1345 (both manufactured by Nippon Zeon Co., Ltd.).
  • Examples of the saturated hydrocarbon resin include Alcon P100, Alcon P125, Alcon P140, and TFS13-030 (all manufactured by Arakawa Chemical Co., Ltd.).
  • the softening point of the tackifier is preferably 50 to 200°C, more preferably 90 to 180°C, from the viewpoint that the resin composition layer is softened in the resin composition layer lamination step and has the desired heat resistance. More preferably, the temperature is 100 to 150°C. Note that the softening point is measured by the ring and ball method according to JIS K2207.
  • the tackifiers may be used alone or in combination of two or more.
  • the content of the tackifier in the resin composition layer is not particularly limited. However, from the viewpoint of maintaining good sealing performance of the resin composition layer, when using a tackifier, the content thereof should be 50% by mass or less based on 100% by mass of non-volatile content of the resin composition layer. is preferable, 40% by mass or less is more preferable, and even more preferably 30% by weight or less. On the other hand, from the viewpoint of having sufficient adhesiveness, when using a tackifier, its content is preferably 5% by mass or more, and 10% by mass or more, based on 100% by mass of the nonvolatile content of the resin composition layer. is even more preferable.
  • Petroleum resins are preferred from the viewpoints of adhesiveness, sealing performance, transparency, etc. of the resin composition layer.
  • Examples of petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins. From the viewpoint of adhesiveness, sealing performance, compatibility, etc. of the resin composition layer, aromatic petroleum resins, aliphatic aromatic copolymer petroleum resins, and alicyclic petroleum resins are more preferred. Furthermore, from the viewpoint of improving transparency, alicyclic petroleum resins are particularly preferred.
  • the alicyclic petroleum resin may also be a hydrogenated aromatic petroleum resin.
  • the hydrogenation rate of the alicyclic petroleum resin is preferably 30 to 99%, more preferably 40 to 97%, even more preferably 50 to 90%. If the hydrogenation rate is too low, there will be a tendency for the problem of decreased transparency due to coloring, and if the hydrogenation rate is too high, production costs will tend to increase.
  • the hydrogenation rate can be determined from the ratio of the 1 H-NMR peak intensities of hydrogen in the aromatic ring before and after hydrogenation.
  • alicyclic petroleum resin cyclohexane ring-containing hydrogenated petroleum resins and dicyclopentadiene hydrogenated petroleum resins are particularly preferred. Petroleum resins may be used alone or in combination of two or more.
  • the number average molecular weight Mn of the petroleum resin is preferably 100 to 2,000, more preferably 700 to 1,500, even more preferably 500 to 1,000.
  • the resin composition layer used in the resin sheet of the present invention may contain a curing agent and/or a curing accelerator (preferably a curing accelerator). Only one type of curing agent and curing accelerator may be used, or two or more types may be used in combination.
  • the curing agent include imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, organic phosphine compounds, and primary and secondary amine compounds.
  • the curing accelerator include imidazole compounds, tertiary and quaternary amine compounds, dimethylurea compounds, and organic phosphine compounds.
  • the tertiary/quaternary amine compounds used as the curing agent and/or curing accelerator in the present invention are not particularly limited, but include, for example, quaternary ammonium salts such as tetramethylammonium bromide and tetrabutylammonium bromide; DBU ( 1,8-diazabicyclo[5.4.0]undecene-7), DBN (1,5-diazabicyclo[4.3.0]nonene-5), DBU-phenol salt, DBU-octylate, DBU-p -Diazabicyclo compounds such as toluenesulfonate, DBU-formate, DBU-phenol novolak resin salt; benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol (TAP) ) and their salts; dimethylurea compounds such as aromatic dimethylurea and aliphatic dimethylurea; and the like.
  • Examples of primary/secondary amine compounds as curing agents in the present invention include aliphatic amines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, , 3-bisaminomethylcyclohexane, dipropylene diamine, diethylaminopropylamine, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, N-aminoethylpiverazine which is an alicyclic amine, Examples include 1,4-bis(3-aminopropyl)piperazine, aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, die
  • dimethylurea compound as a curing agent and/or curing accelerator in the present invention examples include DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea), U-CAT3512T (manufactured by San-Apro) Aromatic dimethylureas such as U-CAT3503N (manufactured by San-Apro Co., Ltd.) and aliphatic dimethylureas may be mentioned. Among them, aromatic dimethylurea is preferably used from the viewpoint of curability.
