JP6468810B2 - 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 that can seal an electronic element and the like, and an electronic device in which the electronic element is sealed.

  In an organic electronic device, for example, a display module having an organic electroluminescence (organic EL) element or electronic paper, or a solar cell module having an organic thin film solar cell element, moisture or oxygen enters the electronic element inside the device. Therefore, it is necessary to prevent moisture and oxygen from entering. 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 element, and a substrate for fixing them, the contact between the glass member and the substrate is fixed with an adhesive, and the electronic element is provided in a space formed between them. There is a method. In the electronic device manufactured as described above, moisture existing outside may permeate the internal space through the fixing adhesive. Patent Documents 1 and 2 disclose a substance 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 in a specific ratio (claim 1 of Patent Document 1). Further, it is disclosed that the total content of the two desiccants in the resin can be 40 to 80% by weight (the same claim 2). This resin is provided in a sheet shape at a position facing the electronic element inside the electronic device, and absorbs moisture present in the electronic device (Japanese Patent Laid-Open No. 2001-277395 cited in Patent Document 1 as Patent Document 1). No. 2).

  Patent Document 2 discloses a composition containing a compound containing an Al—OR bond and a curable monomer. The above compound acts as a hygroscopic agent because it removes water molecules from the surroundings by performing a hydrolysis reaction at the Al-OR bond. This composition absorbs moisture present in the electronic device by being provided in the form of a sheet at a position facing the electronic element inside the electronic device or by filling the space inside the electronic device (Patent Document 2). 1 and 2).

  Moreover, there exists the method of using a film-form sealing material as another method of preventing a water | moisture content permeating into the inside of an electronic device. In this case, the electronic device is manufactured, for example, as a stacked body in which a sealing substrate, a film-shaped sealing material, an electronic element, and a substrate are stacked in this order. In this case, a glass plate, a high gas barrier film, a metal foil, or the like is used for the sealing substrate so that moisture does not enter the thickness direction from the main surface of the laminate. However, there is a possibility that moisture permeates from the end surface of the edge of the laminated body where the film-like sealing material is exposed to the outside and moves in the in-plane direction to reach the electronic device. For this reason, a sealing material having a water vapor barrier property has been developed.

JP 2006-116501 A JP2013-108057A

  However, in a display device module having an organic EL element that has been 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. Since the substances disclosed in Patent Documents 1 and 2 are for drying the space in the electronic device, they cannot be used as a sealing sheet. Furthermore, since the substance of Patent Document 2 is a liquid sealant, workability is poor, for example, it is necessary to provide a dam for preventing flow around the device so that the liquid material does not flow out. Moreover, the conventional film-form sealing material is developed mainly from the viewpoint of preventing the invasion of water vapor from the main surface, and cannot sufficiently prevent the invasion of water vapor from the end surface of the film-shaped sealing material.

  This invention is made | formed in view of such an actual condition, and aims at providing the film-form sealing material, sealing sheet, and electronic device which have the more outstanding water vapor | steam barrier property.

  In order to achieve the above object, first, the present invention provides a film-shaped sealing material comprising a water vapor barrier resin layer or a single layer or a plurality of layers, and both surfaces of the film-shaped sealing material are adherends. The film-like sealing material has a water vapor intrusion rate from the end face of the film-like sealing material in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH of 10 μm / h or less. A sealing material is provided (Invention 1).

  In the film-shaped sealing material according to the invention (Invention 1), since the moving speed of moisture entering from the end surface of the film-shaped sealing material is very slow, the intrusion of water vapor from the end surface of the film-shaped sealing material is suppressed. Very high water vapor barrier properties are achieved.

  In the said invention (invention 1), it is preferable that the said water vapor | steam barrier resin layer contains a hygroscopic agent (invention 2).

  In the above inventions (Inventions 1 and 2), one adhesive resin layer laminated on one surface side of the water vapor barrier resin layer and exhibiting adhesion to an adherend, or the water vapor barrier resin layer It is preferable to further include two adhesive resin layers which are laminated on one surface side and the other surface side, and exhibit adhesion to the adherend (Invention 3).

  In the said invention (invention 1-3), it is preferable that the ratio of the thickness of the said water vapor | steam barrier resin layer is 50 to 100% of the thickness of the said film-form sealing material (invention 4).

  In the said invention (invention 1-4), it is preferable that the said water vapor | steam barrier resin layer contains at least 1 sort (s) of resin selected from the group which consists of rubber-type resin, polyester-type resin, polyolefin-type resin, and epoxy-type resin. (Invention 5).

  In the above invention (Invention 3), the adhesive resin layer preferably contains at least one resin selected from the group consisting of a rubber resin, a polyester resin, a polyolefin resin, and an epoxy resin (Invention 6). ).

In the above invention (Invention 2), the maximum moisture absorption amount of the hygroscopic agent is 1.0 g / m ² or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 μm. Is preferable (Invention 7).

  In the said invention (invention 2), it is preferable that the said hygroscopic agent is a compound containing a metalloxane bond (invention 8).

  In the said invention (invention 2), it is preferable that the said hygroscopic agent is a metal oxide (invention 9).

  In the said invention (invention 2), it is preferable that the said hygroscopic agent is a compound which reacts with a water molecule and produces | generates a hydrate (invention 10).

  In the said invention (invention 1-10), it is preferable that the adhesive force at the time of bonding any one surface of the said film-form sealing material on a glass plate at 120 degreeC is 1 N / 25mm or more (invention 11). ).

  2ndly this invention provides the sealing sheet characterized by including the said film-form sealing material (invention 1-11) and the gas barrier film laminated | stacked on the single side | surface of the said film-form sealing material. (Invention 12).

  Thirdly, the present invention provides an electronic device characterized by being sealed with the film-shaped sealing material (Invention 1 to 11) (Invention 13).

  4thly this invention provides the electronic device characterized by having been sealed by the said sealing sheet (invention 12) (invention 14).

  The film-form sealing material which concerns on this invention can achieve very high water vapor | steam barrier property because the water vapor | steam penetration rate from the end surface of a film-form sealing material is very slow.

It is a schematic sectional drawing of the film-form sealing material which concerns on the 1st Embodiment of this 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 sealant]
The film-shaped sealing material which concerns on embodiment may consist of one layer, and may consist of multiple layers. When the film-shaped sealing material is composed of one layer, the film-shaped sealing material is composed only of the water vapor barrier resin layer. On the other hand, when the film-shaped sealing material is composed of a plurality of layers, the film-shaped sealing material is composed of a water vapor barrier resin layer and one or more other layers.

  In the film-shaped encapsulant composed of 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 another layer, an adhesive resin layer is preferably exemplified.

  Both surfaces of the film-shaped sealing material according to the embodiment exhibit adhesiveness to the adherend. When the film-like sealing material is composed of one layer, that is, when it is composed of only the water vapor barrier resin layer, the water vapor barrier resin layer has adhesiveness. On the other hand, when a film-form sealing material consists of two or more layers, the layer located in the outermost side of a film-form sealing material has adhesiveness. For example, when the water vapor barrier resin layer is present on one surface of the film-shaped sealing material and the adhesive resin layer is present on the other surface, the water vapor barrier resin layer and the adhesive resin layer have adhesiveness. . Moreover, when two adhesive resin layers exist in both surfaces of a film-form sealing material, two adhesive resin layers have adhesiveness.

  A release sheet may be laminated on both surfaces of the film-shaped sealing material according to the embodiment for the purpose of protecting the adhesive surface. This release sheet is appropriately peeled off when using the film-like sealing material.

  In the present specification, the “layer located on the outermost side” refers to a layer located on the outermost side when the film-shaped sealing material is used for sealing. Therefore, a release sheet is not included in the “outermost layer”.

