JP6530900B2 - Film-like sealing material, sealing sheet and electronic device - Google Patents

Description

  The present invention relates to a film-shaped sealing material and a sealing sheet capable of sealing an electronic element and the like, and an electronic device in which the electronic element is sealed by the sealing agent.

  In an organic electronic device, for example, a module for a display device having an organic electroluminescence (organic EL) element, electronic paper, etc., a solar cell module having an organic thin film solar cell element, moisture and oxygen infiltrate into the electronic element inside the device. It is necessary to prevent the ingress of moisture and oxygen because the As an example of such a prevention method, in an organic EL element, there is a method of covering an electronic element using a glass member capable of forming a space.

  When integrating such a glass member, an electronic device, and a substrate for fixing them, the contact between the glass member and the substrate is fixed with an adhesive, and the electronic device is provided in the space formed between them There is a way. In the electronic device manufactured in this manner, there is a possibility that moisture present outside penetrates the adhesive for fixing and penetrates into the internal space. Patent Documents 1 and 2 disclose substances containing a hygroscopic agent for removing such moisture that has entered inside.

  Specifically, Patent Document 1 discloses a resin containing a physical adsorption desiccant and a chemical adsorption desiccant at a specific ratio (claim 1 of Patent Literature 1). Also, 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). The resin is provided in the form of a sheet at a position facing the electronic element inside the electronic device, 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 to remove water molecules from the surroundings by performing a hydrolysis reaction in the Al-OR bond. The composition absorbs moisture present in the electronic device by being provided in a sheet form at a position facing the electronic device inside the electronic device or being filled in a space inside the electronic device (Patent Document 2) Figure 1 and Figure 2).

  Moreover, the method of using a film-form sealing material exists as another method of preventing that water infiltrates into the inside of an electronic device. In this case, the electronic device is manufactured, for example, as a laminate in which a sealing substrate, a film-like sealing material, an electronic element, and a substrate are laminated in this order. In this case, a glass plate, a high gas barrier film, a metal foil or the like is used as the sealing substrate so that moisture does not enter from the surface direction. However, there is a possibility that moisture infiltrates from the portion of the edge of the laminate where the film-like sealing material is exposed to the outside to reach the electronic device. For this reason, sealing materials having water vapor barrier properties have been developed.

JP, 2006-116501, A JP, 2013-108057, A

  However, in a module for a display device having an organic EL element, which is attracting attention in recent years, and an electronic device such as electronic paper, a higher level is required to protect the electronic element from moisture. The substances disclosed in Patent Documents 1 and 2 can not be used as a sealing sheet because they are for drying the space in the electronic device. Furthermore, since the substance of Patent Document 2 is a liquid sealant, it is necessary to provide a flow prevention dam around the device so that the liquid does not flow out.

  The present invention has been made in view of such circumstances, and it is an object of the present invention to provide a film-like sealing material, a sealing sheet and an electronic device having more excellent water vapor barrier properties.

In order to achieve the above object, a first aspect of the present invention is a film-like sealing material comprising one or more layers, which comprises a water vapor barrier resin layer containing a moisture absorbent, wherein the film-like sealing material Both sides show adhesion to the adherend, and the water vapor permeability of the material obtained by removing the hygroscopic agent from the water vapor barrier resin layer is 10 g / (m ² · day) when measured at a thickness of 50 μm. The water vapor transmission rate of the layer other than the water vapor barrier resin layer, which is located on the outermost side of the film sealing material, is 50 μm thick. when measured is at 30g / (m 2 · ^day) or less Te, the ratio of the thickness of the water vapor barrier resin layer is characterized in that 50 to 100% of the thickness of the film-like sealing member A film-like sealing material is provided (Invention 1).

  In the film-like encapsulating material according to the above invention (Invention 1), the material obtained by removing the hygroscopic agent from the water vapor barrier resin layer exhibits high water vapor barrier properties, and in addition to preventing water permeation, the water vapor barrier resin layer Since the moisture intruded in is absorbed by the hygroscopic agent, very high water vapor barrier properties are achieved.

  In the above invention (Invention 1), one adhesive resin layer laminated on one surface side of the water vapor barrier resin layer and exhibiting adhesiveness to an adherend, or one of the water vapor barrier resin layers It is preferable to include two adhesive resin layers laminated on the surface side and the other surface side and showing adhesiveness to the adherend as the outermost layer of the film-like encapsulant (Invention 2) .

In the above invention (Invention 2), the water vapor transmission rate of the adhesive resin layer is preferably 30 g / (m ² · day) or less when measured at a thickness of 50 μm (Invention 3).

In the above inventions (Inventions 1 to 3), the maximum moisture absorption amount of the moisture absorbent is 1.0 g / m ² or more when it is represented by the amount of water which the water vapor barrier resin layer having a thickness of 50 μm absorbs. It is preferable that there exist (invention 4).

  In the said invention (invention 1-4), it is preferable that the said hygroscopic agent is a compound containing a metalloxane bond (invention 5).

In the above invention (Invention 5), the compound containing a metalloxane bond is a compound of 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). Among compounds having a structure represented by an integer, a value obtained by subtracting 2 from the oxidation number of a metal element, m represents an integer of 1 or more), a compound that reacts with water at a site of M-O-M It is preferable that there exist (invention 6).

  In the said invention (invention 1-4), it is preferable that the said hygroscopic agent is a metal oxide (invention 7).

  In the above inventions (Inventions 1 to 4), the hygroscopic agent is preferably a compound that reacts with water molecules to form a hydrate (Invention 8).

  Second, the present invention provides a sealing sheet comprising the film-like sealing material (Inventions 1-8) and a gas barrier film laminated on one side of the film-like sealing material. (Invention 9).

  Thirdly, the present invention provides an electronic device sealed by the film-like sealing material (inventions 1 to 8) (invention 10).

  Fourth, the present invention provides an electronic device sealed by the sealing sheet (invention 9) (invention 11).

  In the film-like encapsulant according to the present invention, the water vapor barrier resin layer is made of a material having high water vapor barrier properties, and the water vapor barrier resin layer further contains a hygroscopic agent to achieve very high water vapor barrier properties. can do.

FIG. 1 is a schematic cross-sectional view of a film-like encapsulant according to a first embodiment of the present invention. It is a schematic sectional drawing of the film-form sealing material which concerns on the 2nd Embodiment of this invention. It is a schematic sectional drawing of the sealing sheet which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the electronic device which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the electronic device which concerns on other embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Film-like sealing material]
The film-like sealant according to the embodiment may consist of one layer or may consist of plural layers. When the film-like encapsulant consists of one layer, the film-like encapsulant consists only of the water vapor barrier resin layer. On the other hand, when the film-like encapsulant is composed of a plurality of layers, the film-like encapsulant is composed of a water vapor barrier resin layer and one or more other layers.

  In the film-like sealing material comprising a plurality of layers, when one other layer is present, the water vapor barrier resin layer and one other layer are directly laminated. On the other hand, when there are a plurality of other layers, 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 As an example of the other layer, an adhesive resin layer is preferably mentioned.

  Both surfaces of the film-like encapsulant according to the embodiment exhibit adhesiveness to the adherend. In the case where the film-like sealing material is formed of one layer, that is, only formed of the water vapor barrier resin layer, the water vapor barrier resin layer has adhesiveness. On the other hand, when the film-like encapsulant is composed of a plurality of layers, the outermost layer of the film-like encapsulant has adhesiveness. For example, when the water vapor barrier resin layer is present on one surface of the film-like 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. . When two adhesive resin layers are respectively present on both sides of the film-like encapsulant, the two adhesive resin layers have adhesiveness.

  A release sheet may be laminated on both sides of the film-like encapsulant according to the embodiment for the purpose of protecting the surface having adhesiveness. This release sheet is appropriately peeled off when using a film-like sealing material.

  In addition, the "layer located in the outermost side" in this specification means the layer located in the outermost side, when a film-form sealing material is provided for sealing. Therefore, the 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-like sealing material 1A according to the first embodiment. As shown in FIG. 1, the film sealant 1 </ b> A according to the first embodiment includes a water vapor barrier resin layer 12.

  FIG. 2 is a schematic cross-sectional view of a film-like sealing material 1B according to a second embodiment. As shown in FIG. 2, the film-shaped encapsulating material 1B according to the second embodiment includes the first and second adhesive resin layers 11A and 11B, and the first adhesive resin layer 11A and the second adhesive resin layer 11A. And a water vapor barrier resin layer 12 positioned between the adhesive resin layer 11B and the adhesive resin layer 11B.