  • Examples of the organic phosphine compound as a curing agent and/or curing accelerator in the present invention include triphenylphosphine, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tri-tert-butylphosphonium tetraphenyl Examples include borate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, triphenylphosphinetriphenylborane, and the like.
  • Specific examples of the organic phosphine compound include TPP, TPP-MK, TPP-K, TTBuP-K, TPP-SCN, and TPP-S (manufactured by Hokko Chemical Industry Co., Ltd.).
  • the total content of the curing agent and curing accelerator in the resin composition layer is not particularly limited, but from the viewpoint of preventing a decrease in transparency etc. of the sealing layer (resin composition layer), It is preferably 5% by mass or less, more preferably 1% by mass or less, based on 100% by mass of nonvolatile content.
  • the total amount is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, based on 100% by mass of the nonvolatile content of the resin composition layer.
  • the content of the curing accelerator in the resin composition layer is not particularly limited, but from the viewpoint of preventing deterioration of the transparency etc. of the sealing layer (resin composition layer), the nonvolatile content of the resin composition layer is 100% by mass. %, preferably 5% by mass or less, more preferably 1% by mass or less. On the other hand, from the viewpoint of suppressing tackiness of the sealing layer, the content is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, based on 100% by mass of the nonvolatile content of the resin composition layer. .
  • the resin composition layer used in the resin sheet of the present invention may further contain a plasticizer.
  • a plasticizer By using a plasticizer, the flexibility and moldability of the resin composition layer can be improved.
  • the plasticizer is not particularly limited, but materials that are liquid at room temperature are preferably used. Specific examples of plasticizers include paraffinic process oil, naphthenic process oil, liquid paraffin, polyethylene wax, polypropylene wax, mineral oil such as petrolatum, castor oil, cottonseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, and olive oil. and liquid poly ⁇ -olefins such as vegetable oils such as liquid polybutene, hydrogenated liquid polybutene, liquid polybutadiene, and hydrogenated liquid polybutadiene.
  • liquid poly ⁇ -olefins are preferable, and liquid polybutadiene is particularly preferable.
  • the liquid poly ⁇ -olefin preferably has a low molecular weight from the viewpoint of adhesion, and preferably has a weight average molecular weight of 500 to 5,000, more preferably 1,000 to 3,000.
  • plasticizers may be used alone or in combination of two or more.
  • liquid here refers to the state of the plasticizer at room temperature (25° C.).
  • its content is preferably 50% by mass or less based on 100% by mass of the nonvolatile content of the resin composition layer, from the viewpoint of not adversely affecting electronic devices.
  • the resin composition layer used in the resin sheet of the present invention may optionally contain components other than the above-mentioned components to the extent that the effects of the present invention are not impaired.
  • Such components include, for example, resins other than the above-mentioned polyolefin resins and epoxy resins (e.g., urethane resins, acrylic resins, polyamide resins, etc.); thickeners such as olben and bentone; silicone-based, fluorine-based, and Examples include molecular antifoaming agents or leveling agents; adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds, and porphyrin compounds; and the like.
  • the thickness of the resin composition layer used in the resin sheet of the present invention is preferably 3 to 100 ⁇ m, more preferably 5 to 90 ⁇ m, and even more preferably 10 to 80 ⁇ m.
  • the thickness of the resin composition layer is less than 3 ⁇ m, the adhesiveness of the resin sheet decreases and sealing cannot be achieved. If it exceeds 100 ⁇ m, there is a concern that residues of the organic solvent used in the resin composition varnish will be generated during formation of the resin sheet, and this may affect electronic devices during sealing.
  • One method for manufacturing the resin sheet of the present invention includes the steps of forming a resin composition layer on the release layer of the first film and laminating the second film or glass plate to the resin composition layer.
  • the method for producing a resin sheet of the present invention includes a step of forming a resin composition layer on the release layer of the first film, and a step of laminating the second film to the resin composition layer. including.
  • the resin composition layer can be formed by applying a resin composition varnish onto the release layer of the first film using a die coater or the like and drying it.
  • a resin composition varnish is prepared by mixing components of a resin composition and an organic solvent using a kneading roller, a rotary mixer, or the like.