  1 and 2 show specific examples of the film-like sealing material.

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

  The water vapor intrusion rate from the end faces of the film-like sealing materials 1A and 1B in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH is 10 μm / h or less, preferably 8 μm / h or less, particularly 5 μm. / H or less is preferable. The water vapor intrusion speed from the end face refers to a speed at which water vapor enters from the end faces of the film-like sealing materials 1A and 1B and moves in the in-plane direction. For example, in FIG. 4, the substrate 31, the electronic element 32 formed on the substrate 31, the film-shaped sealing material 1 </ b> B that seals the electronic element 32, and the electronic element 32 of the film-shaped sealing material 1 </ b> B An electronic device 3B having a sealing member 33 laminated on the opposite side is shown. Water vapor enters the inside from the end face 13 of the film-like sealing material 1B, moves in the horizontal direction, and moves to the electronic element 32. The amount of movement per unit time at that time is the water vapor intrusion speed. The method for measuring the water vapor infiltration rate is as shown in the test examples described later. Thus, even if water vapor enters from the end surfaces of the film-shaped sealing materials 1A and 1B due to the extremely low water vapor intrusion speed from the end surfaces in the film-shaped sealing materials 1A and 1B, moisture can enter the electronic device. It is difficult to reach and as a result, very high water vapor barrier properties can be achieved.

(1) Water vapor barrier resin layer 12
(1.1) Resin constituting the water vapor barrier resin layer 12 The resin constituting the water vapor barrier resin layer 12 is preferably a resin having a low water vapor permeability from the viewpoint of reducing the water vapor infiltration rate. Examples of the resin constituting the water vapor barrier resin layer 12 are a rubber resin, a polyester resin, a polyolefin resin, a cycloolefin resin, and an epoxy resin. These resins can be used alone or in combination of two or more.

  The water vapor barrier resin layer 12 may have adhesiveness. That is, the resin constituting the water vapor barrier resin layer 12 may be selected so that the water vapor barrier resin layer 12 has adhesiveness. In particular, when the adhesive resin layer is not included as in the film-shaped sealing material 1A according to the first embodiment, or when one adhesive resin layer is included, the water vapor barrier resin layer 12 has an adhesive property. It is preferable to have. The water vapor barrier resin layer 12 having adhesiveness can be satisfactorily adhered to a gas barrier film and an electronic element described later.

  The rubber-based resin is preferable because it can achieve high water vapor barrier properties and high adhesiveness at the same time. Examples of rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, halogenated butyl rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate -Butadiene copolymer, urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), ethylene-propylene-nonconjugated diene ternary copolymer Examples include coalescence. These rubber compounds can be used singly or in combination of two or more. Among these, as the rubber resin, those containing a polyisobutylene resin are preferable.

  The polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers. The polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.

  Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more. When the polyisobutylene resin is a copolymer, isobutylene is the maximum amount of monomer as a main component in the raw material monomer.

  Among them, the polyisobutylene resin is an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as a monomer component or a homopolymer consisting of only isobutylene from the point that it has excellent water vapor barrier properties. Preferably there is.

  The number average molecular weight of the rubber-based resin used for the water vapor barrier resin layer 12 is usually 100,000 to 5,000,000, preferably 100,000 to 3,000,000, more preferably 100,000 to 1,000,000.

  The polyester resin is a polymer obtained by polycondensation of a polyvalent carboxylic acid and a polyol, or a modification thereof. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, trimellitic acid and the like. Examples of the polyol include aliphatic alcohols such as ethylene glycol and propylene glycol, and polyether polyols such as polyethylene glycol and polypropylene glycol. These polyester resins can be used singly or in combination of two or more.

  The polyolefin resin refers to a polymer (including the concept of a copolymer) containing only one or two or more olefins as a monomer component constituting the polymer. That is, the polyolefin resin here is a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins. As an olefin, a C2-C8 alpha olefin is preferable, For example, ethylene, propylene, butylene, isobutylene, 1-hexene, styrene etc. are mentioned, Among these, 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 less than ^3), medium density polyethylene (MDPE, density: 915 kg / ^{m 3} or more, less than 942Kg / ^{m 3),} high density polyethylene (HDPE, density: 942Kg / ^{m 3} or higher) such as polyethylene resin, polypropylene resin (PP ), Ethylene-propylene copolymer and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, low density polyethylene is preferable, and linear low density polyethylene is particularly preferable.

  Cycloolefin-based resin refers to a resin whose main component is a polymer (including the concept of copolymer) containing cycloolefin as a monomer component constituting the polymer, and is a polymer containing only cycloolefin as a monomer component. It may be a polymer (copolymer) containing cycloolefin and other monomers as monomer components. The other monomer is not particularly limited as long as it does not hinder the purpose of the film-shaped sealing materials 1A and 1B according to the present embodiment. Examples include esters. In addition, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.

  Among the above, the cycloolefin-based resin is excellent in adhesion with the adhesive resin layers 11A and 11B described later, and can prevent delamination of the film-shaped sealing material 1B, and therefore, cycloolefin and ethylene as monomer components. It is preferable that it is a copolymer containing.

  The cycloolefin 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-based resin is 20 ° C. or higher, the content of cycloolefin as a monomer component in the cycloolefin-based resin increases, and the water vapor barrier property is easily exhibited. In addition, when the glass transition temperature of the cycloolefin resin is 150 ° C. or lower, the water vapor barrier resin layer 12 follows the step of the sealing target such as an electronic element well, and the sealing target is securely sealed. Can be stopped.

  The cycloolefin resin preferably does not have a hydrophilic group. When it has a hydrophilic group, the water vapor barrier property may be lowered. Examples of the hydrophilic group include a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, a sulfonic acid group, and a mercapto group. On the other hand, the cycloolefin-based resin may have a hydrophobic group. If it is a hydrophobic group, there is no possibility that water vapor | steam barrier property will fall. Examples of the hydrophobic group include an alkyl group and an aryl group.

（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、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 preferred cycloolefin-based resin, the following structural formula (a)

(In the formula (a), m and n are .R ¹ and R ² is an integer of 1 or more represents a hydrogen atom or an alkyl group, may be respectively the same, may be different .R ¹ and R ² may combine with each other to form a ring.)
A cycloolefin polymer represented by the formula (a copolymer containing cycloolefin and ethylene as monomer components; 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 may combine with each other to form a ring.)
A cycloolefin polymer represented by the formula (a copolymer containing cycloolefin and ethylene as monomer components; COC), the following structural formula (c)

(In the formula (c), n is an integer of 1 or more, and R ¹ and R ₂ represent a hydrogen atom or an alkyl group, and may be the same or different. R ¹ and R ² May be bonded to form a ring.)
(A polymer containing only cycloolefin as a monomer component; COP), and the following structural formula (d)

(In formula (d), n is an integer of 1 or more, and R ¹ and R ² represent a hydrogen atom or an alkyl group, and may be the same or different. R ¹ and R ² May be bonded to form a ring.)
And a cycloolefin polymer (polymer containing only cycloolefin as a monomer component; COP). These cycloolefin polymers are extremely excellent in water vapor barrier properties and are easily available. These cycloolefin polymers can be used singly or in combination of two or more.

  A commercial item can also be used for a cycloolefin polymer. Examples of commercially available products include ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd., ring-opening metathesis polymer hydrogenated polymer of norbornene monomer), TOPAS (registered trademark) (manufactured by Polyplastics Co., Ltd., copolymer of norbornene and ethylene). ), ZEONOR (registered trademark) (manufactured by Nippon Zeon Co., Ltd., a copolymer based on ring-opening polymerization of dicyclopentadiene and tetracyclopentadecene), Apel (registered trademark) (manufactured by Mitsui Chemicals, ethylene and tetracyclododecene) Copolymer), Arton (registered trademark) (manufactured by JSR, cyclic olefin resin containing a polar group using dicyclopentadiene and methacrylic acid ester as raw materials), and the like.