(1) Water vapor barrier resin layer 12
The water vapor barrier resin layer 12 contains a hygroscopic agent. Furthermore, the material obtained by removing the moisture absorbing agent from the water vapor barrier resin layer 12 (hereinafter referred to as "main material M") has high water vapor barrier properties. Specifically, the water vapor transmission rate of the main material M is 10 g / (m ² · day) or less when measured at a thickness of 50 μm. In addition to the main material M exhibiting a high water vapor barrier property preventing permeation of water, the moisture absorbent takes in the water even if the water enters the water vapor barrier resin layer 12. As a result, the water vapor barrier resin layer 12 has higher water vapor barrier properties, and the water vapor barrier properties of the film-like encapsulants 1A and 1B having such a water vapor barrier resin layer 12 are also very excellent. It becomes a thing. The water vapor barrier resin layer 12 may be a single layer or a plurality of layers.

(1.1) Resin Constituting 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. Examples of the resin constituting the water vapor barrier resin layer 12 are rubber resins, polyester resins, polyolefin resins, cycloolefin resins and epoxy resins. 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), and particularly preferably 6 g / (m ² · day) or less. In the present specification, the water vapor transmission rate is defined as the mass (g / (m ² · day)) of water permeating the 1 m ² area for a measurement object having a certain thickness. Be done. The thickness at this time is, for example, 50 μm. By having a low water vapor transmission rate of 10 g / (m ² · day) or less, the film-like encapsulants 1A and 1B can achieve very high water vapor barrier properties. When the water vapor barrier resin layer 12 contains only the cycloolefin resin in addition to the hygroscopic agent, the preferable water vapor transmission rate of the cycloolefin resin is as described above.

  The water vapor transmission rate of the main material M can be obtained, for example, by producing a layer without using a hygroscopic agent and measuring the water vapor transmission rate.

  The water vapor barrier resin layer 12 may have adhesiveness. That is, you may select resin which comprises the water-vapor-barrier resin layer 12 so that the water-vapor-barrier resin layer 12 has adhesiveness. In particular, when the film-like sealing material 1A according to the first embodiment does not include the adhesive resin layer, or when it includes one adhesive resin layer, the water vapor barrier resin layer 12 has adhesiveness. It is preferable to have. The water vapor barrier resin layer 12 having adhesiveness can be well adhered to a gas barrier film and an electronic element described later.

  Rubber-based resins are preferred in that they can simultaneously achieve high water vapor barrier properties and high adhesion. The rubber-based resin is, for example, natural rubber, modified natural rubber obtained by graft polymerizing one or two or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile to 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 copolymer (SIS), ethylene-propylene-nonconjugated diene ternary copolymer A combination etc. are mentioned. These rubber compounds can be used singly or in combination of two or more. Among these, as the rubber-based resin, one containing a polyisobutylene-based resin is preferable.

  The polyisobutylene resin refers to a polymer (including the concept of a copolymer) containing isobutylene as a monomer component, and 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 a monomer. The polyisobutylene-based resin may be a halogenated polyisobutylene-based resin partially brominated or chlorinated, or one partially substituted with a functional group such as a hydroxyl group or a carboxyl group.

  Examples of the other monomers include isoprene, n-butene, butadiene, isoprene and styrene. The other monomers may be used alone or in combination of two or more. In the case where the polyisobutylene-based resin is a copolymer, isobutylene is a main component of the raw material monomer and is the largest amount of monomer.

  Among the above, a polyisobutylene-based resin is a homopolymer obtained by polymerizing isobutylene and isoprene as a monomer component or a homopolymer comprising only an isobutylene as a monomer component from the viewpoint of excellent water vapor barrier properties. Is preferred.

  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, and 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 modified product thereof. Examples of polyvalent carboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, trimellitic acid and the like. Examples of polyols 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 alone or in combination of two or more.

  The polyolefin resin refers to a polymer (including the concept of copolymer) containing only one or two or more olefins as a monomer component constituting the polymer. That is, the polyolefin resin mentioned here is a homopolymer of one type of olefin or a copolymer of two or more types of olefins. As an olefin, a C2-C8 alpha-olefin is preferable, For example, ethylene, propylene, butylene, isobutylene, 1-hexene, styrene etc. are mentioned, Especially, ethylene and propylene are preferable.

As the polyolefin resin, specifically, 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 ³ ), medium density polyethylene (MDPE, density: 915 kg / m ³ or more, 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), polyethylene resin, polypropylene resin (PP And ethylene-propylene copolymers. These can be used singly or in combination of two or more. Among the above, low density polyethylene is preferable, and linear low density polyethylene is particularly preferable.

  The cycloolefin resin refers to a resin containing as a main component a polymer (including the concept of a copolymer) containing cycloolefin as a monomer component constituting the polymer, and 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 the purpose of the film-shaped encapsulating material 1A or 1B according to the present embodiment is not impaired, and, for example, α-olefins having 2 or more carbon atoms such as ethylene and propylene, (meth) acrylic acid Ester etc. are mentioned. In the present specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. Other similar terms are also the same.

  Among the above, the cycloolefin resin is excellent in adhesion to the adhesive resin layers 11A and 11B described later and can prevent the delamination of the film-like sealing material 1B. It is preferable that it is a copolymer containing

  The cycloolefin 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. When the glass transition temperature of the cycloolefin resin is 20 ° C. or more, the content of the cycloolefin as a monomer component in the cycloolefin resin is increased, and the water vapor barrier property is easily exhibited. In addition, when the glass transition temperature of the cycloolefin resin is 150 ° C. or less, the water vapor barrier resin layer 12 favorably follows the step or the like of the object to be sealed such as an electronic element to reliably seal the object to be sealed. It can stop.

  The cycloolefin resin preferably has no hydrophilic group. When it has a hydrophilic group, the water vapor barrier property may be reduced. As a hydrophilic group, a hydroxyl group, a carboxyl group, an amino group, an amido group, an imide group, a sulfonic acid group, a mercapto group etc. are mentioned, for example. On the other hand, the cycloolefin resin may have a hydrophobic group. If it is a hydrophobic group, there is no possibility that water vapor barrier property will fall. As a hydrophobic group, an alkyl group, an aryl group etc. are mentioned, for example.

（式（ａ）中、ｍおよびｎは１以上の整数である。Ｒ^１およびＲ^２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ^１およびＲ^２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンとエチレンとを含む共重合体；ＣＯＣ）、下記構造式（ｂ）

（式（ｂ）中、ｍおよびｎは１以上の整数である。Ｒ^１およびＲ^２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ^１およびＲ^２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンとエチレンとを含む共重合体；ＣＯＣ）、下記構造式（ｃ）

（式（ｃ）中、ｎは１以上の整数であり、Ｒ^１およびＲ_２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ^１およびＲ^２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンのみを含む重合体；ＣＯＰ）、および下記構造式（ｄ）

（式（ｄ）中、ｍおよびｎは１以上の整数であり、Ｒ^１およびＲ^２は水素原子またはアルキル基を示し、それぞれ同じであってもよいし、異なっていてもよい。Ｒ^１およびＲ^２は、それらが結合して環を形成していてもよい。）
で示されるシクロオレフィン重合体（モノマー成分としてシクロオレフィンのみを含む重合体；ＣＯＰ）が挙げられる。これらのシクロオレフィン重合体は、水蒸気バリア性に非常に優れ、入手も容易である。これらのシクロオレフィン重合体は、１種を単独でまたは２種以上を組み合わせて使用することができる。 As a preferable cycloolefin 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 s} may combine to form a ring.)
Cycloolefin polymer (copolymer containing cycloolefin and ethylene as a monomer component; COC), the following structural formula (b)

(In the formula (b), 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 s} may combine to form a ring.)
Cycloolefin polymer (copolymer containing cycloolefin and ethylene as a monomer component; COC), the following structural formula (c)

(In the formula (c), n is an integer of 1 or more, R ¹ and R ₂ represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R ¹ and R ² And may combine to form a ring).
Cycloolefin polymer (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 s} may combine to form a ring.)
And cycloolefin polymers (polymers containing only cycloolefin as a monomer component; COP). These cycloolefin polymers are very 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 commercial item can also be used for a cycloolefin polymer. Commercially available products include, for example, ZEONEX (registered trademark) (Nippon Zeon Co., a ring-opening metathesis polymer hydrogenated polymer of norbornene-based monomer), TOPAS (registered trademark) (polyplastics, copolymer of norbornene and ethylene) ZEONOR (registered trademark) (Nippon Zeon Co., Ltd., a copolymer based on ring-opening polymerization of dicyclopentadiene and tetracyclopentadodecene), APEL (registered trademark) (Mitsui Chemical Co., Ltd., ethylene and tetracyclododecene) And Copolymers of ARTON (registered trademark) (CSR, cyclic olefin resin containing polar groups starting from dicyclopentadiene and methacrylic acid ester), and the like.