  • the nonvolatile content of the resin composition varnish is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; cellosolve, butyl carbitol, etc. carbitols; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; and aromatic mixed solvents such as solvent naphtha.
  • ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone
  • acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate
  • aromatic mixed solvent products examples include “Swazol” (manufactured by Maruzen Sekiyu Co., Ltd.) and “Ipsol” (manufactured by Idemitsu Kosan Co., Ltd.). Only one type of organic solvent may be used, or two or more types may be used in combination.
  • the drying temperature and drying time can be appropriately set by those skilled in the art depending on the components and organic solvent used.
  • the drying temperature is 80-170°C and the drying time is 3-60 minutes.
  • the drying temperature is preferably 80 to 100°C, and the drying time is preferably 5 to 90 minutes.
  • the drying temperature is preferably 80 to 170°C, and the drying time is preferably 5 to 60 minutes.
  • Step of laminating the second film or glass plate to the resin composition layer After forming a resin composition layer on the release layer of the first film, by laminating a second film (preferably a barrier layer of the second film) or a glass plate to the obtained resin composition layer, A resin sheet can be manufactured.
  • known equipment such as a roll laminator, press machine, vacuum pressure laminator, etc. can be used.
  • the conditions for lamination (temperature, pressure, time, etc.) can be appropriately set by those skilled in the art.
  • the second film is a film that is incorporated into the electronic device as a barrier film when the electronic device is sealed, and has a water vapor permeability of less than 0.01 (g/m 2 /24hr) (i.e., a highly permeable film). humidity).
  • a highly moisture permeable barrier film is used as a support for varnish coating, it tends to warp when heated, and there is also a risk that the barrier layer will be damaged during coating and the performance for sealing electronic devices will deteriorate. occurs.
  • AOI detects air bubbles in the base material of the laminate structure, and thus the suitability for AOI evaluation of the resin composition layer is low.
  • the barrier layer is a metal foil
  • the resin composition layer cannot be evaluated by AOI because it has no light transmittance.
  • glass plates are difficult to apply to coating equipment because they are brittle if they are thin and difficult to form into rolls if they are thick, making it difficult to use them as a support for coating.
  • Another method for producing the resin sheet of the present invention includes a step of forming a resin composition layer on the release layer of the first film, a step of laminating a third film to the resin composition layer, and a step of sealing an electronic device.
  • the third film includes a step of peeling off the third film and laminating the second film or the glass plate to the resin composition layer, and the third film has a release layer and has a water vapor permeability of 0.01 (g /m 2 /24hr) or more and 1 (g/m 2 /24hr) or less, and the adhesive strength with the resin composition layer of the third film is lower than the adhesive strength with the resin composition layer of the first film.
  • the method for producing a resin sheet of the present invention includes a step of forming a resin composition layer on the release layer of the first film, and a step of laminating a third film to the resin composition layer.
  • the third film is peeled off and the second film is bonded to the resin composition layer, the third film has a release layer, and the water vapor permeability thereof is 0. .01 (g/m 2 /24hr) or more and 1 (g/m 2 /24hr) or less
  • the adhesive strength with the resin composition layer of the third film is the adhesive strength with the resin composition layer of the first film. lower than.
  • a resin sheet precursor can be manufactured by laminating the mold release layer of the third film to the obtained resin composition layer.
  • known equipment such as a roll laminator, press machine, vacuum pressure laminator, etc. can be used.
  • the conditions for lamination (temperature, pressure, time, etc.) can be appropriately set by those skilled in the art.
  • Peeling of the third film can be performed by methods known to those skilled in the art.
  • the adhesive strength with the resin composition layer of the third film is lower than the adhesive strength with the resin composition layer of the first film (i.e., the peeling force of the release layer of the third film is lower than the adhesive strength with the resin composition layer of the first film). layer peeling force), the third film is peeled off in preference to the first film.
  • a resin sheet can be manufactured by laminating a second film (preferably, with the barrier layer side of the second film in contact with the resin composition layer) or a glass plate to the exposed resin composition layer.
  • known equipment such as a roll laminator, press machine, vacuum pressure laminator, etc. can be used.
  • the conditions for lamination (temperature, pressure, time, etc.) can be appropriately set by those skilled in the art.
  • the release force of the release layer of the third film is smaller than the release force of the release layer of the first film.
