JPWO2014003196A1 - Electronic device and manufacturing method thereof - Google Patents

Abstract

An electronic device having excellent resistance to bending and temperature change and excellent durability and a method for manufacturing the same are provided. A base material, a sealing member, an electronic element body located between the base material and the sealing member, and a sealant composition joint including a metal and a resin including a single metal or an alloy. An electronic device comprising the body, the electronic element body is sealed by bonding the base material and the sealing member via the sealant composition assembly. Method. [Selection] Figure 1

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).

  In an electronic device using such a flexible resin base material, high flexibility and high sealing performance are required even in the sealing portion, but no means for satisfying these problems has been found. It was.

  On the other hand, Patent Documents 4 and 5 disclose a method in which a low melting point metal is melted and sealed, and Patent Document 6 forms a metal film by spraying metal fine particles at a high speed, and sealing is performed using this metal film. A method is disclosed.

JP 2003-170290 A Japanese Patent Laid-Open No. 2007-200840 JP 2007-73332 A Japanese National Patent Publication No. 11-510647 JP 2005-322580 A JP 2003-272830 A

  However, the techniques described in Patent Documents 4 to 6 have a problem that the sealing performance is lowered when the electronic device is bent or when the temperature changes.

  Therefore, an object of the present invention is to provide an electronic device excellent in resistance to bending and temperature change and excellent in durability and a method for manufacturing the same.

  The present inventor has intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by an electronic device in which an electronic element body is sealed using a sealing agent composition containing a base material, sealing member metal particles, and a resin, and the present invention has been completed. It was.

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

  1. A base material, a sealing member, an electronic element body positioned between the base material and the sealing member, and a sealant composition assembly including a metal and a resin including a metal alone or an alloy; And an electronic device in which the electronic element body is sealed by bonding the base material and the sealing member via the sealant composition assembly.

  2. The melting point of the metal is 80 to 200 ° C. The electronic device according to.

  3. The metal includes tin and at least one of indium and bismuth. Or 2. The electronic device according to.

  4). At least one of the base material and the sealing member assists adhesion between the base material and the sealing member, abuts on the sealant composition assembly, and has an adhesion auxiliary member made of metal. The electronic device according to any one of 1 to 3 above.

  5. A base material, a sealing member, an electronic element body positioned between the base material and the sealing member, and a sealant composition assembly including a metal and a resin including a metal alone or an alloy. A method for manufacturing an electronic device, comprising a step of disposing an electronic element body on the base material, and a metal simple substance or an alloy that is a raw material for forming the sealant composition assembly on the sealing member. A step of applying a sealant composition containing metal particles and a resin, a step of arranging the sealing member to which the sealant composition is applied so as to cover the base material and the electronic element body, Melting the metal particles in the sealant composition to form a metal phase that binds to the base material and the sealing member; curing the resin in the sealant composition; A method of manufacturing an electronic device, the method comprising:

  6). An encapsulant composition that is cured by external energy and is used for encapsulating an electronic device, comprising metal particles containing a single metal or an alloy, and a resin, wherein the metal particles are included in the encapsulant composition. The viscosity of the encapsulant composition when removed is 1 Pa · s or less after standing for 1 minute at the melting point of the metal particles contained in the encapsulant composition, and the viscosity at 25 ° C. before curing. The sealing agent composition for electronic devices whose is 100-1000 Pa.s.

  ADVANTAGE OF THE INVENTION According to this invention, the electronic device excellent in tolerance with respect to a bending | flexion and a temperature change, and 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 mechanism of durability improvement of the electronic device of this invention. It is a schematic diagram which shows the durability improvement mechanism of the electronic device sealed with the base material which has an adhesion auxiliary member, and a sealing member. It is a schematic diagram which shows the structure of the manufacturing apparatus used for formation of the oxygen containing silicon carbide layer of the gas barrier film 2 produced in the Example.

  The present invention relates to a sealant composition joint comprising a base material, a sealing member, an electronic element body located between the base material and the sealing member, and a metal and a metal including a single metal or an alloy. An electronic device in which the electronic element body is sealed by bonding the base material and the sealing member via the sealant composition assembly.

  The present invention is characterized in that an electronic element body is sealed by bonding a base material and a sealing member via a sealant composition assembly including a metal alone or a metal including an alloy and a resin. An electronic device having such a structure has excellent resistance to bending and temperature change, 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 composition assembly 14. . In the present embodiment, the protective layer 15 is provided on the top of the electronic element body 13 so as to cover a part of the electronic element body 13. And the electronic element main body 13 is sealed by joining the base material 11 and the sealing member 12 via the sealant composition assembly 14. That is, the sealing agent composition assembly 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 composition assembly 14. By setting it as this structure, the base material 11 and the sealing member 12 are firmly joined via the sealing agent composition joined body 14, and can prevent intrusion of oxygen and moisture into the electronic element body. The durability of the electronic device can be improved. In addition, the electronic device 10 has excellent resistance to bending and temperature change.

  FIG. 2 is a schematic cross-sectional view showing the basic configuration of an electronic device 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, and a sealant composition assembly. 14 and a sealing agent 16 for filling on the electronic element body 13. The sealing agent 16 for filling is an arbitrary member provided as necessary.

  The reason why the durability of the electronic device of the present invention is improved is unknown, but as shown in FIGS. 3 and 4, at least one of the metal particles 14 a contained in the applied sealant composition 14 ′. It is considered that when the part melts, the metal particles 14 a aggregate and the metal phase 14 c that binds to the base material 11 and the sealing member 12 is formed, and the sealant composition assembly 14 is formed. It is considered that the base material 11 and the sealing member 12 are firmly joined by the metal phase 14c, and oxygen and moisture can be prevented from entering the electronic element body 13. Further, when the resin 14b contained in the applied sealant composition 14 ′ is cured as necessary, the sealant composition is formed by covering the periphery of the metal phase 14c or the adhesion auxiliary member 30 with the cured resin 14b. It is considered that the object bonded body 14 is formed and the base material 11 and the sealing member 12 are bonded more firmly.

  The present invention is not limited to the above mechanism.

  In the embodiment shown in FIGS. 1 to 3, 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 electrode. The electrode (cathode) 21 is formed by being sequentially laminated.

  In the form shown in FIGS. 1 to 3, the electronic device 10 is formed by laminating an electronic element body 13, a protective layer 15, and a sealing member 12 in order on a base material 11. However, the electronic device 10 may have a configuration in which the electronic element body 13, the protective layer 15 and the sealing agent 16 for filling, and the base material 11 are sequentially laminated on the sealing member 12. .