  Examples of the epoxy resin include a monofunctional epoxy compound, a bifunctional epoxy compound, a trifunctional or higher polyfunctional epoxy compound, a polymer or oligomer having an epoxy group, and a vinyl monomer having an epoxy group and other vinyl monomers. And copolymer polymers or oligomers. These epoxy resins can be used alone or in combination of two or more.

  The water vapor barrier resin layer 12 may contain other resin components in addition to the resin. Other resin components include, for example, olefin resins such as ethylene- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, urethane resin, polyurethane Resin, polyester urethane resin, acrylic resin, amide resin, styrene resin, silane resin, and the like.

When the water vapor permeability of a material (hereinafter referred to as “main material M”) obtained by removing the moisture absorbent from the water vapor barrier resin layer 12 containing the resin is measured in the layer 12 made of the main material M having a thickness of 50 μm. In addition, it is preferably 10 g / (m ² · day) or less, particularly preferably 8 g / (m ² · day) or less, and more preferably 6 g / (m ² · day) or less. In this specification, the water vapor transmission rate is defined as the mass (g / (m ² · day)) of water that permeates the 1 m ² region for one day for a measurement target having a certain thickness. Is done. The thickness at this time is, for example, 50 μm. By having a low water vapor permeability of 10 g / (m ² · day) or less, the water vapor intrusion rate from the end face of the water vapor barrier resin layer 12 is reduced, and the film-shaped sealing materials 1A and 1B have higher water vapor barrier properties. Can be achieved.

  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.

(1.2) Hygroscopic agent It is preferable that the water vapor | steam barrier resin layer 12 contains a hygroscopic agent other than the said resin. Since the water vapor barrier resin layer 12 contains a hygroscopic agent, the water vapor that has entered the water vapor barrier resin layer 12 is taken into the hygroscopic agent. Thus, a higher water vapor barrier property can be achieved. In general, hygroscopic agents are roughly classified into two types: chemical hygroscopic agents and physical hygroscopic agents.

  A chemical hygroscopic agent is a hygroscopic agent that takes in surrounding water by using water molecules as a reaction product of a chemical reaction. In the film-like sealing materials 1A and 1B according to the present embodiment, any chemical moisture absorbent can be used, but a metal oxide, a compound that reacts with water molecules to form a hydrate, or a metalloxane bond. It is preferred to use a compound containing. These chemical hygroscopic agents can be used alone or in combination of two or more.

Examples of metal oxides that can be used as chemical humectants are calcium oxide, barium oxide, magnesium oxide and strontium oxide. These metal oxides can be used alone or in combination of two or more. In this, calcium oxide performs reaction of the following formula | equation (1) between water molecules. As a result of this reaction, water molecules are converted into hydroxyl groups in calcium hydroxide which is a reaction product. Metal oxides other than calcium oxide also perform the same reaction as in formula (1).

Examples of compounds that can be used as chemical moisture absorbents and react with water molecules to form hydrates are sodium sulfate, potassium sulfate / aluminum, magnesium sulfate, calcium sulfate, aluminum sulfate, sodium carbonate, sodium acetate, thiosulfate Sodium and copper sulfate. These compounds can be used individually by 1 type or in combination of 2 or more types. In this, magnesium sulfate performs reaction of the following formula | equation (2) between water molecules. As a result of this reaction, water molecules are converted to hydrated water in the hydrate. Compounds other than magnesium sulfate also perform the same reaction as in formula (2).

The compound containing a metalloxane bond is a compound containing a metalloxane bond, that is, a bond between a metal element and oxygen. Examples of such compounds are compounds represented by the general formula M (OR) _n (M is a metal element, R is a compound containing at least hydrogen, carbon and oxygen, and n represents the oxidation number of the metal element), and Formula [M (OR) _{n ′} —O] _m (M is a metal element, R is an alkyl group or an acyl group, n ′ is an integer of 1 or more, and a value obtained by subtracting 2 from the oxidation number of the metal element, m is Represents an integer of 1 or more). Moreover, the compound containing a metalloxane bond generally includes a compound called a metalloxane compound or a polymetalloxane compound. In the present specification, the phrase (poly) metalloxane compound may be used as an expression meaning both the metalloxane compound and the polymetalloxane compound. More specific examples of compounds containing a metalloxane bond are metal alkoxides, metal acylates and metal chelates. The site | part which reacts with the water of the compound containing a metalloxane bond is mainly M-O-R or M-O-M. These compounds can be used individually by 1 type or in combination of 2 or more types.

Metal alkoxides (also known as metal alcoholates) are examples of compounds that react with water at the M-O-R site. Examples of the metal alkoxide 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 (also known as: tetramethoxy titanium (IV), titanium (IV) tetramethoxide), aluminum ethoxide and aluminum oxide isopropoxide trimer. These metal alkoxides can be used individually by 1 type or in combination of 2 or more types.

The aluminum ethoxide performs a reaction of the following formula (3) with water molecules. In this reaction, water molecules are utilized for the hydrolysis of aluminum ethoxide, resulting in the production of aluminum hydroxide and ethanol. Compounds other than aluminum ethoxide perform the same reaction as in formula (3).

Metal acylates are examples of compounds that react with water at the M-O-R or M-O-M sites. In the metal acylate, an example of a compound that reacts with water at the M-O-R site is a compound in which R is an acyl group in the general formula M (OR) _n . An example of a compound that reacts with water at the MOM portion in the metal acylate is a compound having a structure in which R is an acyl group in the formula [M (O—R) _{n ′} —O] _m . Specific examples of the metal acylate are cyclic aluminum oxide octylate and cyclic aluminum oxide stearate. These metal acylates can be used alone or in combination of two or more. The cyclic aluminum oxide octylate reacts with water molecules according to the following formula (4), and there is only one product. Compounds other than cyclic aluminum oxide octylate also perform the same reaction as in formula (4).

  The physical hygroscopic agent is a hygroscopic agent that takes in surrounding water regardless of a chemical reaction, and for example, adsorbs surrounding water molecules on the surface of the hygroscopic agent. In the film-like sealing materials 1A and 1B according to the present embodiment, any physical hygroscopic agent can be used, and for example, zeolite, activated alumina, silica gel, and a clay compound can be used. As the zeolite, a molecular sieve can be used. These hygroscopic agents can be used alone or in combination of two or more.

  The hygroscopic agent is preferably one that has little or no influence on the electronic element. In particular, when a chemical moisture absorbent is used, it is preferable to use a moisture absorbent that does not cause a substance that corrodes the electronic device due to a moisture absorption reaction. In addition, it is preferable to use a hygroscopic agent that does not generate gas due to a moisture absorption reaction or a temperature change, and does not cause expansion of the electronic device. Furthermore, in the production of the water vapor barrier resin layer 12, it is preferable to use a hygroscopic agent that is well mixed with the resin constituting the water vapor barrier resin layer 12 and does not denature even when subjected to a treatment such as heating.

  Considering these viewpoints, it is preferable to use the above-mentioned compound containing a metalloxane bond, a compound that reacts with a metal oxide and a water molecule to form a hydrate, and particularly as a compound containing a metalloxane bond, M- It is preferable to use a compound that reacts with water at the OM site. These hygroscopic agents produce a relatively stable product when a hygroscopic reaction occurs, which is less prone to vaporization and gas generation, and is well mixed with the material resin to provide a water vapor barrier resin. It is difficult to denature in the manufacturing process of the layer 12. As a result, it is possible to obtain the film-shaped sealing materials 1A and 1B exhibiting very excellent water vapor barrier properties.