  As epoxy resin, for example, monofunctional epoxy compound, bifunctional epoxy compound, trifunctional or higher polyfunctional epoxy compound, polymer or oligomer having epoxy group, vinyl monomer having epoxy group and other vinyl monomer Copolymer polymers or oligomers with the like. These epoxy resins can be used singly 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, for example, olefin-based resins such as ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, urethane resin, polyurethane Examples thereof include system resins, polyester urethane resins, acrylic resins, amide resins, styrene resins, and silane resins.

(1.2) Hygroscopic agent The water vapor barrier resin layer 12 contains a hygroscopic agent. Hygroscopic agents are generally classified into two, chemical-based and physical-based hygroscopic agents.

  Chemical-based hygroscopic agents are hygroscopic agents that take in surrounding water by utilizing water molecules as a reactant of chemical reaction. In the film-like encapsulants 1A and 1B according to the present embodiment, any chemical-based hygroscopic agent can be used, but a metal oxide, a compound that reacts with water molecules to form a hydrate, or a metalloxane bond It is preferable to use the compound which contains. These chemical hygroscopic agents can be used singly or in combination of two or more.

Examples of metal oxides that can be used as chemical moisture absorbers are calcium oxide, barium oxide, magnesium oxide and strontium oxide. These metal oxides can be used singly or in combination of two or more. Among these, calcium oxide performs the reaction of the following formula (1) with water molecules. As a result of this reaction, water molecules are converted to hydroxyl groups in calcium hydroxide which is the reaction product. Metal oxides other than calcium oxide also carry out the same reaction as in formula (1).

Examples of compounds that can be used as chemical moisture absorbents and that react with water molecules to form hydrates include sodium sulfate, potassium aluminum sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, sodium carbonate, sodium acetate, thiosulfate Sodium and copper sulfate. These compounds can be used singly or in combination of two or more. Among these, magnesium sulfate performs the reaction of the following formula (2) with water molecules. As a result of this reaction, water molecules are converted to hydration water in the hydrate. Compounds other than magnesium sulfate also carry out the same reaction as in formula (2).

The compound containing a metalloxane bond is a compound containing a metalloxane bond, that is, a bond of a metal element and oxygen. Examples of such compounds are compounds represented by the general formula M (OR) _n (where 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 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 It is a compound having a structure represented by the above integer). The compound of R may further contain oxygen. Also, examples of R are an alkyl group and an acyl group. In addition, compounds containing a metalloxane bond include compounds generally called metalloxane compounds or polymetalloxane compounds. In addition, in this specification, the phrase "(poly) metalloxane compound" may be used as an expression which means both a metalloxane compound and a polymetalloxane compound. More specific examples of compounds containing metalloxane bonds are metal alkoxides, metal acylates and metal chelates. The site which reacts with water of the compound containing a metalloxane bond is mainly M-O-R or M-O-M. These compounds can be used singly or in combination of two or more.

Metal alkoxides (also known as metal alcoholates) are examples of compounds that react with water at the M-O-R site. Examples of metal alkoxides are compounds in which R is an alkyl group in the general formula M (OR) _n , or compounds 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 (alias: tetramethoxy titanium (IV), titanium (IV) tetra methoxide), aluminum ethoxide and aluminum oxide isopropoxide trimer. These metal alkoxides can be used singly or in combination of two or more.

The above-mentioned aluminum ethoxide performs the reaction of the following formula (3) with water molecules. In this reaction, water molecules are utilized for the hydrolysis of aluminum ethoxide, resulting in the formation of aluminum hydroxide and ethanol. Compounds other than aluminum ethoxide also carry out the same reaction as in formula (3).

Metal acylates are examples of compounds that react with water at M-O-R or M-O-M sites. An example of a compound that reacts with water at the M-O-R site among metal acylates is a compound in which R is an acyl group in the general formula M (OR) _n . An example of the compound which reacts with water at the M-O-M site among metal acylates 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 metal acylates 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 performs the reaction of the following formula (4) with water molecules, and the product is only one type. Compounds other than cyclic aluminum oxide octylate also carry out the same reaction as in formula (4).

  A physical hygroscopic agent is a hygroscopic agent that takes in ambient moisture without a chemical reaction, and for example, causes the surface of the hygroscopic agent to adsorb surrounding water molecules. In the film-like encapsulants 1A and 1B according to the present embodiment, any physical hygroscopic agent can be used, and for example, zeolite, activated alumina, silica gel and clay compound can be used. Molecular sieves can be used as the zeolite. These hygroscopic agents can be used singly or in combination of two or more.

  The hygroscopic agent is preferably one which has little or no influence on the electronic device. In particular, in the case of using a chemical-based moisture absorbent, it is preferable to use a moisture absorbent which does not occur due to the reaction of moisture absorption as the substance that corrodes the electronic device. Further, it is preferable to use a hygroscopic agent which does not generate a gas even by the reaction of moisture absorption or temperature change and does not cause the expansion of the electronic device. Furthermore, it is preferable to use a hygroscopic agent that is well mixed with the resin that constitutes the water vapor barrier resin layer 12 and does not denature even when subjected to a process such as heating when the water vapor barrier resin layer 12 is manufactured.

  In view of these points, it is preferable to use the above-described compound containing a metalloxane bond, a metal oxide and a compound that reacts with water molecules to form a hydrate, and the compound containing a metalloxane bond is particularly preferably M- It is preferred to use compounds that react with water at the O-M site. These hygroscopic agents produce relatively stable products when the reaction of moisture absorption occurs, and they are less likely to be vaporized to generate gas, mix well with the material resin, and have a water vapor barrier resin It is hard to denature in the manufacturing process of the layer 12. As a result, film-like sealing materials 1A and 1B exhibiting very excellent water vapor barrier properties can be obtained.

  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 further preferably 5 to 25% by mass. . By being 1 mass% or more, the water | moisture content which permeate | transmits water-vapor-barrier resin layer 12 is fully absorbed moisture, and the water-vapor barrier property of film-form sealing material 1A, 1B further improves. Moreover, when manufacturing the water-vapor-barrier resin layer 12 by being 35 mass% or less, it becomes possible to form a film favorable.

  The shape of the hygroscopic agent is not particularly limited, and may be, for example, liquid, powder or particulate. When it is powder or granular, the average particle size of the hygroscopic agent is not particularly limited, but is preferably 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, and further preferably 0.1 to 5 μm. Is preferred. Here, the "average particle diameter" in the present specification is a value obtained by measurement using a laser diffraction type particle size distribution measuring device.

The maximum moisture absorption of the hygroscopic agent is preferably 1.0 g / m ² or more, particularly 1.5 g / m ² , as represented by the amount of water absorbed by the water vapor barrier resin layer 12 having a thickness of 50 μm. It is preferably m ² or more, and more preferably 2.0 g / m ² or more. By using a hygroscopic agent having a maximum moisture absorption amount of 1.0 g / m ² or more, it is possible to sufficiently absorb moisture passing through the water vapor barrier resin layer 12, and a film having a higher water vapor barrier property Sealing materials 1A and 1B can be obtained.

(1.3) Other Components The water vapor barrier resin layer 12 may contain, if desired, a tackifier, an ultraviolet light absorber, an ultraviolet light stabilizer, an antistatic agent, a pigment, a flame retardant, and a plasticizer, in addition to the resin and the hygroscopic agent. A lubricant, an antiblocking agent, a filler, a dispersant, a crosslinking agent (curing agent; when using a curable resin such as an epoxy resin), various additives such as a silane coupling agent, and the like may be contained. In particular, when the water vapor barrier resin layer 12 contains a rubber-based resin, it is preferable to contain a tackifier. Examples of tackifiers include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5 resins, C9 resins and dicyclopentadiene resins, and synthetic resins such as coumarone indene resins and xylene resins. .

