JP2014056884A - Electronic device and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic device which achieves excellent bending resistance and excellent durability, and to provide a manufacturing method of the electronic device.SOLUTION: An electronic device includes: a flexible base material; a flexible sealing member; an electronic element body positioned between the base material and the sealing member; and a sealant containing polyurea. The base material and the sealing material are joined through the sealant thereby sealing the electronic element body. The above object is achieved by the electronic device and a manufacturing method of the electronic device.

Description

  The present invention relates to an electronic device and a manufacturing method thereof.

  Electronic devices such as organic electroluminescent elements (organic EL elements), organic solar cells, organic transistors, inorganic electroluminescent elements, inorganic solar cells (for example, CIGS solar cells) are sensitive to oxygen and moisture present in the environment of use. . For this reason, many sealing methods for protecting electronic devices from oxygen and moisture have been proposed, and a method of sealing using a barrier substrate using glass or metal has been put into practical use.

  As a sealing method of these base materials, a method of welding the base material and a sealing substrate on which the electronic element body is mounted is conceivable, but it has not been put into practical use due to the heat resistance problem of electronic devices. For this reason, a sealing method using an adhesive made of an organic compound is usually used. However, in such a sealing method using an adhesive, intrusion of moisture and oxygen from the adhesive portion has been a problem. On the other hand, a method of locally fusing using a laser beam or the like has been studied (for example, see Patent Documents 1 and 2). However, there are problems such as dissimilar materials with different coefficients of thermal expansion and large electronic devices that cannot be bonded, and that bonding strength is not sufficient.

  On the other hand, with the spread of electronic devices in recent years, weight reduction, bendability, improved portability by preventing cracking, expansion of installation location by followability to curved surfaces, reduction of production cost by roll-to-roll production It is desired. For this reason, electronic devices using a thin film glass having a thickness of 100 μm or less or a gas barrier film in which a gas barrier layer is provided on a flexible resin base material are proposed as a base material instead of conventional glass. (For example, refer to Patent Document 3).

JP 2003-170290 A Japanese Patent Laid-Open No. 2007-200840 JP 2007-73332 A

  However, the techniques described in Patent Documents 1 to 3 have a problem that the sealing performance is lowered when the electronic device is bent.

  Accordingly, an object of the present invention is to provide an electronic device having excellent resistance to bending and excellent durability and a method for manufacturing the same.

  The present inventor has intensively studied to solve the above problems. As a result, the above problem is solved by an electronic device in which an electronic element body is sealed using a flexible base material, a flexible sealing member, and a sealing agent containing polyurea. The headline and the present invention have been completed.

  That is, the above object is achieved by the following configuration.

  1. A base material having flexibility, a sealing member having flexibility, an electronic element body located between the base material and the sealing member, and a sealing agent containing polyurea. An electronic device in which the electronic element body is sealed by joining the base material and the sealing member via the sealant.

  2. At least one of the base material and the sealing member has a gas barrier layer, as described in 1. above. The electronic device according to.

  3. The gas barrier layer includes at least one of a metal oxide and a metal oxynitride. The electronic device according to.

  4). An electronic device manufacturing method comprising: a base material; a sealing member; an electronic element main body positioned between the base material and the sealing member; and a sealing agent containing polyurea, A step of disposing an electronic element body on a base material; a step of forming a layer containing a polyurea precursor on at least one surface of the base material and the sealing member; and the base material and the sealing member. And a step of sealing the electronic element body.

  5. 3. The process of 4. above, further comprising a step of cooling the substrate and the sealing member to 20 ° C. or lower. The manufacturing method as described in.

  6). 3. The step of sealing the electronic element body includes irradiating an electromagnetic wave having a frequency of 1 MHz to 1 THz. Or 5. The manufacturing method as described in.

  ADVANTAGE OF THE INVENTION According to this invention, the electronic device which is excellent in the tolerance with respect to bending, and is excellent in durability, and its manufacturing method are provided.

1 is a schematic cross-sectional view showing an electronic device according to an embodiment of the present invention. It is a cross-sectional schematic diagram showing an electronic device according to another embodiment of the present invention. It is a schematic diagram which shows the structural example of the chamber with which a vapor deposition polymerization apparatus (CO-1) is provided. It is a schematic diagram which shows the structural example of the chamber with which a vapor deposition polymerization apparatus (CO-2) is provided. It is a schematic diagram which shows the structural example of a spray coating apparatus (CO-3). It is a schematic diagram which shows the structural example and arrangement example of several chambers with which a vapor deposition polymerization apparatus (CO-4) is provided. It is a schematic diagram which shows the structural example and arrangement example of several chambers with which a vapor deposition polymerization apparatus (CO-5) is provided.

  The present invention relates to a base material having flexibility, a sealing member having flexibility, an electronic element body located between the base material and the sealing member, and a sealing agent containing polyurea. And the base material and the sealing member are bonded via the sealing agent, whereby the electronic element body is sealed. The electronic device of the present invention having such a structure has excellent resistance to bending and has excellent durability.

  Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In addition, this invention is not restrict | limited only to the following embodiment. The dimensional ratios in the drawings are exaggerated for convenience of explanation, and may differ from actual ratios.

  The electronic device of the present invention is, for example, an organic electroluminescence (EL) element. In the following description, a case where the electronic device of the present invention is an organic EL element will be described as a representative embodiment, but the technical scope of the present invention is not limited to the following embodiment.

  FIG. 1 is a schematic cross-sectional view of an electronic device 10 according to an embodiment of the present invention. That is, the electronic device 10 shown in FIG. 1 has a base material 11, a sealing member 12, an electronic element body 13 positioned between the base material 11 and the sealing member 12, and a sealing agent 14. In the present invention, the sealant 14 includes polyurea. The electronic element body 13 is sealed by bonding the base material 11 and the sealing member 12 via a sealant 14. That is, the sealing agent 14 is disposed at the interface between the base material 11 and the sealing member 12, and the sealing member 12 and the base material 11 are joined by the sealing agent 14. By setting it as this structure, the base material 11 and the sealing member 12 are joined firmly via the sealing agent 14, and it can prevent the penetration | invasion to the electronic element main body of oxygen and a water | moisture content, and, thereby, durability of an electronic device Can be improved. In addition, the electronic device 10 has excellent resistance to bending.

  FIG. 2 is a schematic cross-sectional view showing a basic configuration of an electronic device 10 according to another embodiment of the present invention. As shown in FIG. 2, the electronic device 10 includes a base material 11, a sealing member 12, an electronic element body 13 positioned between the base material 11 and the sealing member 12, a sealing agent 14, An adhesion assistant 15 is provided so as to be in contact with the stopper 14. The adhesion assistant 15 is an arbitrary member provided as necessary.

  In the electronic device of the present invention, the reason why the resistance to bending is improved is not clear, but when a crosslinkable resin such as a commonly used epoxy resin is used as a sealant, it is relatively Since the structure is less flexible, it cannot keep up with changes such as bending, resulting in a decrease in performance. On the other hand, the polyurea contained in the sealant according to the present invention is a linear polymer and does not necessarily have a cross-linked structure. Therefore, since polyurea is easy to follow a flexible base material and exhibits a low moisture permeability, it is considered that the effect of the present invention can be obtained. In addition, the said mechanism is based on estimation and this invention is not limited to the said mechanism at all.

  In the embodiment shown in FIGS. 1 to 2, the electronic element body 13 is an organic EL element body, and includes a first electrode (anode) 17, a hole transport layer 18, a light emitting layer 19, an electron transport layer 20, and a second. The electrode (cathode) 21 is formed by being sequentially laminated.

  In the form shown in FIGS. 1 to 2, the electronic device 10 is formed by laminating an electronic element body 13 and a sealing member 12 in this order on a base material 11. However, the electronic device 10 may have a configuration in which the electronic element main body 13, the adhesion assistant 15, and the base material 11 are sequentially laminated on the sealing member 12.

  In addition to the base material 11, the sealing member 12, the electronic element body 13, the sealing agent 14, and the adhesion aid 15 described above, the electronic device 10 may further include other layers. Here, the other layer is not particularly limited, and examples thereof include an electrode, a stabilization layer for stabilizing the electronic element body, a gas absorption layer, a protective layer, and an impact absorption layer.

  Hereinafter, members constituting the electronic device of the present invention will be described in detail.