  The content of the hygroscopic agent in the water vapor barrier resin layer 12 is preferably 1 to 35% by mass, particularly preferably 3 to 30% by mass, and further preferably 5 to 25% by mass. . By being 1 mass% or more, the water | moisture content which permeate | transmits the water vapor | steam barrier resin layer 12 is fully moisture-absorbed, and the water vapor | steam barrier property of film-form sealing material 1A, 1B further improves. Moreover, when it is 35 mass% or less, when manufacturing the water vapor | steam barrier resin layer 12, it becomes possible to form into a favorable film.

  The shape of the hygroscopic agent is not particularly limited, but may be, for example, a liquid, a powder, or a granule. In the case of powder or granular form, the average particle diameter of the hygroscopic agent is not particularly limited, but is preferably 0.1 to 20 μm, particularly preferably 0.1 to 10 μm, and more preferably 0.1 to 5 μm. It is preferable that Here, the “average particle diameter” in the present specification is a value obtained by measurement with a laser diffraction particle size distribution measuring apparatus.

The maximum moisture absorption amount of the hygroscopic agent is preferably 1.0 g / m ² or more, particularly 1.5 g / m ² when expressed by the amount of water absorbed by the water vapor barrier resin layer 12 having a thickness of 50 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 of 1.0 g / m ² or more, it becomes possible to sufficiently absorb moisture that permeates the water vapor barrier resin layer 12 and has a higher water vapor barrier property. Sealing materials 1A and 1B can be obtained.

(1.3) Other components In addition to the resin and the hygroscopic agent, the water vapor barrier resin layer 12 is optionally provided with a tackifier, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a pigment, a flame retardant, and a plasticizer. Further, it may contain various additives such as a lubricant, an antiblocking agent, a filler, a dispersant, a crosslinking agent (a curing agent; when a curable resin such as an epoxy resin is used), a silane coupling agent, and the like. In particular, when the water vapor barrier resin layer 12 includes a rubber-based resin, it is preferable to include a tackifier. Examples of the tackifier include natural resins such as rosin resins and polyterpene resins, petroleum resins such as C5, C9, and dicyclopentadiene, and synthetic resins such as coumarone indene resin and xylene resin. .

(1.4) Physical Properties 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 more preferably 15 to 100 μm. Preferably there is. By setting the thickness of the water vapor barrier resin layer 12 to 5 μm or more, a sufficient water vapor barrier property can be obtained. On the other hand, by setting the thickness of the water vapor barrier resin layer 12 to 300 μm or less, the thickness of the film-shaped sealing materials 1A and 1B can be kept thin. The water vapor barrier resin layer 12 may be a single layer or a plurality of layers.

  Moreover, it is preferable that the ratio of the thickness of the water vapor | steam barrier resin layer 12 is 50-100% of the thickness of film-form sealing material 1A, 1B, It is especially preferable that it is 55-100%, Furthermore, It is preferable that it is 60 to 100%. Here, the ratio of the thickness of the water vapor barrier resin layer 12 being 100% means that the film-like sealing materials 1A and 1B are composed of only the water vapor barrier resin layer 12. In addition, the thickness of film-form sealing material 1A, 1B is mentioned later. When the ratio of the thickness of the water vapor barrier resin layer 12 is 50% or more, the film-shaped sealing materials 1A and 1B can contain a sufficient amount of a hygroscopic agent, thereby achieving higher water vapor barrier properties. be able to.

(2) Adhesive resin layer The first adhesive resin layer 11A and the second adhesive resin layer 11B are layers that exhibit adhesion to an adherend, and in this embodiment, a water vapor barrier resin layer. It can be arbitrarily provided on one or both sides of the twelve. When the adhesion of the water vapor barrier resin layer 12 to the adherend is low, a film having better adhesion to the adherend by providing one or both of the first and second adhesive resin layers 11A and 11B. The shaped sealing material 1B can be realized. Each of the first and second adhesive resin layers 11A and 11B may be a single layer or a plurality of layers.

  The resin constituting the first and second adhesive resin layers 11A and 11B is not particularly limited as long as it exhibits adhesiveness to the adherend, and examples thereof include thermoplastic resins and curable resins. Examples of the curable resin include a thermosetting resin and an energy ray curable resin. A thermoplastic resin and a curable resin can also be mixed and used.

  The thermoplastic resin may have thermal adhesiveness or may have pressure sensitive adhesiveness. By including the thermoplastic resin in the first and second adhesive resin layers 11A and 11B, the film-shaped sealing material 1B can be firmly adhered to the adherend, and the first and second adhesive properties can be obtained. The adhesion between the resin layers 11A and 11B and the water vapor barrier resin layer 12 is also improved.

  Examples of the thermoplastic resin include rubber resins, polyolefin resins, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-vinyl acetate copolymers, polyurethane resins. , Polyester urethane resin, acrylic resin, amide resin, styrene resin, silane resin and the like. The polyolefin resin may be a modified one, and examples thereof include an acid-modified polyolefin resin and a silane-modified polyolefin resin. Of these, rubber resins, acid-modified polyolefin resins, and silane-modified polyolefin resins are preferable. 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 glass plates and gas barrier films. In contrast, it shows a higher adhesive force. Further, the adhesion between the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 is also excellent. In addition, the said thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  Examples of rubber resins include natural rubber, modified natural rubber obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene and (meth) acrylonitrile on natural rubber, Polyisobutylene resin, butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymer (SBR), styrene-isoprene copolymer, acrylonitrile-butadiene copolymer (nitrile rubber), methyl methacrylate-butadiene copolymer Examples of the polymer include urethane rubber, styrene-1,3-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and ethylene-propylene-nonconjugated diene terpolymer. It is done. These rubber compounds can be used singly or in combination of two or more. Among these, as the rubber resin, those containing a polyisobutylene resin are preferable.

  The polyisobutylene resin refers to a polymer containing isobutylene as a monomer component (including the concept of a copolymer), the monomer component may be a homopolymer consisting only of isobutylene, and isobutylene and other monomers as a monomer component. It may be a copolymer obtained by polymerizing monomers. The polyisobutylene resin may be a halogenated polyisobutylene resin partially brominated or chlorinated, or may be partially substituted with a functional group such as a hydroxyl group or a carboxyl group.

  Examples of the other monomer include isoprene, n-butene, butadiene, isoprene, and styrene. Other monomers may be used alone or in combination of two or more. When the polyisobutylene resin is a copolymer, isobutylene is the maximum amount of monomer as a main component in the raw material monomer.

  Among these, the polyisobutylene-based resin is a homopolymer whose monomer component is composed only of isobutylene, and is an isobutylene-isoprene copolymer obtained by polymerizing isobutylene and isoprene as the monomer component because it has excellent water vapor barrier properties. Preferably there is.

  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, more preferably 100,000 to 1,000,000.

  A commercially available product can also be used as the rubber-based resin. Commercially available products include, for example, ExxonButyl (manufactured by Japan Butyl), Vistanex (manufactured by Exxon Chemical Co.), Hycar (registered trademark) (manufactured by Goodrich), Opanol (registered trademark) (manufactured by BASF), and Epol (registered trademark) ) (Made by Idemitsu Kosan Co., Ltd.).

  Polyolefin resin (non-modified polyolefin resin) refers to a polymer (including the concept of copolymer) containing olefin as a monomer component constituting the polymer, and the monomer component is a polymer consisting only of olefin. It may be a polymer (copolymer) containing an olefin and another monomer as a monomer component.