(1.4) Physical Properties and the Like of Water Vapor Barrier Resin Layer 12 The thickness of the water vapor barrier resin layer 12 is preferably 5 to 300 μm, particularly preferably 10 to 200 μm, and further preferably 15 to 100 μm. Is preferred. By setting the thickness of the water vapor barrier resin layer 12 to 5 μm or more, sufficient water vapor barrier properties can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 μm or less, the thickness of the film-like encapsulants 1A and 1B can be kept thin.

  The thickness ratio 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 encapsulants 1A and 1B, and more preferably It is preferable that it is 60 to 100%. Here, that the ratio of the thickness of the water vapor barrier resin layer 12 is 100% means that the film-like encapsulants 1A and 1B consist only of the water vapor barrier resin layer 12. The thickness of the film-like encapsulants 1A and 1B will be described later. When the thickness ratio of the water vapor barrier resin layer 12 is 50% or more, the film-like encapsulants 1A and 1B can contain a sufficient amount of a hygroscopic agent to achieve higher water vapor barrier properties. be able to.

(2) Adhesive Resin Layer The first adhesive resin layer 11A and the second adhesive resin layer 11B are layers showing adhesiveness to an adherend, and in the present embodiment, a water vapor barrier resin layer It can be optionally provided on one side or both sides of the twelve. A film having better adhesion to an adherend by providing one or both of the first and second adhesive resin layers 11A and 11B when the adhesion of the water vapor barrier resin layer 12 to the adherend is low 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 transmission rate of the first and second adhesive resin layers 11A and 11B is preferably 30 g / (m ² · day) or less when measured at a thickness of 50 μm, and particularly 25 g / (m ² -It is preferable that it is below day, and it is further more preferable that it is below 20 g / (m < ² > * day). When the adhesive resin layers 11A and 11B have a water vapor transmission rate of 30 g / (m ² · day) or less, when the adhesive resin layer is provided, water moves through the adhesive resin layer to reach the electronic element It is possible to obtain a film-like sealing material 1B having higher water vapor barrier properties.

  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, for example, a thermoplastic resin, a curable resin, etc. Examples of the curable resin include thermosetting resins and energy ray-curable resins. The thermoplastic resin and the curable resin can also be used as a mixture.

  The thermoplastic resin may have heat adhesion or may have pressure sensitive adhesion. When the first and second adhesive resin layers 11A and 11B contain a thermoplastic resin, the film-like encapsulant 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.

  Examples of thermoplastic resins include rubber resins, polyolefin resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-vinyl acetate copolymers, polyurethane resins And polyester urethane resins, acrylic resins, amide resins, styrene resins, silane resins and the like. The polyolefin resin may be modified, and examples thereof include acid-modified polyolefin resins and silane-modified polyolefin resins. Among these, rubber resins, acid-modified polyolefin resins or silane-modified polyolefin resins are preferable. Since 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 a glass plate and a gas barrier film It shows higher adhesion to 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. In addition, the said thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  The rubber-based resin is, for example, natural rubber, modified natural rubber obtained by graft polymerizing one or two or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile to 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 Combination, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-nonconjugated diene terpolymer, etc. Be These rubber compounds can be used singly or in combination of two or more. Among these, as the rubber-based resin, one containing a polyisobutylene-based resin is preferable.

  The polyisobutylene resin refers to a polymer (including the concept of a copolymer) containing isobutylene as a monomer component, and 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 a monomer. The polyisobutylene-based resin may be a halogenated polyisobutylene-based resin partially brominated or chlorinated, or one partially substituted with a functional group such as a hydroxyl group or a carboxyl group.

  Examples of the other monomers include isoprene, n-butene, butadiene, isoprene and styrene. The other monomers may be used alone or in combination of two or more. In the case where the polyisobutylene-based resin is a copolymer, isobutylene is a main component of the raw material monomer and is the largest amount of monomer.

  Among the above, the polyisobutylene-based resin is a homopolymer in which the monomer component is composed only of isobutylene, and an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component from the viewpoint of excellent water vapor barrier properties. Is preferred.

  The number average molecular weight of the rubber-based resin used for the adhesive resin layer is usually 100,000 to 5,000,000, preferably 100,000 to 3,000,000, and more preferably 100,000 to 1,000,000.

  A commercial item can also be used for rubber-type resin. As a commercial item, for example, Exxon Butyl (manufactured by Nippon Butyl Co., Ltd.), Vistanex (manufactured by Exxon Chemical Co.), Hycar (registered trademark) (manufactured by Goodrich), Oppanol (registered trademark) (manufactured by BASF), Epol (registered trademark) (Made by Idemitsu Kosan Co., Ltd.) and the like.

  Polyolefin resin (non-modified polyolefin resin) refers to a polymer (including the concept of a copolymer) containing an olefin as a monomer component constituting the polymer, and a polymer in which the monomer component consists only of an olefin It may be a polymer (copolymer) containing an olefin and other monomers as monomer components.

  As said olefin, C2-C8 alpha-olefin is preferable, For example, ethylene, propylene, butylene, isobutylene, 1-hexene, styrene etc. are mentioned. Among them, ethylene and propylene are preferable, and ethylene is particularly preferable. The other monomer is not particularly limited as long as the purpose of the film-like encapsulating material 1B according to this embodiment is not impaired, and examples thereof include vinyl acetate and (meth) acrylic acid ester.

As the polyolefin-based resin, specifically, 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, 942 kg / m ³ ), high density polyethylene (HDPE, density: 942 kg / m ³ or more), linear low density polyethylene Resin, polypropylene resin (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic An acid ester copolymer etc. are mentioned. These can be used singly or in combination of two or more. Among the above, polyethylene resins such as ultra low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer or olefin elastomer (TPO) are preferable, and in particular Low density polyethylene is preferred.

  The acid-modified polyolefin-based resin means a polyolefin-based resin graft-modified with an acid, and examples thereof include those in which a polyolefin-based resin is reacted with an unsaturated carboxylic acid and a carboxyl group is introduced (graft-modified). In the present specification, unsaturated carboxylic acid includes the concept of carboxylic acid anhydride, and carboxyl group includes the concept of carboxylic anhydride group.

  Examples of unsaturated carboxylic acids to be reacted with the above-mentioned polyolefin resins 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 acid anhydride, norbornene dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride and the like. These can be used singly or in combination of two or more. Among the above, maleic anhydride which is particularly excellent in adhesion is preferred.

  As the acid-modified polyolefin resin, a maleic anhydride-modified polyolefin resin is preferable, and in particular, a maleic anhydride-modified polyethylene resin is preferable.

  The amount of 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 Preferably, it is more preferably 0.2 to 1.0 parts by mass. When the amount of unsaturated carboxylic acid to be reacted is in the above range, the acid-modified polyolefin resin obtained is excellent in adhesion.

  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. When the Vicat softening point is in the above-mentioned range, adhesion does not appear at room temperature, so the handling property of the film-like sealing material 1B is excellent, and adhesion becomes possible by thermocompression bonding in a relatively short time. It is possible to efficiently manufacture a display device module having an organic EL element, and electronic devices such as electronic paper and an organic thin film solar cell. In addition, a Vicat softening point is taken as the value measured based on ASTMD1525.

  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 min, particularly preferably 1 to 15 g / 10 min, Furthermore, it is preferable that it is 2-10 g / 10min. When the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, when the MFR is less than 0.5 g / 10 min, extrusion molding may be difficult, and the MFR is 30 g / 10 min When forming a film by extrusion molding, there is a possibility that thickness accuracy may fall. In addition, MFR in this specification is taken as the value measured based on ASTMD1238.

  A commercial item can also be used for acid-modified polyolefin resin. Examples of commercially available products include Admar (registered trademark) (made by Mitsui Chemicals, Inc.), BondyRam (manufactured by Polyram), orevac (registered trademark) (made by ARKEMA), Modic (registered trademark) (made by Mitsubishi Chemical), etc. It can be mentioned.

  The silane-modified polyolefin resin is a resin obtained by graft-modifying a polyolefin resin by reacting the polyolefin resin with an unsaturated silane compound. The silane-modified polyolefin resin can be strongly adhered, particularly when the adherend is a glass plate.