  • the difference between the release force of the release layer of the third film and the release force of the release layer of the first film [Peel force of the release layer of the first film (mN/25 mm) - the release force of the release layer of the third film]
  • the peeling force (mN/25mm) of the release layer is not particularly limited as long as the third film is peeled off preferentially than the first film, but is preferably 1 to 200mN/25mm, more preferably is 1 to 150 mN/25 mm, more preferably 1 to 100 mN/25 mm.
  • the peeling force of the mold release layer is a value measured by a method described in Examples described later.
  • the present invention also provides a resin sheet precursor having a first film, a resin composition layer, and a third film, wherein the resin composition layer is present between the first film and the third film, and the resin composition layer is present between the first film and the third film.
  • 1 film has a single layer plastic film as a base material, a barrier layer formed on the plastic film surface (preferably one surface of the plastic film), and a barrier layer surface or barrier layer not in contact with the plastic film.
  • the first film is a transparent film, and the first film has a water vapor permeability of 0.
  • the third film has a release layer, and the water vapor permeability of the third film is 0.01 (g/m 2 /24hr). /24hr) or more and 1 (g/m 2 /24hr) or less, and the mold release layer of the first film and the mold release layer of the third film are in contact with the resin composition layer.
  • the first film and resin composition layer used in the resin sheet precursor of the present invention are as explained in the resin sheet of the present invention above.
  • the third film used in the resin sheet precursor of the present invention has a base material and a release layer, and preferably further includes a barrier layer formed on the base material surface (preferably one surface of the base material).
  • the base material means a portion of the film other than the barrier layer.
  • the release layer in the third film is formed on the base material surface (preferably one surface of the base material) when it does not have a barrier layer, and is formed on the barrier layer surface that is not in contact with the base material and the barrier layer when it has a barrier layer. It may be formed on any surface of the base material that does not have a barrier layer, and is preferably formed on the surface of the base material that does not have a barrier layer.
  • the base material and barrier layer are as explained in the second film of the resin sheet of the present invention above.
  • the mold release layer is as explained in the first film of the resin sheet of the present invention.
  • the WVTR of the third film is preferably 0.01 (g/m 2 /24hr) or more and 0.8 (g/m 2 /24hr) or less. This WVTR is a value measured by a method described in Examples described later. Since the third film is peeled off and discarded before sealing the electronic device, within this range, it is possible to simultaneously suppress water absorption of the resin composition layer during storage and reduce costs.
  • the third film having a WVTR of 0.01 (g/m 2 /24 hr) or more and 1 (g/m 2 /24 hr) or less has silicon oxide (silica), aluminum oxide, or oxide on the surface of the base material as a barrier layer, for example.
  • the third film manufactured by such a method is a transparent film.
  • a commercially available product may be used as the third film.
  • Commercial products of the third film include, for example, "Clarista CI” manufactured by Kuraray Co., Ltd., "Tech Barrier HX”, “Tech Barrier LX” and “Tech Barrier L” manufactured by Mitsubishi Plastics, and "IB-PET” manufactured by Dai Nippon Printing Co., Ltd. -PXB” and the "GL, GX series” manufactured by Toppan Printing Co., Ltd.
  • the thickness of the third film is preferably 20 to 100 ⁇ m, more preferably 20 to 90 ⁇ m, and even more preferably 20 to 80 ⁇ m. If the thickness of the third film is less than 20 ⁇ m, warping will occur during the process of forming the release layer. If it exceeds 100 ⁇ m, the obtained resin sheet cannot be wound up into a roll.
  • the resin sheet precursor of the present invention is used as the resin sheet precursor in the above [Resin sheet manufacturing method 2]. Therefore, the third film is peeled off before bonding the second film or the glass plate to the resin composition layer, and functions as a cover film.
  • the resin sheet of the present invention can be used for sealing electronic devices.
  • the electronic device is more preferably an electronic device sensitive to moisture, such as an organic EL device or a solar cell. That is, the resin sheet of the present invention can be particularly suitably used for sealing electronic devices sensitive to moisture, such as organic EL devices and solar cells.
  • Electronic devices can be sealed using the resin sheet of the present invention. Specifically, after peeling off the first film of the resin sheet and exposing the resin composition layer, the exposed resin composition layer is placed on the electronic device side (i.e., the resin composition layer contacts the electronic device). ), the second film or glass plate and the resin composition layer are laminated on the electronic device, the resin composition layer is cured as described below, and the electronic device is sealed with the second film or the glass plate and the resin composition layer. Stop.
