WO2016056625A1 - Matériau d'étanchéité filmogène, feuille d'étanchéité et dispositif électronique - Google Patents

Matériau d'étanchéité filmogène, feuille d'étanchéité et dispositif électronique Download PDF

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Publication number
WO2016056625A1
WO2016056625A1 PCT/JP2015/078624 JP2015078624W WO2016056625A1 WO 2016056625 A1 WO2016056625 A1 WO 2016056625A1 JP 2015078624 W JP2015078624 W JP 2015078624W WO 2016056625 A1 WO2016056625 A1 WO 2016056625A1
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Prior art keywords
film
water vapor
resin layer
sealing material
vapor barrier
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PCT/JP2015/078624
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English (en)
Japanese (ja)
Inventor
佳明 萩原
健太 西嶋
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リンテック株式会社
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Priority claimed from JP2014209460A external-priority patent/JP2016078260A/ja
Priority claimed from JP2014209461A external-priority patent/JP2016078261A/ja
Priority claimed from JP2014209459A external-priority patent/JP6530900B2/ja
Priority claimed from JP2014220292A external-priority patent/JP2016087791A/ja
Priority claimed from JP2014227187A external-priority patent/JP6468810B2/ja
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Publication of WO2016056625A1 publication Critical patent/WO2016056625A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a film-like sealing material and a sealing sheet that can seal an electronic element and the like, and an electronic device in which the electronic element is sealed by them.
  • an organic electronic device for example, a display module having an organic electroluminescence (organic EL) element or electronic paper, or a solar cell module having an organic thin film solar cell element
  • moisture or oxygen enters the electronic element inside the device. Therefore, it is necessary to prevent moisture and oxygen from entering.
  • organic EL element there is a method of covering an electronic element using a glass member capable of forming a space.
  • Patent Documents 1 and 2 disclose a substance containing a hygroscopic agent for removing such moisture that has entered inside.
  • Patent Document 1 discloses a resin containing a physical adsorption desiccant and a chemical adsorption desiccant in a specific ratio (claim 1 of Patent Document 1). Further, it is disclosed that the total content of the two desiccants in the resin can be 40 to 80% by weight (the same claim 2). This resin is provided in a sheet shape inside the electronic device so as to face the electronic element, and absorbs moisture present in the electronic device (Japanese Patent Application Laid-Open No. 2001-277395 cited as Patent Document 1 in Patent Document 1). No. 2).
  • Patent Document 2 discloses a composition containing a compound containing an Al—OR bond and a curable monomer.
  • the above compound acts as a hygroscopic agent because it removes water molecules from the surroundings by performing a hydrolysis reaction at the Al—OR bond.
  • This composition absorbs moisture present in the electronic device by being provided in the form of a sheet at a position facing the electronic element inside the electronic device or by filling the space inside the electronic device (Patent Document 2). 1 and 2).
  • the electronic device is manufactured, for example, as a stacked body in which a sealing substrate, a film-shaped sealing material, an electronic element, and a substrate are stacked in this order.
  • a glass plate, a high gas barrier film, a metal foil, or the like is used for the sealing substrate so that moisture does not enter the thickness direction from the main surface of the laminate.
  • a sealing material having a water vapor barrier property has been developed.
  • Patent Document 3 discloses a film-like sealing material provided with a water vapor barrier resin layer containing a cycloolefin resin.
  • the present invention has been made in view of such a situation, and an object of the present invention is to provide a film-shaped sealing material, a sealing sheet, and an electronic device having better water vapor barrier properties.
  • the present invention is a film-shaped sealing material comprising one or more layers including a water vapor barrier resin layer containing a hygroscopic agent, wherein the film-shaped sealing material Both surfaces show adhesion to the adherend, and the water vapor permeability of the material obtained by removing the moisture absorbent from the water vapor barrier resin layer is 10 g / (m 2 ⁇ day) when measured at a thickness of 50 ⁇ m.
  • the film-shaped sealing material is composed of a plurality of layers, the water vapor permeability of the layers other than the water-vapor barrier resin layer located on the outermost side of the film-shaped sealing material is 50 ⁇ m thick. 30 g / (m 2 ⁇ day) or less, and the ratio of the thickness of the water vapor barrier resin layer is 50 to 100% of the thickness of the film-shaped sealing material.
  • a film-shaped sealing material is provided (Invention 1).
  • the material obtained by removing the moisture absorbent from the water vapor barrier resin layer exhibits high water vapor barrier properties and prevents moisture permeation, in addition to the water vapor barrier resin layer. Moisture that has entered the water is taken in by the hygroscopic agent, so that a very high water vapor barrier property is achieved.
  • the maximum moisture absorption amount of the hygroscopic agent is 1.0 g / m 2 or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 ⁇ m. Is preferred (Invention 2).
  • the second aspect of the present invention is a film-shaped encapsulant comprising one or more layers including a water vapor barrier resin layer containing a hygroscopic agent, wherein both surfaces of the film-form encapsulant are attached to an adherend.
  • the maximum moisture absorption amount of the film-like sealing material is 1.0 g / m 2 or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 ⁇ m
  • the content of the hygroscopic agent is 1 to 35% by mass with respect to the water vapor barrier resin layer, and the ratio of the thickness of the water vapor barrier resin layer is 50 to 100 of the thickness of the film-like sealing material.
  • a film-shaped encapsulant is provided (Invention 3).
  • the moisture absorbent contained in the water vapor barrier resin layer has a high maximum moisture absorption amount, so that the infiltrated moisture is sufficiently taken in by the moisture absorbent and the moisture permeation is permeated. Is effectively prevented. Furthermore, by using a hygroscopic agent having a high maximum moisture absorption amount, the content of the hygroscopic agent can be kept relatively low, and the content of the resin constituting the water vapor barrier resin layer becomes relatively high and high. The water vapor barrier property is achieved, and the water vapor barrier resin layer can be produced satisfactorily. As a result, the water vapor barrier property of the film-shaped sealing material is very excellent.
  • one adhesive resin layer laminated on one surface side of the water vapor barrier resin layer and exhibiting adhesion to an adherend, or the water vapor barrier resin layer It is preferable to include two adhesive resin layers laminated on one surface side and the other surface side and exhibiting adhesion to the adherend as the outermost layer of the film-shaped sealing material (invention). 4).
  • the water-vapor-permeation rate of the said adhesive resin layer is 30 g / (m ⁇ 2 > * day) or less when measured in the thickness of 50 micrometers (invention 5).
  • the hygroscopic agent is preferably a compound containing a metalloxane bond (Invention 6).
  • the compound containing a metalloxane bond has the formula [M (OR) n ′ —O] m
  • M is a metal element
  • R is a compound containing at least hydrogen and carbon
  • n ′ is one or more.
  • m represents an integer of 1 or more
  • a compound that reacts with water at the MOM site It is preferable (Invention 7).
  • the hygroscopic agent is preferably a metal oxide (Invention 8).
  • the hygroscopic agent is preferably a compound that reacts with water molecules to form a hydrate (Invention 9).
  • the present invention is a film-shaped sealing material comprising a single layer or a plurality of layers, including a water vapor barrier resin layer, wherein both surfaces of the film-shaped sealing material exhibit adhesion to an adherend,
  • a film-shaped sealing material characterized in that a water vapor intrusion rate from an end face of the film-shaped sealing material in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH is 10 ⁇ m / h or less (invention). 10).
  • the water vapor barrier resin layer preferably contains a hygroscopic agent (Invention 11).
  • one adhesive resin layer laminated on one surface side of the water vapor barrier resin layer and exhibiting adhesion to an adherend, or the water vapor barrier resin layer It is preferable to further include two adhesive resin layers which are laminated on one surface side and the other surface side of the material and exhibit adhesion to the adherend (Invention 12).
  • the ratio of the thickness of the water vapor barrier resin layer is preferably 50 to 100% of the thickness of the film-like sealing material (Invention 13).
  • the water vapor barrier resin layer preferably contains at least one resin selected from the group consisting of rubber resins, polyester resins, polyolefin resins, and epoxy resins. (Invention 14).
  • the adhesive resin layer preferably contains at least one resin selected from the group consisting of rubber resins, polyester resins, polyolefin resins, and epoxy resins (Invention 15). ).
  • the maximum moisture absorption amount of the moisture absorbent is 1.0 g / m 2 or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 ⁇ m. Is preferred (Invention 16).
  • the hygroscopic agent is preferably a compound containing a metalloxane bond (Invention 17).
  • the hygroscopic agent is preferably a metal oxide (Invention 18).
  • the hygroscopic agent is preferably a compound that reacts with water molecules to form a hydrate (Invention 19).
  • the adhesive strength when any one surface of the film-shaped sealing material is bonded to a glass plate at 120 ° C. is 1 N / 25 mm or more (Invention 20). ).
  • the present invention provides the first and second adhesive resin layers exhibiting adhesion to the adherend, and between the first adhesive resin layer and the second adhesive resin layer.
  • a film-shaped sealing material comprising a water vapor barrier resin layer containing a cycloolefin-based resin and a hygroscopic agent (Invention 21).
  • a high water vapor barrier property is achieved by the cycloolefin resin, and further, moisture that has entered the water vapor barrier resin layer is taken in by the hygroscopic agent. Water vapor barrier properties are achieved.
  • the hygroscopic agent is preferably a metal oxide (Invention 22).
  • the hygroscopic agent is preferably a compound that reacts with water molecules to form a hydrate (Invention 23).
  • the present invention provides first and second adhesive resin layers exhibiting adhesion to an adherend, and the first adhesive resin layer and the second adhesive resin layer.
  • a film-like sealing material comprising a water vapor barrier resin layer containing a cycloolefin-based resin and a hygroscopic agent, having a total light transmittance of 80% or more and a haze value of 10% or less (Invention 24).
  • a high water vapor barrier property is achieved by the cycloolefin-based resin, and further, moisture that has entered the water vapor barrier resin layer is taken in by the hygroscopic agent, which is very high. Water vapor barrier properties are achieved.
  • the high water vapor barrier property of the cycloolefin-based resin enables the content of the hygroscopic agent to be relatively low, the influence of the hygroscopic agent on the optical properties of the film-like sealing material is suppressed, and high light transmittance. Is achieved.
  • the water vapor barrier property is sufficient, it is not necessary to excessively increase the thickness of the film-shaped sealing material 1 or to contain other components, and in this respect, high light transmittance is achieved. .
  • the hygroscopic agent is preferably a compound that reacts with water molecules to form a hydrate (Invention 25).
  • the content of the moisture absorbent is preferably 1 to 35% by mass with respect to the water vapor barrier resin layer (Invention 26).
  • the cycloolefin-based resin has the following structural formula (a) (In the formula (a), m and n are .R 1 and R 2 is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.)
  • R 1 and R 2 May be bonded to form a ring.
  • the maximum moisture absorption amount of the film-shaped sealing material is 1.0 g / m when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 ⁇ m. It is preferably 2 or more (Invention 28).
  • either one surface of the first adhesive resin layer or the second adhesive resin layer in the film sealing material is bonded to a glass plate at 120 ° C. It is preferable that the adhesive force at the time is 5 N / 25 mm or more (Invention 29).
  • the first and second adhesive resin layers are directly laminated on the water vapor barrier resin layer, and preferably have a three-layer structure thereof (Invention 30). .
  • the present invention provides a sealing sheet comprising the film-shaped sealing material (Inventions 21 to 28) and a gas barrier film laminated on one surface of the film-shaped sealing material. (Invention 31).
  • the present invention provides an electronic device characterized by being sealed with the film-like sealing material (Invention 1 to 30) (Invention 31).
  • the present invention provides an electronic device characterized by being sealed by the sealing sheet (Invention 31) (Invention 33).
  • the film-like sealing material according to the present invention has better water vapor barrier properties.
  • the film sealant according to the first embodiment includes a water vapor barrier resin layer containing a hygroscopic agent, and is composed of one layer or a plurality of layers. Both surfaces of the film-like sealing material exhibit adhesiveness to the adherend. Further, the water vapor permeability of the material excluding the moisture absorbent from the water vapor barrier resin layer is 10 g / (m 2 ⁇ day) or less when measured at a thickness of 50 ⁇ m.
  • the water vapor transmission rate of the layers other than the water-vapor barrier resin layer located on the outermost side of the film-like sealing material is measured at a thickness of 50 ⁇ m. In this case, it is 30 g / (m 2 ⁇ day) or less. Further, the ratio of the thickness of the water vapor barrier resin layer is 50 to 100% of the thickness of the film-shaped sealing material.
  • the film-like sealing material according to the first embodiment may be composed of one layer or a plurality of layers.
  • the film-shaped sealing material is composed of one layer
  • the film-shaped sealing material is composed only of the water vapor barrier resin layer.
  • the film-shaped sealing material is composed of a plurality of layers
  • the film-shaped sealing material is composed of a water vapor barrier resin layer and one or more other layers.
  • the water vapor barrier resin layer and one other layer are directly laminated.
  • the water vapor barrier resin layer and the plurality of other layers may be laminated in various orders, for example, the water vapor barrier resin layer is laminated between the plurality of other layers. May be.
  • an adhesive resin layer is preferably exemplified.
  • Both surfaces of the film-like sealing material according to the first embodiment exhibit adhesiveness to the adherend.
  • the film-like sealing material is composed of one layer, that is, when it is composed of only the water vapor barrier resin layer, the water vapor barrier resin layer has adhesiveness.
  • a film-form sealing material consists of two or more layers, the layer located in the outermost side of a film-form sealing material has adhesiveness.
  • the water vapor barrier resin layer is present on one surface of the film-shaped sealing material and the adhesive resin layer is present on the other surface, the water vapor barrier resin layer and the adhesive resin layer have adhesiveness.
  • two adhesive resin layers exist in both surfaces of a film-form sealing material, two adhesive resin layers have adhesiveness.
  • Release films may be laminated on both surfaces of the film-like sealing material according to the first embodiment for the purpose of protecting the adhesive surface. This release sheet is appropriately peeled off when using the film-like sealing material.
  • the “layer located on the outermost side” in this specification refers to a layer located on the outermost side when the film-shaped sealing material is used for sealing. Therefore, a release sheet is not included in the “outermost layer”.
  • 1 and 2 show specific examples of the film-like sealing material.
  • FIG. 1 is a schematic cross-sectional view of a film-shaped sealing material 1A according to an embodiment.
  • the film-shaped sealing material 1 ⁇ / b> A according to this embodiment includes a water vapor barrier resin layer 12.
  • FIG. 2 is a schematic cross-sectional view of a film-shaped sealing material 1B according to another embodiment.
  • the film-shaped sealing material 1B according to the embodiment includes the first and second adhesive resin layers 11A and 11B, the first adhesive resin layer 11A, and the second adhesive property.
  • a water vapor barrier resin layer 12 is provided between the resin layer 11B and the resin layer 11B.
  • the water vapor barrier resin layer 12 contains a hygroscopic agent. Furthermore, the material obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 (hereinafter referred to as “main material M”) has a high water vapor barrier property. Specifically, the water vapor permeability of the main material M is 10 g / (m 2 ⁇ day) or less when measured at a thickness of 50 ⁇ m. In addition to the prevention of moisture permeation by the main material M exhibiting high water vapor barrier properties, even when water enters the water vapor barrier resin layer 12, the moisture absorbent takes in this water.
  • the water vapor barrier resin layer 12 has an even higher water vapor barrier property, and the water vapor barrier properties of the film-shaped sealing materials 1A and 1B having such a water vapor barrier resin layer 12 are also very excellent. It will be a thing.
  • the water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
  • the resin constituting the water vapor barrier resin layer 12 is preferably a resin having a low water vapor transmission rate.
  • the resin constituting the water vapor barrier resin layer 12 are a rubber resin, a polyester resin, a polyolefin resin, a cycloolefin resin, and an epoxy resin. These resins can be used alone or in combination of two or more.
  • Water vapor transmission rate of the main material M comprising the resin as measured by a layer consisting mainly material M of thickness of 50 [mu] m, and a 10g / (m 2 ⁇ day) or less, 8g / (m 2 ⁇ day ) Or less, preferably 6 g / (m 2 ⁇ day) or less.