  As polyolefin resin of silane modification polyolefin resin, polyolefin resin illustrated by the above-mentioned acid modification polyolefin resin is mentioned.

  The silane-modified polyolefin resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and in particular, a silane such as a silane-modified low density polyethylene, a silane-modified ultra-low density polyethylene, and a silane-modified linear low density polyethylene Modified polyethylene resins are preferred.

  As the unsaturated silane compound to be reacted with the above-mentioned polyolefin resin, a vinylsilane compound is preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripenty Roxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, vinyltricarboxysilane and the like. These can be used singly or in combination of two or more.

  The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by mass, particularly preferably 0.3 to 7 parts by mass with respect to 100 parts by mass of the polyolefin resin Preferably, it is more preferably 0.5 to 5 parts by mass. When the amount of the unsaturated silane compound to be reacted is in the above range, the silane-modified polyolefin resin obtained is excellent in adhesion.

  The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 20.2 N is preferably 0.5 to 30 g / 10 min, and particularly preferably 0.5 to 15 g / 10 min. Preferably, it is more preferably 0.5 to 10 g / 10 min. When the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, when the MFR is less than 0.5 g / 10 min, extrusion molding may be difficult, and the MFR is 30 g / 10 min When forming a film by extrusion molding, there is a possibility that thickness accuracy may fall.

  A commercial item can also be used for silane modified polyolefin resin. Commercially available products include, for example, Lincron (registered trademark) (manufactured by Mitsubishi Chemical Corporation) and the like, among which low density polyethylene-based Lincron, linear low density polyethylene-based Lincron, ultra-low density polyethylene-based And those of ethylene-vinyl acetate copolymer system can be preferably used.

  Further, the thermoplastic resin may be an ionomer having intermolecular bonding with metal cations. As an ionomer, an olefin type ionomer, a urethane type ionomer, a styrene type ionomer, a fluorine type ionomer etc. are mentioned, for example. Among these, from the viewpoint of excellent adhesion with the water vapor barrier resin layer 12 containing a cycloolefin resin, it is preferable to use an olefin ionomer. As the olefin ionomer, for example, ethylene- (meth) acrylic acid copolymer, ethylene-fumaric acid copolymer, ethylene-maleic acid copolymer, ethylene-maleic acid monomethyl copolymer, ethylene-maleic acid monoethyl copolymer What combined the molecule | numerator of olefin resin, such as a polymer, with the metal ion is mentioned. Examples of the metal of 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. The ionomers may be used alone or in combination of two or more.

  When a thermoplastic resin is used, the first and second adhesive resin layers 11A and 11B preferably contain 60 to 100% by mass, particularly preferably 70 to 100% by mass, of the thermoplastic resin. Furthermore, it is preferable to contain 80-100 mass%.

  In addition, the thermoplastic resin may be blended with a curable resin described later. The blend mass ratio of the thermoplastic resin to the curable resin is preferably 99: 1 to 1:99, more preferably 10:90 to 90:10, and 20:80 to 80:20. Is particularly preferable, and more preferably 30:70 to 70:30.

  As the curable resin, for example, epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin and urethane resin can be used. These curable resins can be used singly or in combination of two or more.

  Examples of epoxy resins include monofunctional epoxy compounds, bifunctional epoxy compounds, trifunctional or higher polyfunctional epoxy compounds, polymers or oligomers having an epoxy group, vinyl monomers having an epoxy group, and other vinyls. Copolymers or oligomers with monomers etc. can be used. These epoxy resins can be used singly or in combination of two or more.

  When a curable resin is used, the first and second adhesive resin layers 11A and 11B preferably contain 60 to 100% by mass, particularly preferably 70 to 100% by mass, of the curable resin. Furthermore, it is preferable to contain 80-100 mass%.

  The first and second adhesive resin layers 11A and 11B may be, for example, a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, a plasticizer, a lubricant, and the like, if desired. It may contain various additives such as antiblocking agent, dispersing agent, filler, crosslinking agent (curing agent; curing agent when using curable resin such as epoxy resin), silane coupling agent, hygroscopic agent and the like. In particular, when the first and second adhesive resin layers 11A and 11B contain a rubber-based resin, it is preferable to contain a tackifier. Examples of tackifiers include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5 resins, C9 resins and dicyclopentadiene resins, and synthetic resins such as coumarone indene resins and xylene resins. .

  The thickness (one layer) of each of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 μm, more preferably 3 to 80 μm, and further preferably 5 to 50 μm. Is preferred. When the thickness of the first and second adhesive resin layers 11A and 11B is 1 μm or more, sufficient adhesiveness can be obtained. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 μm or less, the thickness of the film-like encapsulant 1B can be kept thin.

  The materials, thicknesses and the like of the first and second adhesive resin layers 11A and 11B may be the same or different.

(3) Physical Properties and the Like of Film Sealing Materials 1A and 1B The thickness of the film sealing materials 1A and 1B is preferably 7 to 500 μm, particularly preferably 15 to 400 μm, and further preferably 20 to 40 μm. It is preferable that it is 200 micrometers. When the thickness of the film-like encapsulants 1A and 1B is 7 μm or more, sufficient water vapor barrier properties and adhesiveness can be obtained. On the other hand, when the thickness of the film-shaped sealing materials 1A and 1B is 500 μm or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin. For example, even when used for electronic devices It can avoid that the thickness of the device becomes too thick.

The water vapor transmission rate of the film-like encapsulants 1A and 1B is preferably 20 g / (m ² · day) or less, as measured with the film-like encapsulants 1A and 1B having a thickness of 50 μm, and in particular It is preferably 15 g / (m ² · day) or less, and more preferably 10 g / (m ² · day) or less. The water vapor from the outside is effectively blocked by the film-like sealing materials 1A and 1B as the water vapor transmission rate of the film-like sealing materials 1A and 1B is 20 g / (m ² · day) or less, and the sealing is performed. The reaching of the object to be stopped is prevented and suppressed, and the object of sealing becomes less susceptible to the adverse effect of moisture. In the film-like encapsulating materials 1A and 1B according to the present embodiment, the water vapor barrier resin layer contains the main material M having high water vapor barrier properties, and the water vapor barrier resin layer further contains a hygroscopic agent; Such water vapor transmission rates can be achieved.

  The film-like sealing materials 1A and 1B have an adhesion of 3N / 25 mm or more when one of the outermost layers of the film-like sealing materials 1A and 1B is bonded to non-alkali glass at 120 ° C. Is particularly preferable, and in particular, 5 N / 25 mm or more. With an adhesive force of 3 N / 25 mm or more, the object to be sealed is reliably sealed, and occurrence of floating, peeling, and the like with an adherend such as a glass plate or a gas barrier film is prevented. Can. In addition, the measuring method of adhesive force is as showing to the test example mentioned later.

(4) Method for producing film-like encapsulating material 1A, 1B The method for forming the water vapor barrier resin layer 12 (water vapor barrier resin film) is not particularly limited, and the resin constituting the water vapor barrier resin layer 12 The method of film-forming the mixture with a hygroscopic agent by the melt extrusion method, a calendar method, a dry method, a solution method etc. is illustrated. In the case of the solution method, a solution obtained by dissolving the resin constituting the water vapor barrier resin layer 12 and a hygroscopic agent in an organic solvent is applied by a known application method, and the obtained coating film is dried appropriately. The conductive resin layer 12 may be formed.

  The method for forming the first and second adhesive resin layers 11A and 11B (the first adhesive resin film and the second adhesive resin film) is not particularly limited, and a melt extrusion method, a calendar method, a dry method A method, a solution method, etc. are illustrated. In the case of the solution method, each layer may be formed by applying a solution obtained by dissolving the above-described resin in an organic solvent by a known application method, and appropriately drying the obtained coating film.

  The film-like encapsulant 1B having the first and second adhesive resin layers 11A and 11B according to the second embodiment can be manufactured by a conventional method. For example, a method of co-extrusion molding the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B so as to be laminated in that order, the first adhesive property First, 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. A method of laminating a second adhesive resin film on the water vapor barrier resin layer 12 after forming the water vapor barrier resin layer 12 on the adhesive resin film, a single layer film as the water vapor barrier resin layer 12 (water vapor A method of preparing a barrier resin film and forming the first and second adhesive resin layers 11A and 11B on both sides of the water vapor barrier resin film, a first adhesive resin film, and a water vapor burr Prepare and sex resin film, and a second adhesive resin film, by a method such as a method of laminating overlapping those three resin film in that order, it is possible to produce a film-like sealing material 1B. In addition, the first and second adhesive resin layers 11A and 11B are formed on the release sheet, and the release sheet with the first and second adhesive resin layers 11A and 11B is prepared, and the water vapor prepared in advance is prepared. The film-shaped sealing material 1B can also be manufactured by a method of laminating a release sheet with the first and second adhesive resin layers 11A and 11B on both sides of the barrier resin film. The film-shaped encapsulating material 1B having only one of the first and second adhesive resin layers 11A and 11B can also be manufactured according to the above method.