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

  In addition to the base material 11, the sealing member 12, the electronic element body 13, the sealant composition assembly 14, the protective layer 15, and the fill sealant 16 described above, the electronic device 10 is still another It may have a layer. Here, the other layer is not particularly limited, and examples thereof include an electrode, a stabilization layer for stabilizing the electronic element body, and a gas absorption layer.

  Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not limited to these.

[Base material]
The base material according to the present invention is not particularly limited. Examples thereof include a glass substrate, 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.

  Examples of the glass substrate include a quartz glass substrate, a borosilicate glass substrate, a soda glass substrate, and a non-alkali glass substrate. As the metal foil, aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), indium (In), Examples of the metal foil include tin (Sn), lead (Pb), titanium (Ti), and alloys thereof.

  Furthermore, the gas barrier film suitably used as the substrate will be described below.

<Support>
The support is long and can hold a gas barrier layer having a gas barrier property (also simply referred to as “barrier property”) described later, and is formed of the following materials. In particular, it is not 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 metal compound 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 metal nitrides, metal carbides, metal oxynitrides, metal oxyborides, diamond-like carbon (DLC), and combinations thereof. Indium tin oxide (ITO), silicon oxide, aluminum oxide, aluminum silicate (SiAlO _x ), silicon nitride, 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, 2-pole AC flat-plate magnetron sputtering, 2-pole AC rotating 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 .

  Specifically, the polysilazane according to the present invention preferably has the following structure. The polysilazane having the following structure can be ceramicized at a relatively low temperature and modified to silica, and therefore is particularly suitable when a film substrate that is easily damaged under high temperature conditions is used.

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. In this case, 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 preferred from the viewpoint of the denseness of the resulting 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, especially 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 being bonded to the substrate 11 described above via the sealant composition assembly 14. 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).

  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 metal foil such as aluminum foil and copper foil, and a laminate of an inorganic layer and an organic layer described in the section of the gas barrier film.

  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.

It is preferable that the base material and the sealing member have flexibility. In this specification, “flexibility” refers to a property that is flexible and deforms when a force is applied, but returns to its original shape when the force is removed. Specifically, in JIS K7171: 2008 The prescribed flexural modulus is, for example, 1.0 × 10 ^{3 to} 4.5 × 10 ³ [N / mm ² ] or less.

[Adhesion auxiliary member]
At least one of the base material and the sealing member has an adhesion auxiliary member made of metal that assists the adhesion between the base material and the sealing member, abuts on a sealant composition assembly, which will be described later. It is preferable.

  FIG. 4 is a schematic diagram showing the electronic device 10 sealed with the base material 11 having the adhesion assisting member 30 and the sealing member 12.

  The sealant composition 14 ′ according to the present invention forms the metal phase 14c by heating the metal particles 14a, which is one of its components, and melting and aggregating at least a part of the metal particles 14a. The sealant composition assembly 14 is formed and exhibits excellent sealing performance. The molten metal particles 14a have a very high affinity for metal. However, when the affinity for the base material 11 or the sealing member 12 is low, the base material 11 and / or the sealing member 12 is provided with the adhesion assisting member 30 at a portion to be joined, so that the base material 11 and // The sealing member 12 becomes easy to bind to the metal phase 14c formed by melting and aggregating the metal particles 14a in the sealant composition 14 ′, and is formed using the sealant composition 14 ′. In the sealing agent composition assembly 14, higher sealing performance can be exhibited. The material (metal) of the adhesion assisting member 30 preferably has a high affinity with the metal particles 14a included in the sealant composition 14 '. For example, when using metal particles (solder particles) such as Ag—Sn—Cu, Sn—Bi, Sn—In, and Sn—Bi—In, Sn, Cu, Ag, Au, Ni, and the like are preferably used. In the case of using Ag, Cu metal nanoparticles, Ag, Cu, Au or the like is preferably used. The method for installing the adhesion assisting member 30 on the base material 11 or the sealing member 12 is not particularly limited as long as it is a method capable of placing the metal in close contact with the base material 11 or the sealing member 12. Specifically, for example, physical methods such as vapor deposition, sputtering, etc .; chemical methods such as plating, printing of metal ink containing metal powder, metal nanoparticles, etc., reduction of metal salts, and the like are used.

[Sealing Agent Composition Assembly and Sealant Composition of Raw Material for Forming Sealant Composition Assembly]
The sealant composition assembly according to the present invention includes a metal and a resin including a single metal or an alloy. Moreover, the sealing agent composition which is a raw material for forming the sealing agent composition assembly includes metal particles including a single metal or an alloy and a resin. By melting at least a part of the metal particles contained in the sealant composition, a sealant composition assembly can be formed.

(Metal and metal particles)
The metal contained in the encapsulant composition assembly according to the present invention and the metal particles contained in the encapsulant composition both contain a simple metal or an alloy. Examples of simple metals or alloys include, for example, indium (In), bismuth (Bi), lead (Pb), tin (Sn), cadmium (Cd), copper (Cu), silver (Ag), and antimony (Sb). , Zinc (Zn), gallium (Ga), germanium (Ge) or the like, or a metal alloy of two or more of the above metals.

  Among these, indium, bismuth, tin, silver, or an alloy thereof is preferable. More preferably, it is a metal or metal particle containing tin and at least one of indium and bismuth. When bismuth is included, it is preferable from the viewpoint of low melting point and low toxicity. Moreover, when it contains indium, it is preferable from a viewpoint that the ductility and the wettability with respect to the inorganic oxide contained in the said gas barrier layer etc. improve.

  In a metal or metal particle containing tin and at least one of indium and bismuth, which is a more preferable form, the content of tin is 10 to 60, where the total amount of tin and at least one of indium and bismuth is 100% by mass. Mass% is preferred.

  Particularly preferred alloys include Bi57In26Sn17 (melting point 79 ° C.), Bi54In29.7Sn16.3 (melting point 81 ° C.), In52.2Sn46Zn1.8 (melting point 108 ° C.), Bi67In23Sn10 (melting point 109 ° C.), In52Sn48 (melting point 138 ° C.). Is mentioned.

  Generally, the metal simple substance and alloy used in the above-mentioned sealant composition, the surface is oxidized and covered with an oxide, which prevents the melting, in the metal particles contained in the sealant composition, It is preferable to use a flux component having a flux characteristic that reduces oxide on the surface and promotes melting.

  In the present invention, the flux component is preferably a carboxylic acid anhydride. As an example of the carboxylic anhydride, it is preferable to include at least one compound selected from the compounds represented by the following structural formulas (1) to (5).