  • the water vapor transmission rate is defined as the mass (g / (m 2 ⁇ day)) of water that permeates the 1 m 2 region for one day for a measurement target having a certain thickness. Is done.
  • the thickness at this time is, for example, 50 ⁇ m.
  • the film-shaped sealing materials 1A and 1B can achieve a very high water vapor barrier property.
  • steam barrier resin layer 12 contains only a cycloolefin type resin other than a hygroscopic agent, the preferable water vapor permeability of a cycloolefin type resin becomes as above-mentioned water vapor permeability.
  • the water vapor permeability of the main material M can be obtained, for example, by producing a layer without using a hygroscopic agent and measuring the water vapor permeability.
  • the water vapor barrier resin layer 12 may have adhesiveness. That is, the resin constituting the water vapor barrier resin layer 12 may be selected so that the water vapor barrier resin layer 12 has adhesiveness. In particular, when the adhesive resin layer is not included as in the film-shaped sealing material 1A shown in FIG. 1 or when one adhesive resin layer is included, the water vapor barrier resin layer 12 has adhesiveness. Is preferred. The water vapor barrier resin layer 12 having adhesiveness can be satisfactorily adhered to a gas barrier film and an electronic element described later.
  • Rubber-based resins are preferable in that high water vapor barrier properties and high adhesiveness can be achieved at the same time.
  • rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, halogenated butyl rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate -Butadiene copolymer, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copo
  • the polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers.
  • the polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.
  • Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more.
  • isobutylene resin is a copolymer
  • isobutylene is the maximum amount of monomer as a main component in the raw material monomer.
  • the polyisobutylene-based resin is an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as a monomer component or a homopolymer whose monomer component is composed only of isobutylene because it has excellent water vapor barrier properties.
  • isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as a monomer component or a homopolymer whose monomer component is composed only of isobutylene because it has excellent water vapor barrier properties.
  • the number average molecular weight of the rubber-based resin used for the water vapor barrier resin layer 12 is usually 100,000 to 5,000,000, preferably 100,000 to 3,000,000, more preferably 100,000 to 1,000,000.
  • the polyester resin is a polymer obtained by polycondensation of a polyvalent carboxylic acid and a polyol, or a modification thereof.
  • the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, trimellitic acid and the like.
  • the polyol include aliphatic alcohols such as ethylene glycol and propylene glycol, and polyether polyols such as polyethylene glycol and polypropylene glycol. These polyester resins can be used singly or in combination of two or more.
  • the polyolefin resin refers to a polymer (including the concept of a copolymer) containing only one or two or more olefins as a monomer component constituting the polymer. That is, the polyolefin resin here is a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins.
  • the olefin is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and examples thereof include ethylene, propylene, butylene, isobutylene, 1-hexene, styrene, etc. Among them, ethylene and propylene are preferable.
  • a linear low density polyethylene (LLDPE, density: 910 kg / m 3 or more and less than 915 kg / m 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more, 915 kg / m less than 3), medium density polyethylene (MDPE, density: 915 kg / m 3 or more, less than 942Kg / m 3), high density polyethylene (HDPE, density: 942Kg / m 3 or higher) such as polyethylene resin, polypropylene resin (PP ) And ethylene-propylene copolymer.
  • LLDPE low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene resin
  • PP polypropylene resin
  • ethylene-propylene copolymer ethylene-propylene copolymer
  • Cycloolefin-based resin refers to a resin whose main component is a polymer (including the concept of copolymer) containing cycloolefin as a monomer component constituting the polymer, and is a polymer containing only cycloolefin as a monomer component. It may be a polymer (copolymer) containing cycloolefin and other monomers as monomer components.
  • the other monomer is not particularly limited as long as it does not hinder the purpose of the film-shaped sealing materials 1A and 1B according to the first embodiment.
  • ethylene, propylene and other ⁇ -olefins having 2 or more carbon atoms, (meth) Examples include acrylic acid esters.
  • (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
  • the cycloolefin-based resin is excellent in adhesion with the adhesive resin layers 11A and 11B described later, and can prevent delamination of the film-shaped sealing material 1B, and therefore, cycloolefin and ethylene as monomer components. It is preferable that it is a copolymer containing.
  • the cycloolefin-based resin preferably has a glass transition temperature of 20 to 150 ° C., particularly preferably 25 to 130 ° C., and more preferably 30 to 110 ° C.
  • the glass transition temperature of the cycloolefin-based resin is 20 ° C. or higher, the content of cycloolefin as a monomer component in the cycloolefin-based resin increases, and the water vapor barrier property is easily exhibited.
  • the glass transition temperature of the cycloolefin resin is 150 ° C. or lower, the water vapor barrier resin layer 12 follows the step of the sealing target such as an electronic element well, and the sealing target is securely sealed. Can be stopped.
  • the cycloolefin resin does not have a hydrophilic group.
  • the water vapor barrier property may be lowered.
  • the hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, a sulfonic acid group, and a mercapto group.
  • the cycloolefin-based resin may have a hydrophobic group. If it is a hydrophobic group, there is no possibility that water vapor
  • the hydrophobic group include an alkyl group and an aryl group.
  • cycloolefin-based resin As a preferred cycloolefin-based resin, the following structural formula (a) (In the formula (a), m and n are .R 1 and R 2 is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.)
  • R 1 and R 2 May be bonded to form a ring.
  • a polymer containing only cycloolefin as a monomer component; COP), and the following structural formula (d) In the formula (d), m and n is an integer of 1 or more, R 1 and R 2 represents a hydrogen atom or an alkyl group, it may be respectively the same, may be different .R 1 and R 2 may combine with each other to form a ring.
  • a cycloolefin polymer polymer containing only cycloolefin as a monomer component; COP). These cycloolefin polymers are extremely excellent in water vapor barrier properties and are easily available. These cycloolefin polymers can be used singly or in combination of two or more.
  • a commercially available product can also be used as the cycloolefin polymer.
  • Examples of commercially available products include ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd., ring-opening metathesis polymer hydrogenated polymer of norbornene monomer), TOPAS (registered trademark) (manufactured by Polyplastics Co., Ltd., copolymer of norbornene and ethylene).
  • ZEONOR registered trademark
  • Apel registered trademark
  • Mitsui Chemicals ethylene and tetracyclododecene Copolymer
  • Arton registered trademark
  • the epoxy resin examples include a monofunctional epoxy compound, a bifunctional epoxy compound, a trifunctional or higher polyfunctional epoxy compound, a polymer or oligomer having an epoxy group, and a vinyl monomer having an epoxy group and other vinyl monomers. And copolymer polymers or oligomers. These epoxy resins can be used alone or in combination of two or more.
  • the water vapor barrier resin layer 12 may contain other resin components in addition to the above resin.
  • other resin components include olefin resins such as ethylene- (meth) acrylic acid copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic ester copolymers, urethane resins, polyurethanes, etc. Resin, polyester urethane resin, acrylic resin, amide resin, styrene resin, silane resin, and the like.
  • Hygroscopic agent The water vapor barrier resin layer 12 contains a hygroscopic agent.
  • hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents.
  • Chemical type hygroscopic agent is a hygroscopic agent that takes in surrounding water by using water molecules as reactants of chemical reaction.
  • any chemical moisture absorbent can be used, but a metal oxide, a compound that reacts with water molecules to form a hydrate, or a metalloxane. It is preferred to use a compound containing a bond.
  • These chemical hygroscopic agents can be used alone or in combination of two or more.
  • metal oxides that can be used as chemical humectants are calcium oxide, barium oxide, magnesium oxide and strontium oxide. These metal oxides can be used alone or in combination of two or more.
  • calcium oxide performs reaction of the following formula
  • water molecules are converted into hydroxyl groups in calcium hydroxide which is a reaction product.
  • Metal oxides other than calcium oxide also perform the same reaction as in formula (1).
  • Examples of compounds that can be used as chemical moisture absorbents and react with water molecules to form hydrates are sodium sulfate, potassium sulfate / aluminum, magnesium sulfate, calcium sulfate, aluminum sulfate, sodium carbonate, sodium acetate, thiosulfate Sodium and copper sulfate. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • magnesium sulfate performs reaction of the following formula
  • Compounds other than magnesium sulfate also perform the same reaction as in formula (2).
  • the compound containing a metalloxane bond is a compound containing a metalloxane bond, that is, a bond between a metal element and oxygen.
  • examples of such compounds include compounds represented by the general formula M (OR) n (M is a metal element, R is a compound containing at least hydrogen and carbon, and n is the oxidation number of the metal element), and the formula [ M (OR) n ′ —O] m (M is a metal element, R is a compound containing hydrogen and carbon, n ′ is an integer of 1 or more, and a value obtained by subtracting 2 from the oxidation number of the metal element, m is 1 A compound having a structure represented by the above integer).
  • the R compound may further contain oxygen.
  • R examples of R are an alkyl group and an acyl group.
  • the compound containing a metalloxane bond generally includes a compound called a metalloxane compound or a polymetalloxane compound.
  • the phrase (poly) metalloxane compound may be used as an expression meaning both the metalloxane compound and the polymetalloxane compound.
  • More specific examples of compounds containing a metalloxane bond are metal alkoxides, metal acylates and metal chelates.
  • the site of the compound containing a metalloxane bond that reacts with water is mainly M—O—R or M—O—M. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • Metal alkoxides are examples of compounds that react with water at the M-O-R site.
  • the metal alkoxide are a compound in which R is an alkyl group in the general formula M (OR) n or a compound having a structure in which R is an alkyl group in the formula [M (O—R) n ′ —O] m .
  • More specific examples of metal alkoxides are tetramethyl orthotitanate (also known as: tetramethoxy titanium (IV), titanium (IV) tetramethoxide), aluminum ethoxide and aluminum oxide isopropoxide trimer. These metal alkoxides can be used individually by 1 type or in combination of 2 or more types.
  • the aluminum ethoxide performs a reaction of the following formula (3) with water molecules.
  • water molecules are utilized for the hydrolysis of aluminum ethoxide, resulting in the production of aluminum hydroxide and ethanol.
  • Compounds other than aluminum ethoxide perform the same reaction as in formula (3).
  • Metal acylates are examples of compounds that react with water at the MOR or MOM sites.
  • an example of a compound that reacts with water at the M—O—R moiety is a compound in which R is an acyl group in the general formula M (OR) n .
  • An example of a compound that reacts with water at the MOM site in the metal acylate is a compound having a structure in which R is an acyl group in the formula [M (O—R) n ′ —O] m .
  • Specific examples of the metal acylate are cyclic aluminum oxide octylate and cyclic aluminum oxide stearate. These metal acylates can be used alone or in combination of two or more.
  • the cyclic aluminum oxide octylate reacts with water molecules according to the following formula (4), and there is only one product. Compounds other than cyclic aluminum oxide octylate also perform the same reaction as in formula (4).
  • the physical hygroscopic agent is a hygroscopic agent that takes in surrounding water regardless of a chemical reaction, and for example, adsorbs surrounding water molecules on the surface of the hygroscopic agent.
  • any physical hygroscopic agent can be used, and for example, zeolite, activated alumina, silica gel, and a clay compound can be used.
  • zeolite a molecular sieve can be used.
  • the hygroscopic agent preferably has little or no influence on the electronic element.
  • a chemical moisture absorbent it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction.
  • a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device.
  • a hygroscopic agent that is well mixed with the resin constituting the water vapor barrier resin layer 12 and does not denature even when subjected to a treatment such as heating.
  • the above-described compound containing a metalloxane bond, a metal oxide and a compound that forms a hydrate by reacting with water molecules it is preferable to use a compound that reacts with water at the OM site.
  • These hygroscopic agents produce a relatively stable product when a hygroscopic reaction occurs, which is less prone to vaporization and gas generation, and is well mixed with the material resin to provide a water vapor barrier resin. It is difficult to denature in the manufacturing process of the layer 12. As a result, it is possible to obtain the film-shaped sealing materials 1A and 1B exhibiting very excellent water vapor barrier properties.
  • the content of the hygroscopic agent in the water vapor barrier resin layer 12 is preferably 1 to 35% by mass, particularly preferably 3 to 30% by mass, and more preferably 5 to 25% by mass. .
  • steam barrier resin layer 12 is fully moisture-absorbed, and the water vapor
  • it is 35 mass% or less, when manufacturing the water vapor
  • the shape of the hygroscopic agent is not particularly limited, but may be, for example, liquid, powder, or granular.
  • the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and more preferably 0.1 to 5 ⁇ m. It is preferable that Here, the “average particle diameter” in the present specification is a value obtained by measurement with a laser diffraction particle size distribution measuring apparatus.
  • the maximum moisture absorption amount of the hygroscopic agent is preferably 1.0 g / m 2 or more, particularly 1.5 g / m 2 when expressed by the amount of water absorbed by the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m. It is preferably m 2 or more, and more preferably 2.0 g / m 2 or more.
  • a hygroscopic agent having a maximum moisture absorption of 1.0 g / m 2 or more it becomes possible to sufficiently absorb moisture that permeates the water vapor barrier resin layer 12 and has a higher water vapor barrier property. Sealing materials 1A and 1B can be obtained.
  • the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, and a plasticizer. Further, it may contain various additives such as a lubricant, an antiblocking agent, a filler, a dispersant, a crosslinking agent (a curing agent; when a curable resin such as an epoxy resin is used), a silane coupling agent, and the like. In particular, when the water vapor barrier resin layer 12 includes a rubber-based resin, it is preferable to include a tackifier.
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and more preferably 15 to 100 ⁇ m. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 ⁇ m or more, a sufficient water vapor barrier property can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin.
  • the ratio of the thickness of the water vapor barrier resin layer 12 is preferably 50 to 100%, particularly preferably 55 to 100% of the thickness of the film-like sealing materials 1A and 1B. 60 to 100% is preferable.
  • the ratio of the thickness of the water vapor barrier resin layer 12 being 100% means that the film-like sealing materials 1A and 1B are composed of only the water vapor barrier resin layer 12.
  • the thickness of film-form sealing material 1A, 1B is mentioned later.
  • the film-shaped sealing materials 1A and 1B can contain a sufficient amount of a hygroscopic agent, thereby achieving higher water vapor barrier properties. be able to.
  • the first adhesive resin layer 11A and the second adhesive resin layer 11B are layers that exhibit adhesion to the adherend, and in the first embodiment, water vapor barrier properties. It can be arbitrarily provided on one side or both sides of the resin layer 12. When the adhesion of the water vapor barrier resin layer 12 to the adherend is low, a film having better adhesion to the adherend by providing one or both of the first and second adhesive resin layers 11A and 11B.
  • the shaped sealing material 1B can be realized.
  • Each of the first and second adhesive resin layers 11A and 11B may be a single layer or a plurality of layers.
  • the water vapor permeability of the first and second adhesive resin layers 11A and 11B is preferably 30 g / (m 2 ⁇ day) or less, particularly 25 g / (m 2 ), when measured at a thickness of 50 ⁇ m. ⁇ Day) or less, more preferably 20 g / (m 2 ⁇ day) or less.
  • the adhesive resin layers 11A and 11B have a water vapor permeability of 30 g / (m 2 ⁇ day) or less, when the adhesive resin layer is provided, moisture moves through the adhesive resin layer and reaches the electronic device. This can be prevented, and a film-like sealing material 1B having higher water vapor barrier properties can be obtained.
  • the resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it exhibits adhesiveness to the adherend, and examples thereof include thermoplastic resins and curable resins.
  • examples of the curable resin include a thermosetting resin and an energy ray curable resin.
  • a thermoplastic resin and a curable resin can also be mixed and used.
  • the thermoplastic resin may have thermal adhesiveness or pressure-sensitive adhesiveness.
  • the film-shaped sealing material 1B can be firmly adhered to the adherend, and the first and second adhesive properties can be obtained.
  • the adhesion between the resin layers 11A and 11B and the water vapor barrier resin layer 12 is also improved.
  • thermoplastic resin examples include rubber resins, polyolefin resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-vinyl acetate copolymers, polyester resins. , Polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins, and the like.
  • the polyolefin resin may be a modified one, and examples thereof include an acid-modified polyolefin resin and a silane-modified polyolefin resin. Of these, rubber resins, acid-modified polyolefin resins, and silane-modified polyolefin resins are preferable.