[Base material]
The base material according to the present invention is not particularly limited. Examples thereof include a metal foil, a gas barrier film having a support and a gas barrier layer.

The water vapor permeability of the substrate according to the present invention is preferably 5 × 10 ⁻³ g / m ² · day or less at 60 ° C. and 90% RH, preferably 5 × 10 ⁻⁴ g / m ² · day or less. More preferably, it is 5 × 10 ⁻⁵ g / m ² · day or less.

Moreover, the base material which concerns on this invention has flexibility. In this specification, “flexibility” is a property that is flexible and deforms when a force is applied, but returns to its original shape when the force is removed. Specifically, it is defined in JIS K7171: 2008. The bending elastic modulus is, for example, 1.0 × 10 ^{3 to} 4.5 × 10 ³ [N / mm ² ].

  Examples of the metal foil include aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), indium ( Metal foils such as In), tin (Sn), lead (Pb), titanium (Ti), and alloys thereof can be used.

  Further, a gas barrier film having a support and a gas barrier layer that is suitably used as a substrate will be described below.

<Support>
The support is long and can hold a gas barrier layer having a gas barrier property (hereinafter also simply referred to as “barrier property”) described later, and is formed of the following material. However, it is not particularly limited to these.

  Examples of the support include, for example, polyacrylate ester, polymethacrylate ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC). , Polyethylene (PE), polypropylene (PP), cycloolefin polymer (COP), cycloolefin copolymer (COC), triacetate cellulose (TAC), styrene (PS), nylon (Ny), aromatic polyamide, polyether ether ketone, Polysulfone, polyethersulfone, polyimide, polyetherimide and other resin films, heat-resistant transparent films based on silsesquioxane having an organic-inorganic hybrid structure (for example, Product name Sila-DEC; manufactured by Chisso Corporation, and product name Sylplus (registered trademark); manufactured by Nippon Steel Chemical Co., Ltd., etc.), and a resin film constituted by laminating two or more layers of the resin. it can.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), etc. are preferably used, and are cast because of their optical transparency and low birefringence. TAC, COC, COP, PC, etc. produced by the above method are preferably used, and silsesquioxane having an organic-inorganic hybrid structure in terms of optical transparency, heat resistance, and adhesion to the gas barrier layer A heat-resistant transparent film having a basic skeleton is preferably used.

  On the other hand, for example, when a gas barrier film is used for an electronic device application of a flexible display, the process temperature may exceed 200 ° C. in the array manufacturing process. In the case of roll-to-roll manufacturing, since a certain amount of tension is always applied to the support, when the support is placed at a high temperature and the support temperature rises, the support temperature will change to the glass transition point. When it exceeds, the elasticity modulus of a support body will fall rapidly, there exists a concern which a support body may be extended by tension | tensile_strength and a gas barrier layer may be damaged. Therefore, in such applications, it is preferable to use a heat resistant material having a glass transition point of 150 ° C. or higher as the support. That is, it is preferable to use a heat-resistant transparent film having polyimide, polyetherimide, or silsesquioxane having an organic / inorganic hybrid structure as a basic skeleton. However, since the heat-resistant resin represented by these is non-crystalline, the water absorption rate is larger than that of crystalline PET or PEN, and the dimensional change of the support due to humidity becomes larger, so that the gas barrier layer There is a concern of damaging it. However, even when these heat-resistant materials are used as a support, by forming a gas barrier layer on both sides, the dimensional change due to moisture absorption / desorption of the support film itself under severe conditions of high temperature and high humidity is suppressed. And damage to the gas barrier layer can be suppressed. Therefore, it is one of the more preferable embodiments that a heat resistant material is used as a support and a gas barrier layer is formed on both sides. Moreover, in order to reduce the expansion-contraction of the support body at the time of high temperature, the support body containing glass fiber, a cellulose, etc. is also used preferably.

  The thickness of the support is preferably about 5 to 500 μm, more preferably 25 to 250 μm.

  The support is preferably transparent. The term “transparent” as used herein means that the light transmittance of visible light (400 to 700 nm) is 80% or more.

  Since the support is transparent and the gas barrier layer formed on the support is also transparent, a transparent gas barrier film can be obtained, and thus a transparent substrate such as an organic EL element can be obtained. Because.

  In addition, the support using the above-described resins or the like may be an unstretched film or a stretched film.

  The support according to the present invention can be produced by a conventionally known general method. For example, an unstretched support that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching.

  Further, the unstretched support is uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, and other known methods, such as the flow (vertical axis) direction of the support, or A stretched support can be produced by stretching in the direction perpendicular to the flow direction of the support (horizontal axis).

  The draw ratio in this case can be appropriately selected according to the resin as the raw material of the support, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction, respectively. Furthermore, in order to improve the dimensional stability of the substrate in the stretched film, it is preferable to perform relaxation treatment after stretching.

  Moreover, in the support body which concerns on this invention, you may give a corona treatment to the surface, before forming a gas barrier layer.

  As the surface roughness of the support used in the present invention, the 10-point average roughness Rz defined by JIS B0601: 2001 is preferably in the range of 1 to 500 nm, and more preferably in the range of 5 to 400 nm. Preferably, it exists in the range of 300-350 nm.

  Further, on the surface of the support, the center line average surface roughness (Ra) defined by JIS B0601: 2001 is preferably in the range of 0.5 to 12 nm, and more preferably in the range of 1 to 8 nm.

<Gas barrier layer>
The material for the gas barrier layer used in the present invention is not particularly limited, and various inorganic barrier materials can be used. Examples of inorganic barrier materials include, for example, silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), titanium (Ti), copper (Cu), cerium (Ce) and Examples thereof include at least one metal selected from the group consisting of tantalum (Ta) and a metal compound such as an oxide, nitride, carbide, oxynitride, or oxycarbide of the above metal.

More specific examples of the inorganic barrier material include silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), tantalum oxide, zirconium oxide, niobium oxide, aluminum silicate (SiAlO _x ). , Boron carbide, tungsten carbide, silicon carbide, oxygen-containing silicon carbide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconium boride, titanium boride, and composites thereof Inorganic barrier materials such as metal oxides such as bodies, metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, diamond-like carbon (DLC), and combinations thereof.

Among these inorganic barrier materials, at least one of metal oxide and metal oxynitride is preferable, indium tin oxide (ITO), silicon oxide, aluminum oxide, aluminum silicate (SiAlO _x ), silicon oxynitride, and combinations thereof are: Particularly preferred inorganic barrier materials. ITO is an example of a special member of ceramic material that can be made conductive by appropriately selecting the respective elemental components.

  The method for forming the gas barrier layer is not particularly limited, and includes, for example, a sputtering method (for example, magnetron cathode sputtering, flat plate magnetron sputtering, two-pole AC flat plate magnetron sputtering, two-pole AC rotary magnetron sputtering), a vapor deposition method (for example, resistance heating). Vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), photo CVD method, plasma CVD method (PE-CVD), an epitaxial growth method, an atomic layer growth method, a chemical vapor deposition method such as a reactive sputtering method, and the like.

  The gas barrier layer may include an organic layer containing an organic polymer. That is, the gas barrier layer may be a laminate of an inorganic layer containing the inorganic barrier material and an organic layer.

  The organic layer can be polymerized and required using, for example, an electron beam device, UV light source, discharge device, or other suitable device, for example, by applying an organic monomer or oligomer to the support to form the layer It can be formed by crosslinking according to the above. The organic layer can also be formed, for example, by depositing an organic monomer or oligomer capable of flash evaporation and radiation crosslinking and then forming a polymer from the organic monomer or organic oligomer. Coating efficiency can be improved by cooling the support. Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating), spray coating (for example, electrostatic spray coating), and the like. Moreover, as an example of the laminated body of an inorganic layer and an organic layer, the laminated body of the international publication 2012/003198, international publication 2011/013341, etc. are mentioned, for example.

  In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The thickness of the inorganic layer is preferably 3 to 1000 nm, more preferably 10 to 300 nm. The thickness of the organic layer is preferably 100 nm to 100 μm, more preferably 1 μm to 50 μm.

  Furthermore, a coating liquid containing an inorganic precursor such as polysilazane and tetraethyl orthosilicate (TEOS) is wet-coated on a support and then subjected to a modification treatment by irradiation with vacuum ultraviolet light, etc. The gas barrier layer is also formed by metallization techniques such as metal plating on the support and adhesion of the metal foil and the resin support.