  As said olefin, a C2-C8 alpha olefin is preferable, for example, ethylene, propylene, butylene, isobutylene, 1-hexene etc. are mentioned. Of these, ethylene and propylene are preferable, and ethylene is particularly preferable. The other monomer is not particularly limited as long as it does not hinder the purpose of the film-shaped sealing material 1B according to the present embodiment, 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, 942Kg / ^{m 3),} high density polyethylene (HDPE, density: 942kg / ^{m 3} or higher), linear low density polyethylene, such as polyethylene Resin, polypropylene resin (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic Examples include acid ester copolymers. These can be used individually by 1 type or in combination of 2 or more types. Among the above, polyethylene resins such as ultra-low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene, ethylene-propylene copolymer or olefin elastomer (TPO) are preferable, especially Low density polyethylene is preferred.

  The acid-modified polyolefin resin means a polyolefin resin graft-modified with an acid, and examples thereof include those obtained by reacting an unsaturated carboxylic acid with a polyolefin resin to introduce a carboxyl group (graft modification). In the present specification, the unsaturated carboxylic acid includes the concept of a carboxylic acid anhydride, and the carboxyl group includes the concept of an anhydrous carboxyl group.

  Examples of the unsaturated carboxylic acid to be reacted with the polyolefin-based resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, Examples thereof include citraconic anhydride, aconitic anhydride, norbornene dicarboxylic acid anhydride, and tetrahydrophthalic acid anhydride. These can be used individually by 1 type or in combination of 2 or more types. Among the above, maleic anhydride, which is particularly excellent in adhesive strength, is preferable.

  As the acid-modified polyolefin resin, maleic anhydride-modified polyolefin resin is preferable, and maleic anhydride-modified polyethylene resin is particularly preferable.

  The amount of the unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by mass, particularly 0.2 to 3 parts by mass with respect to 100 parts by mass of the polyolefin resin. It is preferably 0.2 to 1.0 part by mass. When the amount of the unsaturated carboxylic acid to be reacted is in the above range, the resulting acid-modified polyolefin resin is excellent in adhesive strength.

  The acid-modified polyolefin resin preferably has a Vicat softening point of 90 ° C. or less, particularly preferably 30 to 70 ° C., and more preferably 30 to 60 ° C. When the Vicat softening point is in the above range, the adhesiveness does not appear at room temperature, so the film-like sealing material 1B is excellent in handleability and can be bonded by thermocompression bonding in a relatively short time. Electronic devices such as display device modules having organic EL elements, electronic paper, and organic thin-film solar cells can be efficiently produced. The Vicat softening point is a value measured based on ASTM D1525.

  The acid-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly preferably 1 to 15 g / 10 minutes. 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, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion. In addition, MFR in this specification shall be the value measured based on ASTMD1238.

  A commercially available product may be used as the acid-modified polyolefin resin. Examples of commercially available products include Admer (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation), and the like. Can be mentioned.

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

  Examples of the polyolefin resin of the silane-modified polyolefin resin include the polyolefin resins exemplified for the acid-modified polyolefin resin.

  The silane-modified polyolefin-based resin is preferably a silane-modified polyethylene resin and a silane-modified ethylene-vinyl acetate copolymer, and particularly silanes such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene. A modified polyethylene resin is preferred.

  As the unsaturated silane compound to be reacted with the polyolefin-based resin, a vinyl silane compound is preferable. For example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl triisopropoxy silane, vinyl tributoxy silane, vinyl tripentyl. Examples include loxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. These can be used individually by 1 type or in combination of 2 or more types.

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

  The silane-modified polyolefin resin preferably has a melt flow rate (MFR) at 190 ° C. and a load of 20.2 N of 0.5 to 30 g / 10 minutes, particularly 0.5 to 15 g / 10 minutes. More preferably, it is 0.5 to 10 g / 10 min. When the first and second adhesive resin layers 11A and 11B are formed by extrusion molding, if the MFR is less than 0.5 g / 10 minutes, the extrusion molding may be difficult, and the MFR is 30 g / 10 minutes. If it exceeds 1, the thickness accuracy may be lowered when the film is formed by extrusion.

  A commercial item can also be used for a silane modified polyolefin resin. Commercially available products include, for example, Linklon (registered trademark) (manufactured by Mitsubishi Chemical Corporation), among others, low density polyethylene-based linklon, linear low-density polyethylene-based linkron, and ultra-low-density polyethylene-based. Of these, Rincron of ethylene-vinyl acetate copolymer system can be preferably used.

  Further, the thermoplastic resin may be an ionomer in which molecules are bonded by a metal cation. Examples of the ionomer include olefin-based ionomers, urethane-based ionomers, styrene-based ionomers, and fluorine-based ionomers. Among these, it is preferable to use an olefin ionomer in terms of excellent adhesion to the water vapor barrier resin layer 12 containing a cycloolefin resin. Examples of olefinic ionomers include ethylene- (meth) acrylic acid copolymers, ethylene-fumaric acid copolymers, ethylene-maleic acid copolymers, ethylene-monomethyl monomethyl copolymers, and ethylene-monoethyl maleate copolymers. The thing which couple | bonded between molecules of olefin resin, such as a polymer, with the metal ion is mentioned. Examples 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. An ionomer can be used individually by 1 type or in mixture of 2 or more types.

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

  Moreover, you may blend a thermoplastic resin with the curable resin mentioned later. The blending mass ratio of the thermoplastic resin and the curable resin is preferably 99: 1 to 1:99, more preferably 10:90 to 90:10, and 20:80 to 80:20. Particularly preferred is 30:70 to 70:30.

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

  Examples of the epoxy resin include a monofunctional epoxy compound, a bifunctional epoxy compound, a trifunctional or higher polyfunctional epoxy compound, a polymer or oligomer having an epoxy group, a vinyl monomer having an epoxy group, and another vinyl. Copolymer polymers or oligomers with monomers etc. can be used. These epoxy resins can be used singly or in combination of two or more.

  When using curable resin, it is preferable that 1st and 2nd adhesive resin layer 11A, 11B contains 60-100 mass% of curable resin, It is preferable to contain especially 70-100 mass%, Furthermore, it is preferable to contain 80-100 mass%.

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

The water vapor permeability of the first and second adhesive resin layers 11A and 11B is preferably 30 g / (m ² · day) or less, particularly 25 g / (m ² ), when measured at a thickness of 50 μm. · Day) or less, more preferably 20 g / (m ² · day) or less. When the water vapor permeability of the adhesive resin layers 11A and 11B is 30 g / (m ² · day) or less, the water vapor intrusion rate from the end faces of the adhesive resin layers 11A and 11B can be easily reduced, and the adhesive resin layer When the film is provided, it is possible to prevent moisture from moving through the adhesive resin layer and reaching the electronic element, and to obtain a film-shaped sealing material 1B having higher water vapor barrier properties.

  The thickness (one layer) of the first and second adhesive resin layers 11A and 11B is preferably 1 to 100 μm, particularly preferably 3 to 80 μm, and more preferably 5 to 50 μm. Is preferred. Sufficient adhesiveness is acquired because the thickness of 1st and 2nd adhesive resin layer 11A, 11B is 1 micrometer or more. On the other hand, when the thickness of the first and second adhesive resin layers 11A and 11B is 100 μm or less, the thickness of the film-shaped sealing material 1B can be kept thin.

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

(3) Physical properties of the film-like sealing materials 1A and 1B The thickness of the film-like sealing materials 1A and 1B is preferably 7 to 500 μm, particularly preferably 15 to 400 μm, and more preferably 20 to It is preferable that it is 200 micrometers. Sufficient water vapor barrier property and adhesiveness can be obtained because the film-shaped sealing materials 1A and 1B have a thickness of 7 μm or more. On the other hand, since 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 in an electronic device, It can be avoided that the thickness of the device becomes too thick.