  • the thermoplastic resin is a rubber-based resin, an acid-modified polyolefin-based resin, or a silane-modified polyolefin-based resin
  • the first and second adhesive resin layers 11A and 11B are particularly adherends such as glass plates and gas barrier films. In contrast, it shows a higher adhesive force. Further, the adhesion between the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 is also excellent.
  • the said thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
  • rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate-butadiene copolymer Examples thereof include urethane, rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene-propylene-nonconjugated diene terpolymer. It is done. These rubber compounds can be
  • the polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers.
  • the polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.
  • Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more.
  • isobutylene resin is a copolymer
  • isobutylene is the maximum amount of monomer as a main component in the raw material monomer.
  • the polyisobutylene resin is a homopolymer whose monomer component is composed only of isobutylene, and is an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component because it has excellent water vapor barrier properties.
  • the polyisobutylene resin is a homopolymer whose monomer component is composed only of isobutylene, and is an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component because it has excellent water vapor barrier properties.
  • the number average molecular weight of the rubber-based resin used for the adhesive resin layer is usually 100,000 to 5 million, preferably 100,000 to 3 million, more preferably 100,000 to 1 million.
  • Polyolefin resin refers to a polymer (including the concept of copolymer) containing olefin as a monomer component constituting the polymer, and the monomer component is a polymer consisting only of olefin. It may be a polymer (copolymer) containing an olefin and another monomer as a monomer component.
  • the olefin is preferably an ⁇ -olefin having 2 to 8 carbon atoms, and examples thereof include ethylene, propylene, butylene, isobutylene, 1-hexene and styrene. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable.
  • the other monomer is not particularly limited as long as it does not hinder the purpose of the film-shaped sealing material 1B according to the first embodiment, and examples thereof include vinyl acetate and (meth) acrylic acid ester.
  • ultra low density polyethylene VLDPE, density: 880 kg / m 3 or more and less than 910 kg / m 3
  • low density polyethylene LDPE, density: 910 kg / m 3 or more, 915 kg / m 3
  • medium density polyethylene MDPE, density: 915 kg / m 3 or more, 942Kg / m 3
  • high density polyethylene HDPE, density: 942kg / m 3 or higher
  • linear low density polyethylene such as polyethylene Resin, polypropylene resin (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic Examples include acid ester copolymers.
  • polyethylene resins such as ultra-low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, ethylene-propylene copolymer or olefin elastomer (TPO) are preferable, especially Low density polyethylene is preferred.
  • the acid-modified polyolefin resin means a polyolefin resin graft-modified with an acid, and examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and introducing a carboxyl group (graft modification).
  • the unsaturated carboxylic acid includes the concept of a carboxylic acid anhydride
  • the carboxyl group includes the concept of an anhydrous carboxyl group.
  • Examples of the unsaturated carboxylic acid to be reacted with the polyolefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, Examples thereof include citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic acid anhydride. These can be used individually by 1 type or in combination of 2 or more types. Among the above, maleic anhydride, which is particularly excellent in adhesive strength, is preferable.
  • the acid-modified polyolefin resin is preferably a maleic anhydride-modified polyolefin resin, particularly preferably a maleic anhydride-modified polyethylene resin.
  • the amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, particularly 0.2 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 0.2 to 1 part by mass.
  • the amount of the unsaturated carboxylic acid to be reacted is in the above range, the resulting acid-modified polyolefin resin is excellent in adhesive strength.
  • the acid-modified polyolefin resin preferably has a Vicat softening point of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C.
  • a Vicat softening point of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C.
  • the adhesiveness does not appear at room temperature, so the film-like sealing material 1B is excellent in handleability and can be bonded by thermocompression bonding in a relatively short time.
  • Electronic devices such as display device modules having organic EL elements, electronic paper, and organic thin-film solar cells can be efficiently produced.
  • the Vicat softening point is a value measured based on ASTM D1525.
  • the acid-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly preferably 1 to 15 g / 10 minutes. Further, it is preferably 2 to 10 g / 10 minutes.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • MFR in this specification shall be the value measured based on ASTMD1238.
  • the silane-modified polyolefin resin is obtained by graft-modifying a polyolefin resin by reacting an unsaturated silane compound with the polyolefin resin.
  • the silane-modified polyolefin resin can be firmly bonded particularly when the adherend is a glass plate.
  • polyolefin resin of the silane-modified polyolefin resin examples include the polyolefin resins exemplified for the acid-modified polyolefin resin.
  • the silane-modified polyolefin-based resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and in particular, silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • a modified polyethylene resin is preferred.
  • a vinyl silane compound is preferable.
  • the amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, the content is 0.5 to 5 parts by mass.
  • the amount of the unsaturated silane compound to be reacted is in the above range, the resulting silane-modified polyolefin resin is excellent in adhesive strength.
  • the silane-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly 0.5 to 15 g / 10 minutes. More preferably, it is 0.5 to 10 g / 10 min.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • silane-modified polyolefin resin Commercially available products can also be used as the silane-modified polyolefin resin.
  • Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based.
  • Linklon registered trademark
  • Low density polyethylene-based linklon linear low-density polyethylene-based linkron
  • ultra-low-density polyethylene-based ultra-low-density polyethylene-based.
  • Rincron of ethylene-vinyl acetate copolymer system can be preferably used.
  • the thermoplastic resin may be an ionomer in which molecules are bonded by a metal cation.
  • the ionomer include olefin-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers.
  • olefinic ionomers examples include ethylene- (meth) acrylic acid copolymers, ethylene-fumaric acid copolymers, ethylene-maleic acid copolymers, ethylene-monomethyl monomethyl copolymers, and ethylene-monoethyl maleate copolymers.
  • bonded between molecules of olefin resin, such as a polymer, with the metal ion is mentioned.
  • the metal ion include alkali metals such as sodium and lithium, and polyvalent metals such as alkaline earth metals such as zinc, magnesium and calcium.
  • An ionomer can be used individually by 1 type or in mixture of 2 or more types.
  • the first and second adhesive resin layers 11A and 11B preferably contain 60 to 100% by mass of the thermoplastic resin, particularly preferably 70 to 100% by mass, Further, it is preferably contained in an amount of 80 to 100% by mass.
  • thermoplastic resin may be blended with a curable resin described later.
  • the blending mass ratio of the thermoplastic resin and the curable resin is preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, and 20:80 to 80:20. Particularly preferred is 30:70 to 70:30.
  • curable resin for example, an epoxy resin, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, and a urethane resin can be used. These curable resins can be used alone or in combination of two or more.
  • Examples of the epoxy resin include a monofunctional epoxy compound, a bifunctional epoxy compound, a trifunctional or higher polyfunctional epoxy compound, a polymer or oligomer having an epoxy group, a vinyl monomer having an epoxy group, and another vinyl. Copolymer polymers or oligomers with monomers etc. can be used. These epoxy resins can be used singly or in combination of two or more.
  • the first and second adhesive resin layers 11A and 11B preferably contain 60 to 100% by mass of the curable resin, particularly preferably 70 to 100% by mass, Further, it is preferably contained in an amount of 80 to 100% by mass.
  • the first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, You may contain various additives, such as a blocking inhibitor, a dispersing agent, a filler, a crosslinking agent (hardening agent; when using curable resins, such as an epoxy resin), a silane coupling agent, and a hygroscopic agent.
  • a tackifier an ultraviolet absorber
  • an ultraviolet stabilizer an antistatic agent
  • a pigment e.g., a pigment, a flame retardant, a plasticizer, a lubricant
  • You may contain various additives, such as a blocking inhibitor, a dispersing agent, a filler, a crosslinking agent (hardening agent; when using curable resins, such as an epoxy resin), a silane coupling agent, and a hyg
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the thickness (one layer) of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 ⁇ m, particularly preferably 3 to 80 ⁇ m, and more preferably 5 to 50 ⁇ m. Is preferred. Sufficient adhesiveness is acquired because the thickness of 1st and 2nd adhesive resin layer 11A, 11B is 1 micrometer or more. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 ⁇ m or less, the thickness of the film-shaped sealing material 1B can be kept thin.
  • first and second adhesive resin layers 11A and 11B may be the same or different.
  • the thickness of the film-like sealing materials 1A, 1B is preferably 7 to 500 ⁇ m, particularly preferably 15 to 400 ⁇ m, and more preferably 20 to It is preferable that it is 200 micrometers. Sufficient water vapor barrier property and adhesiveness can be obtained because the film-shaped sealing materials 1A and 1B have a thickness of 7 ⁇ m or more. On the other hand, since the thickness of the film-shaped sealing materials 1A and 1B is 500 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin. For example, even when used in an electronic device, It can be avoided that the thickness of the device becomes too thick.
  • the water vapor permeability of the film-shaped sealing materials 1A and 1B is preferably 20 g / (m 2 ⁇ day) or less when measured with the film-shaped sealing materials 1A and 1B having a thickness of 50 ⁇ m. It is preferably 15 g / (m 2 ⁇ day) or less, more preferably 10 g / (m 2 ⁇ day) or less.
  • water vapor permeability of the film-shaped sealing materials 1A and 1B is 20 g / (m 2 ⁇ day) or less, water vapor from the outside is effectively blocked by the film-shaped sealing materials 1A and 1B and sealed. Reaching the object to be stopped is prevented / suppressed, and the object to be sealed is hardly affected by moisture.
  • the water vapor barrier resin layer contains a main material M having a high water vapor barrier property, and the water vapor barrier resin layer further contains a hygroscopic agent.
  • the water vapor transmission rate as described above can be achieved.
  • the film-like sealing materials 1A and 1B have an adhesive force of 3N / 25 mm or more when any one of the outermost layers of the film-like sealing materials 1A and 1B is bonded to alkali-free glass at 120 ° C. It is particularly preferable that the thickness is 5 N / 25 mm or more.
  • the adhesive force is 3 N / 25 mm or more, so that the object to be sealed is reliably sealed, and the occurrence of floating or peeling between the glass plate and the adherend such as a gas barrier film is prevented. Can do.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • the method for forming the first and second adhesive resin layers 11A and 11B is not particularly limited, and is a melt extrusion method, a calendar method, a dry method. Examples thereof include a method and a solution method.
  • a solution obtained by dissolving the above-described resin in an organic solvent is applied by a known application method, and each layer may be formed by appropriately drying the obtained coating film.
  • the film-like sealing material 1B having the first and second adhesive resin layers 11A and 11B shown in FIG. 2 can be manufactured by a conventional method.
  • a method in which the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B are co-extruded so as to be laminated in that order, the first adhesive property A single-layer film (first adhesive resin film) as the resin layer 11A and a single-layer film (second adhesive resin film) as the second adhesive resin layer 11B are prepared, respectively.
  • first and second adhesive resin layers 11A and 11B are formed on the release sheet, and the release sheets with the first and second adhesive resin layers 11A and 11B are prepared, respectively.
  • the film-like sealing material 1B can also be manufactured by a method of laminating release sheets with the first and second adhesive resin layers 11A and 11B on both surfaces of the barrier resin film. Note that the film-shaped sealing material 1B having only one of the first and second adhesive resin layers 11A and 11B can also be manufactured by following the above method.
  • first and second adhesive resin layers 11A and 11B first adhesive resin film, second adhesive resin film
  • water vapor barrier resin layer 12 water vapor barrier resin film
  • the heating temperature is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B (first adhesive resin film and second adhesive resin film) are softened.
  • the film-like sealing materials 1A and 1B according to the first embodiment are very excellent in water vapor barrier properties, they can be used for sealing various things. In particular, it can be suitably used for sealing an electronic element in an electronic device. Specifically, a module for a display device having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, an electronic paper, a solar cell module, and the like can be given. Among these, in the display device module (organic EL module) and electronic paper having an organic EL element, high water vapor barrier properties are required. Therefore, the film-like sealing materials 1A and 1B according to the first embodiment are suitable. Can be used for
  • the film-like sealant according to the second embodiment includes a water vapor barrier resin layer containing a hygroscopic agent, and is composed of one layer or a plurality of layers. Both surfaces of the film-like sealing material exhibit adhesiveness to the adherend. Further, the maximum moisture absorption amount of the film-shaped sealing material is 1.0 g / m 2 or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 ⁇ m. The content of the hygroscopic agent is 1 to 35% by mass with respect to the water vapor barrier resin layer. Further, the ratio of the thickness of the water vapor barrier resin layer is 50 to 100% of the thickness of the film-shaped sealing material.
  • the film-shaped sealing material according to the second embodiment may have the same layer configuration as the layer configuration described above in the film-shaped sealing agent according to the first embodiment. Moreover, both surfaces of the film-form sealing material which concerns on 2nd Embodiment show the adhesiveness mentioned above similarly to the film-form sealing agent which concerns on 1st Embodiment. Furthermore, the release sheet mentioned above may be laminated
  • the water vapor barrier resin layer contains a hygroscopic agent
  • the maximum moisture absorption amount of the film-shaped sealing material is that the water vapor barrier resin layer having a thickness of 50 ⁇ m absorbs moisture. It is 1.0 g / m 2 or more when expressed by the amount of water to be used.
  • the content of the hygroscopic agent is 1 to 35% by mass with respect to the water vapor barrier resin layer.
  • the water vapor barrier resin layer contains moisture absorbent having the above maximum moisture absorption in the above content, so that moisture that has entered the water vapor barrier resin layer is contained.
  • the hygroscopic agent can be taken in sufficiently by the hygroscopic agent and can effectively prevent moisture from permeating through the water vapor barrier resin layer. Moreover, since the maximum moisture absorption amount of the hygroscopic agent is large as described above, the content of the hygroscopic agent can be kept relatively low. Specifically, the content of the hygroscopic agent can be 35% by mass or less, whereby the content of the resin constituting the water vapor barrier resin layer can be relatively increased, and the high water vapor barrier property. Is achieved, and the water vapor barrier resin layer can be produced satisfactorily. As a result, the water vapor barrier property of the film-shaped sealing material having this water vapor barrier resin layer is very excellent.
  • the water vapor barrier resin layer 12 contains a hygroscopic agent.
  • the water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
  • the resin constituting the water vapor barrier resin layer 12 is preferably a resin having a low water vapor transmission rate.
  • the resin constituting the water vapor barrier resin layer 12 are a rubber resin, a polyester resin, a polyolefin resin, a cycloolefin resin, and an epoxy resin. These resins can be used alone or in combination of two or more.
  • the rubber-based resin, polyester-based resin, polyolefin-based resin, cycloolefin-based resin, and epoxy-based resin described above that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the water vapor barrier resin layer 12 may have adhesiveness. That is, the resin constituting the water vapor barrier resin layer 12 may be selected so that the water vapor barrier resin layer 12 has adhesiveness. In particular, when the adhesive resin layer is not included as in the film-shaped sealing material 1A according to the first embodiment, or when one adhesive resin layer is included, the water vapor barrier resin layer 12 has an adhesive property. It is preferable to have.
  • the water vapor barrier resin layer 12 having adhesiveness can be satisfactorily adhered to a gas barrier film and an electronic element described later.
  • the water vapor barrier resin layer 12 may contain other resin components in addition to the above resin.
  • other resin components include olefins such as ethylene- ⁇ olefin copolymers, ethylene- (meth) acrylic acid copolymers, ethylene-vinyl acetate copolymers, and ethylene- (meth) acrylic acid ester copolymers.
  • main material M When the water vapor permeability of a material (hereinafter referred to as “main material M”) obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 containing the resin is measured in the layer 12 made of the main material M having a thickness of 50 ⁇ m.
  • main material M a material obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 containing the resin is measured in the layer 12 made of the main material M having a thickness of 50 ⁇ m.
  • it is preferably 10 g / (m 2 ⁇ day) or less, particularly preferably 8 g / (m 2 ⁇ day) or less, and more preferably 6 g / (m 2 ⁇ day) or less.
  • the film-shaped sealing materials 1A and 1B can achieve higher water vapor barrier properties.
  • the water vapor permeability of the main material M can be obtained, for example, by producing a layer without using a hygroscopic agent and measuring the water vapor permeability.
  • the water vapor barrier resin layer 12 contains a hygroscopic agent.