  In this case, the carboxylic acid anhydrides represented by the structural formulas (1) to (3) have a cyclic structure having an internal strain, so that they are likely to cause chemical and thermal ring opening. The carboxylic acid anhydrides represented by the structural formulas (4) to (5) which are anhydrides are ester-like “-(C═O) —O— (C═O) —” which is easily hydrolyzed inside the molecule. Due to the structure, ring opening is likely to occur chemically and thermally. For this reason, these carboxylic acid anhydrides have high reactivity of hydrolysis reaction, and the flux component exhibits an excellent flux action at a low heating temperature.

  In the present invention, the carboxylic acid anhydride is represented by succinic acid anhydride, glutaric acid anhydride, diglycolic acid anhydride, thiodiglycolic acid anhydride, and the following structural formulas (6) to (7). It is also preferable to include at least one compound selected from the group consisting of polymer acid anhydrides.

  In this case, succinic anhydride, glutaric anhydride, diglycolic anhydride, and thiodiglycolic anhydride are particularly susceptible to ring opening because the internal strain of the cyclic structure is particularly large, and the structural formula ( The polymer type acid anhydrides represented by 6) to (7) also have an ester-like structure of “— (C═O) —O— (C═O) —” which is easily hydrolyzed inside the molecule, so that the ring is opened. Is particularly likely to occur. For this reason, these carboxylic acid anhydrides have very high reactivity of hydrolysis reaction, and the flux component exhibits particularly excellent flux action at a low heating temperature.

  In the present invention, the sealant composition may contain a reaction accelerator containing at least one compound selected from the group consisting of a heterocyclic compound having a nitrogen atom, a polyamine compound, and an adduct thereof. preferable.

  The addition amount of the flux component is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the entire sealant composition.

  The particle size of the metal particles contained in the sealant composition is not particularly limited, but is preferably 50 μm or less, and preferably 20 μm or less from the viewpoint of ease of melting and joining. Moreover, it is preferable that it is 5 micrometers or more at the point which is hard to be influenced by an oxide film, and it is more preferable that it is 10 micrometers or more. From the viewpoint of increasing the packing density of the metal particles in the sealant composition, it is also preferable to mix metal particles having different particle diameters. As the particle size, a value of 50% particle size (median particle size) obtained by a laser diffraction / scattering method is adopted.

  The metal particles may be metal nanoparticles having a particle size of 100 nm or less. Metal particles are known to have a lower sintering start temperature (melting point) by reducing the particle size. From the viewpoint that additives such as flux components are not required for silver, gold, etc., which are difficult to oxidize. In the present invention, metal nanoparticles can be preferably used. The type of metal in the case of metal nanoparticles is not particularly limited, but gold, silver, copper, platinum, and a silver-copper alloy are preferable from the viewpoints of ease of manufacture, stability, and the like.

  An amine compound may be deposited on the surface of the metal nanoparticles. Since the amine compound attached to the metal nanoparticles forms a protective film on the surface of the metal nanoparticles, after a certain number of metal atoms gather to form the metal nanoparticles, the amine protective film further increases the It is thought that it becomes difficult for metal atoms to bond. For this reason, it is considered that metal nanoparticles having a uniform particle diameter can be obtained stably.

  Examples of the amine compound include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, 2,2 -Dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N′-dimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Diaminooctane, 2-ethoxyethylamine, dipropylamine, dibutylamine, hexylamine, cyclohexane Shiruamin, heptyl amine, 3-butoxy-propylamine, octylamine, nonylamine, decylamine, 3-aminopropyltriethoxysilane, dodecylamine, but oleylamine and the like, but is not limited thereto.

  As a method for producing metal nanoparticles coated with an amine compound, for example, a metal oxalate and an amine compound are reacted to form a complex compound, and then the complex compound is heated in a range of 100 to 200 ° C. The method of carrying out low temperature thermal decomposition is mentioned.

  The particle size of the metal nanoparticles is not particularly limited, but is preferably 50 nm or less, and preferably 20 nm or less, from the viewpoint of ease of melting and joining. The lower limit is not particularly limited, but is preferably 5 nm or more, and more preferably 10 nm or more. From the viewpoint of increasing the packing density of metal particles, it is also preferable to mix particles having different particle sizes. In addition, the particle diameter (median particle diameter) observed with the scanning electron microscope shall be employ | adopted for the particle diameter of a metal nanoparticle.

  The shape of the metal particles is not particularly limited, and examples thereof include a polyhedral shape, a regular polyhedral shape, a spherical shape, a spheroid shape, a scale shape, a disc shape, a dendritic shape, and a fibrous shape. From the viewpoint of the viscosity of the resin / metal particle mixture and the surface area per volume of the metal particles being small, it is preferably spherical.

  The melting point of the metal particles is not particularly limited, but is preferably 80 to 200 ° C., more preferably 100 to 160 ° C., and more preferably 110 to 140 ° C. from the viewpoints of ease of manufacturing an electronic device and thermal stability. More preferably.

  The content of the metal particles in the sealant composition is preferably 50 to 90 parts by weight, more preferably 60 to 85 parts by weight, with the total amount of the sealant composition being 100 parts by weight. preferable.

  In addition, you may use the said metal particle individually or in combination of 2 or more types.

(Resin contained in sealant composition assembly and sealant composition)
The resin contained in the encapsulant composition assembly and the encapsulant composition is not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and photocurable resins. In the case of a curable resin, the resin contained in the encapsulant composition is in an uncured state, and the resin contained in the encapsulant composition assembly is in a cured state.

  More specific examples include, for example, epoxy resins, acrylic resins, polyolefin resins, fluororesins, polyvinylidene chloride resins, ionomer resins, urethane resins, ethylene-vinyl acetate copolymer resins, polyimide resins, cyanate ester resins, Examples include benzoxazine resin. Especially, it is more preferable that at least one of an epoxy resin and an acrylic resin is included.

(Viscosity of sealant composition when metal particles are not included)
In the present invention, in the sealant composition (mixture of components other than metal particles such as the resin and the flux component) when the metal particles are removed from the sealant composition, the sealant composition The viscosity after standing for 1 minute at the melting point of the metal particles contained in the substrate is preferably 1 Pa · s or less, and more preferably 100 mPa · s or less. The melting point known from the composition of the alloy is used here as the melting point of the encapsulated metal particles. When the melting point from the solid phase and the melting point from the liquid phase are different as in an alloy, the average is taken as the melting point. Further, when two or more kinds of metal particles having different compositions are mixed, the melting point of the metal contained is the weight average value of the melting points of the metal particles. In addition, the value measured with the E-type viscosity meter shall be employ | adopted for the viscosity of the said resin.

  In addition, these resin may be used individually or in combination of 2 or more types, a commercial item may be used, and a synthetic item may be used.

  The content of the resin in the encapsulant composition assembly or encapsulant composition is 5 to 50 parts by weight, where the total amount of the encapsulant composition assembly or encapsulant composition is 100 parts by weight. It is preferable that it is 10-20 weight part.