  From the viewpoint of obtaining high gas barrier properties and the effects of the present invention more effectively, the gas barrier layer is formed by modifying a layer containing polysilazane or is a laminate of an inorganic layer and an organic layer. It is preferable.

  The gas barrier layer may be a single layer or a laminated structure of two or more layers. In the case of a laminated structure of two or more layers, the material of each layer may be the same or different.

  Hereinafter, the gas barrier layer formed by modifying the layer containing polysilazane will be described in detail.

(Polysilazane)
The polysilazane used for forming the gas barrier layer according to the present invention is a polymer having a silicon-nitrogen bond, SiO ₂ having a bond such as Si—N, Si—H, or N—H, Si ₃ N ₄ , and Ceramic intermediate inorganic polymers such as both intermediate solid solutions SiO _x N _y .

In the general formula (I), R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. At this time, R ₁ , R ₂ and R ₃ may be the same or different.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. preferable.

In the present invention, perhydropolysilazane in which all of R ₁ , R _2, and R ₃ are hydrogen atoms is particularly preferable from the viewpoint of the denseness as a film of the obtained gas barrier layer.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a coating solution for forming a polysilazane layer. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.

  The solvent for preparing the coating liquid containing polysilazane (hereinafter also simply referred to as polysilazane-containing coating liquid) is not particularly limited as long as it can dissolve polysilazane, but water and reaction that easily react with polysilazane. An organic solvent that does not contain a functional group (for example, a hydroxyl group or an amine group) and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, as a solvent for preparing a polysilazane-containing coating solution, an aprotic solvent; for example, an aliphatic hydrocarbon such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, and turben, an alicyclic hydrocarbon Hydrocarbon solvents such as aromatic hydrocarbons; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatics such as dibutyl ether, dioxane and tetrahydrofuran Ethers such as ether and alicyclic ether: for example, tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes) and the like can be mentioned. The solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the polysilazane-containing coating solution is about 0.2 to 35% by mass, although it varies depending on the film thickness of the target gas barrier layer and the pot life of the coating solution.

  The polysilazane-containing coating solution preferably contains a catalyst together with polysilazane in order to promote modification to silicon oxynitride. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and further preferably 0.5 to 2% by mass, based on polysilazane. It is. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, decrease in film density, increase in film defects, and the like.

  In the polysilazane-containing coating solution according to the present invention, the following additives can be used as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, in particular urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes and the like.

  As a method of applying the polysilazane-containing coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include spin coating method, die coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably about 10 nm to 10 μm after drying, more preferably 15 nm to 1 μm, and even more preferably 20 to 500 nm. If the thickness of the polysilazane layer is 10 nm or more, sufficient barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained when forming the polysilazane layer, and high light transmittance can be realized.

(Modification process)
As a method of the modification treatment, a coating liquid containing polysilazane is applied on a support to form a layer (coating film) containing polysilazane, and then the coating film is irradiated with vacuum ultraviolet rays having a wavelength of 200 nm or less. Is preferred.

The coating film containing polysilazane is modified in the vacuum ultraviolet irradiation process to have a specific composition of SiO _x N _y .

(Oxygen concentration during irradiation with vacuum ultraviolet rays (VUV))
Oxygen is required for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the vacuum ultraviolet irradiation process tends to be lowered. Therefore, it is preferable to perform the irradiation with vacuum ultraviolet rays in a state where the oxygen concentration is as low as possible.

(Middle layer)
An intermediate layer may be further formed between the support for the gas barrier film and the gas barrier layer. The intermediate layer preferably has a function of improving the adhesion between the support surface and the gas barrier layer. A commercially available support with an easy-adhesion layer can also be preferably used.

(Smooth layer)
In the gas barrier film according to the present invention, the intermediate layer may be a smooth layer. The smooth layer used in the present invention is provided in order to flatten the rough surface of the support where protrusions and the like are present, or to fill the unevenness and pinholes generated in the gas barrier layer due to the protrusions existing on the support. It is done. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

(Bleed-out prevention layer)
The gas barrier film according to the present invention may have a bleed-out preventing layer on the support surface opposite to the surface on which the gas barrier layer is provided. A bleed-out prevention layer can be provided. The bleed-out prevention layer is used for the purpose of suppressing the phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the film support to the surface and contaminate the contact surface. It is provided on the opposite surface of the supporting body. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

(Overcoat layer)
An overcoat layer may be provided on the gas barrier layer according to the present invention.

  As materials used for the overcoat layer, organic resins such as organic monomers, oligomers, and polymers, and organic-inorganic composite resins using monomers, oligomers, and polymers of siloxane and silsesquioxane having an organic group are preferably used. it can.

[Sealing member]
The sealing member 12 has a function of sealing the electronic element body 13 by bonding to the base material 11 described above via a sealing agent 14 containing polyurea. The sealing member 12 is disposed to face the base material 11 with the electronic element body 13 interposed therebetween.

  The sealing member 12 may be the gas barrier film described above. Further, when the sealing member is a gas barrier film, the sealing member 12 and the substrate 11 may have the same configuration or different configurations (materials, layer configurations). However, at least one of the base material 11 and the sealing member 12 preferably has a gas barrier layer.

  Further, as the sealing member 12, in addition to the gas barrier film described above, aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel (Ni), cobalt ( Co foils such as Co), copper (Cu), indium (In), tin (Sn), lead (Pb), titanium (Ti), and alloys thereof may be used.

  Further, the sealing member 12 may be a member composed only of a gas barrier layer having no support in the gas barrier film. Specific examples thereof include a metal foil such as an aluminum foil and a copper foil, and a laminate of an inorganic layer and an organic layer described in the section of the base material.

  In addition, since the details of the configuration of the sealing member are the same as the contents described in the section of the base material, the description is omitted here.

  The sealing member has flexibility. Since the definition of flexibility is the same as described above, description thereof is omitted here.

[Sealant]
The sealant according to the present invention contains polyurea. Polyurea can be obtained by a polyaddition reaction of a diisocyanate compound that is a polyurea precursor and a diamine compound. Below, the reaction formula of the polyaddition reaction of 1,12- diaminododecane and hexamethylene diisocyanate is shown as an example.

Specific examples of the diisocyanate compound include, for example, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate. (M-XDI), m-tetramethylxylene diisocyanate (m-TMXDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 3,3′-dimethylbiphenyl-4, Aromatic diisocyanate compounds such as 4'-diisocyanate; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethyl hexasamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate Over DOO, 1,3-bis (isocyanatomethyl) cyclohexane _(H 6 XDI), 4,4'-methylenebis (cyclohexyl _isocyanate) (H 12 MDI), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1 , 3- (isocyanatomethyl) cyclohexane, 3,3-bis (isocyanatemethyl) cyclohexane, norbornene diisocyanate and the like: an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate, etc. Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate. These diisocyanate compounds can be used alone or in combination of two or more. In addition, as the diisocyanate compound, a commercially available product or a synthetic product may be used.

Among these diisocyanate compounds, 4,4′-diphenylmethane diisocyanate (MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI), p-xylylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate Is preferred.