The water vapor permeability of the film-shaped sealing materials 1A and 1B is preferably 20 g / (m ² · day) or less when measured with the film-shaped sealing materials 1A and 1B having a thickness of 50 μm. It is preferably 15 g / (m ² · day) or less, more preferably 10 g / (m ² · day) or less. When the water vapor transmission rate of the film-shaped sealing materials 1A and 1B is 20 g / (m ² · day) or less, the penetration of water vapor from the end faces of the film-shaped sealing materials 1A and 1B is effectively blocked, and the film Since the intrusion of water vapor in the thickness direction from the main surfaces of the sealing materials 1A and 1B is also suppressed, the moisture is prevented and suppressed from reaching the object to be sealed, and the object to be sealed has an adverse effect of moisture. It becomes difficult to receive. In the film-shaped sealing materials 1A and 1B according to the present embodiment, the water vapor barrier resin layer includes the main material M having a high water vapor barrier property, and the water vapor barrier resin layer further contains a hygroscopic agent. Such a water vapor transmission rate can be achieved.

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

(4) Manufacturing method of film-form sealing material 1A, 1B It does not specifically limit as a method to form the water vapor | steam barrier resin layer 12 (water vapor | steam barrier resin film), and resin which comprises the water vapor | steam barrier resin layer 12 Examples thereof include a method of forming a film of a mixture with a hygroscopic agent by a melt extrusion method, a calendar method, a dry method, a solution method, or the like. In the case of the solution method, a solution in which the resin constituting the water vapor barrier resin layer 12 and the hygroscopic agent are dissolved in an organic solvent is applied by a known application method, and the obtained coating film is appropriately dried to appropriately dry the water vapor barrier. The conductive resin layer 12 may be formed.

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

  The film-shaped sealing material 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 in which the first adhesive resin layer 11A, the water vapor barrier resin layer 12, and the second adhesive resin layer 11B are co-extruded so as to be laminated in that order, the first adhesive property A single-layer film (first adhesive resin film) as the resin layer 11A and a single-layer film (second adhesive resin film) as the second adhesive resin layer 11B are prepared, respectively. A method of laminating the 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 (water vapor as the water vapor barrier resin layer 12) Barrier resin film) is prepared, and the first and second adhesive resin layers 11A and 11B are formed on both surfaces of the water vapor barrier resin film, the first adhesive resin film, and the water vapor barrier. 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. Further, the first and second adhesive resin layers 11A and 11B are formed on the release sheet, and the release sheets with the first and second adhesive resin layers 11A and 11B are prepared, respectively. The film-like sealing material 1B can also be manufactured by a method of laminating release sheets with the first and second adhesive resin layers 11A and 11B on both surfaces of the barrier resin film. Note that the film-shaped sealing material 1B having only one of the first and second adhesive resin layers 11A and 11B can also be manufactured by following the above method.

  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 (first adhesive resin film and second adhesive resin film) are softened.

(5) Applications of the film-like sealing materials 1A and 1B Since the film-like sealing materials 1A and 1B according to the present embodiment are very excellent in water vapor barrier properties, they can be used for sealing various things. It can be suitably used for sealing an electronic element in an electronic device. Specifically, a module for a display device having a liquid crystal element, a light emitting diode (LED element), an organic electroluminescence (organic EL) element, an electronic paper, a solar cell module, and the like can be given. Among these, since a high water vapor barrier property is required for a display device module (organic EL module) or electronic paper having an organic EL element, the film-like sealing materials 1A and 1B according to this embodiment are preferably used. can do.

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

  The gas barrier film 21 is a film having characteristics that make it difficult for gas such as water vapor and oxygen to pass therethrough. Depending on the application target of the sealing sheet 2, the gas barrier film 21 needs to be transparent. The gas barrier film 21 is preferably a laminate of a base film and a gas barrier layer. As such a gas barrier film 21, for example, one having a gas barrier layer formed directly or via another layer on one or both sides of a base film, or having a gas barrier layer in the middle of a base film is used. can do.

  Examples of the base film include polyolefin such as polyethylene, polypropylene, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, polyester such as polyethylene terephthalate and polybutylene terephthalate, polychlorinated Acrylic resins such as vinyl, polystyrene, polyurethane, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, polymethyl methacrylate, polybutene, polybutadiene, polymethylpentene, ethylene vinyl acetate copolymer, Examples thereof include a film made of a resin such as ABS resin and ionomer resin, or a laminated film thereof. Among these, from the viewpoint of strength, a film made of polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyamide, polyimide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate and the like is preferable. The base film may be a stretched film or an unstretched film. Further, the base film may contain various additives such as an ultraviolet absorber.

  The thickness of the base film is preferably 1 to 500 μm, particularly preferably 5 to 300 μm, and more 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 property of the gas barrier film 21 can be set to a desired level. Examples of the material for the gas barrier layer include silicon compounds such as polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, and tetraorganosilane compounds, silicon oxide, silicon oxynitride, aluminum oxide, aluminum oxynitride, and magnesium oxide. Inorganic oxides such as zinc oxide, indium oxide, and tin oxide, inorganic nitrides such as silicon nitride and aluminum nitride, inorganic oxynitrides such as silicon oxynitride, and metals such as aluminum, magnesium, zinc, and tin It is done. These can be used individually by 1 type or in combination of 2 or more types.

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

  The gas barrier layer may be a single layer or a plurality of layers, but the gas barrier layer is preferably a plurality of layers from the viewpoint of obtaining higher gas barrier properties.

  The method for forming the gas barrier layer may be appropriately selected according to the material to be used. For example, the gas barrier layer material is formed on a base film by vapor deposition, sputtering, ion plating, thermal CVD, plasma CVD, or the like, or the gas barrier layer material is dissolved in an organic solvent. Examples include a method in which a solution is applied to a base film and plasma ions are implanted into the obtained coating film. Examples of ions implanted by plasma ion implantation include rare gases such as argon, helium, neon, krypton, and xenon, ions such as fluorocarbon, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur; gold, Examples include ions of metals such as silver, copper, platinum, nickel, palladium, chromium, titanium, molybdenum, niobium, tantalum, tungsten, and aluminum.

The water vapor transmission rate of the gas barrier film 21 is preferably 0.5 g / (m ² · day) or less, particularly 0.1 g / (m ² · day) or less at 40 ° C. and 90% RH. More preferably, it is 0.05 g / (m ² · day) or less.

  In order to manufacture the sealing sheet 2, the film-like sealing materials 1A and 1B and the gas barrier film 21 may be laminated and laminated. In the film-shaped sealing materials 1A and 1B according to the present embodiment, the water vapor barrier resin layer 12 itself has adhesiveness, or the film-shaped sealing material 1B has adhesive resin layers 11A and 11B. Adheres firmly to the film 21. Therefore, when an electronic device or the like is sealed using the sealing sheet 2, it is possible to effectively prevent water vapor from entering between the gas barrier film 21 and the film-like sealing materials 1A and 1B. . In addition, when the gas barrier film 21 has a gas barrier layer on one side, the gas barrier film 21 and the film-shaped sealing materials 1A and 1B may be laminated so that the gas barrier layer is on the film-shaped sealing material 1A and 1B side. preferable.

  When laminating the film-shaped sealing materials 1A and 1B and the gas barrier film 21, they may be laminated while being heated. The heating temperature is preferably equal to or higher than the temperature at which the adhesive resin layer 11 of the film-like sealing materials 1A and 1B is softened.

  The sealing sheet 2 according to the present embodiment can be used for the same applications as those of the film-shaped sealing materials 1A and 1B described above, and in particular, a display device having an organic EL element or the like that requires high water vapor barrier properties. It can use suitably for sealing of the electronic element in electronic devices, such as a module for electronic devices, electronic paper, and a solar cell module. When sealing is performed using the sealing sheet 2, the surface opposite to the side on which the gas barrier film 21 is laminated (second adhesive resin layer 11 </ b> B in FIG. 3) is bonded to the adherend. Can be sealed.