  When laminating the first and second adhesive resin layers 11A and 11B (first adhesive resin film, second adhesive resin film) and the water vapor barrier resin layer 12 (water vapor barrier resin film) May be laminated while heating. The heating temperature is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B (the first adhesive resin film and the second adhesive resin film) are softened.

(5) Use of film-like sealing material 1A, 1B Since film-like sealing material 1A, 1B which concerns on this embodiment is very excellent in water-vapor barrier property, it can be used for sealing of various things, especially It can be suitably used for sealing of 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 and the like, an electronic paper, a solar cell module and the like can be mentioned. Above all, in a module for display devices having organic EL elements (organic EL module) and electronic paper, high water vapor barrier properties are required, so the film-like encapsulating materials 1A and 1B according to the present embodiment are suitably used. can do.

[Sealing sheet]
FIG. 3: is a schematic sectional drawing of the sealing sheet 2 which concerns on this embodiment provided with the film-form sealing material 1B which concerns on 2nd Embodiment. This sealing sheet 2 is equipped with the gas barrier film 21 laminated | stacked on the single side | surface of the film-shaped sealing material 1B other than the film-shaped sealing material 1B. In addition, the sealing sheet 2 which concerns on this embodiment is not limited to what is shown by FIG. 3, and it replaces with the film-shaped sealing material 1B which concerns on 2nd Embodiment, and the film-like sealing which concerns on 1st Embodiment. It may be provided with the stopper 1A. That is, the first and second adhesive resin layers 11A and 11B may be removed from the sealing sheet 2 of FIG. Furthermore, in the sealing sheet according to the present embodiment, either one of the first and second adhesive resin layers 11A and 11B may be removed from the sealing sheet 2 of FIG. 3.

  The gas barrier film 21 is a film having the property of being difficult to permeate gas such as water vapor and oxygen. The gas barrier film 21 needs to be transparent depending on the application target of the sealing sheet 2. As the gas barrier film 21, a laminate of a base film and a gas barrier layer is preferable. As such a gas barrier film 21, for example, one having a gas barrier layer formed directly or via another layer on one side or both sides of a substrate film, one having a gas barrier layer provided in the middle of the substrate film, etc. can do.

  Examples of the base film include polyolefins such as polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polychlorinated Acrylic resins such as vinyl, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, The film which consists of resin, such as an ABS resin and an ionomer resin, or those laminated films etc. are mentioned. Among them, from the viewpoint of strength, a film made of polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyamide, polyimide, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate and the like is preferable. The base film may be a stretched film or a non-stretched film. Moreover, the base film may contain various additives such as a UV absorber.

  The thickness of the substrate film is preferably 1 to 500 μm, particularly preferably 5 to 300 μm, and further preferably 10 to 100 μm.

  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 properties of the gas barrier film 21 can be made to a desired level. The material of the gas barrier layer includes, for example, polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, silicon compounds such as tetraorganosilane compounds, silicon oxides, silicon oxynitrides, aluminum oxynitrides, aluminum oxides, aluminum oxynitrides, magnesium oxides And 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. Be These can be used singly or in combination of two or more.

  The thickness of the gas barrier layer is preferably 1 nm to 10 μm, more preferably 10 to 1000 nm, particularly preferably 20 to 500 nm, and still more preferably 50 to 200 nm.

  The gas barrier layer may be a single layer or a plurality of layers, but it is preferable that the gas barrier layer is a plurality of layers from the viewpoint that higher gas barrier properties can be obtained.

  The method of forming the gas barrier layer may be appropriately selected according to the material to be used. For example, a method of forming the material of the gas barrier layer on a substrate film by a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method or the like, or a material of the gas barrier layer was dissolved in an organic solvent A solution is apply | coated to a base film, the method of carrying out plasma ion implantation with respect to the obtained coating film, etc. are mentioned. Examples of ions to be implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton and xenon, fluorocarbons, hydrogen, ions of nitrogen, oxygen, carbon dioxide, chlorine, fluorine, sulfur and the like; Examples thereof 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 at 40 ° C. and 90% RH, and particularly preferably 0.1 g / (m ² · day) or less Preferably, it is more preferably 0.05 g / (m ² · day) or less.

  In order to manufacture the sealing sheet 2, the film-like sealing materials 1A and 1B and the gas barrier film 21 may be stacked and laminated. In the film-like encapsulants 1A and 1B according to the present embodiment, the water vapor barrier resin layer 12 itself has adhesiveness or the film-like encapsulant 1B has adhesive resin layers 11A and 11B. It adheres firmly to the film 21. Therefore, when the electronic device and the like are sealed using the sealing sheet 2, it is possible to effectively prevent the water vapor from invading between the gas barrier film 21 and the film-like sealing materials 1A and 1B. . When the gas barrier film 21 has a gas barrier layer on one side, the gas barrier film 21 and the film sealants 1A and 1B may be laminated such that the gas barrier layer is on the film sealants 1A and 1B. preferable.

  When laminating film-shaped sealing material 1A, 1B and the gas barrier film 21, you may laminate, heating. The heating temperature is preferably equal to or higher than the temperature at which the adhesive resin layer 11 of the film-like encapsulants 1A and 1B is softened.

  The sealing sheet 2 which concerns on this embodiment can be used for the use similar to the use of film-form sealing material 1A, 1B mentioned above, and is especially a display apparatus which has an organic EL element etc. with which high water-vapor barrier property is calculated | required. It can be suitably used for sealing electronic devices in electronic devices such as electronic modules, electronic paper, and solar cell modules. When sealing is performed using the sealing sheet 2, the surface on the opposite side to the side on which the gas barrier film 21 is laminated (the second adhesive resin layer 11B in FIG. 3) is bonded to the adherend. , Can be sealed.

[Electronic device]
The electronic device according to one embodiment of the present invention is sealed by the film-like sealing materials 1A and 1B according to the above-described embodiment. Specifically, as shown in FIG. 4, the electronic device 3A according to the present embodiment is a substrate 31, an electronic element 32 formed on the substrate 31, and a film-like sealing material for sealing the electronic element 32. 1B and a sealing member 33 laminated on the opposite side of the film-like sealing material 1B to the electronic element 32. There is no restriction | limiting in particular as the sealing member 33, For example, a glass plate etc. are mentioned.

  Moreover, the electronic device which concerns on other embodiment of this invention is sealed by the sealing sheet 2 which concerns on embodiment mentioned above. Specifically, as shown in FIG. 5, the electronic device 3B according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a sealing sheet 2 for sealing the electronic element 32. Equipped with In addition, the sealing sheet 2 is a laminated body of the film-shaped sealing material 1B and the gas barrier film 21 laminated | stacked on the single side | surface of this film-shaped sealing material 1B.

  Note that the electronic device according to the present embodiment is not limited to those shown in FIGS. 4 and 5, and instead of the film-like sealing material 1B according to the second embodiment, the film-like sealing according to the first embodiment. It may be provided with the stopper 1A. That is, the first and second adhesive resin layers 11A and 11B may be removed from the electronic devices 3A and 3B in FIG. 4 or 5. Furthermore, in the electronic device according to the present embodiment, either one of the first and second adhesive resin layers 11A and 11B may be removed from the electronic device 3A or 3B in FIG. 4 or 5.

  These electronic devices 3A and 3B are, for example, a module for a display device having a liquid crystal element, an LED element, an organic EL element or the like as the electronic element 32, an electrophoretic element as the electronic element 32, an electronic powder type element, a cholesteric liquid crystal element Although it is an electronic paper which has etc., a solar cell module which has a solar cell as an electronic element 32, etc., it is not limited to these. The electronic devices 3A and 3B may be top emission type electronic devices or bottom emission type electronic devices. For example, when the electronic devices 3A and 3B are bottom emission devices, the substrate 31 is preferably a transparent substrate. When the electronic devices 3A and 3B are top emission type electronic devices, 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 preferably includes, for example, a glass plate and a base film. Examples of 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 or the like, hybrid glass, etc. It can be mentioned. As a base film, what was illustrated with the gas barrier film 21 is mentioned, for example.