  Specific examples of the diamine compound include, for example, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane (DAD), 1,12-diaminododecane, trimethyl-1,6-hexanediamine, 2,2′-dimethyl-1,3-propanediamine, 2-methylpenta Methylenediamine, 1,3-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, bis (hexamethylene) triamine, 5-amino-2,2,4-trimethyl-1-cyclopentamethylamine 1,2-diaminocyclohexane, 4,4′-methylenebis (2-methylcyclohexylamine) 1,3-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,9-dioxa-1,12-dodecanediamine, 2,2′-ethylenedianiline 2-aminophenyl disulfide, 4,4′-ethylenedianiline, 4,4′-diaminostilbene, 3,3′-methylenedianiline, 4,4′-methylenedianiline (MDA), 4,4′- Methylenebis (3-chloro-2,6-diethylamine), 4,4′-oxydianiline, 4-aminophenyl disulfide, 4,4′-thiodianiline, 2,3-diaminophenol, 4,4′-ethylenedi-M -Toluidine, o-tolidine, 5,5 '-(hexafluoroisopropylidene) -di-o-toluidine, 4,4' Methylenebis (2,6-dimethylaniline), 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2,6-diisopropylaniline), 3,3 ′, 5,5′- Tetramethylbenzidine, 2,3-diaminotoluene, 4-chloro-1,2-phenylenediamine, 4,5-dichloro-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, 1,4- Phenylenediamine, 1,2-phenylenediamine, 1,3-diaminotoluene, 4-methoxy-1,2-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 4,5-dimethyl-1, 2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 4- (2-hydroxythio) -1,3-ph Enylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,5-diaminotoluidine, 2,5-dichloro-1,4-phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2, 5-dimethyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3,3 ′-(hexafluoropropylidene) dianiline, 3,3′-dimethoxybenzidine, 4,4′-diaminodiphenylamine 3,3′-dimethylnaphthidine, 2,2′-dithiobis (1-naphthylamine), 1,5-diaminonaphthalene, 1,1′-binaphthyl-2,2′-diamine, 2,7-diaminofluorene, 1,8-diaminonaphthalene, 9,10-diaminophenanthrene, 4.4′-diaminodiphenylmethane, '- diamino diphenyl ether - ether, and the like 4,4'-diamino -3.3'- dimethylphenyl methane. These diamine compounds can be used singly or in combination of two or more. As the diamine compound, a commercially available product or a synthetic product may be used.

  Among these diamine compounds, 4,4'-methylenedianiline (MDA), 4.4'-diaminodiphenyl ether, and 1,10-diaminodecane (DAD) are preferable.

  When the electronic device body is sealed using the sealant according to the present invention, the base material and the sealing member are joined before the polyaddition reaction of the diisocyanate compound and the diamine compound to the polyurea is completed. There is a need to. However, since the polyaddition reaction between the diisocyanate compound and the diamine compound forming polyurea proceeds rapidly, in order to delay the progress of the polyaddition reaction, either one of the diisocyanate compound and the diamine compound is used in an excess amount, that is, It is preferable to form a layer containing a polyurea precursor by applying or vapor-depositing the diisocyanate compound and the diamine compound in a molar ratio. The molar ratio in this case is diisocyanate compound: diamine compound = 1: 0.8 to 1: 1.2 (except 1: 1), or diisocyanate compound: diamine compound = 0.8: 1 to 1. It is preferably 1.2: 1 (excluding 1: 1).

  The sealant may contain other additives as necessary. Specific examples of other additives include plasticizers, surfactants, antistatic agents and the like.

  The arrangement of the sealant is not particularly limited, and may be arranged so as to cover the entire electronic element body 13 as shown in FIGS. .

  When preparing the sealant, for example, a method of stirring and mixing the polyurea precursor shown above and other components as necessary at -20 to 40 ° C for 1 to 24 hours is applied. The

  The polyurea precursor polyaddition reaction proceeds in the layer containing the polyurea precursor, and the layer containing the polyurea precursor becomes a layer containing a sealing agent containing polyurea. Under the present circumstances, the layer (sealing agent layer) containing a sealing agent may be a single layer structure, and may be a laminated structure of two or more layers. The thickness (total thickness) of the layer containing the sealant is preferably 1 to 100 μm, and more preferably 2 to 30 μm, from the viewpoint of bonding strength and sealing performance.

[Electronic element body]
The electronic element body is the body of the electronic device. 1 to 2, the electronic element body is an organic EL element body. However, the electronic element body of the present invention is not limited to such a form, and a known electronic device body to which sealing by a gas barrier film can be applied can be used. For example, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, a thin film transistor, a touch panel, and the like can be given. There is no restriction | limiting in particular also about the structure of the main body of these electronic devices, It can have a well-known structure.

  1 to FIG. 2, the electronic element body (organic EL element body) 13 includes a first electrode (anode) 17, a hole transport layer 18, a light emitting layer 19, an electron transport layer 20, and a second electrode (cathode). ) 21 etc. In addition, if necessary, a hole injection layer may be provided between the first electrode 17 and the hole transport layer 18, or an electron injection layer may be provided between the electron transport layer 20 and the second electrode 21. May be provided. In the organic EL element, the hole injection layer, the hole transport layer 18, the electron transport layer 20, and the electron injection layer are arbitrary layers provided as necessary.

  Hereinafter, an organic EL element will be described as an example of a specific configuration of an electronic device.

(First electrode: anode)
As the first electrode (anode), an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used.

(Hole injection layer: anode buffer layer)
A hole injection layer (anode buffer layer) may be present between the first electrode (anode) and the light emitting layer or the hole transport layer. The hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission luminance.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

(Light emitting layer)
The light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. An electron injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.

(Electron injection layer: cathode buffer layer)
The electron injection layer (cathode buffer layer) formed in the electron injection layer forming step is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. An electron injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance.

(Second electrode: cathode)
As the second electrode (cathode), a material having a small work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used.

[Protective layer]
The electronic device of the present invention may have a protective layer on the electronic element body as necessary. The protective layer has a function of preventing deterioration of the electronic device body such as moisture and oxygen from entering the device, a function of insulating the electronic device body disposed on the substrate 11, or the like. It has a function to eliminate the level difference caused by the electronic element body. The protective layer may be a single layer or a laminated structure of two or more layers. In this invention, it is preferable that the sealing agent and the electronic device are insulated by the protective layer.

[Electronic device manufacturing method]
The manufacturing method of the electronic device 10 of the present invention is not particularly limited, and conventionally known knowledge can be referred to as appropriate.

  According to an embodiment of the present invention, (1) a step of arranging an electronic element body on a base material, and (2) a polyurea precursor on at least one surface of the base material and the sealing member. There is provided an electronic device manufacturing method including: a step of forming a layer including: (3) a step of bonding the base material and the sealing member; and (4) a step of sealing the electronic element body. The

  Hereinafter, although the manufacturing method of the electronic device by one Embodiment of the said invention is demonstrated, this invention is not limited to this at all.

(1) The process of arrange | positioning an electronic element main body on a base material First, an electronic element main body is arrange | positioned on a base material. Usually, on the substrate, the layers constituting the electronic element body, for example, the first electrode layer, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer, the second electrode layer, etc. in order. It is formed by laminating. These forming methods are not particularly limited, and can be produced by appropriately referring to known methods.

(2) Step of forming a layer containing a polyurea precursor on at least one surface of the substrate and the sealing member Next, a polyurea precursor is included on at least one surface of the substrate and the sealing member Form a layer. The method for forming the layer containing the polyurea precursor is not particularly limited, and examples thereof include a method of applying or evaporating the polyurea precursor.

  Examples of the polyurea precursor coating method include a micro gravure coating method, a gravure coating method, a bar coating method, a wire bar coating method, a roll coating method, a dip coating method, a flexographic printing method, an offset printing method, and a screen printing method. Is mentioned. Further, for example, spray coating may be performed using a spray coating apparatus (CO-3) having a structure as shown in FIG.

  As a polyurea precursor vapor deposition method, for example, a vapor deposition polymerization apparatus (CO-1, CO-2) having a chamber having a structure as shown in FIG. 3 or FIG. 4 or a structure as shown in FIG. Examples thereof include a method using a vapor deposition polymerization apparatus (CO-4, CO-5) provided with chambers arranged as shown in FIGS.

  When the diisocyanate compound and the diamine compound, which are polyurea precursors, are mixed, the polyaddition reaction proceeds rapidly. Therefore, when applying a diisocyanate compound and a diamine compound, a method of mixing and applying at the time of application or immediately before application is preferable. Moreover, when making it vapor-deposit, it is preferable to vaporize a diisocyanate compound and a diamine compound separately, and to vapor-deposit a diisocyanate compound and a diamine compound on a base material or a sealing member.

  Furthermore, when the diisocyanate compound and the diamine compound are vapor-deposited, if the deposition speed of the polyurea precursor is slow, the polymerization of the initially deposited portion is completed, the layer becomes hard, and it becomes difficult to follow the unevenness of the substrate, resulting in adhesion. Since it falls, it is preferable that the deposition rate (evaporation rate) of a polyurea precursor is 100 nm / s or more, and it is more preferable that it is 1000 nm / s or more.

  In addition, as described above, in order to delay the progress of the polyaddition reaction of the diisocyanate compound and the diamine compound, the coating or vapor deposition may be performed by biasing the molar ratio of the diisocyanate compound and the diamine compound.