  The sealant composition may include a curing agent for the resin. There is no restriction | limiting in particular as a hardening | curing agent, What is necessary is just a compound which has a functional group reactive with the said resin. Specifically, for example, triphenylmethane triisocyanate, methylene bis (4-phenylmethane triisocyanate), triallyl isocyanate, dimer acid diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6- Tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate (4,4′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), 1,4-phenylene diisocyanate, Xylylene diisocyanate (XDI), tetramethylxylidene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), trimethylhexene Methylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI), transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI), H6-XDI (hydrogenated XDI), H12-MDI (hydrogenated MDI) Adducts of the above isocyanates such as carbodiimide-modified diisocyanates of the above diisocyanates, or isocyanurate-modified diisocyanates, trimethylolpropane / tolylene diisocyanate trimer adducts, and polyol compounds such as trimethylolpropane, these isocyanates -Type isocyanate curing agents such as biuret and isocyanurate; phenol novolac resin, cresol novolac resin, phenol Phenolic curing agents such as aralkyl (including phenylene and biphenylene skeleton) resins, naphthol aralkyl resins, triphenolmethane resins, dicyclopentadiene type phenol resins; ethylenediamine, triethylenediamine, hexamethylenediamine, 2,4-diamino-6 Triazine compounds such as [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), triethylenediamine, benzyldimethylamine, triethanol Amine-based curing agents such as amines; acid anhydride-based curing such as phthalic anhydride, maleic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, benzophenone tetracarbanoic dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. Agent Monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; amino-formaldehyde resins such as methylol urea, methylol melamine, alkylated methylol urea, alkylated methylolated melamine, acetoguanamine, condensates of benzoguanamine and formaldehyde; Furthermore, salts of divalent to tetravalent metals such as sodium, potassium, magnesium, calcium, aluminum, iron, nickel, zirconium and oxides thereof can be mentioned. These curing agents may be used alone or in combination of two or more.

  The content of the curing agent in the sealant composition is preferably 1 to 10 parts by weight, with the total amount of the sealant composition being 100 parts by weight.

  The sealant composition may contain other additives as necessary. Specific examples of other additives include, for example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, bis [ 4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, diallyl iodonium hexafluoroantimonate, diethoxyacetophenone, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propyl Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- ( 2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propyl ketone, curing catalyst such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, flux such as levulinic acid, silane coupling agent, curing accelerator, Ionic liquid, lithium salt, inorganic filler, softener, antioxidant, anti-aging agent, stabilizer, tackifier resin, leveling agent, antifoaming agent, plasticizer, dye (pigment pigment, extender pigment, etc.), treatment Agents, UV blockers, fluorescent brighteners, dispersants, heat stabilizers, light stabilizers, UV absorbers, antistatic agents, lubricants, and the like.

  The sealant composition, which is a raw material for bonding the sealant composition, preferably forms a sealant composition assembly by curing with external energy. The curing method is not particularly limited, and examples thereof include heating, ultraviolet irradiation, electron beam irradiation, and laser irradiation.

  Although it does not restrict | limit especially about arrangement | positioning of the said sealing agent composition conjugate | zygote and the sealing agent composition which is the raw material, It is preferable to arrange | position outside the electronic element main body 13 like FIGS. The effects of the present invention can be obtained more efficiently by arranging the sealant composition assembly and the sealant composition that is a raw material thereof.

  A commercially available product or a synthetic product (prepared product) may be used as the sealant composition that is the raw material of the sealant composition assembly. When preparing a sealant composition, for example, a method of stirring and mixing the above-described metal particles, resin, and other components as necessary at -20 to 40 ° C. for 1 to 24 hours. Applied.

  The viscosity at 25 ° C. before curing of the sealant composition, which is a raw material of the sealant composition assembly according to the present invention, is preferably 100 to 1000 Pa · s. If it is this range, it can apply | coat as a sealing agent for dams in the liquid crystal dropping method (ODF method) mentioned later, and the sealing agent for fills can be enclosed. In addition, the value measured with the E-type viscosity meter shall be employ | adopted for the viscosity of the said sealing agent composition.

[Electronic element body]
The electronic element body is the body of the electronic device. 1 to 4, 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 4, 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)
As shown in FIG. 2, 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 plurality of layers may be stacked. In this invention, it is preferable that the sealing compound composition 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 one embodiment of the present invention, (1) a step of placing an electronic element body on a substrate, and (2) the sealing agent of the raw material for forming the sealing agent composition assembly on a sealing member A step of applying the composition, (3) a step of disposing a sealing member on the base material and the electronic element body, and (4) a step of melting metal particles in the sealing agent composition to form a metal phase. And (5) a step of curing the resin in the sealant composition, a method for producing an electronic device is provided.

  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.

  Next, a protective layer is formed as necessary. The method for forming the protective layer is not particularly limited, and can be manufactured by appropriately referring to known methods.

(2) The process of apply | coating the said sealing agent composition which is a raw material for formation of the said sealing agent composition conjugate | zygote on a sealing member Then, the said sealing agent composition is apply | coated on the said sealing member, Form a coating film. For example, when the electronic device 10 having the form shown in FIGS. 1 to 4 is manufactured, the peripheral portion (outer periphery) of the sealing member 12 is surrounded so as to surround the periphery of the electronic element main body 13 disposed on the central portion of the base material 11. The sealant composition 14 ′ may be applied in a band shape on the part).

  Examples of the method for applying the sealant composition 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. Etc. A liquid crystal dropping method (ODF, One Drop Filling) in which a liquid sealant composition is applied with a dispenser is preferably used because of the ease of controlling the amount of sealant.

  If necessary, as shown in FIG. 2, the sealing material for filling is placed inside the sealing agent composition (see reference numeral 14 'in FIGS. 3 and 4), which is a raw material for forming the sealing agent composition connector 14. A stop agent 16 is applied. As shown in FIG. 2, it may be applied to the upper surface of the electronic element body 13, or when the protective layer 15 is provided, may be applied to the upper surface of the protective layer 15, or a part of the electronic element body 13 or You may form on the upper surface of all the structure layers.

  Examples of the sealing agent for fill include sealing agents containing epoxy resin, acrylic resin, polyolefin resin, fluororesin, polyvinylidene chloride resin, and the like. The fill sealant may include a curing agent. These resins may be used alone or in combination of two or more.

(3) Step of disposing sealing member on base material and electronic element body Subsequently, as shown in FIGS. 1 to 4, a sealing member is formed so as to cover the upper part of the base material 11 and the electronic element body 13. 12 is arranged.