  The thickness of the substrate 31 is appropriately set in accordance with the type of the electronic devices 3A and 3B.

  The method of manufacturing the electronic device 3A is not particularly limited. For example, first, the electronic element 32 is formed on the substrate 31 by a conventional method. Thereafter, 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 further placed on the film-like sealing materials 1A and 1B. By bonding them together and sealing the electronic element 32, the electronic device 3A can be manufactured. The electronic device 3A may be manufactured by obtaining a laminate in which the film-like sealing materials 1A and 1B and the sealing member 33 are bonded in advance, and bonding the laminate to the electronic element 32.

  On the other hand, the method of manufacturing the electronic device 3B is also not particularly limited. For example, the sealing sheet 2 is placed so that the film-like 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 attached to each other. The electronic device 3B can be manufactured by sealing the element 32.

  Sealing may be performed at normal pressure, may be performed in a reduced pressure atmosphere, or may be performed in combination. Moreover, when bonding together film-form sealing material 1A, 1B and the electronic device 32, you may heat. 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.

  It is preferable that the heating temperature at the time of bonding is normally higher than the temperature at which the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 soften.

  In the electronic devices 3A and 3B according to the present embodiment, since the electronic elements 32 are covered with the film-like encapsulants 1A and 1B according to the present embodiment, water vapor from the outside is the film-like encapsulant 1A. Because the water vapor barrier resin layer 12 is blocked by the resin layer 12 and is prevented from reaching the electronic element 32, the electronic element 32 is less susceptible to the adverse effect of moisture. Further, in the film-like sealing materials 1A and 1B, since the water-vapor barrier resin layer 12 has adhesiveness or the first and second adhesive resin layers 11A and 11A, the film-like sealing materials 1A and 1B are used. 1A and 1B and the substrate 31, the film sealing materials 1A and 1B and the electronic element 32, the film sealing materials 1A and 1B and the sealing member 33, and the film sealing materials 1A and 1B and the gas barrier film 21 firmly It adhere | attaches and it is prevented and suppressed that floats, peeling, etc. generate | occur | produce among them, or that water vapor | steam infiltrates among them.

  The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

  Hereinafter, the present invention will be more specifically described by way of examples and the like, but the scope of the present invention is not limited to these examples and the like.

Example 1
<Production of film-like sealing material>
The material constituting the adhesive resin layer and the water vapor barrier resin layer shown in Table 1 is co-extruded by an extruder (made by Toyo Seiki Seisakusho Co., Ltd.), and a first adhesive resin layer having a thickness of 7.5 μm, A film-shaped sealing material was manufactured by laminating a water vapor barrier resin layer having a thickness of 35 μm and a second adhesive resin layer having a thickness of 7.5 μm in that order.

<Production of sealing sheet>
Aluminum of a gas barrier film (a laminated film in which a 12 μm thick polyethylene terephthalate sheet is adhered to a single surface of a 7 μm thick aluminum foil with a urethane adhesive layer), aluminum foil The foil surface was bonded while heating at 120 ° C. to obtain a sealing sheet.

<Manufacturing of bottom emission type electronic devices>
By the following method, an anode, a light emitting layer and a cathode were laminated in this order on a glass substrate to form an electronic element (organic EL element).

  First, an indium tin oxide (ITO) film (thickness: 150 nm, sheet resistance: 30 Ω / □) is formed on the surface of a glass substrate by a sputtering method, and then an anode is produced by solvent cleaning and UV / ozone treatment. did.

  On the obtained anode (ITO film), N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidene) (manufactured by Luminescence Technology) 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 Luminescence Technology) at 10 nm, lithium (8-hydroxy-quinolinolate) (Luminescence) Technology) was sequentially deposited at a rate of 10 nm and 0.1 to 0.2 nm / s to form a light emitting layer.

Aluminum (Al) (manufactured by High Purity Chemical Laboratory Co., Ltd.) was vapor-deposited on the obtained light emitting layer at a rate of 0.1 nm / s to 100 nm to form a cathode, whereby an organic EL element was obtained. In addition, the vacuum degree at the time of vapor deposition was all 1 * 10 <^-4> Pa or less.

  Next, the sealing sheet was heated at 120 ° C. for 30 minutes using a hot plate under a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left as it is and cooled to room temperature. Then, the sealing sheet is placed so that the film-like sealing material is on the organic EL element side so as to cover the organic EL element formed on the glass substrate, and from the end of the sealing sheet to the organic EL element It adjusted so that distance of 5 mm. They were bonded while heating at 100 ° C. to seal the organic EL element, to obtain a bottom emission type electronic device.

[Examples 2 and 3]
A film-like encapsulant was manufactured in the same manner as in Example 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 sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

Example 4
A coating solution 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 attached onto it, with an adhesion of 7.5 μm thickness A resin layer was formed, and two adhesive resin layers in which release sheets were laminated on both sides were produced.

  On the other hand, a mixture of the resin constituting the water vapor barrier resin layer shown in Table 1 and a hygroscopic agent was extruded by an extruder (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a water vapor barrier resin film with a thickness of 35 μm.

  Then, the adhesive resin layer was bonded to each of both sides of the obtained water vapor barrier resin film while heating at 120 ° C. At this time, 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. Next, the other release sheet was released to produce a film-shaped encapsulant. Using this film-like sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

[Examples 5 and 6]
A coating solution containing the 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, a release sheet is attached thereto, and a 25 μm thick water vapor barrier property A resin layer was obtained and used as a film-like encapsulant. Using this film-like sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

[Comparative Examples 1, 2 and 4]
A film-like encapsulant was manufactured in the same manner as in Example 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 sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

Comparative Example 3
A film-like encapsulant was manufactured in the same manner as in Example 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 sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

Comparative Example 5
A film-like encapsulant was manufactured in the same manner as in Example 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 sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

The details of the abbreviations and the like described in Table 1 are as follows.
[Adhesive resin layer]
・ Admer SF 731: Maleic anhydride-modified polyethylene (Mitsui Chemical Co., Ltd., trade name “Admer SF 731”, Vicat softening point 43 ° C.)
・ Exxon Butyl 365: Isobutylene resin (manufactured by ExxonMobil, trade name "Exxon Butyl 365")
・ Tackifier: Aliphatic petroleum resin (Nippon Zeon Co., Ltd., trade name "Quinton A-100")
・ Polyester SNT: Ester-based resin (manufactured by Japan Synthetic Chemical Co., Ltd., trade name "Polyester SNT")
・ Sumikasen L705: Low density polyethylene (Sumitomo Chemical Co., Ltd., trade name "Sumikasen L705", softening point 86 ° C)
[Water vapor barrier resin layer]
· TOPAS9506F-04: cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics Co., Ltd., trade name "TOPAS9506F-04", glass transition temperature 65 ° C)
・ Sumikasen L705: Low density polyethylene (Sumitomo Chemical Co., Ltd., trade name "Sumikasen L705", softening point 86 ° C)
・ Exxon Butyl 365: Isobutylene resin (manufactured by ExxonMobil, trade name "Exxon Butyl 365")
・ Tackifier: Aliphatic petroleum resin (Nippon Zeon Co., Ltd., trade name "Quinton A-100")
・ Admer SF 731: Maleic anhydride-modified polyethylene (Mitsui Chemical Co., Ltd., trade name “Admer SF 731”, Vicat softening point 43 ° C.)
· Calcium oxide: Calcium oxide (Omi Chemical Industry Co., Ltd., trade name "CML # 35", average particle size 15 μm)
· Magnesium sulfate: anhydrous magnesium sulfate (manufactured by Tomita Pharmaceutical, trade name "anhydrous magnesium sulfate", average particle diameter 10 μm)
・ Cyclic aluminum oligomer: Metal acylate compound (manufactured by Kawaken Fine Chemical Co., Ltd., trade name “Algomer 800 AF”)
Aluminoxane: polymetalloxane compound represented by the following structural formula (e) (wherein, L represents ethyl 3-oxobutanoate as an organic ligand, n represents an integer of 1 or more) (art science) Product name "Polyaluminoxane 50% toluene solution"