  The layer containing the polyurea precursor may be a single layer or a laminated structure of two or more layers. In the case of a laminated structure of two or more layers, it is preferable that the layer in which the molar ratio of the diisocyanate compound and the diamine compound is biased is located in the outermost layer.

  The thickness (total thickness) of the layer containing the polyurea precursor is preferably 1 to 100 μm, and more preferably 2 to 30 μm.

  In order to further increase the sealing force by the sealant, an adhesion aid may be further applied as necessary. The adhesion aid is preferably applied so as to be in contact with the layer containing the polyurea precursor.

  Examples of the adhesion assistant include, for example, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, N- (α-methyldimethoxysilyl). Methyl) amine, N- (α-trimethoxysilylmethyl) amine, N- (α-diethylmethoxysilylmethyl) amine, N- (α-ethyldimethoxysilylmethyl) amine, N- (α-methyldiethoxysilylmethyl) ) Amine, N- (α-triethoxysilylmethyl) amine, N- (α-trimethoxysilylethyl) amine, 3,5-dimercaptoaniline, methyldimethoxysilylmethyl isocyanate, trimethoxysilylmethyl isocyanate, dimethylmethoxysilyl Methyl isocyania , Ethyldimethoxysilylmethyl isocyanate, methyldiethoxysilylmethyl isocyanate, triethoxysilylmethyl isocyanate, ethyldiethoxysilylmethyl isocyanate, methyldimethoxysilylethyl isocyanate, trimethoxysilylethyl isocyanate, ethyldimethoxysilylethyl isocyanate, methyldiethoxy Examples include silylethyl isocyanate, trimethoxysilylethyl isocyanate, and ethyldiethoxysilylethyl isocyanate. These adhesion aids may be used alone or in combination of two or more. Further, the layer containing the adhesion assistant may have a single layer structure or a multilayer structure of two or more layers.

(3) The process of joining a base material and a sealing member Then, the said base material and the said sealing member are joined. A layer containing a polyurea precursor is formed on at least one of the base material and the sealing member, and it is necessary to join the base material and the sealing member before the polyaddition reaction to polyurea is completed. . However, since the polyaddition reaction proceeds rapidly, it is preferable to include a step of cooling the substrate and the sealing member to 20 ° C. or lower in order to delay the polyaddition reaction. The cooling temperature is more preferably 10 ° C. or lower. The lower limit of the cooling temperature is not particularly limited, but is preferably −20 ° C. or higher because the diisocyanate compound or the diamine compound may be crystallized at less than −20 ° C.

  In addition, the process of cooling a base material and a sealing member may be performed in said process (2) other than this process, and may be performed in both processes of (2) and (3). Preferably, it is performed in this step.

(4) Step of sealing the electronic element body Next, the electronic element body is sealed. Sealing is performed by forming polyurea by polyaddition reaction of a diisocyanate compound and a diamine compound, which are polyurea precursors. However, it is preferable to supply energy from the outside, such as pressure bonding and heating with a vacuum laminator or the like, from the viewpoint that sealing becomes easier to proceed. For example, in the case of heating, it is preferable to heat at a temperature of 50 to 200 ° C. for 1 to 100 minutes.

  It is also preferable to irradiate an electromagnetic wave having a frequency of 1 MHz to 1 THz. Since polyurea has properties as a ferroelectric substance, when irradiated with electromagnetic waves, the polyurea molecule moves, the regularity of the arrangement of the polyurea molecule is improved, and the bonding force between the substrate and the sealing member is increased. It will be stronger.

  In addition to the above manufacturing method, (1) a step of disposing an electronic element body on the sealing member, and (2) a layer containing a polyurea precursor on at least one surface of the base material and the sealing member And (3) a step of joining the base material and the sealing member, and (4) a step of sealing the electronic element body.

  The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited only to the following examples. Further, in the examples, “part” or “%” is used, but “part by mass” or “% by mass” is expressed unless otherwise specified.

[Preparation of gas barrier film 1]
<Production of support>
<Preparation of support (a)>
As a thermoplastic resin support, a 125 μm thick polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films Ltd.) with easy adhesion processing on both sides was used. As shown below, a bleed-out prevention layer was opposite on one side. What formed the smooth layer in the surface was made into the support body (a).

<Formation of bleed-out prevention layer>
A UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Corporation is applied to one surface side of the thermoplastic resin support under the condition that the film thickness after drying is 4.0 μm. Then, as a curing condition, a high pressure mercury lamp was used in an air atmosphere with an irradiation energy amount of 1 J / cm ² , and a curing process was performed for 3 minutes at a drying condition of 80 ° C. to form a bleed-out prevention layer.

<Formation of smooth layer>
Next, the UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation is dried on the surface of the thermoplastic resin support opposite to the surface on which the bleed-out prevention layer is formed. After coating under the condition that the film thickness becomes 4.0 μm after that, the film is dried at 80 ° C. for 3 minutes, and then irradiated with an irradiation energy amount of 1 J / cm ² as a curing condition using a high-pressure mercury lamp in an air atmosphere. And cured to form a smooth layer.

  The obtained smooth layer had a surface roughness Ra of 1 nm as measured in accordance with the method defined in JIS B 0601: 2001. Rz was 20 nm. The coated surface of the smooth layer was the surface of the anchor coat layer.

  The surface roughness was measured using an AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII. The measurement range at one time is 80 μm × 80 μm, the measurement location is changed and the measurement is performed three times, and the Ra value obtained by each measurement and the average of the 10-point average roughness Rz are measured. Value.

<Formation of gas barrier layer>
<Formation of polysilazane layer 1>
On the smooth layer of the support (a), a coating solution containing the following polysilazane (polysilazane-containing coating solution 1) is applied using a spin coater so that the film thickness after drying becomes 150 nm at a coating speed of 30 m / min. It was applied with. The drying conditions were 100 ° C. and 2 minutes.

<Preparation of polysilazane-containing coating solution 1>
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and 1% by mass of N, N, N ′, N′-tetramethyl-1 as an amine catalyst , 6-diaminohexane and a dibutyl ether solution containing 19% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) are mixed at a ratio of 4: 1, and the amine catalyst content is applied. It adjusted to 1 mass% with respect to solid content of a liquid.

<Vacuum ultraviolet irradiation treatment>
After the polysilazane layer 1 is formed as described above, modification is performed by performing irradiation treatment with a vacuum ultraviolet ray of 172 nm under a nitrogen atmosphere (oxygen concentration: 1000 ppm) so that the irradiation energy amount is 3000 mJ / cm ^2. It was.

<Formation of polysilazane layer 2>
Further, the polysilazane-containing coating solution 1 is applied in the same manner on the polysilazane layer 1 obtained as described above, and is subjected to vacuum ultraviolet irradiation (irradiation amount: 1700 mJ / cm ² ). The dry film thickness is 50 nm on the polysilazane layer 1. A gas barrier film 1 in which a certain polysilazane layer 2 was laminated was produced.

  As a result of analysis by an X-ray photoelectron spectroscopy (XPS) apparatus (Quanta SXM, manufactured by ULVAC-PHI), the composition of the gas barrier layer 1 is SiON, and the thickness of the gas barrier layer 1 (the total thickness of the polysilazane layer 1 and the polysilazane layer 2). Was 200 nm.

When the water vapor permeability (WVTR) (60 ° C., relative humidity 90% RH) of the obtained gas barrier film 1 was measured by the Ca method described in JP 2012-000546 A, WVTR (60 ° C., 90 ° % RH) was 4 × 10 ⁻⁵ g / m ² · 24 h.

[Preparation of gas barrier film 2]
<Formation of oxygen-containing silicon carbide layer>
Using the plasma CVD roll coater W35 series manufactured by Kobe Steel Co., Ltd. on the smooth layer of the support (a) and using the plasma CVD method described in JP 2012-84355 A, oxygen-containing silicon carbide An inorganic layer consisting of The film formation conditions of the laminated film are as follows: the supply amount of hexamethyldisiloxane is 285 sccm in terms of 1 atm at an area velocity of 1 m ² of the support (a), and the supply amount of oxygen gas is the support (a). per area rate 1m ^2, 0 ℃, 2860sccm in terms of 1 atm, degree of vacuum in the vacuum chamber is 3 Pa, applied electric power from the plasma generation power source is 0.8 kW, the frequency of the plasma generation power source 70 kHz, the support ( A) The conveyance speed was 0.5 m / min. The thickness of the inorganic layer in the obtained laminated film was 0.3 μm.