[Electronic device]
The electronic device according to one embodiment of the present invention is sealed with the film-shaped sealing materials 1A and 1B according to the above-described embodiments. Specifically, as shown in FIG. 4, the electronic device 3 </ b> A according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a film-like sealing material that seals the electronic element 32. 1B and the sealing member 33 laminated | stacked on the opposite side to the electronic element 32 of the film-form sealing material 1B are provided. 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 with the sealing sheet 2 which concerns on embodiment mentioned above. Specifically, as shown in FIG. 5, the electronic device 3 </ b> B according to the present embodiment includes a substrate 31, an electronic element 32 formed on the substrate 31, and a sealing sheet 2 that seals the electronic element 32. Is provided. 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.

  The electronic device according to this embodiment is not limited to that shown in FIGS. 4 and 5, but instead of the film-like sealing material 1 </ b> B according to the second embodiment, the film-like sealing according to the first embodiment. The stop material 1A may be provided. That is, the first and second adhesive resin layers 11A and 11B may be removed from the electronic devices 3A and 3B shown in FIG. Furthermore, the electronic device according to the present embodiment may be obtained by removing one of the first and second adhesive resin layers 11A and 11B from the electronic devices 3A and 3B in FIG.

  These electronic devices 3A and 3B include, for example, a liquid crystal element, an LED element, an organic EL element, and the like as an electronic element 32, an electrophoretic element, an electronic granular element, and a cholesteric liquid crystal element as the electronic element 32. However, the present invention 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 type devices, the substrate 31 is preferably a transparent substrate. Further, 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 preferred examples include 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, hybrid glass, and the like. Can be mentioned. As a base film, what was illustrated by the gas barrier film 21 is mentioned, for example.

  The thickness of the substrate 31 is appropriately set according to the types of the electronic devices 3A and 3B.

  The method for manufacturing the electronic device 3A is not particularly limited. 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 placed on the film-like sealing materials 1A and 1B. The electronic device 3A can be manufactured by bonding them together and sealing the electronic element 32. In addition, the laminated body which bonded together the film-form sealing materials 1A and 1B, and the sealing member 33 may be obtained, and this laminated body may be bonded together with the electronic element 32, and electronic device 3A may be manufactured.

  On the other hand, the method for manufacturing the electronic device 3B is not particularly limited. For example, the sealing sheet 2 is placed so that the film-shaped sealing materials 1A and 1B are on the electronic element 32 side so as to cover the electronic element 32 formed on the substrate 31, and they are bonded to each other. The electronic device 3B can be manufactured by sealing the element 32.

  Sealing may be performed at normal pressure, in a reduced pressure atmosphere, or a combination thereof. Moreover, you may heat when bonding the film-form sealing materials 1A and 1B and the electronic element 32 together. By heating, the film-like sealing materials 1A and 1B and the electronic element 32, the substrate 31, and the sealing member 33 or the gas barrier film 21 are firmly bonded.

  Usually, the heating temperature at the time of bonding is preferably equal to or higher than the temperature at which the first and second adhesive resin layers 11A and 11B and the water vapor barrier resin layer 12 are softened.

  In the electronic devices 3A and 3B according to the present embodiment, the electronic element 32 is covered with the film-shaped sealing materials 1A and 1B according to the present embodiment in which the water vapor intrusion speed is controlled. Since the intrusion of water vapor from the end faces of 1A and 1B is effectively blocked and the moisture is prevented / suppressed from reaching the electronic device 32, the electronic device 32 is not easily affected by the moisture. . Further, since the film-like sealing materials 1A and 1B have the adhesiveness of the water vapor barrier resin layer 12 or the first and second adhesive resin layers 11A and 11A, the film-like sealing material 1A, 1B and the substrate 31, the film-shaped sealing materials 1A and 1B and the electronic element 32, the film-shaped sealing materials 1A and 1B and the sealing member 33, and the film-shaped sealing materials 1A and 1B and the gas barrier film 21 are strong. It is prevented and restrained from adhering and causing floating and peeling between them, and intrusion of water vapor between them.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Example 1]
<Production of film-like encapsulant>
The materials constituting the adhesive resin layer and the water vapor barrier resin layer shown in Table 1 were coextruded by an extruder (manufactured by Toyo Seiki Seisakusho), and the first adhesive resin layer having a thickness of 5 μm and the thickness A film-shaped sealing material was produced by laminating a 40 μm water vapor barrier resin layer and a 5 μm thick second adhesive resin layer in that order.

<Preparation of sealing sheet>
Aluminum of the obtained film-like sealing material and a gas barrier film having an aluminum foil (a laminated film in which a polyethylene terephthalate sheet having a thickness of 12 μm is bonded to one surface of an aluminum foil having a thickness of 7 μm with a urethane adhesive layer, manufactured by Aya Aluminum Co.) The foil surface was bonded while heating at 120 ° C. to obtain a sealing sheet.

<Manufacture 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: 30Ω / □) is formed on the surface of the glass substrate by sputtering, and then an anode is prepared 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) at 60 nm, Tris (8-hydroxy) -Quinolinate) Aluminum (manufactured by Luminescence Technology) at 40 nm, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (manufactured by Luminesense Technology) at 10 nm, (8-hydroxy-quinolinolate) lithium (Luminescence Technology) The light emitting layer was formed by sequentially vapor-depositing at a rate of 10 nm and 0.1 to 0.2 nm / s.

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

  Next, the sealing sheet was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left to cool to room temperature. And a sealing sheet is mounted so that a film-form sealing material may become the organic EL element side so that the organic EL element formed on the glass substrate may be covered, from the edge part of an sealing sheet to an organic EL element The distance was adjusted to 5 mm. They were bonded together while heating at 100 ° C. to seal the organic EL element, thereby obtaining a bottom emission type electronic device.

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

Example 3
A coating liquid containing a material constituting the water vapor barrier resin layer shown in Table 1 is applied onto a release sheet, dried at 100 ° C. for 2 minutes, and the release sheet is bonded thereon to form a water vapor barrier with a thickness of 20 μm. A resin layer was obtained and used as a film-like sealing material. Using this film-form sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

[Comparative Examples 1-3]
A film-like sealing material was produced 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-form 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 4]
A film-shaped sealing material was produced in the same manner as in Example 3 except that the material constituting the water vapor barrier resin layer was changed as shown in Table 1. Using this film-form sealing material, a sealing sheet was produced in the same manner as in Example 1 to obtain a bottom emission type electronic device.

Details of the abbreviations and the like described in Table 1 are as follows.
[Adhesive resin layer]
Admer SF731: maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
[Water vapor barrier resin layer]
-TOPAS 9506F-04: cycloolefin polymer represented by the above structural formula (a) (manufactured by Polyplastics, trade name “TOPAS 9506F-04”, glass transition temperature 65 ° C.)
Exxon Butyl 365: Isobutylene resin (exxon mobile, trade name “Exxon Butyl 365”)
Admer SF731: maleic anhydride modified polyethylene (Mitsui Chemicals, trade name “Admer SF731”, Vicat softening point 43 ° C.)
・ Calcium oxide: Calcium oxide (Omi Chemical Industries, trade name “CML # 35”, average particle size 15 μm)
Magnesium sulfate: anhydrous magnesium sulfate (Tonda Pharmaceutical Co., Ltd., trade name “anhydrous magnesium sulfate”, average particle size 10 μm)
-Cyclic aluminum oligomer: Metal acylate compound (manufactured by Kawaken Fine Chemical Co., Ltd., trade name "Algomer 800AF")