  • the content of the hygroscopic agent in the water vapor barrier resin layer 12 is 1 to 35% by mass, preferably 2 to 30% by mass, particularly 3 to 25% by mass with respect to the water vapor barrier resin layer. It is preferable.
  • the hygroscopic agent is contained at 1% by mass or more, the moisture that has entered the water vapor barrier resin layer 12 is sufficiently taken into the hygroscopic agent.
  • the content of the hygroscopic agent is 35% by mass or less, the content of the resin constituting the water vapor barrier resin layer 12 is relatively high, and high water vapor barrier properties are achieved. It becomes possible to manufacture the barrier resin layer 12 satisfactorily. As a result, film-shaped sealing materials 1A and 1B having very high water vapor barrier properties can be obtained.
  • the hygroscopic agent may be a substance generally used for moisture absorption.
  • hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents.
  • chemical hygroscopic agents the above-mentioned chemical hygroscopic agents and physical hygroscopic agents that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the hygroscopic agent preferably has little or no influence on the electronic element.
  • a chemical moisture absorbent it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction.
  • a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device.
  • a hygroscopic agent that is well mixed with the resin constituting the water vapor barrier resin layer 12 and does not denature even when subjected to a treatment such as heating.
  • the above-described compound containing a metalloxane bond, a metal oxide and a compound that forms a hydrate by reacting with water molecules it is preferable to use a compound that reacts with water at the OM site.
  • These hygroscopic agents produce a relatively stable product when a hygroscopic reaction occurs, which is less prone to vaporization and gas generation, and is well mixed with the material resin to provide a water vapor barrier resin. It is difficult to denature in the manufacturing process of the layer 12. As a result, it is possible to obtain the film-shaped sealing materials 1A and 1B exhibiting very excellent water vapor barrier properties.
  • the shape of the hygroscopic agent is not particularly limited, but may be, for example, liquid, powder, or granular.
  • the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and more preferably 0.1 to 5 ⁇ m. It is preferable that
  • the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, and a plasticizer.
  • a lubricant such as a lubricant, an anti-blocking agent, a dispersant, and a crosslinking agent (a curing agent; when a curable resin such as an epoxy resin is used) may be contained.
  • a tackifier when the water vapor barrier resin layer 12 includes a rubber-based resin, it is preferable to include a tackifier.
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and more preferably 15 to 100 ⁇ m. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 ⁇ m or more, a sufficient water vapor barrier property can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin.
  • the ratio of the thickness of the water vapor barrier resin layer 12 is 50 to 100%, preferably 55 to 100%, particularly 60 to 100% of the thickness of the film-like sealing materials 1A and 1B. Preferably there is.
  • the ratio of the thickness of the water vapor barrier resin layer 12 being 100% means that the film-like sealing material is composed only of the water vapor barrier resin layer 12.
  • the thickness of film-form sealing material 1A, 1B is mentioned later.
  • the film-shaped sealing materials 1A and 1B can contain a sufficient amount of a hygroscopic agent, thereby achieving higher water vapor barrier properties. be able to.
  • the first adhesive resin layer 11A and the second adhesive resin layer 11B are layers that exhibit adhesion to the adherend, and in the second embodiment, water vapor barrier properties. It can be arbitrarily provided on one side or both sides of the resin layer 12. When the adhesion of the water vapor barrier resin layer 12 to the adherend is low, a film having better adhesion to the adherend by providing one or both of the first and second adhesive resin layers 11A and 11B.
  • the shaped sealing materials 1A and 1B can be realized.
  • Each of the first and second adhesive resin layers 11A and 11B may be a single layer or a plurality of layers.
  • the water vapor permeability of the first and second adhesive resin layers 11A and 11B is preferably 30 g / (m 2 ⁇ day) or less, particularly 25 g / (m 2 ), when measured at a thickness of 50 ⁇ m. ⁇ Day) or less, more preferably 20 g / (m 2 ⁇ day) or less.
  • the adhesive resin layers 11A and 11B have a water vapor permeability of 30 g / (m 2 ⁇ day) or less, when the adhesive resin layer is provided, moisture moves through the adhesive resin layer and reaches the electronic device. This can be prevented, and film-like sealing materials 1A and 1B having higher water vapor barrier properties can be obtained.
  • the resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it exhibits adhesiveness to the adherend, and examples thereof include thermoplastic resins and curable resins.
  • the curable resin include a thermosetting resin and an energy ray curable resin.
  • a thermoplastic resin and a curable resin can also be mixed and used.
  • the thermoplastic resin and the curable resin the above-described thermoplastic resin and curable resin that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the compounding quantity in the case of using these resin individually or in combination can be made into the compounding quantity mentioned above about the film-form sealing material which concerns on 1st Embodiment.
  • the first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, You may contain various additives, such as a blocking inhibitor, a dispersing agent, a filler, a crosslinking agent (a hardening
  • a tackifier such as an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the thickness (one layer) of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 ⁇ m, particularly preferably 3 to 80 ⁇ m, and more preferably 5 to 50 ⁇ m. Is preferred. Sufficient adhesiveness is acquired because the thickness of 1st and 2nd adhesive resin layer 11A, 11B is 1 micrometer or more. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 ⁇ m or less, the thickness of the film-like sealing materials 1A and 1B can be kept thin.
  • first and second adhesive resin layers 11A and 11B may be the same or different.
  • the maximum moisture absorption amount of the film-like sealing material is 1 when the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m absorbs moisture. and a .0g / m 2 or more, preferably 1.5 g / m 2 or more, and particularly preferably 2.0 g / m 2 or more.
  • the maximum moisture absorption amount is 1.0 g / m 2 or more, it becomes possible to sufficiently absorb moisture that permeates the water vapor barrier resin layer 12, and a film-like sealing material 1 A having a very high water vapor barrier property. , 1B can be obtained.
  • the thickness of the film-like sealing materials 1A and 1B is preferably 7 to 500 ⁇ m, particularly preferably 15 to 400 ⁇ m, and further preferably 20 to 200 ⁇ m. Sufficient water vapor barrier property and adhesiveness can be obtained because the film-shaped sealing materials 1A and 1B have a thickness of 7 ⁇ m or more. On the other hand, since the thickness of the film-shaped sealing materials 1A and 1B is 500 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin. For example, even when used in an electronic device, It can be avoided that the thickness of the device becomes too thick.
  • the water vapor permeability of the film-shaped sealing materials 1A and 1B is preferably 20 g / (m 2 ⁇ day) or less when measured with the film-shaped sealing materials 1A and 1B having a thickness of 50 ⁇ m. It is preferably 15 g / (m 2 ⁇ day) or less, more preferably 10 g / (m 2 ⁇ day) or less.
  • water vapor permeability of the film-shaped sealing materials 1A and 1B is 20 g / (m 2 ⁇ day) or less, water vapor from the outside is effectively blocked by the film-shaped sealing materials 1A and 1B and sealed. Reaching the object to be stopped is prevented / suppressed, and the object to be sealed is hardly affected by moisture.
  • the film-like sealing materials 1A and 1B have an adhesive force of 3N / 25 mm or more when any one of the outermost layers of the film-like sealing materials 1A and 1B is bonded to alkali-free glass at 120 ° C. It is particularly preferable that the thickness is 5 N / 25 mm or more.
  • the adhesive force is 3 N / 25 mm or more, so that the object to be sealed is reliably sealed, and the occurrence of floating or peeling between the glass plate and the adherend such as a gas barrier film is prevented. Can do.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • film-shaped sealing material 1A, 1B The film-shaped sealing material which concerns on 2nd Embodiment can be used for the use mentioned above about the film-shaped sealing material which concerns on 1st Embodiment.
  • Film-form sealing agent which concerns on 3rd Embodiment contains a water vapor
  • the film-shaped sealing material according to the third embodiment may have the same layer configuration as that described above in the film-shaped sealing agent according to the first embodiment. Moreover, both surfaces of the film-form sealing material which concerns on 3rd Embodiment show the adhesiveness mentioned above similarly to the film-form sealing agent which concerns on 1st Embodiment. Furthermore, the release sheet mentioned above may be laminated
  • the water vapor intrusion rate from the end faces of the film-like sealing materials 1A and 1B in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH is 10 ⁇ m / h or less, preferably 8 ⁇ m / h or less, particularly 5 ⁇ m. / H or less is preferable.
  • the water vapor intrusion speed from the end face refers to a speed at which water vapor enters from the end faces of the film-like sealing materials 1A and 1B and moves in the in-plane direction. For example, in FIG.
  • Water vapor barrier resin layer 12 (1.1) Resin constituting the water vapor barrier resin layer 12
  • the resin constituting the water vapor barrier resin layer 12 is preferably a resin having a low water vapor permeability from the viewpoint of reducing the water vapor infiltration rate.
  • the resin constituting the water vapor barrier resin layer 12 are a rubber resin, a polyester resin, a polyolefin resin, a cycloolefin resin, and an epoxy resin. These resins can be used alone or in combination of two or more.
  • the rubber-based resin, polyester-based resin, polyolefin-based resin, cycloolefin-based resin, and epoxy-based resin described above that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the water vapor barrier resin layer 12 may have adhesiveness. That is, the resin constituting the water vapor barrier resin layer 12 may be selected so that the water vapor barrier resin layer 12 has adhesiveness. In particular, when the adhesive resin layer is not included as in the film-shaped sealing material 1A according to the first embodiment, or when one adhesive resin layer is included, the water vapor barrier resin layer 12 has an adhesive property. It is preferable to have.
  • the water vapor barrier resin layer 12 having adhesiveness can be satisfactorily adhered to a gas barrier film and an electronic element described later.
  • the water vapor barrier resin layer 12 may contain other resin components in addition to the above resin.
  • other resin components include olefin resins such as ethylene- (meth) acrylic acid copolymers, ethylene-vinyl acetate copolymers, ethylene- (meth) acrylic ester copolymers, urethane resins, polyurethanes, etc. Resin, polyester urethane resin, acrylic resin, amide resin, styrene resin, silane resin, and the like.
  • main material M water vapor permeability of a material (hereinafter referred to as “main material M”) obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 containing the resin is measured in the layer 12 made of the main material M having a thickness of 50 ⁇ m.
  • main material M a material obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 containing the resin is measured in the layer 12 made of the main material M having a thickness of 50 ⁇ m.
  • it is preferably 10 g / (m 2 ⁇ day) or less, particularly preferably 8 g / (m 2 ⁇ day) or less, and more preferably 6 g / (m 2 ⁇ day) or less.
  • the film-shaped sealing materials 1A and 1B have higher water vapor barrier properties. Can be achieved.
  • the water vapor permeability of the main material M can be obtained, for example, by producing a layer without using a hygroscopic agent and measuring the water vapor permeability.
  • Hygroscopic agent It is preferable that the water vapor
  • hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents. As these hygroscopic agents, the above-mentioned chemical hygroscopic agents and physical hygroscopic agents that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the hygroscopic agent preferably has little or no influence on the electronic element.
  • a chemical moisture absorbent it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction.
  • a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device.
  • a hygroscopic agent that is well mixed with the resin constituting the water vapor barrier resin layer 12 and does not denature even when subjected to a treatment such as heating.
  • the above-described compound containing a metalloxane bond, a metal oxide and a compound that forms a hydrate by reacting with water molecules it is preferable to use a compound that reacts with water at the OM site.
  • These hygroscopic agents produce a relatively stable product when a hygroscopic reaction occurs, which is less prone to vaporization and gas generation, and is well mixed with the material resin to provide a water vapor barrier resin. It is difficult to denature in the manufacturing process of the layer 12. As a result, it is possible to obtain the film-shaped sealing materials 1A and 1B exhibiting very excellent water vapor barrier properties.
  • the content of the hygroscopic agent in the water vapor barrier resin layer 12 is preferably 1 to 35% by mass, particularly preferably 3 to 30% by mass, and more preferably 5 to 25% by mass. .
  • steam barrier resin layer 12 is fully moisture-absorbed, and the water vapor
  • it is 35 mass% or less, when manufacturing the water vapor
  • the shape of the hygroscopic agent is not particularly limited, but may be, for example, liquid, powder, or granular.
  • the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and more preferably 0.1 to 5 ⁇ m. It is preferable that
  • the maximum moisture absorption amount of the hygroscopic agent is preferably 1.0 g / m 2 or more, particularly 1.5 g / m 2 when expressed by the amount of water absorbed by the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m. It is preferably m 2 or more, and more preferably 2.0 g / m 2 or more.
  • a hygroscopic agent having a maximum moisture absorption of 1.0 g / m 2 or more it becomes possible to sufficiently absorb moisture that permeates the water vapor barrier resin layer 12 and has a higher water vapor barrier property. Sealing materials 1A and 1B can be obtained.
  • the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, and a plasticizer. Further, it may contain various additives such as a lubricant, an antiblocking agent, a filler, a dispersant, a crosslinking agent (a curing agent; when a curable resin such as an epoxy resin is used), a silane coupling agent, and the like. In particular, when the water vapor barrier resin layer 12 includes a rubber-based resin, it is preferable to include a tackifier.
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and more preferably 15 to 100 ⁇ m. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 ⁇ m or more, a sufficient water vapor barrier property can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin.
  • the water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
  • the ratio of the thickness of the water vapor barrier resin layer 12 is preferably 50 to 100%, particularly preferably 55 to 100% of the thickness of the film-like sealing materials 1A and 1B. 60 to 100% is preferable.
  • the ratio of the thickness of the water vapor barrier resin layer 12 being 100% means that the film-like sealing materials 1A and 1B are composed of only the water vapor barrier resin layer 12.
  • the thickness of film-form sealing material 1A, 1B is mentioned later.
  • the film-shaped sealing materials 1A and 1B can contain a sufficient amount of a hygroscopic agent, thereby achieving higher water vapor barrier properties. be able to.
  • the first adhesive resin layer 11A and the second adhesive resin layer 11B are layers exhibiting adhesiveness to the adherend, and in the third embodiment, the water vapor barrier property. It can be arbitrarily provided on one side or both sides of the resin layer 12. When the adhesion of the water vapor barrier resin layer 12 to the adherend is low, a film having better adhesion to the adherend by providing one or both of the first and second adhesive resin layers 11A and 11B.
  • the shaped sealing material 1B can be realized.
  • Each of the first and second adhesive resin layers 11A and 11B may be a single layer or a plurality of layers.
  • the resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it exhibits adhesiveness to the adherend, and examples thereof include thermoplastic resins and curable resins.
  • the curable resin include a thermosetting resin and an energy ray curable resin.
  • a thermoplastic resin and a curable resin can also be mixed and used.
  • the thermoplastic resin and the curable resin the above-described thermoplastic resin and curable resin that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the compounding quantity in the case of using these resin individually or in combination can be made into the compounding quantity mentioned above about the film-form sealing material which concerns on 1st Embodiment.
  • the thermoplastic resin may have thermal adhesiveness or pressure-sensitive adhesiveness.
  • the film-shaped sealing material 1B can be firmly adhered to the adherend, and the first and second adhesive properties can be obtained.
  • the adhesion between the resin layers 11A and 11B and the water vapor barrier resin layer 12 is also improved.
  • the first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, You may contain various additives, such as a blocking inhibitor, a dispersing agent, a filler, a crosslinking agent (hardening agent; when using curable resins, such as an epoxy resin), a silane coupling agent, and a hygroscopic agent.
  • a tackifier an ultraviolet absorber
  • an ultraviolet stabilizer an antistatic agent
  • a pigment e.g., a pigment, a flame retardant, a plasticizer, a lubricant
  • You may contain various additives, such as a blocking inhibitor, a dispersing agent, a filler, a crosslinking agent (hardening agent; when using curable resins, such as an epoxy resin), a silane coupling agent, and a hyg
  • tackifier examples include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .
  • the water vapor permeability of the first and second adhesive resin layers 11A and 11B is preferably 30 g / (m 2 ⁇ day) or less, particularly 25 g / (m 2 ), when measured at a thickness of 50 ⁇ m. ⁇ Day) or less, more preferably 20 g / (m 2 ⁇ day) or less.