(4) Step of melting metal particles in a sealant composition, which is a raw material for forming a sealant composition connector, and forming a metal phase that binds to a base material and a sealing member Next, FIG. As shown in ˜4, at least a part of the metal particles 14 a in the sealant composition 14 ′ is melted and aggregated to form a metal phase 14 c that binds to the base material 11 and the sealing member 12.

  The method for melting the metal particles is not particularly limited, and examples thereof include heating.

  The heating temperature for melting the metal particles by heating is not particularly limited, but is preferably 100 to 200 ° C. Moreover, it is preferable that heating time is 1 minute-30 minutes.

(5) Step of curing resin in sealant composition (step of forming sealant composition assembly)
Finally, as shown in FIGS. 3 to 4, the resin 14b in the sealant composition 14 ′ is cured. As a result, a sealant composition assembly 14 is formed, and the base material 11 and the sealing member 12 are joined via the sealant composition assembly 14 to seal the electronic element body 13. Then, the electronic device 10 is formed.

  The method for curing the resin 14b in the sealant composition 14 'is not particularly limited, and examples thereof include heating, ultraviolet irradiation, electron beam irradiation, and laser irradiation. In addition, when hardening by a heating or laser irradiation, this process may serve as the process of said (4). That is, the step (4) and this step may be performed by one heating or laser irradiation.

  In addition to the above manufacturing method, as shown in FIGS. 1 to 4, (1) a step of placing the electronic element body 13 on the sealing member 12, and (2) a sealing agent composition 14 ′ on the substrate 11. (3) a step of disposing the base material 11 on the sealing member 12 and the electronic element body 13, and (4) a metal phase 14c by melting the metal particles 14a in the sealant composition 14 ′. And (5) a step of curing the resin 14b in the sealant composition 14 ′ (forming the sealant composition assembly 14), and a method of manufacturing the electronic device 10. .

  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 at 80 ° C. for 3 minutes to form a bleedout 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 is 4.0 μm after that, the film is dried at 80 ° C. for 3 minutes, and then irradiated with an irradiation energy 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 in 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 onto the polysilazane layer 1 obtained above, vacuum ultraviolet irradiation (irradiation amount: 1700 mJ / cm ² ) is performed, and the dry film thickness is 50 nm on the polysilazane layer 1. A gas barrier layer 1 on which a certain polysilazane layer 2 was laminated was formed on a smooth layer.

  As a result of analysis by an X-ray photoelectron spectroscopy (XPS) apparatus (Quantac 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>
On the smooth layer of the support (a), an inorganic layer made of oxygen-containing silicon carbide was formed by plasma CVD using the manufacturing apparatus shown in FIG. 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 thin film layer in the obtained laminated film was 0.3 μm.

  Here, the manufacturing apparatus 31 shown in FIG. 5 includes a feed roller 32, transport rollers 33, 34, 35, and 36, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a generator. Magnetic field generators 43 and 44 installed inside the film rollers 39 and 40 and a winding roller 45 are provided. In the manufacturing apparatus 31, film forming rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and magnetic field generation apparatuses 43 and 44 are disposed in a vacuum chamber (not shown). Further, in the manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and a vacuum pump that can adjust the pressure in the vacuum chamber is used. Using the manufacturing apparatus 31 shown in FIG. 5, a film forming gas (raw material gas or the like) is supplied into the vacuum chamber under the film forming conditions of the laminated film 1 described above, while a pair of film forming rollers (film forming rollers). 39 and 40), the film-forming gas (raw material gas or the like) is decomposed by plasma, and a support (on the surface of the substrate 2 on the film-forming roller 39 and on the film-forming roller 40) is generated. A) A laminated film 1 was produced in which an inorganic layer 3 made of oxygen-containing silicon carbide was formed on the surface of 2 by a plasma CVD method.

  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 coated on 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 ), on the layer made of oxygen-containing silicon carbide. A gas barrier layer 2 in which a polysilazane layer having a dry film thickness of 50 nm was laminated on the smooth layer of the support (a) to obtain 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. It 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. It was ² · 24h.

[Preparation of gas barrier film 4]
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 4 was produced in the same manner as the gas barrier film 3 except that the gas barrier layer 4 on which an inorganic layer was laminated was produced.

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. It was ² · 24h.

[Preparation of sealant composition]
<Comparative sealant composition DT-1>
30 parts by weight of silica particles having an average particle diameter of 6 μm as inorganic fillers, 11 parts by weight of a liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), and a curing agent (manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure (registered trademark) PN- 23) 2 parts by weight were uniformly mixed using a disper (mixing temperature: 25 ° C., mixing time: 1 hour) to obtain a sealant composition DT-1. The viscosity of DT-1 measured with an E-type viscometer was 150 Pa (25 ° C.).

<Sealing agent composition DT-2>
Sn42Bi58 was used as the solder particles, and solder particles were produced according to a conventional method. The produced solder particles had an average particle size of 15 μm and a melting point of 138 ° C. 85 parts by weight of the solder particles, 11 parts by weight of a liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), 2 parts by weight of a curing agent (manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure (registered trademark) PN-23), and 2 parts by weight of levulinic acid as a flux was uniformly mixed using a disper (mixing temperature 25 ° C., mixing time 1 hour) to obtain a sealant composition DT-2. The viscosity of DT-2 measured with an E-type viscometer was 200 Pa (25 ° C.). The viscosity of the mixture other than metal particles after standing at 138 ° C. for 1 minute was 30 mPa · s.

<Sealing agent composition DT-3>
In58Sn42 was used as solder particles, and solder particles were produced according to a conventional method. The produced solder particles had an average particle size of 15 μm and a melting point of 118 ° C. 85 parts by weight of the solder particles, 11 parts by weight of a liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), 2 parts by weight of a curing agent (manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure (registered trademark) PN-23), 2 parts by weight of levulinic acid as an agent was uniformly mixed using a disper (mixing temperature: 25 ° C., mixing time: 1 hour) to obtain a sealant composition DT-3. The viscosity of DT-3 measured with an E-type viscometer was 250 Pa (25 ° C.). The viscosity of the mixture other than the metal particles after standing at 118 ° C. for 1 minute was 80 mPa · s.

<Sealing agent composition DT-4>
5.35 g (20 mmol) of oleylamine, 2.02 g (20 mmol) of hexylamine and 5 ml of methanol were mixed, 1.519 g (5 mmol) of silver oxalate was added to this mixed solution, and 1 ml of water was further added at room temperature. The mixture was stirred for 2 hours to dissolve the silver oxalate. The product obtained at this time was confirmed to be a complex compound containing silver, oxalate ion, oleylamine and hexylamine by analysis using FT-IR.