  The atomic ratio at each distance from the film surface of the laminated film was confirmed by elemental composition analysis in the depth direction using an X-ray photoelectron spectroscopy (XPS) device (Quanta SXM, manufactured by ULVAC-PHI). It has an extreme value, and it was confirmed that the difference between the maximum and minimum carbon concentration was 7 at%.

<Formation of polysilazane layer>
Further, the polysilazane-containing coating solution 1 is applied onto the inorganic layer obtained above in the same manner as the gas barrier film 1 and is irradiated with vacuum ultraviolet rays (irradiation amount: 2000 mJ / cm ² ) to form a layer made of oxygen-containing silicon carbide. A gas barrier layer 2 on which a polysilazane layer having a dry film thickness of 50 nm was laminated was formed on the smooth layer of the support (a) to produce a gas barrier film 2.

When the water vapor permeability (WVTR) (60 ° C., 90% RH) of the obtained gas barrier film 2 was measured by the Ca method described in JP 2012-000546 A, 7 × 10 ⁻⁶ g / m. was ² · 24h.

[Preparation of gas barrier film 3]
<Production of support>
<Production of support (a)>
As a thermoplastic resin support, a 125 μm-thick polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was used as the support (I).

<Formation of gas barrier layer>
Three layers each of an inorganic layer (SiAlO _x film having a thickness of 30 nm) and an organic layer are formed on the support (a) in the same manner as described in Example 1 of International Publication No. 2012/003198. The laminated gas barrier layer 3 was provided, and the gas barrier film 3 was produced.

When the water vapor permeability (WVTR) (60 ° C., 90% RH) of the obtained gas barrier film 3 was measured by the Ca method described in JP 2012-000546 A, 4 × 10 ⁻⁵ g / m. was ² · 24h.

[Preparation of gas barrier film 4]
<Production of support>
<Production of support (a)>
As a thermoplastic resin support, a 125 μm-thick polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films, Ltd.) that was easily bonded on both sides was used as the support (I).

<Formation of gas barrier layer>
On the support (a), an inorganic layer (SiAlO _x film having a thickness of 30 nm) and an organic layer are alternately laminated in the same manner as described in Example 1 of International Publication No. 2012/003198, A gas barrier film 4 was prepared by stacking four organic layers and three inorganic layers, and providing a gas barrier layer 4 whose outermost surface was an organic layer.

When the water vapor permeability (WVTR) (60 ° C., 90% RH) of the obtained gas barrier film 4 was measured by the Ca method described in JP 2012-000546 A, 5 × 10 ⁻⁵ g / m. was ² · 24h.

[Preparation of gas barrier film 5]
Instead of the gas barrier layer 3, three barrier films (SiO ₂ film having a thickness of 30 nm) produced by the same method as described in Example E2 of WO 2011/013341 were bonded together, and the organic layer and A gas barrier film 5 was produced in the same manner as the gas barrier film 3 except that the gas barrier layer 5 on which the inorganic layer was laminated was produced.

When the water vapor permeability (WVTR) (60 ° C., 90% RH) of the obtained gas barrier film 5 was measured by the Ca method described in JP2012-000546A, 5 × 10 ⁻⁵ g / m. was ² · 24h.

[Preparation of gas barrier film 6]
A 12 μm thick polyethylene naphthalate (PEN) film was bonded to the surface of the gas barrier layer 5 of the gas barrier film 5 to prepare a gas barrier film 6.

Example 1
<< Production of electronic devices >>
An organic / inorganic hybrid insulating film is formed on a stainless steel (SUS430) foil having a thickness of 100 μm in the same manner as in Example 1-3 described in JP-A-2008-255242, and an SUS foil with an insulating film is formed. Was made. Using the obtained SUS foil with an insulating film as a base material, an organic EL element, which is an organic thin film electronic device, was produced on the insulating film by the following procedure.

[Production of organic EL elements]
(Formation of first electrode layer)
A 100 nm-thick Ag film was formed on a SUS substrate with an insulating film by a sputtering method, and patterned by a photolithography method to form a first electrode layer.

(Formation of hole transport layer)
On the first electrode layer formed above, the hole transport layer forming coating solution shown below was applied by an extrusion coater so that the thickness after drying was 50 nm, and then dried to form a hole transport layer. Formed.

Before coating the hole transport layer forming coating solution, the substrate was subjected to a cleaning surface modification treatment using a low pressure mercury lamp having a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

<Application conditions>
The coating process was performed in the atmosphere at 25 ° C. and a relative humidity of 50% RH.

<Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Clevios (registered trademark) P AI 4083 manufactured by Heraeus) with pure water at 65% and methanol at 5% is prepared as a coating solution for forming a hole transport layer. did.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent was removed by applying hot air at a height of 100 mm toward the film formation surface, a discharge air speed of 1 m / s, a width of 5% of the wide air speed, and a temperature of 100 ° C. Subsequently, a back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. using a heat treatment apparatus to form a hole transport layer.

(Formation of light emitting layer)
Subsequently, on the hole transport layer formed above, the following coating solution for forming a white light emitting layer was applied by an extrusion coater so that the thickness after drying was 40 nm, and then dried to form a light emitting layer. .

<White luminescent layer forming coating solution>
1.0 g of host material HA, 100 mg of dopant material DA, 0.2 mg of dopant material DB, and 0.2 mg of dopant material DC are dissolved in 100 g of toluene as a coating solution for forming a white light emitting layer. Got ready. The chemical structures of the host material HA, the dopant material DA, the dopant material DB, and the dopant material DC are as shown in the following chemical formula.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

<Drying and heat treatment conditions>
After applying the white light-emitting layer forming coating solution, after removing the solvent by applying hot air at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a width of 5% of the wide wind speed, and a temperature of 60 ° C. Then, heat treatment was performed at a temperature of 130 ° C. to form a light emitting layer.

(Formation of electron transport layer)
Subsequently, an electron transport layer forming coating solution shown below was applied on the light emitting layer formed above by an extrusion coater so that the thickness after drying was 30 nm, and then dried to form an electron transport layer. .

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more, the coating temperature of the electron transport layer forming coating solution was 25 ° C., and the coating speed was 1 m / min.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving EA (see the following chemical formula) in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution, which was used as an electron transport layer forming coating solution.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, hot air was applied at a height of 100 mm toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., and the solvent was removed. Subsequently, heat treatment was performed at a temperature of 200 ° C. in the heat treatment section to form an electron transport layer.

(Formation of electron injection layer)
Subsequently, an electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a decompression chamber and decompressed to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode)
Subsequently, on the electron injection layer formed above, ITO (indium tin oxide) having a thickness of 150 nm was formed into a mask pattern by sputtering, and the second electrode was laminated.

(Formation of protective layer)
Subsequently, except for the portions to be taken out of the first electrode and the second electrode, SiON was laminated with a thickness of 200 nm by a CVD method, and a protective layer was formed on the second electrode layer.

  In this way, an electronic element body was produced.

(Formation of layer containing polyurea precursor, sealing of electronic device body)
A vapor deposition polymerization apparatus (CO-1) having a chamber as shown in FIG. 3 is used so as to cover the electronic element body produced as described above, and 4,4′-diphenylmethane diisocyanate (MDI) and 4 are used as polyurea precursors. , 4′-methylenedianiline (MDA) (MDI: MDA = 1: 1 (molar ratio)) was used to deposit MDI and MDA so that the layer containing the polyurea precursor had a thickness of 3 μm. . At this time, the degree of vacuum of the CO-1 deposition chamber was 1 × 10 ⁻² Pa, the substrate temperature was 10 ° C., the deposition time was 10 seconds, and the deposition time was controlled by opening and closing the shutter. In addition, the molar ratio and deposition amount of MDI and MDA, which are polyurea precursors, were adjusted by heating and adjusting the vapor pressure.

  Immediately after the deposition, the barrier layer side of the gas barrier film 1 serving as a sealing member was placed on the layer containing the polyurea precursor so as to be inward, and adhered using a vacuum laminator. Then, heat processing were performed for 30 minutes at 110 degreeC, and the electronic device (sample No. 101) was obtained.