  • the water vapor permeability of the adhesive resin layers 11A and 11B is 30 g / (m 2 ⁇ day) or less, the water vapor intrusion rate from the end faces of the adhesive resin layers 11A and 11B can be easily reduced, and the adhesive resin layer When the film is provided, it is possible to prevent moisture from moving through the adhesive resin layer and reaching the electronic element, and to obtain a film-shaped sealing material 1B having higher water vapor barrier properties.
  • the thickness (one layer) of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 ⁇ m, particularly preferably 3 to 80 ⁇ m, and more preferably 5 to 50 ⁇ m. Is preferred. Sufficient adhesiveness is acquired because the thickness of 1st and 2nd adhesive resin layer 11A, 11B is 1 micrometer or more. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 ⁇ m or less, the thickness of the film-shaped sealing material 1B can be kept thin.
  • first and second adhesive resin layers 11A and 11B may be the same or different.
  • the thickness of the film-like sealing materials 1A, 1B is preferably 7 to 500 ⁇ m, particularly preferably 15 to 400 ⁇ m, and more preferably 20 to It is preferable that it is 200 micrometers. Sufficient water vapor barrier property and adhesiveness can be obtained because the film-shaped sealing materials 1A and 1B have a thickness of 7 ⁇ m or more. On the other hand, since the thickness of the film-shaped sealing materials 1A and 1B is 500 ⁇ m or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin. For example, even when used in an electronic device, It can be avoided that the thickness of the device becomes too thick.
  • the water vapor permeability of the film-shaped sealing materials 1A and 1B is preferably 20 g / (m 2 ⁇ day) or less when measured with the film-shaped sealing materials 1A and 1B having a thickness of 50 ⁇ m. It is preferably 15 g / (m 2 ⁇ day) or less, more preferably 10 g / (m 2 ⁇ day) or less.
  • the water vapor barrier resin layer contains a main material M having a high water vapor barrier property, and the water vapor barrier resin layer further contains a hygroscopic agent. The water vapor transmission rate as described above can be achieved.
  • the film-like sealing materials 1A and 1B have an adhesive force of 1 N / 25 mm or more when any one of the outermost layers of the film-like sealing materials 1A and 1B is bonded to alkali-free glass at 120 ° C.
  • it is preferably 3 N / 25 mm or more, more preferably 5 N / 25 mm or more.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • film-shaped sealing material 1A, 1B The film-shaped sealing material which concerns on 3rd Embodiment can be used for the use mentioned above about the film-shaped sealing material which concerns on 1st Embodiment.
  • the film-form sealing agent which concerns on 4th Embodiment The film-form sealing agent which concerns on 4th Embodiment,
  • the 1st and 2nd adhesive resin layer which shows adhesiveness with respect to a to-be-adhered body, the said 1st A water vapor barrier resin layer containing a cycloolefin resin and a hygroscopic agent, which is located between the first adhesive resin layer and the second adhesive resin layer.
  • the film-shaped sealing material 1B includes the first and second adhesive resin layers 11A and 11B, the first adhesive resin layer 11A, and the second adhesive.
  • the water vapor barrier resin layer 12 is provided between the conductive resin layer 11B.
  • 1st and 2nd adhesive resin layer 11A, 11B is laminated
  • the first adhesive resin layer 11A and / or the second adhesive resin layer 11B may be laminated on the water vapor barrier resin layer 12 via other layers.
  • a release sheet may be laminated on the first adhesive resin layer 11A and / or the second adhesive resin layer 11B.
  • the release sheet is used for forming the adhesive resin layer or is provided for the purpose of protecting the adhesive resin layer, and is peeled off when the film-shaped sealing material 1B is used.
  • the water vapor barrier resin layer 12 contains a cycloolefin resin and a hygroscopic agent.
  • Resin constituting the water vapor barrier resin layer 12 As the cycloolefin-based resin, the above-described cycloolefin-based resin that can be used for the film-shaped sealing material according to the first embodiment can be used. .
  • the water vapor barrier resin layer 12 may contain other resin components in addition to the cycloolefin resin.
  • Other resin components include polyethylene, polypropylene, polybutene, ethylene- ⁇ olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer Olefin resins such as coalescence (excluding cycloolefin resins), urethane resins, rubber resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins And silane-based resins.
  • the water vapor barrier resin layer 12 is preferably composed only of a cycloolefin resin as a component other than the hygroscopic agent. However, when the water vapor barrier resin layer 12 includes the above other resin components, the water vapor barrier resin layer 12 is a cycloolefin resin. Is preferably contained in an amount of 50% by mass or more, particularly preferably 60% by mass or more.
  • the water vapor permeability of the water vapor barrier resin layer 12 made of a material excluding the hygroscopic agent is 7 g / (m 2 .multidot.m) when measured with the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m excluding the hygroscopic agent. day) or less, particularly preferably 5 g / (m 2 ⁇ day or less, and more preferably 3 g / (m 2 ⁇ day) or less.
  • the film-shaped sealing material 1B having a higher water vapor barrier property can be obtained by setting the water vapor barrier property to be as high as 7 g / (m 2 ⁇ day) or less.
  • a preferable water vapor permeability of the cycloolefin resin is as described above.
  • Hygroscopic agent The water vapor barrier resin layer 12 contains a hygroscopic agent.
  • hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents. As these hygroscopic agents, the above-mentioned chemical hygroscopic agents and physical hygroscopic agents that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the hygroscopic agent preferably has little or no influence on the electronic element.
  • a chemical moisture absorbent it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction.
  • a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device.
  • a hygroscopic agent that is well mixed with the cycloolefin-based resin and does not denature even when subjected to a treatment such as heating.
  • a compound that reacts with a metal oxide or water molecule to form a hydrate is used. It is preferable. These hygroscopic agents produce a relatively stable product when a hygroscopic reaction occurs, which is less prone to vaporization and gas generation, and is well mixed with cycloolefin-based resins. It is difficult to denature in the manufacturing process of the layer 12. As a result, it is possible to obtain a film-shaped sealing material 1B that exhibits very excellent water vapor barrier properties.
  • the content of the hygroscopic agent in the water vapor barrier resin layer 12 is preferably 1 to 35% by mass, particularly preferably 3 to 30% by mass, and more preferably 5 to 25% by mass. .
  • the content of the hygroscopic agent is 1% by mass or more, moisture that permeates the water vapor barrier resin layer 12 is sufficiently absorbed, and the water vapor barrier property of the film-shaped sealing material 1B is further improved.
  • the content of the hygroscopic agent is 35% by mass or less, it is possible to form a film satisfactorily when the water vapor barrier resin layer 12 is manufactured.
  • the shape of the hygroscopic agent is not particularly limited, but may be, for example, powder or granular.
  • the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably, for example, 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and further preferably 0.1 to 5 ⁇ m.
  • the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, and a flame retardant.
  • various additives such as a plasticizer, a lubricant, an antiblocking agent, and a dispersant may be contained.
  • the thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and more preferably 15 to 100 ⁇ m. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 ⁇ m or more, a sufficient water vapor barrier property can be obtained. On the other hand, the thickness of the film-form sealing material 1B can be kept thin by setting the thickness of the water vapor barrier resin layer 12 to 300 ⁇ m or less.
  • the ratio of the thickness of the water vapor barrier resin layer 12 is preferably 10 to 99%, more preferably 30 to 95%, and more preferably 40 to 90% of the thickness of the film-like sealing material 1B. Particularly preferred is 50 to 80%. In addition, the thickness of the film-form sealing material 1B is mentioned later.
  • a sufficient water vapor barrier property can be obtained by setting the ratio of the thickness of the water vapor barrier resin layer 12 to 10% or more of the thickness of the film sealing material 1B.
  • the first and second adhesive resin layers 11A and 11B have a sufficient thickness. Thus, sufficient adhesiveness can be achieved.
  • the first adhesive resin layer 11A and the second adhesive resin layer 11B are layers that exhibit adhesion to the adherend, and in the fourth embodiment, a film-like seal It is provided in the outermost layer on both surfaces of the stopper 1B.
  • the water vapor barrier resin layer 12 described above has low adhesion to the adherend and cannot be used as a sealant only with the water vapor barrier resin layer 12, but the film-like sealant according to the fourth embodiment.
  • 1B by laminating the first and second adhesive resin layers 11A and 11B on both surfaces of the water vapor barrier resin layer 12, the adhesiveness to the adherend is excellent.
  • Each of the first and second adhesive resin layers 11A and 11B may be a single layer or a plurality of layers.
  • the resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it exhibits adhesiveness to the adherend.
  • a thermoplastic resin a thermosetting resin
  • examples include energy ray curable resins.
  • the 1st and 2nd adhesive resin layers 11A and 11B contain a thermoplastic resin.
  • the thermoplastic resin may have thermal adhesiveness or may have pressure sensitive adhesiveness.
  • thermoplastic resin examples include polyolefin resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins, rubber resins, and the like.
  • the polyolefin resin may be a modified one, and examples thereof include an acid-modified polyolefin resin and a silane-modified polyolefin resin. Among these, an acid-modified polyolefin resin or a silane-modified polyolefin resin is preferable.
  • the thermoplastic resin is an acid-modified polyolefin resin or a silane-modified polyolefin resin
  • the first and second adhesive resin layers 11A and 11B are particularly high for adherends such as glass plates and gas barrier films. Indicates adhesive strength. Moreover, it is excellent also in the adhesiveness of 1st and 2nd adhesive resin layer 11A, 11B and the water vapor
  • the polyolefin-based resin for example, ultra low density polyethylene (VLDPE, density: 880 kg / m 3 or more and less than 910 kg / m 3), low density polyethylene (LDPE, density: 910 kg / m 3 or more and less than 915 kg / m 3), medium density polyethylene (MDPE, density: 915 kg / m 3 or more and less than 942kg / m 3), high density polyethylene (HDPE, density: 942kg / m 3 or higher) such as a polyethylene resin, Polypropylene resin (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl acetate-maleic anhydride copolymer, ethylene- (meth) acrylic acid Copolymer, ethylene- (meth) acrylate ester
  • VLDPE ultra low density polyethylene
  • LDPE low density: 9
  • ethylene-vinyl acetate copolymer EVA
  • ethylene-acetic acid ethylene-acetic acid
  • Vinyl-maleic anhydride copolymers ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers and ethylene- (meth) acrylic acid ester-maleic anhydride copolymers are preferred, From the viewpoint of adhesive strength, ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid ester-maleic anhydride copolymers are more preferable.
  • the acid-modified polyolefin resin means a polyolefin resin graft-modified with an acid, and examples thereof include those obtained by reacting a polyolefin resin with an unsaturated carboxylic acid and introducing a carboxyl group (graft modification).
  • Examples of the unsaturated carboxylic acid to be reacted with the polyolefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, Examples thereof include citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic acid anhydride. These can be used individually by 1 type or in combination of 2 or more types. Among the above, maleic anhydride, which is particularly excellent in adhesive strength, is preferable.
  • the acid-modified polyolefin resin is preferably a maleic anhydride-modified polyolefin resin, particularly preferably a maleic anhydride-modified polyethylene resin.
  • the amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, particularly 0.2 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, it is 0.2 to 1 part by mass.
  • the amount of the unsaturated carboxylic acid to be reacted is in the above range, the resulting acid-modified polyolefin resin is excellent in adhesive strength.
  • the acid-modified polyolefin resin preferably has a Vicat softening point of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C.
  • a Vicat softening point of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C.
  • the adhesiveness does not appear at room temperature, so the film-like sealing material 1B is excellent in handleability and can be bonded by thermocompression bonding in a relatively short time.
  • Electronic devices such as display device modules having organic EL elements, electronic paper, and organic thin-film solar cells can be efficiently produced.
  • the Vicat softening point is a value measured based on ASTM D1525.
  • the acid-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly preferably 1 to 15 g / 10 minutes. Further, it is preferably 2 to 10 g / 10 minutes.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • the silane-modified polyolefin resin is obtained by graft-modifying a polyolefin resin by reacting an unsaturated silane compound with the polyolefin resin.
  • the silane-modified polyolefin resin can be firmly bonded particularly when the adherend is a glass plate.
  • polyolefin resin of the silane-modified polyolefin resin examples include the polyolefin resins exemplified for the acid-modified polyolefin resin.
  • the silane-modified polyolefin-based resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and in particular, silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene.
  • a modified polyethylene resin is preferred.
  • a vinyl silane compound is preferable.
  • the amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin. More preferably, the content is 0.5 to 5 parts by mass.
  • the amount of the unsaturated silane compound to be reacted is in the above range, the resulting silane-modified polyolefin resin is excellent in adhesive strength.
  • the silane-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly 0.5 to 15 g / 10 minutes. More preferably, it is 0.5 to 10 g / 10 min.
  • MFR melt flow rate
  • the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.
  • silane-modified polyolefin resin Commercially available products can also be used as the silane-modified polyolefin resin.
  • Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based.
  • Linklon registered trademark
  • Low density polyethylene-based linklon linear low-density polyethylene-based linkron
  • ultra-low-density polyethylene-based ultra-low-density polyethylene-based.
  • Rincron of ethylene-vinyl acetate copolymer system can be preferably used.
  • the thermoplastic resin may be an ionomer in which molecules are bonded by a metal cation.
  • the ionomer include olefin-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers.
  • olefinic ionomers examples include ethylene- (meth) acrylic acid copolymers, ethylene-fumaric acid copolymers, ethylene-maleic acid copolymers, ethylene-monomethyl monomethyl copolymers, and ethylene-monoethyl maleate copolymers.
  • bonded between molecules of olefin resin, such as a polymer, with the metal ion is mentioned.
  • the metal ion include alkali metals such as sodium and lithium, and polyvalent metals such as alkaline earth metals such as zinc, magnesium and calcium.
  • An ionomer can be used individually by 1 type or in mixture of 2 or more types.
  • polyester resin any resin having adhesiveness may be used, and a known resin can be used.
  • the first and second adhesive resin layers 11A and 11B preferably contain 60 to 100% by mass of thermoplastic resin, particularly preferably 70 to 100% by mass, and more preferably 80 to 100% by mass. It is preferable to do.
  • the first and second adhesive resin layers 11A and 11B may include, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, You may contain various additives, such as an antiblocking agent, a dispersing agent, a filler, and a hygroscopic agent.
  • the thickness (one layer) of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 ⁇ m, particularly preferably 3 to 80 ⁇ m, and more preferably 5 to 50 ⁇ m. Is preferred. Sufficient adhesiveness is acquired because the thickness of 1st and 2nd adhesive resin layer 11A, 11B is 1 micrometer or more. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 ⁇ m or less, the thickness of the film-shaped sealing material 1B can be kept thin.
  • first and second adhesive resin layers 11A and 11B may be the same or different.
  • the maximum moisture absorption amount of the film-like sealing material 1B is expressed as follows when the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m represents the amount of water absorbed. It is preferably 0 g / m 2 or more, particularly preferably 1.5 g / m 2 or more, and more preferably 2.0 g / m 2 or more.
  • the maximum amount of moisture absorption of the film-like sealing material 1B is 1.0 g / m 2 or more, it becomes possible to sufficiently absorb moisture that has entered the film-like sealing material 1B, and to have a higher water vapor barrier property.
  • the film-form sealing material 1B which has can be obtained.
  • the thickness of the film-like sealing material 1B is preferably 7 to 500 ⁇ m, particularly preferably 15 to 400 ⁇ m, and further preferably 20 to 200 ⁇ m. Sufficient water vapor barrier property and adhesiveness can be obtained because the thickness of the film-form sealing material 1B is 7 ⁇ m or more. On the other hand, since the thickness of the film-shaped sealing material 1B is 500 ⁇ m or less, the thickness of the film-shaped sealing material 1B can be kept thin. For example, even when used for an electronic device, the thickness of the electronic device Can be prevented from becoming too thick.
  • the water vapor transmission rate of the film-shaped sealing material 1B is preferably 7 g / (m 2 ⁇ day) or less, particularly 5 g / (m, when measured with a film-shaped sealing material 1B having a thickness of 50 ⁇ m. 2 ⁇ day) or less, more preferably 3 g / (m 2 ⁇ day) or less.
  • the water vapor transmission rate of the film-shaped sealing material 1B is 7 g / (m 2 ⁇ day) or less, water vapor from the outside is effectively blocked by the film-shaped sealing material 1B, and the sealing target object Reaching is prevented / suppressed, and the object to be sealed is hardly affected by moisture.