  Thereafter, methanol was removed at 40 ° C. using an evaporator, and then the mixture was heated to 150 ° C. and stirred for 1 hour to obtain a brown liquid. To this was added 30 ml of hexane, stirred for about 30 minutes, separated by a centrifuge, and the supernatant was filtered. This operation was repeated three times. Furthermore, after removing hexane at 45 ° C. using an evaporator, 20 ml of methanol was added and separated by a centrifuge to remove the supernatant. This operation was also repeated three times, and then powder metal nanoparticles NP-A composed of metallic silver and organic matter adsorbed on metallic silver were obtained by drying under reduced pressure (melting point (sintering start temperature): 115 ° C.). . The obtained powder was analyzed and evaluated as follows.

  The obtained powder was analyzed with an X-ray diffractometer (manufactured by Rigaku Corporation, Miniflex), and it was confirmed that metallic silver was produced from the X-ray diffraction pattern.

  Moreover, observation with a scanning transmission electron microscope was performed, and it was confirmed that NP-A was composed of spherical monodisperse ultrafine particles having a particle size of 12.5 nm. The yield as silver was 87.8%. Further, it was confirmed by IR analysis that oleylamine and hexylamine were adhered. The weight ratio of Ag was 90%.

  85 parts by weight of NP-A obtained above, 11 parts by weight of liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), and curing agent (manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure (registered trademark) PN-23) 2 parts by weight were uniformly mixed using a disper (mixing temperature: 25 ° C., mixing time: 1 hour) to obtain a sealant composition DT-4. The viscosity of DT-4 measured with an E-type viscometer was 300 Pa (25 ° C.). The viscosity of the mixture other than the metal particles after standing at 115 ° C. for 1 minute was 100 mPa · s.

<Fill sealant FT-1>
11 parts by weight of a liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128) and 2 parts by weight of a curing agent (manufactured by Ajinomoto Fine Techno Co., Ltd., Amicure (registered trademark) PN-23) are uniformly mixed using a disper. (Mixing temperature 25 ° C., mixing time 1 hour) to obtain a sealant composition FT-1. The viscosity of FT-1 measured with an E-type viscometer was 750 mPa (25 ° C.).

Example 1
<< Production of electronic devices >>
The organic EL element which is an organic thin film electronic device was produced in the following procedures using 0.7 mm-thick alkali-free glass as a base material.

[Production of organic EL elements]
(Formation of first electrode layer)
On the gas barrier layer of the gas barrier film 1, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering, and patterned by photolithography 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 applying the coating liquid for forming the hole transport layer, the cleaning surface modification treatment of the gas barrier film was performed using a low pressure mercury lamp with 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 an atmosphere of 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, Baytron (registered trademark) P AI 4083 manufactured by Bayer) 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, the following electron transport layer forming coating solution 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, a mask pattern is formed by vapor deposition using aluminum as a second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa and having an extraction electrode. A second electrode having a thickness of 100 nm was stacked.

(Formation of protective layer)
Subsequently, SiO ₂ was laminated with a thickness of 200 nm by a CVD method, except for a portion to be the extraction portion of the first electrode and the second electrode, and a protective layer was formed on the second electrode layer.

  In this way, an electronic element body was produced.

[Sealing]
As shown in FIG. 4, as a sealing member (reference numeral 12), a polyethylene terephthalate (PET) film (12 μm thickness) is applied to a 30 μm-thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) and an adhesive (2 What was dry-laminated using a liquid reaction type urethane adhesive) (adhesive layer thickness 1.5 μm) was prepared. Furthermore, a width of 0.5 mm and a thickness as an adhesion protection member (reference numeral 30) are provided on the base material (reference numeral 11) and on the sealing member (reference numeral 12) in contact with the sealing agent composition (reference numeral 14 '). Copper was deposited by a vacuum deposition method with a thickness of 50 nm.

  The encapsulant composition DT-2 (symbol 14 ′) is applied to the copper (symbol 30) portion on the aluminum foil of the sealing member (symbol 12) using a dispenser manufactured by Musashi Engineering Co., Ltd. by the ODF method. Set up. The coated size was 45 mm × 45 mm, and R = 1 mm at the right angle part. Sealant FT-1 for fill (reference numeral 16) was dropped into the sealant composition DT-2 (reference numeral 14 ') at equal intervals at 10 × 10 locations. Using this sealing member (reference numeral 12), a vacuum bonding apparatus manufactured by Run Technical Service Co., Ltd., so that the thickness of the sealant layer (the coating film of the sealant composition DT-2) is 20 μm. Bonding with the electronic element body (reference numeral 13) on which the protective layer (reference numeral 15) is formed, heating at 160 ° C. for 5 minutes, solder particles (symbol 14a) of the sealant composition DT-2 (reference numeral 14 ′) ) Is melted and agglomerated to form a solder phase (reference numeral 14c), and a thermosetting liquid epoxy resin (reference numeral 14b in the upper diagram of FIG. 4) is thermally cured to give an epoxy resin (reference numeral 14b in the lower diagram of FIG. 4). ) Was formed, sealing agent composition assembly DT-2 (symbol 14) was formed, sealing was completed, and an organic EL element 102 as an electronic device (symbol 10) was obtained.

(Examples 2-11, Comparative Examples 1-4)
The organic EL elements 101 and 103 to 115 were prepared in the same manner as in Example 1 except that the base material, the sealing member, the sealing agent composition, and the sealing agent for fill as shown in Table 1 below were used. Produced.

  In addition, in the organic EL elements 105 (Comparative Example 2) and 112 (Comparative Example 4), after sealing as described above, the method described in the example of JP-A-2005-322580 (melting a low melting point metal) In accordance with the above-described sealing method, the outer side of the encapsulant composition assembly formed by the sealing process was further metal-sealed with indium (In).

(Example 12)
After using the gas barrier film 2 and producing the electron injection layer in the same manner as in Example 1, a transparent organic EL lighting element was produced as follows.

<Formation of second electrode layer>
On the formed electron injection layer, ITO having a thickness of 150 nm was formed by sputtering under a vacuum of 5 × 10 ⁻⁴ Pa, and a mask pattern was formed so that the light emitting portion was 4 cm × 4 cm. A second electrode layer having a thickness of 100 nm was stacked.

<Formation of protective layer>
Subsequently, SiO ₂ was laminated with a thickness of 200 nm by a CVD method, except for the portions to be taken out of the first electrode layer and the second electrode layer, and a protective layer was formed on the second electrode layer.