(Example 2)
Using a vapor deposition polymerization apparatus (CO-2) having a chamber as shown in FIG. 4, MDI and MDA (molar ratio: 1) are used as polyurea precursors on the electronic element body and on the gas barrier film 1 as a sealing member. 1) were vapor-deposited to a thickness of 3 μm to form a layer containing a polyurea precursor, and immediately bonded together, followed by heating at 110 ° C. for 30 minutes.

  An electronic device (sample No. 102) was obtained in the same manner as in Example 1 except that the electronic element body was sealed in this manner.

(Example 3)
A spray coating apparatus CO-3 as shown in FIG. 5 was used. As a polyurea precursor, MDI and MDA (molar ratio 1: 1) are mixed immediately before spray application, and MDI and MDA are used as polyurea precursors on the electronic element body and on the gas barrier film 1 as a sealing member. (Molar ratio 1: 1) was vapor-deposited so as to have a film thickness of 3 μm, and immediately bonded together, followed by heating at 110 ° C. for 30 minutes.

  An electronic device (sample No. 103) was obtained in the same manner as in Example 1 except that the electronic element body was sealed in this manner.

Example 4
Except that 1,3-bis (isocyanatomethyl) cyclohexane (H ₆ XDI) was used instead of MDI, and 1,10-diaminodecane (DAD) was used instead of MDA, the same as Example 2 was used. An electronic device (Sample No. 104) was obtained.

(Comparative Example 1)
In the same manner as in Example 1, 4,4′-diphenylmethane diisocyanate (MDI) and 4,4′-methylenedianiline (MDA) (MDI: MDA = 1: 1 (molar ratio)) were used as polyurea precursors. Used, it was vapor-deposited on the electronic device body so that the layer containing the polyurea precursor had a thickness of 3 μm. After the deposition, a polyurea film was formed by irradiating the layer containing the polyurea precursor with ultraviolet rays for 30 minutes using a low-pressure mercury lamp (center wavelength: 254 nm, 10 W) under vacuum. Subsequently, an electronic device main body in which an epoxy-based sealing adhesive (manufactured by Three Bond Co., Ltd., TB1655 thickness 20 μm) is bonded to the barrier layer side of the gas barrier film 1 as a sealing member to form a polyurea film. And using a vacuum laminator. Thereafter, the electronic device main body is sealed by heating at 100 ° C. for 2 hours to cure the adhesive, and the electronic device (sample No. 105) sealed with the epoxy-based sealing adhesive is used. Obtained.

(Comparative Example 2)
In the same manner as in Example 1, instead of a polyurea precursor, pyromellitic anhydride (PMDA) and oxydianiline (ODA) (PMDA: ODA = 1: 1 (molar ratio)) were used as polyimide precursors. Used, PMDA and ODA were vapor-deposited so that the layer containing the polyimide precursor had a thickness of 3 μm. An electronic device (sample No. 106) was obtained in the same manner as in Example 1 except that the electronic element body was sealed in this manner.

<< Evaluation of organic EL elements >>
About the electronic device produced above (sample Nos. 101 to 106), durability was evaluated according to the following method.

(Adhesiveness of base material and sealing member)
Adhesiveness of the substrate and the sealing member was carried out by a 180 ° peel test according to JIS K6850: 1999. Practically, it is preferably 5 N / 25 mm or more.

(Evaluation of sunspot: Durability test not conducted)
A current of 1 mA / cm ² was applied to each organic EL element to continuously emit light for 24 hours, and then a part of the panel with a 100 × microscope (MORITEX MS-804, lens MP-ZE25-200). The photo was taken toward the organic EL device at two locations, the central portion and the peripheral portion of the organic EL device. The photographed image was cut out to 5 mm square, the black spot generation area ratio was determined, and the average value of the central part and the peripheral part was defined as “the black spot area generated in the element not subjected to the degradation process”. After that, in a state where no current is passed, the deterioration treatment is performed at 60 ° C. and 90% for 500 hours, the current of 1 mA / cm ² is applied, and the light emission is continuously performed for 24 hours. The area of the black spots generated in the processed element was determined, and the element deterioration resistance rate was obtained from the following formula.

(Evaluation of sunspot: durability test, bending test)
Similar to the above, after measuring the “area of the black spots generated in the element not subjected to deterioration treatment”, as an endurance test, the organic EL element was wound around a cylinder having a diameter of 10 cm and left for 5 minutes, and then spread on a plane for 5 minutes. The leaving operation was performed 100 times. It was not carried out when a glass substrate was used. Thereafter, a deterioration process is performed for 500 hours under the conditions of 60 ° C. and 90% RH, and “the area of the black spots generated in the element subjected to the deterioration process” is obtained in the same manner as described above. Asked.

(Spot evaluation: endurance test thermal cycle)
After measuring “area of black spots generated in non-degraded element” in the same manner as described above, after performing a thermal cycle of −40 ° C. to 85 ° C. 500 times on the organic EL element as a durability test Then, a deterioration process was performed for 500 hours under the conditions of 60 ° C. and 90% RH, “area of black spots generated in the element subjected to the deterioration process” was determined, and the element deterioration resistance rate was determined in the same manner as described above.

  Sample No. The configurations of 101 to 106 are shown in Table 1 below, and the evaluation results are shown in Table 2 below.

  As is apparent from Table 2 above, it was confirmed that the electronic devices (Examples 1 to 4) of the present invention had good sealing performance even after the durability test.

(Examples 5 to 9)
An electronic device (sample Nos. 112 to 116) was produced in the same manner as in Example 2 except that the material shown in Table 3 was used instead of the gas barrier film 1. The adhesive force and the element deterioration resistance rate were measured in the same manner as the measurement method described in the above section <Evaluation of organic EL element>. The evaluation results are shown in Table 3 below. In Table 3, the results of Example 2 are also listed for reference.

  As is apparent from Table 3 above, it was confirmed that the electronic devices (Examples 5 to 9) of the present invention had good sealing performance even after the durability test.

(Examples 10 to 19)
Using the apparatus (CO-4) having the chamber arrangement as shown in FIG. 6 as the vapor deposition polymerization apparatus, and changing the type, molar ratio, and thickness of the diisocyanate compound and diamine compound as shown in Table 4 below, Three layers containing a polyurea precursor were formed on the electronic device body. In addition, the order of the layers is the first layer, the second layer, and the third layer from the side closer to the electronic element body. The degree of vacuum in each of the deposition chambers of Ch-11, 12 and 13 was 1 × 10 ⁻² Pa, the deposition time was 10 seconds, and the temperature of the base material during the deposition was 10 ° C.

  The layer containing the polyurea precursor (third layer) formed in this way is overlaid so that the gas barrier layer 2 side of the gas barrier film 2 serving as a sealing member is on the inside, and is adhered using a vacuum laminator. It was. Thereafter, heat treatment was performed at 110 ° C. for 30 minutes. In Examples 13 to 19, a gas barrier layer 2 coated with an adhesion assistant was used.

  An electronic device (Sample Nos. 121 to 130) was obtained in the same manner as in Example 1 except that the electronic element body was sealed in this manner.

  The adhesive force and the element deterioration resistance rate were measured in the same manner as the measurement method described in the above section <Evaluation of organic EL element>. Sample No. The configurations of 121 to 130 are shown in Table 4 below, and the evaluation results are shown in Table 5 below.

  As is clear from Table 5 above, it was confirmed that the electronic devices (Examples 10 to 19) of the present invention had good sealing performance even after the durability test.

(Examples 20 to 24)
Using a device (CO-5) having a chamber arrangement as shown in FIG. 7 as a vapor deposition polymerization device, the types, molar ratios, and thicknesses of diisocyanate compounds and diamine compounds as shown in Tables 6 and 7 below are changed. Thus, three layers containing a polyurea precursor were formed on the electronic element main body and the gas barrier film 2 as a sealing member. In addition, the order of the layers is a first layer, a second layer, and a third layer from the side close to the electronic element body or the sealing member. The degree of vacuum in each of the deposition chambers of Ch-11, 12, 13, 21, 22, and 23 is 1 × 10 ⁻² Pa, the deposition time is 10 seconds, and the temperature of the base material and the sealing member during the deposition is 10 ° C.