  • the lamination method may be a batch method or a continuous method using rolls. In this way, an electronic device sealed with the resin sheet of the present invention can be manufactured.
  • the third film of the resin sheet precursor is peeled off, and a second film or a mold release layer that does not have a release layer and has a water vapor permeability of less than 0.01 (g/m 2 /24hr) is prepared.
  • a glass plate that does not contain the resin composition layer to the resin composition layer to obtain a resin sheet having the first film, the resin composition layer and the second film or the glass plate
  • the first film of the resin sheet is peeled off and the resin composition layer is laminated. It is also possible to laminate the second film or the glass plate and the resin composition layer on the electronic device with the layer facing the electronic device side, and then seal the electronic device with the second film or the glass plate and the resin composition layer.
  • the lamination method may be a batch method or a continuous method using rolls.
  • Curing of the resin composition layer is usually carried out by thermal curing.
  • examples of such means include heating using a hot air circulation oven, an infrared heater, a heat gun, a high frequency induction heating device, and compression using a heat tool.
  • the curing temperature is preferably 50°C or higher, more preferably 55°C or higher, and the curing time is 10 minutes. or more is preferable, and 20 minutes or more is more preferable.
  • Table 1 lists the plastic films (Films A to H) used in the following Examples and Comparative Examples, their WVTR, etc. measured by the method described below.
  • Polyester adhesive tape NO. manufactured by Nitto Denko Corporation was applied to the release layer surface. 31B were bonded together, pressed together with a rubber roller, and left at room temperature for 20 hours, the T-peel strength (release layer peel force [mN/25 mm]) was measured at a peel rate of 300 mm/min.
  • the total light transmittance (%) of the plastic films listed in Table 1 was measured using HZ-V3 manufactured by Suga Test Instruments Co., Ltd. in accordance with JIS K7361-1. Note that the measurement light was a D65 light source, and the measurement was performed using air as a reference.
  • a mixture was obtained by dispersion.
  • the resulting mixture was added with 200 parts by mass of a 20% by mass Swasol solution of a glycidyl methacrylate-modified polypropylene-polybutene copolymer ("T-YP341" manufactured by Seiko PMC) and an anionic polymerizable curing agent (2,4,6-tris( 0.5 parts by mass of dimethylaminomethyl)phenol) and 16 parts by mass of toluene were blended, and the resulting mixture was uniformly dispersed with a high-speed rotating mixer to obtain polyolefin resin composition varnish A.
  • T-YP341 glycidyl methacrylate-modified polypropylene-polybutene copolymer
  • an anionic polymerizable curing agent (2,4,6-tris( 0.5 parts by mass of dimethylaminomethyl)phenol
  • Polyolefin resin composition varnish B It was prepared in the same manner as polyolefin resin composition varnish A except that the semi-calcined hydrotalcite was changed to calcium oxide ("HAL-G" manufactured by Yoshizawa Lime Industries Co., Ltd.).
  • Epoxy resin composition varnish C 56 parts by mass of liquid bisphenol A epoxy resin (JER828EL manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: approximately 185), 1.2 parts by mass of silane coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd., talc powder (Nippon Talc Co., Ltd.) After kneading 2 parts by mass of "FG15” manufactured by Kyowa Kagaku Kogyo Co., Ltd. and 15 parts by mass of semi-calcined hydrotalcite (DHT-4A-2 manufactured by Kyowa Chemical Industry Co., Ltd.), the mixture was dispersed in a three-roll mill to obtain a mixture.
  • silane coupling agent KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.
  • talc powder Nippon Talc Co., Ltd.
  • Epoxy resin composition varnish C was obtained by blending and uniformly dispersing with a high-speed rotating mixer.
  • Example 1 Film A was used as the first film and film H was used as the second film.
  • the polyolefin resin composition varnish A obtained in Production Example 1 was uniformly applied to the release layer surface of the first film using a die coater, and heated at 130° C. for 60 minutes to obtain a resin composition with a thickness of 20 ⁇ m.
  • a film having a resin composition layer was obtained (residual solvent amount in resin composition layer: about 1% by mass).
  • the resin composition layer of the obtained film and the barrier layer of the second film were bonded together and wound up into a roll so that they were in contact with each other.