  • the water vapor barrier resin layer 12 containing the cycloolefin resin and the hygroscopic agent it is possible to achieve the water vapor transmission rate as described above. it can.
  • the film-like encapsulant 1B preferably has an adhesive force to alkali-free glass of 5 N / 25 mm or more when bonded at 120 ° C., particularly preferably 10 N / 25 mm or more.
  • the adhesive force is 5 N / 25 mm or more, so that the object to be sealed is surely sealed, and the occurrence of floating or peeling between the adherend such as a glass plate or a gas barrier film is prevented. Can do.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • the film-shaped sealing material 1B can be manufactured by a conventional method. For example, a method in which the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B are co-extruded so as to be laminated in that order, the first adhesive property A single-layer film (first adhesive resin film) as the resin layer 11A and a single-layer film (second adhesive resin film) as the second adhesive resin layer 11B are prepared, respectively.
  • first and second adhesive resin layers 11A and 11B are formed on the release sheet, and the release sheets with the first and second adhesive resin layers 11A and 11B are prepared, respectively.
  • the film-like sealing material 1B can also be manufactured by a method of laminating release sheets with the first and second adhesive resin layers 11A and 11B on both surfaces of the barrier resin film.
  • the method of forming the first and second adhesive resin layers 11A and 11B is not particularly limited, and is a melt extrusion method or a calendar method. Examples thereof include a dry method and a solution method.
  • a solution obtained by dissolving the above-described resin in an organic solvent is applied by a known application method, and each layer may be formed by appropriately drying the obtained coating film.
  • steam barrier resin layer 12 water vapor
  • the mixture of a cycloolefin type resin and a hygroscopic agent is made into a melt extrusion method, a calendar method, a dry method, a solution.
  • the method of forming into a film by the method etc. is illustrated.
  • the solution method a solution obtained by dissolving a cycloolefin resin and a hygroscopic agent in an organic solvent is applied by a known application method, and the obtained coating film is appropriately dried to form the water vapor barrier resin layer 12. That's fine.
  • first and second adhesive resin layers 11A and 11B first adhesive resin film, second adhesive resin film
  • water vapor barrier resin layer 12 water vapor barrier resin film
  • the heating temperature is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B (first adhesive resin film and second adhesive resin film) are softened.
  • the film-shaped sealing material 1B which concerns on 4th Embodiment is excellent in water vapor
  • a module for a display device having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, an electronic paper, a solar cell module, and the like can be given.
  • a display device module (organic EL module) or electronic paper having an organic EL element a high water vapor barrier property is required. Therefore, the film-like sealing material 1B according to the fourth embodiment is preferably used. can do.
  • the film-form sealing agent which concerns on 5th Embodiment is the 1st and 2nd adhesive resin layer which shows adhesiveness with respect to a to-be-adhered body, the said 1st A water vapor barrier resin layer containing a cycloolefin resin and a hygroscopic agent, which is located between the first adhesive resin layer and the second adhesive resin layer.
  • the film-like sealant has a total light transmittance of 80% or more and a haze value of 10% or less.
  • the film-shaped sealing material 1B includes the first and second adhesive resin layers 11A and 11B, the first adhesive resin layer 11A, and the second adhesive.
  • the water vapor barrier resin layer 12 is provided between the conductive resin layer 11B.
  • 1st and 2nd adhesive resin layer 11A, 11B is laminated
  • the first adhesive resin layer 11A and / or the second adhesive resin layer 11B may be laminated on the water vapor barrier resin layer 12 via other layers.
  • a release sheet may be laminated on the first adhesive resin layer 11A and / or the second adhesive resin layer 11B.
  • the release sheet is used for forming the adhesive resin layer or is provided for the purpose of protecting the adhesive resin layer, and is peeled off when the film-shaped sealing material 1B is used.
  • the water vapor barrier resin layer 12 contains a cycloolefin-based resin and a hygroscopic agent. And the film-form sealing material 1 has a total light transmittance of 80% or more and a haze value of 10% or less. Since the cycloolefin resin generally has a high water vapor barrier property, the water vapor barrier resin layer 12 containing the cycloolefin resin is excellent in the water vapor barrier property. Even if moisture enters the water vapor barrier resin layer 12, the moisture is taken in by the hygroscopic agent.
  • the water vapor barrier resin layer 12 has an even higher water vapor barrier property, and the water vapor barrier property of the film-shaped sealing material 1 having such a water vapor barrier resin layer 12 is very excellent.
  • the high water vapor barrier property of the cycloolefin-based resin enables the content of the hygroscopic agent to be relatively low, the influence of the hygroscopic agent on the optical properties of the film-like sealing material is suppressed, and high light transmittance. Is achieved.
  • the water vapor barrier resin layer 12 contains a cycloolefin resin and a hygroscopic agent.
  • the water vapor barrier resin layer 12 may be a single layer or a plurality of layers.
  • the water vapor barrier resin layer 12 contains a cycloolefin resin.
  • a cycloolefin resin the above-described cycloolefin-based resin that can be used for the film-shaped sealing material according to the first embodiment can be used.
  • the water vapor barrier resin layer 12 may contain other resin components in addition to the cycloolefin resin.
  • Other resin components include polyethylene, polypropylene, polybutene, ethylene- ⁇ olefin copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer Olefin resins such as coalescence (excluding cycloolefin resins), urethane resins, rubber resins, polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, amide resins, styrene resins And silane-based resins.
  • the water vapor barrier resin layer 12 is preferably composed only of a cycloolefin resin as a component other than the hygroscopic agent. However, when the water vapor barrier resin layer 12 includes the above other resin components, the water vapor barrier resin layer 12 is a cycloolefin resin. Is preferably contained in an amount of 50% by mass or more, particularly preferably 60% by mass or more.
  • the water vapor permeability of the water vapor barrier resin layer 12 made of a material excluding the hygroscopic agent is 7 g / (m 2 .multidot.m) when measured with the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m excluding the hygroscopic agent. day) or less, particularly preferably 5 g / (m 2 ⁇ day) or less, and more preferably 3 g / (m 2 ⁇ day) or less.
  • the preferable water vapor permeability of a cycloolefin type resin becomes as above-mentioned water vapor permeability.
  • Hygroscopic agent The water vapor barrier resin layer 12 contains a hygroscopic agent.
  • hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents.
  • Chemical type hygroscopic agent is a hygroscopic agent that takes in surrounding water by using water molecules as reactants of chemical reaction.
  • any chemical moisture absorbent can be used.
  • Compounds that contain a bond can be used.
  • These chemical hygroscopic agents can be used alone or in combination of two or more.
  • metal oxides that can be used as chemical humectants are calcium oxide, barium oxide, magnesium oxide and strontium oxide. These metal oxides can be used alone or in combination of two or more.
  • calcium oxide performs reaction of the following formula
  • water molecules are converted into hydroxyl groups in calcium hydroxide which is a reaction product.
  • Metal oxides other than calcium oxide also perform the same reaction as in formula (1).
  • Examples of compounds that can be used as chemical moisture absorbents and react with water molecules to form hydrates are sodium sulfate, potassium sulfate / aluminum, magnesium sulfate, calcium sulfate, aluminum sulfate, sodium carbonate, sodium acetate, thiosulfate Sodium and copper sulfate. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • magnesium sulfate performs reaction of the following formula
  • Compounds other than magnesium sulfate also perform the same reaction as in formula (2).
  • potassium sulfate / aluminum sulfate or magnesium sulfate is preferably used as the compound that reacts with water molecules to form a hydrate.
  • the compound containing a metalloxane bond is a compound containing a metalloxane bond, that is, a bond between a metal element and oxygen.
  • a compound represented by the general formula M (OR) n M represents a metal element, R represents an alkyl group or an acyl group, and n represents an oxidation number of the metal element
  • M (OR) n ′ —O] m M is a metal element, R is an alkyl group or an acyl group, n ′ is an integer of 1 or more, and is obtained by subtracting 2 from the oxidation number of the metal element, m is an integer of 1 or more
  • the compound containing a metalloxane bond generally includes a compound called a metalloxane compound or a polymetalloxane compound.
  • More specific examples of compounds containing a metalloxane bond are metal alkoxides, metal acylates and metal chelates.
  • the site of the compound containing a metalloxane bond that reacts with water is mainly M—O—R or M—O—M. These compounds can be used individually by 1 type or in combination of 2 or more types.
  • Metal alkoxides are examples of compounds that react with water at the M-O-R site.
  • the metal alkoxide are a compound in which R is an alkyl group in the general formula M (OR) n or a compound having a structure in which R is an alkyl group in the formula [M (O—R) n ′ —O] m .
  • Specific examples of metal alkoxides are tetramethyl orthotitanate (also known as: tetramethoxy titanium (IV), titanium (IV) tetramethoxide) and aluminum ethoxide. These metal alkoxides can be used individually by 1 type or in combination of 2 or more types.
  • aluminum ethoxide performs reaction of the following formula
  • water molecules are utilized for the hydrolysis of aluminum ethoxide, resulting in the production of aluminum hydroxide and ethanol.
  • Compounds other than aluminum ethoxide perform the same reaction as in formula (3).
  • Metal acylates are examples of compounds that react with water at the MOR or MOM sites.
  • an example of a compound that reacts with water at the M—O—R moiety is a compound in which R is an acyl group in the general formula M (OR) n .
  • An example of a compound that reacts with water at the MOM site in the metal acylate is a compound having a structure in which R is an acyl group in the formula [M (O—R) n ′ —O] m .
  • Specific examples of the metal acylate are cyclic aluminum oxide octylate and cyclic aluminum oxide stearate. These metal acylates can be used alone or in combination of two or more.
  • the cyclic aluminum oxide octylate reacts with water molecules according to the following formula (4), and there is only one product. Compounds other than cyclic aluminum oxide octylate also perform the same reaction as in formula (4).
  • the physical hygroscopic agent is a hygroscopic agent that takes in surrounding water regardless of a chemical reaction, and for example, adsorbs surrounding water molecules on the surface of the hygroscopic agent.
  • any physical hygroscopic agent can be used, and for example, zeolite, activated alumina, silica gel, and a clay compound can be used.
  • zeolite a molecular sieve can be used.
  • the hygroscopic agent preferably has little or no influence on the electronic element.
  • a chemical moisture absorbent it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction.
  • a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device.
  • a hygroscopic agent that is well mixed with the cycloolefin-based resin and does not denature even when subjected to a treatment such as heating.
  • the hygroscopic agent has a small influence on the optical characteristics of the film-shaped sealing material 1, and it is particularly preferable that the light-transmitting property of the film-shaped sealing material 1 is not easily lowered.
  • a chemical moisture absorbent when used for the film-shaped sealing material 1 according to the fifth embodiment, it is preferable to use a compound that reacts with water molecules to form a hydrate.
  • potassium sulfate / aluminum sulfate or magnesium sulfate is preferably used as the compound that reacts with water molecules to form a hydrate.
  • hygroscopic agents have sufficient hygroscopicity, the content in the water vapor barrier resin layer 12 can be relatively reduced, suppressing the influence on the optical properties of the film-shaped sealing material 1, High light transmission can be achieved. As a result, it is possible to obtain a film-shaped sealing material 1 that exhibits extremely excellent water vapor barrier properties and light transmittance.
  • the content of the hygroscopic agent in the water vapor barrier resin layer 12 is preferably 1 to 35% by mass, more preferably 2 to 20% by mass, and particularly preferably 3 to 10% by mass, Further, it is preferably 3 to 8% by mass.
  • the content of the hygroscopic agent is 1% by mass or more, moisture that permeates the water vapor barrier resin layer 12 is sufficiently absorbed, and the water vapor barrier property of the film-shaped sealing material 1 is further improved.
  • the moisture-absorbing agent content is 35% by mass or less, it is possible to satisfactorily form a film when the water vapor barrier resin layer 12 is produced, and the optical characteristics of the water vapor barrier resin layer 12 are obtained. Can be suppressed, and light transmittance can be improved.
  • the content in the water vapor barrier resin layer 12 is preferably 1 to 10%.
  • magnesium sulfate is used as the hygroscopic agent
  • its content in the water vapor barrier resin layer 12 is preferably 2 to 8%
  • potassium sulfate / aluminum is used, The content in the barrier resin layer 12 is preferably 3 to 6%.
  • the shape of the hygroscopic agent is not particularly limited, but may be, for example, powder or granular.
  • the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably, for example, 0.1 to 20 ⁇ m, particularly preferably 0.1 to 10 ⁇ m, and further preferably 0.1 to 5 ⁇ m.
  • the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, and a flame retardant.
  • various additives such as a plasticizer, a lubricant, an antiblocking agent, and a dispersant may be contained.
  • the thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 ⁇ m, particularly preferably 10 to 200 ⁇ m, and more preferably 15 to 100 ⁇ m. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 ⁇ m or more, a sufficient water vapor barrier property can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 ⁇ m or less, the thickness of the film-shaped sealing material 1 can be kept thin, and the optical path in the film-shaped sealing material 1 can be shortened. And light transmittance can be improved.
  • the ratio of the thickness of the water vapor barrier resin layer 12 is preferably 10 to 99%, more preferably 30 to 95%, and more preferably 40 to 90% of the thickness of the film-like sealing material 1. Particularly preferred is 50 to 80%. In addition, about the thickness of the film-form sealing material 1, it mentions later. A sufficient water vapor barrier property can be obtained by setting the ratio of the thickness of the water vapor barrier resin layer 12 to 10% or more of the thickness of the film sealing material 1. On the other hand, when the ratio of the thickness of the water vapor barrier resin layer 12 is 99% or less of the thickness of the film sealing material 1, the first and second adhesive resin layers 11A and 11B have a sufficient thickness. Thus, sufficient adhesiveness can be achieved.
  • Adhesive resin layer As the adhesive resin layer in the film-shaped sealing material according to the fifth embodiment, the adhesive resin layer described above in the film-shaped sealing material according to the fourth embodiment is used. Can do.
  • the total light transmittance of the film-shaped sealing material 1 is 80% or more, preferably 83% or more, and particularly preferably 86% or more.
  • the total light transmittance refers to a value measured according to JIS K7361: 1997.
  • the method for measuring the total light transmittance is as shown in the test examples described later.
  • the water vapor barrier property of the cycloolefin resin is high, the content of the hygroscopic agent can be relatively reduced, and the influence of the hygroscopic agent on the optical characteristics of the film-shaped sealing material. Is kept low.
  • the haze value of the film-shaped sealing material 1 is 10% or less, preferably 8% or less, more preferably 5% or less, and particularly preferably 3% or less.
  • the haze value refers to a value measured according to JIS K7136: 2000.
  • the measuring method of a haze value is as showing to the test example mentioned later.
  • the water vapor barrier property of the cycloolefin resin is high, the content of the hygroscopic agent can be relatively reduced, and the influence of the hygroscopic agent on the optical characteristics of the film-shaped sealing material. Is kept low.
  • the maximum amount of moisture absorption of the film-shaped sealing material 1 is preferably 1.0 g / m 2 or more when expressed by the amount of water absorbed by the water vapor barrier resin layer 12 having a thickness of 50 ⁇ m. It is preferably 1.5 g / m 2 or more, more preferably 2.0 g / m 2 or more.
  • the maximum moisture absorption amount of the film-shaped sealing material 1 is 1.0 g / m 2 or more, it is possible to sufficiently absorb moisture that has entered the film-shaped sealing material 1, and to have a higher water vapor barrier property.
  • the film-form sealing material 1 which has can be obtained.
  • the thickness of the film-shaped sealing material 1 is preferably 7 to 500 ⁇ m, particularly preferably 15 to 400 ⁇ m, and further preferably 20 to 200 ⁇ m.
  • the thickness of the film-form sealing material 1 is 7 ⁇ m or more, sufficient water vapor barrier properties and adhesiveness can be obtained.
  • the thickness of the film-shaped sealing material 1 is 500 ⁇ m or less, the thickness of the film-shaped sealing material 1 can be kept thin. For example, even when used for an electronic device, the thickness of the electronic device Can be prevented from becoming too thick, the optical path in the film-shaped sealing material 1 can be shortened, and the light transmittance can be improved.