  Then, it joined so that 3rd layers on an electronic element main body and a sealing member might overlap, it was made to contact | adhere using a vacuum laminator, and the heat processing were performed at 110 degreeC for 30 minute (s). In Examples 23 to 24, an adhesion assistant was applied between the third layer on the electronic element body and the third layer on the sealing member.

  Electronic devices (Sample Nos. 131 to 133, 139 to 140) were obtained in the same manner as in Example 1 except that the electronic element body was sealed in this manner.

  The adhesive force and the element deterioration resistance rate were measured in the same manner as the measurement method described in the above section <Evaluation of organic EL element>. Sample No. The configurations of 131 to 133 and 139 to 140 are shown in Table 6 and Table 7 below, and the evaluation results are shown in Table 8 below.

  As is apparent from Table 8 above, it was confirmed that the electronic devices of the present invention (Examples 20 to 24) had good sealing performance even after the durability test.

(Examples 25-27)
A polyurea film was formed in the same manner as in Example 20 except that the temperature of the base material or the sealing member when forming the layer containing the polyurea precursor was changed as shown in Table 9 and Table 10 below. To obtain an electronic device (Sample Nos. 141 to 143).

(Examples 28 to 30)
A polyurea film was formed in the same manner as in Example 21 except that the temperature of the base material or the sealing member when forming the layer containing the polyurea precursor was changed as shown in Table 9 and Table 10 below. To obtain an electronic device (Sample Nos. 144 to 146).

  Sample No. The configurations of 141 to 146 are shown in Table 9 and Table 10 below, and the evaluation results are shown in Table 11, respectively. Tables 9 to 11 show the configurations and evaluation results of Example 20 and Example 21 for reference.

  As is clear from Table 11 above, it was confirmed that the electronic device of the present invention (Examples 25 to 30) had good sealing performance even after the durability test.

(Example 31)
On the gas barrier layer 2 of the gas barrier film 2 produced above, an indium tin oxide (ITO) transparent conductive film deposited as a first electrode (anode) with a thickness of 150 nm (sheet resistance 12Ω / square) is used. The first electrode was formed by patterning to a width of 10 mm using a normal photolithography method and wet etching. The patterned first electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried by nitrogen blowing, and finally subjected to ultraviolet ozone cleaning. Next, PEDOT-PSS (CLEVIOS (registered trademark) PVP AI 4083, manufactured by Helios Co., Ltd., conductivity: 1 × 10 ⁻³ S / cm) made of a conductive polymer and a polyanion is used as a hole transport layer. An isopropanol solution containing 0% by mass was prepared, and the substrate was applied and dried using a blade coater whose temperature was adjusted to 65 ° C. so that the dry film thickness was about 30 nm. Then, it heat-processed with the warm air of 120 degreeC for 20 second, and formed the positive hole transport layer on said 1st electrode. From then on, it was brought into the glove box and worked under a nitrogen atmosphere.

  First, the element formed up to the hole transport layer was heated at 120 ° C. for 3 minutes in a nitrogen atmosphere.

  Next, 0.8% by mass of the following compound A as a p-type organic semiconductor material, and PC60BM (manufactured by Frontier Carbon Corporation, nanom (registered trademark) spectra E100H) as an n-type organic semiconductor material are added to o-dichlorobenzene. An organic photoelectric conversion material composition solution mixed with 6 mass% was prepared (p-type organic semiconductor material: n-type organic semiconductor material = 33: 67 (mass ratio)). After completely dissolving by stirring (60 minutes) while heating to 100 ° C. with a hot plate, the substrate was applied using a blade coater whose temperature was adjusted to 40 ° C. so that the dry film thickness was about 170 nm. The film was dried at 0 ° C. for 2 minutes to form a photoelectric conversion layer on the hole transport layer.

  Subsequently, the compound B was dissolved in a mixed solvent of 1-butanol: hexafluoroisopropanol = 1: 1 so as to have a concentration of 0.02% by mass to prepare a solution. This solution was applied and dried using a blade coater whose temperature was adjusted to 65 ° C. so that the dry film thickness was about 5 nm. Thereafter, heat treatment was performed for 2 minutes with warm air at 100 ° C. to form an electron transport layer on the photoelectric conversion layer.

Next, the element on which the electron transport layer was formed was placed in a vacuum deposition apparatus. Then, after setting the element so that the shadow mask of 10 mm width is orthogonal to the transparent electrode, the inside of the vacuum deposition apparatus was depressurized to 10 ⁻³ Pa or less, and then silver was deposited to 100 nm at a deposition rate of 2 nm / second, A second electrode (cathode) was formed on the electron transport layer.

  As a sealing member, a polyethylene terephthalate (PET) film (12 μm thickness) is used on a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.), and an adhesive for dry lamination (a two-component reaction type urethane adhesive) is used. A dry laminate (adhesive layer thickness 1.5 μm) was prepared. On the aluminum foil of the sealing member, a layer containing a polyurea precursor composed of MDI: MDA = 1: 1 (molar ratio) was formed by vapor deposition with a thickness of 5 μm, and immediately bonded to the electronic element body. Thereafter, heating was performed at 120 ° C. for 30 minutes, the electronic element body was sealed, and an electronic device (sample No. 201) was produced.

<Evaluation of organic photoelectric conversion element>
The sample before the durability test, the sample subjected to the bending test and the sample subjected to the thermal cycle in the same manner as described above (assessment of black spot: durability test bending test) and (evaluation of black spot: durability test thermal cycle) The sample was allowed to stand for 1000 hours in an environment of 60 ° C. and 90% RH, and the open circuit voltage, the fill factor, and the photoelectric conversion efficiency were evaluated.

<Measurement of short-circuit current density, open-circuit voltage, fill factor, and photoelectric conversion efficiency>
The produced organic photoelectric conversion element is irradiated with light having an intensity of 100 mW / cm ² using a solar simulator (AM1.5G filter), a mask having an effective area of 1 cm ² is overlaid on the light receiving portion, and IV characteristics are evaluated. Thus, the short circuit current density Jsc (mA / cm ² ), the open circuit voltage Voc (V), and the fill factor FF were measured, and the photoelectric conversion efficiency η was calculated by the following formula. The evaluation results are shown in Table 12 below.

  As is clear from Table 12 above, it was confirmed that the electronic device 201 obtained in Example 31 had a good sealing performance with almost no decrease in performance before and after the deterioration test.

(Example 32)
A layer containing a polyurea precursor was formed by vapor deposition to a thickness of 5 μm, and immediately bonded to the electronic device body. Then, instead of heating at 120 ° C. for 30 minutes, an electronic device (sample) was obtained in the same manner as in Example 31 except that the microwave of 2450 MHz and 300 W was irradiated for 1 minute to seal the electronic element body. No. 202) was produced. Almost no deterioration in performance was observed before and after the deterioration test, and it was confirmed that the film had good sealing performance.

10 electronic devices,
11, 31 base material,
12, 32 sealing member,
13 Electronic element body,
14 sealant,
15 Adhesive aid,
17 First electrode (anode),
18 hole transport layer,
19 light emitting layer,
20 electron transport layer,
21 Second electrode (cathode),
33 Temperature control plate,
34 Shutter,
35 rolls,
36 spray nozzles,
Ch chamber,
NCO diisocyanate compound,
NH ₂ diamine compound.

Claims (6)

A flexible substrate;
A flexible sealing member;
An electronic element body located between the base material and the sealing member;
A sealant comprising polyurea;
Including
An electronic device in which the electronic element body is sealed by bonding the base material and the sealing member via the sealant.   The electronic device according to claim 1, wherein at least one of the base material and the sealing member has a gas barrier layer.   The electronic device according to claim 2, wherein the gas barrier layer includes at least one of a metal oxide and a metal oxynitride. A substrate;
A sealing member;
An electronic element body located between the base material and the sealing member;
A sealant comprising polyurea;
A method for manufacturing an electronic device, comprising:
Placing the electronic element body on the substrate;
Forming a layer containing a polyurea precursor on at least one surface of the substrate and the sealing member;
Attaching the base material and the sealing member;
Sealing the electronic element body;
A method for manufacturing an electronic device, comprising:   The manufacturing method of Claim 4 which further includes the process of cooling the said base material and the said sealing member to 20 degrees C or less.   The manufacturing method according to claim 4, wherein the step of sealing the electronic element body includes irradiating an electromagnetic wave having a frequency of 1 MHz to 1 THz.