<Preparation of Sealant Composition DU-1>
In58Sn42 was used as solder particles, and solder particles were produced according to a conventional method. The produced solder particles had an average particle size of 15 microns and a melting point of 118 ° C. 85 parts by weight of the solder particles, 40 parts by weight of a liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), 40 parts by weight of 1,6-bis (2,3-epoxypropoxy) naphthalene, bis-4-dodecylphenyliodonium hexa As an inorganic filler, 2 parts by weight of fluoroantimonate and 20 parts by weight of silica particles having an average particle diameter of 6 μm were mixed and uniformly mixed using a disper to prepare a UV curable encapsulant composition DU-1. . The viscosity of DU-1 measured with an E-type viscometer was 120 Pa (25 ° C.).

<Fill sealant FT-2>
Disperser used 25 parts by weight of liquid epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD128), 25 parts by weight of 1,6-bis (2,3-epoxypropoxy) naphthalene, and 50 parts by weight of tetrahydromethylphthalic anhydride. Were mixed uniformly to prepare a sealant FT-2 for fill. The viscosity of FT-2 measured with an E-type viscometer was 550 mPa (25 ° C.).

<Sealing>
As shown in FIG. 3, the gas barrier film 2 excellent in ultraviolet transparency is used as the sealing member (reference numeral 12) (for curing the UV curable encapsulant composition DU-1 by ultraviolet irradiation), On gas barrier layer 2, sealant composition DU-1 (symbol 14 ') was coated by ODF method using a dispenser made by Musashi Engineering Co., Ltd. The coated size was 45 mm × 45 mm, and R = 1 mm at the right angle part. Sealant FT-2 for fill (reference numeral 16) was dropped into the sealant composition DU-1 (reference numeral 14 ') at 10 × 10 locations at equal intervals. Using this sealing member (reference numeral 12), a vacuum bonding apparatus manufactured by Run Technical Service Co., Ltd., so that the thickness of the sealing agent layer (the coating film of the sealing agent composition DU-1) is 20 μm. Then, it was bonded to the electronic element body (reference numeral 13) on which the protective layer (reference numeral 15) was formed.

In a state where the surface pressure is 0.05 MPa, continuous wave Nd: YAG laser light (wavelength: 1064 nm, frequency: 1000 Hz, output: 17 W) is set to a laser beam convergence angle of 2.5 ° at the focal point of the laser light. The laser diameter was irradiated to the encapsulant composition DU-1 (symbol 14 ′) while moving the light diameter (beam diameter) to 300 μm at a laser scanning speed of 15 mm / sec, and then a 395 nm semiconductor laser was spotted with a spot diameter of 2 mm. , Irradiated with an irradiation energy amount of 3000 mJ / cm ² and heated in an oven at 85 ° C. for 30 minutes to melt and aggregate the solder particles (symbol 14a) of the encapsulant composition DU-1 (symbol 14 ′) to form a solder phase (Symbol 14c) and UV curing liquid epoxy resin (symbol 14b in the upper diagram of FIG. 3) is UV cured to form an epoxy resin (lower diagram of FIG. 3). By forming the code 14b), to form a sealant composition conjugates DU-1 (reference numeral 14) to complete the sealing. This obtained the organic EL element 201 which is an electronic device (code | symbol 10).

<< Evaluation of organic EL elements >>
Durability was evaluated according to the following method about the produced said organic EL elements 101-115,201. A plurality of organic EL elements 101 to 115 and 201 were manufactured and subjected to the following tests.

(Evaluation of sunspot: Durability test not conducted)
A current of 1 mA / cm ² was applied to each of the organic EL elements 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 area of the black spots generated in the element not subjected to the accelerated deterioration process”. After that, a deterioration process was performed for 500 hours at 60 ° C. and 90% in a state where no current was applied, and a current of 1 mA / cm ² was applied to continuously emit light 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.

A: The element deterioration resistance rate is 90% or more. B: The element deterioration resistance ratio is 60% or more and less than 90%. Δ: The element deterioration resistance ratio is 20% or more and less than 60%. The deterioration resistance rate is less than 20%.

(Evaluation of sunspot: durability test, bending test)
In the same manner as described above, after measuring the “area of black spots generated in an element not subjected to accelerated 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. The operation of standing for 100 minutes 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 accelerated deterioration process” is obtained in the same manner as described above. Asked.

(Evaluation of sunspot: endurance test thermal cycle (1))
In the same manner as above, after measuring the “area of black spots generated in an element not subjected to accelerated deterioration treatment”, the organic EL element was subjected to a thermal cycle of −40 ° C. to 85 ° C. 500 times as a durability test. After that, a deterioration process is performed for 500 hours under the conditions of 60 ° C. and 90% RH, and “the area of the black spot generated in the element subjected to the accelerated deterioration process” is obtained in the same manner as described above, and the element deterioration resistance rate is determined in the same manner as described above. Asked.

(Evaluation of sunspot: durability test thermal cycle (2))
In the same manner as above, after measuring the “area of black spots generated in an element not subjected to accelerated deterioration treatment”, the organic EL element was subjected to a thermal cycle of −40 ° C. to 85 ° C. 500 times as a durability test. Then, 1000 hr deterioration treatment was performed under conditions of 85 ° C. and 85% RH, and “the area of black spots generated in the device subjected to accelerated deterioration treatment” was obtained in the same manner as above, and the element deterioration resistance rate was obtained in the same manner as above. Asked.

  The evaluation results are shown in Table 1 below.

  As is apparent from the results shown in Table 1 above, the electronic devices 102 to 104, 107 to 111, 113 to 115, and 201 (Examples 1 to 12) of the present invention are the electronic devices of Comparative Examples 1 to 4. In comparison, it can be seen that the device is excellent in device deterioration resistance after deterioration treatment (durability test is not performed), and is further excellent in device deterioration resistance (durability) when subjected to deterioration treatment after various durability tests. Specifically, it can be seen that the element deterioration resistance (durability) after the bending test, after the thermal cycle (1) and after the thermal cycle (2) is excellent as a durability test. Furthermore, among the electronic devices of Examples 1 to 12, various kinds of solder particles (Sn and In or Bi) having a size smaller than that of nano metal particles (nano silver particles) (Examples 3, 7, and 8) as metal particles. It was found that those using the examples (Examples 1, 2, 4 to 6, 9 to 12) were excellent in element deterioration resistance (durability) after the thermal cycle (1) and after the thermal cycle (2). In addition, the device deterioration resistance rate after the deterioration treatment (endurance test is not performed) is more in the case of using the adhesion auxiliary member (Examples 5 and 8) than in the case of not using the adhesion auxiliary member (Examples 4 and 7). It was found that both the element deterioration resistance rate after the deterioration treatment after the bending test and the element deterioration resistance rate after the deterioration treatment after the thermal cycle (1) were improved by about 3 to 15%. Further, in the case of using the adhesion auxiliary member (Examples 5 and 8), the difference in the element deterioration resistance rate after the thermal cycle (1) and after the thermal cycle (2) is as very small as 1 to 2%, and it is long-term. As a result, it was found that the thermal cycle deterioration was greatly suppressed.