  • the water vapor transmission rate of the film-shaped sealing material 1 is preferably 7 g / (m 2 ⁇ day) or less, particularly 5 g / (m) when measured with the film-shaped sealing material 1 having a thickness of 50 ⁇ m. 2 ⁇ day) or less, more preferably 3 g / (m 2 ⁇ day) or less.
  • the water vapor transmission rate of the film-shaped sealing material 1 is 7 g / (m 2 ⁇ day) or less, the water vapor from the outside is effectively blocked by the film-shaped sealing material 1, and is sealed on the object to be sealed. Reaching is prevented / suppressed, and the object to be sealed is hardly affected by moisture.
  • the above water vapor permeability can be achieved. it can.
  • the film-like sealing material 1 preferably has an adhesive strength to non-alkali glass of 5 N / 25 mm or more when bonded at 120 ° C., particularly preferably 10 N / 25 mm or more.
  • the adhesive force is 5 N / 25 mm or more, so that the object to be sealed is surely sealed, and the occurrence of floating or peeling between the adherend such as a glass plate or a gas barrier film is prevented. Can do.
  • the measuring method of adhesive force is as showing to the test example mentioned later.
  • film-shaped sealing material 1 The film-shaped sealing material which concerns on 5th Embodiment can be used for the use mentioned above about the film-shaped sealing material which concerns on 4th Embodiment.
  • a sealing sheet according to an embodiment of the present invention includes the film-shaped sealing material according to the first to fifth embodiments and a gas barrier film laminated on one surface of the film-shaped sealing material.
  • FIG. 3 is a schematic cross-sectional view of the sealing sheet 2 provided with the film-like sealing material 1B shown in FIG.
  • This sealing sheet 2 is provided with the gas barrier film 21 laminated
  • the sealing sheet 2 is not limited to the one shown in FIG. 3, but includes the film-like sealing material 1A shown in FIG. 1 instead of the film-like sealing material 1B shown in FIG. It's okay. That is, the first and second adhesive resin layers 11A and 11B may be removed from the sealing sheet 2 in FIG. Furthermore, the sealing sheet may be obtained by removing one of the first and second adhesive resin layers 11A and 11B from the sealing sheet 2 in FIG.
  • the gas barrier film 21 is a film having characteristics that make it difficult for gas such as water vapor and oxygen to pass therethrough. Depending on the application target of the sealing sheet 2, the gas barrier film 21 needs to be transparent.
  • the gas barrier film 21 is preferably a laminate of a base film and a gas barrier layer. As such a gas barrier film 21, for example, one having a gas barrier layer formed directly or via another layer on one or both sides of a base film, or having a gas barrier layer in the middle of a base film is used. can do.
  • the base film examples include polyolefin such as polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyester such as polyethylene terephthalate and polybutylene terephthalate, polychlorinated Acrylic resins such as vinyl, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, Examples thereof include a film made of a resin such as an ABS resin or an ionomer resin, or a laminated film thereof.
  • a resin such as an ABS resin or an ionomer resin, or a laminated film thereof.
  • a film made of polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate and the like is preferable.
  • the base film may be a stretched film or an unstretched film. Further, the base film may contain various additives such as an ultraviolet absorber.
  • the thickness of the base film is preferably 1 to 500 ⁇ m, particularly preferably 5 to 300 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • the gas barrier layer is laminated for the purpose of imparting gas barrier properties to the base film.
  • the material of the gas barrier layer is not particularly limited as long as the gas barrier property of the gas barrier film 21 can be set to a desired level.
  • Examples of the material for the gas barrier layer include silicon compounds such as polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds, silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, and magnesium oxide.
  • Inorganic oxides such as zinc oxide, indium oxide, and tin oxide, inorganic nitrides such as silicon nitride and aluminum nitride, inorganic oxynitrides such as silicon oxynitride, and metals such as aluminum, magnesium, zinc, and tin It is done. These can be used individually by 1 type or in combination of 2 or more types.
  • the thickness of the gas barrier layer is preferably 1 nm to 10 ⁇ m, more preferably 10 to 1000 nm, particularly preferably 20 to 500 nm, and further preferably 50 to 200 nm.
  • the gas barrier layer may be a single layer or a plurality of layers, but from the viewpoint of obtaining higher gas barrier properties, the gas barrier layer is preferably a plurality of layers.
  • the method for forming the gas barrier layer may be appropriately selected according to the material to be used.
  • the gas barrier layer material is formed on a base film by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like, or the gas barrier layer material is dissolved in an organic solvent. Examples include a method in which a solution is applied to a base film and plasma ions are implanted into the obtained coating film.
  • Examples of ions implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, Examples include ions of metals such as silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.
  • the water vapor transmission rate of the gas barrier film 21 is preferably 0.5 g / (m 2 ⁇ day) or less, particularly 0.1 g / (m 2 ⁇ day) or less at 40 ° C. and 90% RH. More preferably, it is 0.05 g / (m 2 ⁇ day) or less.
  • the film-like sealing materials 1A and 1B and the gas barrier film 21 may be laminated and laminated.
  • the water vapor barrier resin layer 12 itself has adhesiveness, or the film-shaped sealing material 1B has the adhesive resin layers 11A and 11B. Therefore, it adheres firmly to the gas barrier film 21. Therefore, when an electronic device or the like is sealed using the sealing sheet 2, it is possible to effectively prevent water vapor from entering between the gas barrier film 21 and the film-like sealing materials 1A and 1B. .
  • the gas barrier film 21 has a gas barrier layer on one side
  • the gas barrier film 21 and the film-shaped sealing materials 1A and 1B may be laminated so that the gas barrier layer is on the film-shaped sealing material 1A and 1B side. preferable.
  • the heating temperature is preferably equal to or higher than the temperature at which the adhesive resin layer 11 of the film-like sealing materials 1A and 1B is softened.
  • the sealing sheet 2 can be used for the same applications as those of the film-shaped sealing materials 1A and 1B described above, and in particular, a module for a display device and an electronic paper having an organic EL element or the like that requires high water vapor barrier properties. It can be suitably used for sealing electronic elements in electronic devices such as solar cell modules.
  • the surface opposite to the side on which the gas barrier film 21 is laminated (second adhesive resin layer 11 ⁇ / b> B in FIG. 3) is bonded to the adherend. Can be sealed.
  • the electronic device according to one embodiment of the present invention is sealed with the film-like sealing materials 1A and 1B according to the first to fifth embodiments.
  • the electronic device 3 ⁇ / b> A according to the embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a film-like sealing material that seals the electronic element 32. 1B and the sealing member 33 laminated
  • the sealing member 33 For example, a glass plate etc. are mentioned.
  • an electronic device is sealed with a sealing sheet 2 according to the first to fifth embodiments.
  • the electronic device 3 ⁇ / b> B according to the embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a sealing sheet 2 that seals the electronic element 32.
  • the sealing sheet 2 is a laminated body of the film-shaped sealing material 1B and the gas barrier film 21 laminated
  • the electronic device is not limited to the one shown in FIGS. 4 and 5 but includes the film-like sealing material 1A shown in FIG. 1 instead of the film-like sealing material 1B shown in FIG. It's okay. That is, the first and second adhesive resin layers 11A and 11B may be removed from the electronic devices 3A and 3B shown in FIG. Furthermore, the electronic device may be one obtained by removing one of the first and second adhesive resin layers 11A and 11B from the electronic devices 3A and 3B of FIG.
  • These electronic devices 3A and 3B include, for example, a liquid crystal element, an LED element, an organic EL element, and the like as an electronic element 32, an electrophoretic element, an electronic granular element, and a cholesteric liquid crystal element as the electronic element 32.
  • the electronic devices 3A and 3B may be top emission type electronic devices or bottom emission type electronic devices.
  • the substrate 31 is preferably a transparent substrate.
  • the sealing member 33 and the gas barrier film 21 are preferably transparent.
  • the substrate 31 is appropriately selected according to the type of the electronic devices 3A and 3B, and preferred examples include a glass plate and a base film.
  • the material of the glass plate include non-alkali glass, soda lime glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, barium / strontium-containing glass, inorganic glass made of quartz, hybrid glass, and the like. Can be mentioned.
  • As a base film what was illustrated by the gas barrier film 21 is mentioned, for example.
  • the thickness of the substrate 31 is appropriately set according to the types of the electronic devices 3A and 3B.
  • the method for manufacturing the electronic device 3A is not particularly limited.
  • the electronic element 32 is formed on the substrate 31 by a conventional method.
  • the film-like sealing materials 1A and 1B are placed so as to cover the electronic element 32, and the sealing member 33 such as a glass plate is placed on the film-like sealing materials 1A and 1B.
  • the electronic device 3A can be manufactured by bonding them together and sealing the electronic element 32.
  • the laminated body which bonded together the film-form sealing materials 1A and 1B, and the sealing member 33 may be obtained, and this laminated body may be bonded together with the electronic element 32, and electronic device 3A may be manufactured.
  • the method for manufacturing the electronic device 3B is not particularly limited.
  • the sealing sheet 2 is placed so that the film-shaped sealing materials 1A and 1B are on the electronic element 32 side so as to cover the electronic element 32 formed on the substrate 31, and they are bonded to each other.
  • the electronic device 3B can be manufactured by sealing the element 32.
  • Sealing may be performed at normal pressure, in a reduced pressure atmosphere, or a combination thereof. Moreover, you may heat when bonding the film-form sealing materials 1A and 1B and the electronic element 32 together. By heating, the film-like sealing materials 1A and 1B and the electronic element 32, the substrate 31, and the sealing member 33 or the gas barrier film 21 are firmly bonded.
  • the heating temperature at the time of pasting is usually preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 are softened.
  • the film-like sealing materials 1A and 1B have the adhesiveness of the water vapor barrier resin layer 12 or the first and second adhesive resin layers 11A and 11A, the film-like sealing material 1A, 1B and the substrate 31, the film-shaped sealing materials 1A and 1B and the electronic element 32, the film-shaped sealing materials 1A and 1B and the sealing member 33, and the film-shaped sealing materials 1A and 1B and the gas barrier film 21 are strong. It is prevented and restrained from adhering and causing floating and peeling between them, and intrusion of water vapor between them.
  • Example 1-1 ⁇ Production of film-like encapsulant>
  • the materials constituting the adhesive resin layer and the water vapor barrier resin layer shown in Table 1 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and a first adhesive resin layer having a thickness of 7.5 ⁇ m;
  • a film-shaped sealing material was produced by laminating a 35 ⁇ m thick water vapor barrier resin layer and a 7.5 ⁇ m thick second adhesive resin layer in that order.
  • ⁇ Preparation of sealing sheet> Aluminum of the obtained film-like sealing material and a gas barrier film having an aluminum foil (a laminated film in which a polyethylene terephthalate sheet having a thickness of 12 ⁇ m is bonded to one surface of an aluminum foil having a thickness of 7 ⁇ m with a urethane adhesive layer, manufactured by Aya Aluminum Co. The foil surface was bonded while heating at 120 ° C. to obtain a sealing sheet.
  • ITO indium tin oxide
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (manufactured by Luminescence Technology) was 60 nm
  • Tris (8- Hydroxy-quinolinate) Aluminum (manufactured by Luminescence Technology) at 40 nm
  • 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminesense Technology) at 10 nm
  • (8-hydroxy-quinolinolate) lithium was sequentially deposited at a rate of 10 nm and 0.1 to 0.2 nm / s to form a light emitting layer.
  • Al aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, whereby an organic EL device was obtained.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • the sealing sheet was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left to cool to room temperature. And a sealing sheet is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, from the edge part of an sealing sheet to an organic EL element The distance was adjusted to 5 mm. They were bonded together while heating at 100 ° C. to seal the organic EL element, thereby obtaining a bottom emission type electronic device.
  • Examples 1-2 and 1-3 A film-shaped sealing material was produced in the same manner as in Example 1-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 1. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Example 1-4 A coating liquid containing the material constituting the adhesive resin layer shown in Table 1 is applied onto a release sheet, dried at 100 ° C. for 2 minutes, and the release sheet is bonded thereon to form an adhesive having a thickness of 7.5 ⁇ m. A resin layer was formed, and two adhesive resin layers having release sheets laminated on both sides were produced.
  • the adhesive resin layer was bonded to each of both surfaces of the obtained water vapor barrier resin film while heating at 120 ° C.
  • one release sheet laminated on the adhesive resin layer was peeled off, and the exposed surface of the adhesive resin layer and the surface of the water vapor barrier resin layer were bonded together.
  • the other release sheet was peeled off to produce a film-like sealing material.
  • an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Examples 1-5 and 1-6 A coating liquid containing a material constituting the water vapor barrier resin layer shown in Table 1 is applied onto a release sheet, dried at 100 ° C. for 2 minutes, and the release sheet is bonded thereon to have a water vapor barrier property of 25 ⁇ m in thickness. A resin layer was obtained and used as a film-like sealing material. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Example 1-1 A film-shaped sealing material was produced in the same manner as in Example 1-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 1. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Example 1-3 A film-shaped sealing material was produced in the same manner as in Example 1-4, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 1. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Example 1-5 A film-like sealing material was produced in the same manner as in Example 1-1, except that the materials and thicknesses constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 1. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 1-1 to obtain a bottom emission type electronic device.
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • Exxon Butyl 365 Isobutylene resin (exxon mobile, trade name “Exxon Butyl 365”)
  • Tackifier Aliphatic petroleum resin (manufactured by Nippon Zeon Co., Ltd., trade name “Quinton A-100”)
  • Polyester SNT Ester resin (made by Nippon Synthetic Chemical Co., Ltd., trade name “Polyester SNT”)
  • Sumikasen L705 Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikasen L705”, softening point 86 ° C.)
  • Water vapor barrier resin layer TOPAS 9506F-04: cycloole
  • the obtained test piece was bonded and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, and then in that environment, a tensile tester (manufactured by Orientec Co., Tensilon) was used, and the peeling rate was 300 mm. / Min, a peel test was performed under the conditions of a peel angle of 180 °, and the adhesive strength (N / 25 mm) was measured. The results are shown in Table 1. In Table 1, when the adhesive strength was 1 N / 25 mm or less, it was expressed as “ ⁇ 1”.
  • the film-like sealing materials obtained in the examples were excellent in water vapor barrier properties and adhesiveness. Further, in the electronic device obtained in the example, moisture hardly entered from the end. Furthermore, the organic EL element sealed with the film-like sealing material obtained in the examples was excellent in durability, almost no non-light emitting portion was seen, and the performance of the electronic device was good.
  • the film-like sealing material of Comparative Example 1-1 had a very low adhesive force and could not seal the electronic device. Therefore, electronic device evaluation could not be performed.
  • the film-form sealing materials of Comparative Examples 1-2 to 1-5 were able to seal the electronic element, they were inferior in terms of evaluation of the electronic device.
  • the water vapor permeability of the main material M was high.
  • the water vapor transmission rate of the adhesive resin layer was very high.
  • the film-like sealing material of Comparative Example 1-4 could not absorb moisture because it did not contain a hygroscopic agent.
  • the moisture-absorbing ability was insufficient because the water vapor barrier resin layer was thin.
  • Example 2-1 A film-shaped sealing material, a sealing sheet, and an electronic device were manufactured by the same manufacturing method as in Example 1-1.
  • Example 2-2 A film-like sealing material was produced in the same manner as in Example 2-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 2. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 2-1, and a bottom emission type electronic device was obtained.
  • Example 2-3 A coating liquid containing a material constituting the water vapor barrier resin layer shown in Table 2 is applied onto a release sheet, dried at 100 ° C. for 2 minutes, and the release sheet is bonded thereon to have a 25 ⁇ m thick water vapor barrier property. A resin layer was formed to obtain a film-like sealing material. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 2-1, and a bottom emission type electronic device was obtained.
  • Example 2-1 A film-like sealing material was produced in the same manner as in Example 2-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 2. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 2-1, and a bottom emission type electronic device was obtained.
  • Example 2-3 A film-like sealing material was produced in the same manner as in Example 2-3 except that the material constituting the water vapor barrier resin layer was changed as shown in Table 2. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 2-1, and a bottom emission type electronic device was obtained.