  • the rolled resin sheet was slit into a width of 450 mm to obtain a resin sheet with a size of 450 x 300 mm.
  • Examples 2 to 4 and Comparative Examples 1 to 4 A resin composition was prepared by using the films shown in Table 2 below as the first film or the second film, and using the polyolefin resin composition varnishes A and B or epoxy resin composition varnish C obtained in Production Examples 1 to 3. Resin sheets of Examples 2 to 4 and Comparative Examples 1 to 4 were produced basically in the same manner as in Example 1 except that the layers were formed (the thickness of the resin composition layer was 20 ⁇ m). The composition of the obtained resin sheet is shown in Table 2 below. In addition, in Example 3 using epoxy resin composition varnish C, after coating the epoxy resin composition varnish C, it was dried at 80 to 100 °C (average 90 °C) for 5 minutes to form a resin composition layer ( Amount of residual solvent in the resin composition layer: approximately 2% by mass).
  • Examples 5-6 and Comparative Examples 5-8 Basically, except that the films shown in Table 3 below were used as the first film or the third film, and the polyolefin resin composition varnish A obtained in Production Example 1 was used to form the resin composition layer.
  • Resin sheet precursors of Examples 5 to 6 and Comparative Examples 5 to 8 were produced in the same manner as in Example 1 (resin composition layer thickness: 20 ⁇ m). The composition of the obtained resin sheet precursor is shown in Table 3 below.
  • the prepared resin sheets and resin sheet precursors were cut into 7 cm square pieces, and only the first film of the resin sheets of Examples 1 to 4 and Comparative Examples 1 to 4 was peeled off.
  • the first and third films of the resin sheet precursor No. 8 were peeled off, and these were used as samples before storage to measure the water content of the resin composition layer using a coulometric Karl Fischer moisture meter (Mitsubishi Chemical Analytech). It was measured using a "Trace Moisture Analyzer CA-200" manufactured by Co., Ltd.
  • the moisture content before storage is shown in Tables 2 and 3 below.
  • the device consists of a glass container in which a heatable sample is placed, and a titration device containing a reaction liquid to titrate the water vaporized when the sample is heated.
  • the vaporized water is transferred from the glass container to the reaction liquid side of the titration device by flowing nitrogen at a flow rate of 250 ⁇ 25 ml/min.
  • a sample was placed in a glass container in a nitrogen atmosphere (water vapor content ⁇ 0.1 ppm (mass standard)), and the amount of vaporized water was titrated at 130°C. The water content was calculated.
  • the first film alone or the first and third films were prepared in the same manner as above.
  • the water content of the resin composition layer was measured in the same manner by peeling them off and using them as samples after storage.
  • the water content after storage (moisture content after storage II) is shown in Tables 2 and 3 below.
  • moisture content increase rate II/I moisture content increase rate II/I
  • the resin sheet and resin sheet precursor were evaluated based on the following criteria based on the ratio of the water content after storage to the water content before storage (water content increase rate II/I). The results are also shown in Tables 2 and 3 below. (Evaluation criteria for moisture content increase rate) ⁇ (Good): Moisture content increase rate is less than 2.5 ⁇ (Poor): Moisture content increase rate is 2.5 or more
  • the resin sheets and resin sheet precursors of the Examples of the present invention have a good evaluation of the water content increase rate, and therefore can suppress water absorption of the resin composition layer during storage. It can be seen that the detection accuracy of the number of AOI-detected defects in the resin composition layer is good, and the warpage evaluation is good, so that stable mass production is possible.
  • the resin sheet and resin sheet precursor of the present invention can suppress water absorption of the resin composition layer during storage (especially water absorption of the resin composition layer containing semi-calcined hydrotalcite or calcium oxide), and have a high It is possible to accurately inspect the resin composition layer of a resin sheet for foreign substances using an automatic optical visual inspection device (AOI), and to suppress warpage when forming the resin composition layer.
  • AOI automatic optical visual inspection device

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KR1020247035582A KR20240163738A (ko) 2022-03-25 2023-03-24 수지 시트 및 이의 제조 방법
EP23775086.4A EP4501627A4 (en) 2022-03-25 2023-03-24 RESIN SHEET AND ITS PRODUCTION PROCESS
US18/894,796 US20250296296A1 (en) 2022-03-25 2024-09-24 Resin sheet and production method therefor
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