[Test Example 1] (Measurement of Water Vapor Permeability of Main Material M)
The water vapor transmission rate of the main material M was measured for the film-like encapsulant obtained in the example or the comparative example. Specifically, a resin film is produced using only the material obtained by removing the moisture absorbing agent from the water vapor barrier resin layer shown in Table 1, and using a transmittance measurement machine “L80-5000” manufactured by LYSSY, 40 ° C., 90% The water vapor transmission rate of this resin film was measured under the condition of RH. From the measurement results, the water vapor transmission rate was calculated when the thickness of the resin film was 50 μm, using the following formula. The results are shown in Table 1.
Water vapor transmission rate (converted to 50 μm) = water vapor transmission rate (measured value) × (measured film thickness / 50)

[Test Example 2] (Measurement of Water Vapor Permeability of Adhesive Resin Layer)
The water vapor transmission rate of the adhesive resin layer was measured for the film-like encapsulant obtained in Examples 1 to 4 or Comparative Examples 1 to 5. Specifically, with respect to one obtained by peeling one release sheet from the adhesive resin layer in which release sheets are laminated on the both sides, using a transmittance measurement machine “L80-5000” manufactured by LYSSY, 40 ° C., 90 The water vapor transmission rate of the adhesive resin layer was measured under the conditions of% RH. From the measurement results, the water vapor transmission rate was calculated when the thickness of the measurement sample was 50 μm using the following formula. The results are shown in Table 1.
Water vapor transmission rate (converted to 50 μm) = water vapor transmission rate (measured value) × (measured film thickness / 50)

[Test Example 3] (Measurement of Maximum Moisture Absorption)
The maximum moisture absorption of the film-like encapsulant obtained in the example or the comparative example was measured. Specifically, the film-shaped sealing material cut into 70 mm × 70 mm was thermally laminated at 70 ° C. at 70 ° C. at 120 ° C. to obtain a measurement sample. The mass (the total mass of the glass and the film-like encapsulant) was measured within one hour after the sample preparation. After measurement, it is left in an environment at 60 ° C and 90% RH to absorb moisture until there is no change in mass, and the mass is measured again, and water vapor is obtained by subtracting the mass value before moisture absorption from the mass value after moisture absorption. The amount of moisture absorption was determined. From the measurement results, the maximum moisture absorption amount (g / m ² ) in the water vapor barrier resin layer having a thickness of 50 μm was calculated using the following formula. The results are shown in Table 1.
Maximum moisture absorption amount (50 μm conversion) = {water vapor moisture absorption amount (measured value) / (0.07 × 0.07)} × (50 / thickness of water vapor barrier resin layer)

[Test Example 4] (Measurement of Adhesive Strength)
With respect to the sealing sheet obtained in the example or the comparative example, one release sheet is peeled off, and the surface of the exposed first adhesive resin layer is bonded to a polyethylene terephthalate sheet as a backing substrate, 25 mm × 300 mm It was cut to the size of. Next, the other release sheet is peeled off, and the surface of the exposed second adhesive resin layer is superimposed on a glass plate (soda lime glass, manufactured by Nippon Sheet Glass Co., Ltd.) as an adherend, and heated at 120 ° C. It bonded together and obtained the test piece.

  After bonding the obtained test pieces, they are left under an environment of 23 ° C. and 50% RH for 24 hours, and then under the same environment, the peeling speed is 300 mm using a tensile tester (manufactured by Orientec Co., Ltd., Tensilon). The peeling test was carried out under the conditions of a peeling angle of 180 ° and the adhesion strength (N / 25 mm) was measured. The results are shown in Table 1. In addition, in Table 1, when adhesive force is 1 N / 25 mm or less, it described as "<1."

[Test Example 5] (Evaluation of Electronic Device)
After leaving the bottom emission type electronic device obtained in the example or the comparative example for 500 hours in an environment of 60 ° C. and 90% RH, the organic EL element is activated, and the area of the non-light emitting portion is measured. Evaluated on the basis of The results are shown in Table 1.
A: The area of the non-emitting portion is less than 10% of the initial light emitting area B: The area of the non-emitting portion is 10 or more of the initial light emitting area

  As can be seen from Table 1, the film-like encapsulant obtained in the examples was excellent in water vapor barrier properties and adhesion. Further, in the electronic device obtained in the example, there was almost no infiltration of water from the end. Furthermore, the organic EL element sealed by the film-shaped sealing material obtained in the Example was excellent in durability, hardly any non-light emitting part was observed, and the performance of the electronic device was good.

  On the other hand, the film-like sealing material of Comparative Example 1 had very low adhesive strength and could not seal the electronic device. Therefore, no electronic device evaluation could be performed. Although the film-like sealing material of Comparative Examples 2-5 was able to seal an electronic device, it was inferior in the point of electronic device evaluation. Moreover, in the film-like encapsulant of Comparative Example 2, the water vapor transmission rate of the main material M was high. In the film-like encapsulant of Comparative Example 3, the water vapor transmission rate of the adhesive resin layer was very high. In the film-like encapsulant of Comparative Example 4, it was not possible to absorb moisture because it does not contain a moisture absorbent. In the film-like encapsulant of Comparative Example 5, the moisture-absorbing ability was insufficient because the thickness of the water vapor barrier resin layer was thin.

  The film-shaped encapsulating material and the encapsulating sheet according to the present invention are suitably used, for example, in an organic EL module or an electronic paper. The electronic device according to the present invention is suitable, for example, as an organic EL module or electronic paper.

1A, 1B: film sealing material 11A: first adhesive resin layer 11B: second adhesive resin layer 12: water vapor barrier resin layer 2: sealing sheet 21: gas barrier film 3A, 3B: electronic device 31 ... Substrate 32 ... Electronic element 33 ... Sealing member

Claims (11)

What is claimed is: 1. A film sealing material comprising one or more layers comprising a water vapor barrier resin layer containing a hygroscopic agent, wherein
Both sides of the film-like encapsulant exhibit adhesion to the adherend,
The water vapor transmission rate of the material obtained by removing the hygroscopic agent from the water vapor barrier resin layer is 10 g / (m ² · day) or less when measured at a thickness of 50 μm,
When the film-like encapsulating material is composed of a plurality of layers, the water vapor permeability of the layer other than the water vapor barrier resin layer located on the outermost side of the film-like encapsulating material is measured at a thickness of 50 μm. Less than 30 g / (m ² · day),
The thickness ratio of the water vapor barrier resin layer, Ri 50-100% der thickness of the film-like sealing member,
Content of the said hygroscopic agent in the said water-vapor-barrier resin layer is 1-35 mass%, The film-form sealing material characterized by the above-mentioned. One adhesive resin layer laminated on one side of the water vapor barrier resin layer and exhibiting adhesiveness to an adherend, or one side and the other side of the water vapor barrier resin layer The film-like sealing according to claim 1, characterized in that it comprises two adhesive resin layers which are laminated and show adhesiveness to an adherend as the outermost layer of the film-like sealing material. Material. The film sealing material according to claim 2, wherein a water vapor transmission rate of the adhesive resin layer is 30 g / (m ² · day) or less when measured at a thickness of 50 μm. The maximum moisture absorption amount of the moisture absorbent is 1.0 g / m ² or more when it is represented by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 μm. The film-like sealing material as described in any one of 3.   The film-form sealing material according to any one of claims 1 to 4, wherein the hygroscopic agent is a compound containing a metalloxane bond. The compound having a metalloxane bond is represented by the formula [M (OR) _{n ′} —O] _m (where M is a metal element, R is a compound containing at least hydrogen and carbon, n ′ is an integer of 1 or more, and oxidation of the metal element). Among compounds having a structure represented by a value obtained by subtracting 2 from a number, m represents an integer of 1 or more), the compound reacts with water at a site of M-O-M. The film-like sealing material as described in 5.   The film-like sealing material according to any one of claims 1 to 4, wherein the hygroscopic agent is a metal oxide.   The film-shaped sealing material according to any one of claims 1 to 4, wherein the hygroscopic agent is a compound that reacts with water molecules to form a hydrate. The film-like sealing material as described in any one of Claims 1-8,
And a gas barrier film laminated on one side of the film-like sealing material.   An electronic device sealed by the film-like sealing material according to any one of claims 1 to 8.   It sealed by the sealing sheet of Claim 9, The electronic device characterized by the above-mentioned.

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