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • Polyester SNT Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name “Polyester SNT”)
  • Tackifier Aliphatic petroleum resin (manufactured by Nippon Zeon Co., Ltd., trade name “Quinton A-100”)
  • TOPAS 9506F-04 cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics Co., Ltd., trade name “TOPAS 9506F-04”, glass transition temperature 65 ° C.)
  • Exxon Butyl 365 Isobutylene resin (exxon mobile, trade name “Exxon Butyl 365”) ⁇ Calcium oxide
  • the film-like encapsulants obtained in the examples were excellent in water vapor barrier properties and adhesiveness. Further, in the electronic device obtained in the example, moisture hardly entered from the end. Furthermore, the organic EL element sealed with the film-shaped sealing material obtained in the examples was excellent in durability, almost no dark spots were observed, and the performance of the electronic device was good.
  • the film-like encapsulating materials of Comparative Examples 2-2 and 2-4 were poor in film formability and could not obtain a good film-like encapsulating material, and therefore could not encapsulate the electronic device. Therefore, electronic device evaluation could not be performed.
  • the film-shaped sealing materials of Comparative Examples 2-1 and 2-3 were able to seal the electronic element, they were inferior in terms of electronic device evaluation.
  • the maximum moisture absorption amount of the moisture absorbent was low.
  • the moisture-absorbing ability was insufficient because the thickness of the water vapor barrier resin layer was thin.
  • Example 3-1 ⁇ Production of film-like encapsulant>
  • the materials constituting the adhesive resin layer and the water vapor barrier resin layer shown in Table 3 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the first adhesive resin layer having a thickness of 5 ⁇ m and the thickness
  • a film-shaped sealing material was produced by laminating a 40 ⁇ m water vapor barrier resin layer and a 5 ⁇ m thick second adhesive resin layer in that order.
  • ⁇ Preparation of sealing sheet> Aluminum of the obtained film-like sealing material and a gas barrier film having an aluminum foil (a laminated film in which a polyethylene terephthalate sheet having a thickness of 12 ⁇ m is bonded to one surface of an aluminum foil having a thickness of 7 ⁇ m with a urethane adhesive layer, manufactured by Aya Aluminum Co., Ltd.) The foil surface was bonded while heating at 120 ° C. to obtain a sealing sheet.
  • ITO indium tin oxide
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene manufactured by Luminescence Technology
  • 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Liescence Technology
  • 8-hydroxy-quinolinolate lithium (Luminescence Technology)
  • Al aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, whereby an organic EL device was obtained.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • the sealing sheet was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left to cool to room temperature. And a sealing sheet is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, from the edge part of an sealing sheet to an organic EL element The distance was adjusted to 5 mm. They were bonded together while heating at 100 ° C. to seal the organic EL element, thereby obtaining a bottom emission type electronic device.
  • Example 3-2 A film-like sealing material was produced in the same manner as in Example 3-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 3. Using this film-form sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.
  • Example 3-3 A coating liquid containing a material constituting the water vapor barrier resin layer shown in Table 3 is applied onto a release sheet, dried at 100 ° C. for 2 minutes, and the release sheet is laminated thereon to form a water vapor barrier property having a thickness of 20 ⁇ m. A resin layer was obtained and used as a film-like sealing material. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 3-1, and a bottom emission type electronic device was obtained.
  • Example 3-3 A film-like sealing material was produced in the same manner as in Example 3-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 3. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 3-1, and a bottom emission type electronic device was obtained.
  • Example 3-4 A film-shaped sealing material was produced in the same manner as in Example 3-3, except that the material constituting the water vapor barrier resin layer was changed as shown in Table 3. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 3-1, and a bottom emission type electronic device was obtained.
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • Water vapor barrier resin layer TOPAS 9506F-04: cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics Co., Ltd., trade name “TOPAS 9506F-04”, glass transition temperature 65 ° C.)
  • Exxon Butyl 365 Isobutylene resin (exxon mobile, trade name “Exxon Butyl 365”)
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • Calcium oxide Calcium oxide (Omi Chemical Industries, trade name “CML # 35”, average particle size 15 ⁇ m) Magnesium
  • the obtained test piece was bonded and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, and then in that environment, a tensile tester (manufactured by Orientec Co., Tensilon) was used, and the peeling rate was 300 mm. / Min, a peel test was performed under the conditions of a peel angle of 180 °, and the adhesive strength (N / 25 mm) was measured. The results are shown in Table 3.
  • the sealing sheets obtained in Examples 3-1 to 3-3 or Comparative Examples 3-1 to 3-4 were heated at 120 ° C. for 30 minutes in a nitrogen atmosphere using a hot plate, and sealed. After removing the water contained in the stop sheet, it was left as it was and cooled to room temperature. And the sealing sheet was mounted on the glass substrate so that the metal calcium formed on the glass substrate and the surface of the film-form sealing material of a sealing sheet may contact. At this time, the whole metal calcium was covered with the sealing sheet, and further, the distance from the end of the sealing sheet to the metal calcium was adjusted to 5 mm. Then, they were bonded together while heating at 100 ° C., and metallic calcium was sealed with a sealing sheet to obtain a test piece for evaluating the water vapor infiltration rate.
  • the film-like encapsulants obtained in the examples exhibited a very slow water vapor infiltration rate, and exhibited a low water vapor transmission rate and a high adhesive force.
  • the organic EL element sealed with the film-like sealing material obtained in the examples was excellent in durability, almost no non-light emitting portion was seen, and the performance of the electronic device was good.
  • the film-like encapsulants of Comparative Examples 3-1 to 3-4 showed a fast water vapor infiltration rate, and were evaluated as low in electronic device evaluation.
  • Example 4-1 A film-shaped sealing material, a sealing sheet, and an electronic device were manufactured by the same manufacturing method as in Example 1-1.
  • Examples 4-2 to 4-4 A film-shaped sealing material was produced in the same manner as in Example 4-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 4. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 4-1, and a bottom emission type electronic device was obtained.
  • Example 4-3 A film-shaped sealing material was produced in the same manner as in Example 4-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 4. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 4-1, and a bottom emission type electronic device was obtained.
  • Example 4-4 The material which comprises the adhesive resin layer shown in Table 4 was extrusion-molded with the extruder (made by Toyo Seiki Seisakusho), and the film-form sealing material which consists of an adhesive resin layer with a thickness of 50 micrometers was manufactured. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 4-1, and a bottom emission type electronic device was obtained.
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • LINKLON XLE815N Silane-modified linear low-density polyethylene (Mitsubishi Chemical Corporation, trade name “LINKLON XLE815N”)
  • Sumikasen L705 Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name “Sumikasen L705”, softening point 86 ° C.)
  • TOPAS 9506F-04 cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics Co., Ltd., trade name “TOPAS 9506F-04”, glass transition temperature 65 ° C.)
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.
  • the film-like encapsulants obtained in the examples were excellent in water vapor barrier properties and adhesiveness. Moreover, the organic EL element sealed with the film-form sealing material obtained in the Example was excellent in durability, almost no non-light emitting portion was seen, and the performance of the electronic device was good.
  • the film-like sealing material of Comparative Example 4-1 having an adhesive resin layer made of low-density polyethylene showed a very small adhesive force and could not seal the organic EL element. Therefore, electronic device evaluation could not be performed.
  • the film-like sealing material of Comparative Example 3 having a water vapor barrier resin layer containing a cycloolefin resin but no hygroscopic agent obtained a certain water vapor barrier property and adhesiveness. It did not reach those of the 4-4 film-like encapsulant.
  • Example 5-1 ⁇ Production of film-like encapsulant>
  • the materials constituting the adhesive resin layer and the water vapor barrier resin layer shown in Table 5 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the first adhesive resin layer having a thickness of 5 ⁇ m and the thickness
  • a film-shaped sealing material was produced by laminating a 40 ⁇ m water vapor barrier resin layer and a 5 ⁇ m thick second adhesive resin layer in that order.
  • ⁇ Preparation of sealing sheet> Aluminum of the obtained film-like sealing material and a gas barrier film having an aluminum foil (a laminated film in which a polyethylene terephthalate sheet having a thickness of 12 ⁇ m is bonded to one surface of an aluminum foil having a thickness of 7 ⁇ m with a urethane adhesive layer, manufactured by Aya Aluminum Co. The foil surface was bonded while heating at 120 ° C. to obtain a sealing sheet.
  • ITO indium tin oxide
  • N, N′-bis (naphthalen-1-yl) -N, N′-bis (phenyl) -benzidene) (manufactured by Luminescence Technology) was 60 nm
  • Tris (8- Hydroxy-quinolinate) Aluminum (manufactured by Luminescence Technology) at 40 nm
  • 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminesense Technology) at 10 nm
  • (8-hydroxy-quinolinolate) lithium was sequentially deposited at a rate of 10 nm and 0.1 to 0.2 nm / s to form a light emitting layer.
  • Al aluminum (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was deposited to a thickness of 100 nm at a rate of 0.1 nm / s to form a cathode, whereby an organic EL device was obtained.
  • the degree of vacuum at the time of vapor deposition was 1 ⁇ 10 ⁇ 4 Pa or less.
  • the sealing sheet was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left to cool to room temperature. And a sealing sheet is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, from the edge part of an sealing sheet to an organic EL element The distance was adjusted to 5 mm. They were bonded together while heating at 100 ° C. to seal the organic EL element, thereby obtaining a bottom emission type electronic device.
  • Examples 5-2 and 5-3 A film-shaped sealing material was produced in the same manner as in Example 5-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 5. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 5-1, and a bottom emission type electronic device was obtained.
  • Example 5-1 A film-shaped sealing material was produced in the same manner as in Example 5-1, except that the materials constituting the adhesive resin layer and the water vapor barrier resin layer were changed as shown in Table 5. Using this film-like encapsulant, an encapsulating sheet was produced in the same manner as in Example 5-1, and a bottom emission type electronic device was obtained.
  • Admer SF731 maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
  • LINKLON XLE815N Silane-modified linear low-density polyethylene (Mitsubishi Chemical Corporation, trade name “LINKLON XLE815N”)
  • TOPAS 9506F-04 cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics Co., Ltd., trade name “TOPAS 9506F-04”, glass transition temperature 65 ° C.)
  • Calcium oxide Calcium oxide (Omi Chemical Industries, trade name “CML # 35”, average particle size 15 ⁇ m)
  • Magnesium sulfate anhydrous magnesium sulfate (Tonda Pharmaceutical Co., Ltd., trade name “anhydrous magnesium s
  • Test pieces were produced in the same manner as in Test Example 4 for the film-like sealing materials obtained in Examples 5-1 to 5-3 or Comparative Examples 5-1 to 5-2. About this test piece, haze value (%) was measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, NDH-2000) based on JISK7136: 2000. The results are shown in Table 5.
  • the film-like encapsulants obtained in the examples were excellent in water vapor barrier properties and adhesiveness. Furthermore, the film-form sealing materials obtained in the examples exhibited high total light transmittance and low haze value, and were excellent in light transmittance. Moreover, the organic EL element sealed with the film-form sealing material obtained in the Example was excellent in durability, almost no non-light emitting portion was seen, and the performance of the electronic device was good.
  • Comparative Example 5-1 in which 10 parts by mass of calcium oxide was used as the hygroscopic agent, the total light transmittance was inferior to that of the Example, and the haze value was very high, so that sufficient light transmittance was obtained. I could't. Comparative Example 5-2 containing no hygroscopic agent did not show hygroscopicity, resulting in inferior electronic device evaluation.
  • the film-like sealing material and the sealing sheet according to the present invention are suitably used for, for example, an organic EL module and electronic paper.
  • the electronic device according to the present invention is suitable as an organic EL module or electronic paper, for example.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)

Abstract

　L'invention concerne un matériau d'étanchéité filmogène 1A, 1B comprenant une ou une pluralité de couches, comprenant une couche-barrière à la vapeur d'eau 12 contenant un absorbant d'humidité, les deux côtés du matériau d'étanchéité filmogène 1A, 1B présentant une adhérence à une surface à coller ; la perméabilité à la vapeur d'eau du matériau de la couche-barrière à la vapeur d'eau 12, à l'exclusion de l'absorbant d'humidité, mesurée à une épaisseur de 50 µm, est de 10 g/(m2•jour) ou moins ; lorsque le matériau d'étanchéité filmogène 1A, 1B comprend de multiples couches, la perméabilité à la vapeur d'eau de la couche qui, en plus de la couche-barrière à la vapeur d'eau 12, se situe le plus loin à l'extérieur dans le matériau d'étanchéité filmogène de 1B, mesurée à une épaisseur de 50 µm, est de 30 g/(m2•jour) ou moins ; et l'épaisseur de la couche-barrière à la vapeur d'eau 12, proportionnellement à l'épaisseur du matériau d'étanchéité filmogène 1A, 1B, est de 50-100 %. Ce matériau d'étanchéité filmogène 1A, 1B présente de meilleures propriétés de barrière à la vapeur d'eau.
PCT/JP2015/078624 2014-10-10 2015-10-08 Matériau d'étanchéité filmogène, feuille d'étanchéité et dispositif électronique WO2016056625A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP2014-209459 2014-10-10
JP2014209460A JP2016078260A (ja) 2014-10-10 2014-10-10 フィルム状封止材、封止シートおよび電子デバイス
JP2014-209460 2014-10-10
JP2014209461A JP2016078261A (ja) 2014-10-10 2014-10-10 フィルム状封止材、封止シートおよび電子デバイス
JP2014-209461 2014-10-10
JP2014209459A JP6530900B2 (ja) 2014-10-10 2014-10-10 フィルム状封止材、封止シートおよび電子デバイス
JP2014220292A JP2016087791A (ja) 2014-10-29 2014-10-29 フィルム状封止材、封止シートおよび電子デバイス
JP2014-220292 2014-10-29
JP2014-227187 2014-11-07
JP2014227187A JP6468810B2 (ja) 2014-11-07 2014-11-07 フィルム状封止材、封止シートおよび電子デバイス

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WO2018047422A1 (fr) * 2016-09-07 2018-03-15 リンテック株式会社 Stratifié doté de propriétés barrière au gaz, et corps de scellement
WO2018179458A1 (fr) * 2017-03-30 2018-10-04 リンテック株式会社 Stratifié formant barrière aux gaz, et élément d'étanchéité
US20210390361A1 (en) * 2019-01-11 2021-12-16 Me Innovation Srl Multilayer electronic device and method for the construction and fixing of the device
CN114980980A (zh) * 2020-01-24 2022-08-30 凸版印刷株式会社 灭火体

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TWI656021B (zh) * 2018-03-30 2019-04-11 台虹科技股份有限公司 堆疊膜層

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JP2011161778A (ja) * 2010-02-09 2011-08-25 Dainippon Printing Co Ltd 防湿性積層体
JP2011194653A (ja) * 2010-03-18 2011-10-06 Dainippon Printing Co Ltd 防湿性積層体
JP2011230454A (ja) * 2010-04-30 2011-11-17 Dainippon Printing Co Ltd ガスバリア性積層体
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JP2011161778A (ja) * 2010-02-09 2011-08-25 Dainippon Printing Co Ltd 防湿性積層体
JP2011194653A (ja) * 2010-03-18 2011-10-06 Dainippon Printing Co Ltd 防湿性積層体
JP2011230454A (ja) * 2010-04-30 2011-11-17 Dainippon Printing Co Ltd ガスバリア性積層体
JP2014124927A (ja) * 2012-12-27 2014-07-07 Lintec Corp フィルム状封止材、封止シートおよび電子デバイス

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Publication number Priority date Publication date Assignee Title
WO2018047422A1 (fr) * 2016-09-07 2018-03-15 リンテック株式会社 Stratifié doté de propriétés barrière au gaz, et corps de scellement
WO2018179458A1 (fr) * 2017-03-30 2018-10-04 リンテック株式会社 Stratifié formant barrière aux gaz, et élément d'étanchéité
US20210390361A1 (en) * 2019-01-11 2021-12-16 Me Innovation Srl Multilayer electronic device and method for the construction and fixing of the device
CN114980980A (zh) * 2020-01-24 2022-08-30 凸版印刷株式会社 灭火体

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