  Moreover, according to the method of Example 12, the thermal history of an electronic device can be reduced by performing UV hardening process of a sealing agent composition.

(Example 13)
On the gas barrier layer 2 of the gas barrier film 2, 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 as a normal photo. A first electrode was formed by patterning to a width of 10 mm using a lithography 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 with a width of 10 mm is orthogonal to the transparent electrode, the inside of the vacuum deposition apparatus is depressurized to 10 ⁻³ Pa or less, and then silver is deposited to 100 nm at a deposition rate of 2 nm / second, A second electrode (cathode) was formed on the electron transport layer.

  As shown in FIG. 3, as a sealing member (reference numeral 12), a polyethylene terephthalate (PET) film (12 μm thickness) is applied to a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) and an adhesive (2 What was dry-laminated using a liquid reaction type urethane adhesive) (adhesive layer thickness 1.5 μm) was prepared. On the aluminum foil of this sealing member (code | symbol 12), sealing agent composition DT-3 (code | symbol 14 ') was coated by ODF method using the dispenser by Musashi engineering. The coated size was 45 mm × 45 mm, and R = 1 mm at the right angle part. Sealant FT-1 for fill (reference numeral 16) was dropped into the sealant composition DT-3 (reference numeral 14 ') at equal intervals at 10 × 10 locations. Using this sealing member (reference numeral 12), a vacuum bonding apparatus manufactured by Run Technical Service Co., Ltd., so that the thickness of the sealing agent layer (the coating film of the sealing agent composition DT-3) is 20 μm. The electronic element body (reference numeral 13) on which the protective layer (reference numeral 15) is formed is bonded, heated at 160 ° C. for 5 minutes, and solder particles of the sealant composition DT-3 (reference numeral 14 ′) (reference numeral 14a). ) Is melted and agglomerated to form a solder phase (reference numeral 14c), and a thermosetting liquid epoxy resin (reference numeral 14b in the upper diagram of FIG. 4) is thermally cured to give an epoxy resin (reference numeral 14b in the lower diagram of FIG. 4). ) Was formed, sealing agent composition joined body DT-3 (symbol 14) was formed, sealing was completed, and the organic photoelectric conversion element 301 which is an electronic device (symbol 10) was obtained.

<Evaluation of organic photoelectric conversion element>
Sample A before the durability test, Sample B subjected to the bending test in the same manner as the above (Evaluation of black spot: Durability test Bending test) and (Evaluation of the black spot: Durability test Thermal cycle) and Sample subjected to the thermal cycle C was left as an accelerated deterioration treatment in an environment of 60 ° C. and 90% RH for 1000 hr, and the open circuit voltage, the fill factor, and the photoelectric conversion efficiency were evaluated. Here, the sample A before the durability test refers to a sample in which neither the accelerated deterioration treatment nor the durability test is performed for the organic photoelectric conversion element 301. Sample B subjected to the bending test is 100 times as an durability test (bending test) for the organic photoelectric conversion element 301, which is wound on a cylinder having a diameter of 10 cm, left for 5 minutes, then spread on a plane and left for 5 minutes. Refers to the sample performed. The sample C subjected to the thermal cycle refers to a sample obtained by performing a thermal cycle of −40 ° C. to 85 ° C. 500 times as a durability test (thermal cycle) on the organic photoelectric conversion element 301.

<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 was calculated by the following formula. The evaluation results are shown in Table 2 below.

  As is clear from Table 2 above, it was confirmed that the organic photoelectric conversion element 301 of Example 13 did not show performance deterioration in durability evaluation, and good sealing performance was obtained. That is, the short-circuit current density before the accelerated deterioration treatment between the sample A before the durability test, the sample B after the durability test (bending test), and the sample C after the durability test (thermal cycle) is opened. There was no significant difference in voltage, fill factor and photoelectric conversion efficiency. Similarly, no significant difference was observed between the sample A and the samples B and C in the short-circuit current density, the open-circuit voltage, the fill factor, and the photoelectric conversion efficiency after the accelerated deterioration treatment. Furthermore, no significant difference was observed in the short-circuit current density, open-circuit voltage, fill factor, and photoelectric conversion efficiency before and after the accelerated degradation process for each sample, and no performance degradation due to the accelerated degradation process was observed. From the above, it was confirmed that good sealing performance was obtained.

1 Laminated film in which an inorganic layer is formed on a support (a),
2 Support (A),
3 an inorganic layer comprising oxygen-containing silicon carbide,
10 electronic devices,
11 substrate,
12 sealing member,
13 Electronic element body,
14 Sealant composition,
14a metal particles,
14b resin,
14c metal phase,
15 protective layer,
16 Sealant for fill,
17 First electrode (anode),
18 hole transport layer,
19 light emitting layer,
20 electron transport layer,
21 Second electrode (cathode),
30 Adhesion auxiliary member,
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 Deposition roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 Take-up roller.

Claims (6)

A substrate;
A sealing member;
An electronic element body located between the base material and the sealing member;
A sealant composition assembly comprising a metal and a resin including a single metal or an alloy; and
Including
An electronic device in which the electronic element body is sealed by bonding the base material and the sealing member via the sealant composition assembly.   The electronic device according to claim 1, wherein a melting point of the metal is 80 to 200 ° C.   The electronic device according to claim 1, wherein the metal includes tin and at least one of indium and bismuth.   At least one of the base material and the sealing member assists adhesion between the base material and the sealing member, abuts on the sealant composition assembly, and has an adhesion auxiliary member made of metal. The electronic device according to claim 1. A substrate;
A sealing member;
An electronic element body located between the base material and the sealing member;
A sealant composition assembly comprising a metal and a resin including a single metal or an alloy; and
A method for manufacturing an electronic device, comprising:
Placing the electronic element body on the substrate;
A step of applying a sealant composition containing metal particles including a simple substance of metal or an alloy and a resin, which is a raw material for forming the sealant composition assembly on the sealing member;
Arranging the sealing member coated with the sealing agent composition so as to cover the base material and the electronic element body; and
Melting the metal particles in the sealant composition to form a metal phase that binds to the substrate and the sealing member;
Curing the resin in the sealant composition and forming the sealant composition assembly;
A method for manufacturing an electronic device, comprising: A sealant composition that is cured by external energy and used for sealing an electronic device,
Including metal particles including a simple metal or an alloy, and a resin,
The viscosity of the sealant composition when the metal particles are removed from the sealant composition after being left for 1 minute at the melting point of the metal particles included in the sealant composition is 1 Pa · s. The sealing composition for electronic devices which is below and the viscosity in 25 degreeC before hardening is 100-1000 Pa.s.