[Test Example 1] (Measurement of water vapor transmission rate of film-shaped sealing material)
The water vapor transmission rate of the film-like sealing material obtained in the examples or comparative examples was measured. Specifically, the transmittance was measured using a transmittance measuring machine “L80-5000” manufactured by LYSSY under the conditions of 40 ° C. and 90% RH. From the measurement results, the water vapor transmission rate when the thickness of the measurement sample was 50 μm was calculated using the following calculation formula. The results are shown in Table 1.
Water vapor transmission rate (50 μm conversion) = Water vapor transmission rate (actual value) × (actual film thickness / 50)

[Test Example 2] (Measurement of maximum moisture absorption)
The maximum moisture absorption amount of the film-shaped sealing material obtained in the examples or comparative examples was measured. Specifically, a film-shaped sealing material cut to 70 mm × 70 mm was heat-laminated to a glass of 70 mm × 70 mm at 120 ° C. to obtain a measurement sample. The mass (total mass of glass and film-like encapsulant) was measured within 1 hour after sample preparation. After measurement, leave it in an environment of 60 ° C. and 90% RH to absorb moisture until there is no change in mass, measure the mass again, and subtract 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 (g / m ² ) in the water vapor barrier resin layer having a thickness of 50 μm was calculated using the following calculation formula. The results are shown in Table 1.
Maximum moisture absorption (converted to 50 μm) = {Water vapor moisture absorption (actual value) / (0.07 × 0.07)} × (50 / thickness of water vapor barrier resin layer)

[Test Example 3] (Measurement of adhesive strength)
About the sealing sheet obtained by the Example or the comparative example, one peeling sheet was peeled and the surface of the exposed 1st adhesive resin layer was affixed on the polyethylene terephthalate sheet (50 micrometers in thickness) as a backing substrate. Combined and cut into a size of 25 mm × 300 mm. Next, the other release sheet is peeled off, and the exposed surface of the second adhesive resin layer is overlapped with a glass plate (soda lime glass, manufactured by Nippon Sheet Glass Co., Ltd.) as an adherend and heated at 120 ° C. The test piece was obtained by bonding.

  The obtained test piece was bonded and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, and then in that environment, a tensile tester (manufactured by Orientec Co., Tensilon) was used, and the peeling rate was 300 mm. / Min, a peel test was performed under the conditions of a peel angle of 180 °, and the adhesive strength (N / 25 mm) was measured.

[Test Example 4] (Measurement of water vapor penetration rate)
First, metal calcium was vapor-deposited on a glass substrate by the following method to form a test piece for evaluating the water vapor infiltration rate. First, the glass substrate was cleaned by solvent (acetone and isopropyl alcohol) and UV / ozone treatment. Next, metallic calcium (manufactured by Sigma-Aldrich) was deposited on the glass substrate at a rate of 0.1 to 0.2 nm / s. The degree of vacuum at the time of vapor deposition was 1 × 10 ⁻⁴ Pa or less. As a result, a glass substrate on which metallic calcium having a thickness of 150 nm was deposited was obtained.

  Next, the sealing sheet obtained in the example or the comparative example was heated at 120 ° C. for 30 minutes using a hot plate in a nitrogen atmosphere to remove moisture contained in the sealing sheet, and then left as it was. And cooled to room temperature. And the sealing sheet was mounted on the glass substrate so that the metal calcium formed on the glass substrate and the surface of the film-form sealing material of a sealing sheet may contact. At this time, the whole metal calcium was covered with the sealing sheet, and further, the distance from the end of the sealing sheet to the metal calcium was adjusted to 5 mm. Then, they were bonded together while heating at 100 ° C., and metallic calcium was sealed with a sealing sheet to obtain a test piece for evaluating the water vapor infiltration rate.

The obtained specimen for evaluating the water vapor infiltration rate was left in an environment of 60 ° C. and 90% RH, and the time until the end of the metal calcium reacted with the invading water and became transparent was measured. From the measurement results, the water vapor intrusion rate (μm / h) was calculated using the following calculation formula. The results are shown in Table 1.
Water vapor permeation rate (μm / h) = distance from end of sealing sheet to metallic calcium (μm) / time until metallic calcium end reacts with infiltrated water and becomes transparent (h)

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

  As can be seen from Table 1, the film-like encapsulants obtained in the examples exhibited a very slow water vapor penetration rate, and exhibited a low water vapor transmission rate and a high adhesive force. As a result, the organic EL element sealed with the film-like sealing material obtained in the examples was excellent in durability, almost no non-light emitting portion was seen, and the performance of the electronic device was good.

  On the other hand, the film-form sealing materials of Comparative Examples 1 to 4 showed a fast water vapor intrusion rate, and were low in electronic device evaluation.

  The film-form sealing material and sealing sheet which concern on this invention are used suitably for an organic EL module and electronic paper, for example. The electronic device according to the present invention is suitable as an organic EL module or electronic paper, for example.

DESCRIPTION OF SYMBOLS 1A, 1B ... Film-form sealing material 11A ... 1st adhesive resin layer 11B ... 2nd adhesive resin layer 12 ... Water vapor | steam barrier resin layer 13 ... End surface 2 ... Sealing sheet 21 ... Gas barrier film 3A, 3B ... Electronic device 31 ... Substrate 32 ... Electronic element 33 ... Sealing member

Claims (14)

A film-like encapsulant comprising one or more layers, including a water vapor barrier resin layer,
Both surfaces of the film-like sealing material show adhesion to the adherend,
Temperature 60 ° C., the water vapor penetration rate from the end face of the film-like sealing material in an environment of a relative humidity of 90% RH is state, and are less 10 [mu] m / h,
The film-like sealing material, wherein the water vapor barrier resin layer includes at least one resin selected from the group consisting of a rubber resin, a polyolefin resin, and an epoxy resin .   The film-shaped sealing material according to claim 1, wherein the water vapor barrier resin layer contains a hygroscopic agent.   The film-shaped sealing material according to claim 2, wherein a content of the hygroscopic agent in the water vapor barrier resin layer is 1 to 35% by mass. One adhesive resin layer laminated on one surface side of the water vapor barrier resin layer and exhibiting adhesiveness to an adherend, or on one surface side and the other surface side of the water vapor barrier resin layer The film-shaped sealing material according to any one of claims 1 to 3, further comprising two adhesive resin layers that are laminated and exhibit adhesion to an adherend.   The ratio of the thickness of the said water vapor | steam barrier resin layer is 50 to 100% of the thickness of the said film-form sealing material, The film-form sealing as described in any one of Claims 1-4 characterized by the above-mentioned. Stop material.   The film-like seal according to claim 4, wherein the adhesive resin layer includes at least one resin selected from the group consisting of a rubber-based resin, a polyester-based resin, a polyolefin-based resin, and an epoxy-based resin. Stop material. The maximum moisture absorption amount of the hygroscopic agent is 1.0 g / m ² or more when expressed by the amount of water absorbed by the water vapor barrier resin layer having a thickness of 50 μm. 3. The film-shaped sealing material according to 3.   The film-shaped sealing material according to claim 2 or 3, wherein the hygroscopic agent is a compound containing a metalloxane bond.   The film-shaped sealing material according to claim 2 or 3, wherein the hygroscopic agent is a metal oxide.   The film-shaped sealing material according to claim 2 or 3, wherein the hygroscopic agent is a compound that reacts with water molecules to form a hydrate. The adhesive force at the time of bonding any one surface of the said film-form sealing material on a glass plate at 120 degreeC is 1 N / 25mm or more, It is any one of Claims 1-10 characterized by the above-mentioned. The film-form sealing material of description. A film-shaped sealing material according to any one of claims 1 to 11
A sealing sheet comprising a gas barrier film laminated on one side of the film-shaped sealing material. An electronic device sealed with the film-like sealing material according to any one of claims 1 to 11 . An electronic device sealed with the sealing sheet according to claim 12 .

Images