JP5835083B2 - Organic electronics devices - Google Patents

Description

  The present invention relates to organic electronic devices.

  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. On the other hand, in recent years, with the spread of electronic devices, weight reduction, bendability, improved portability by preventing cracking, expansion of installation location by followability to curved surfaces, production cost by roll-to-roll production Reduction of such is desired. For this reason, an electronic device using a flexible resin base material as a base material instead of glass has been proposed (see Patent Document 1). In such an electronic device, a flexible barrier film having sufficient barrier performance against oxygen and moisture, an adhesive that bonds at least a part of the flexible barrier film, and, if necessary, surrounded by the barrier film It is composed of an oxygen and moisture absorbing material provided in the vicinity of the electronic device.

  In general, a barrier film that can be used in an electronic device is formed by forming a thin film of a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide on a plastic substrate surface to form a barrier layer. As a film formation method, for example, an organic silicon compound typified by tetraethoxysilane (TEOS) is used, and a chemical deposition method (plasma CVD method: Chemical Vapor Deposition, in which oxygen plasma oxidation is performed under reduced pressure on a substrate. Patent Document 2) and physical deposition methods (e.g., vacuum vapor deposition and sputtering methods; see Patent Documents 3 to 5) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen. Gas phase methods are known.

  In contrast to the above vapor phase method, although it is a vapor phase method, an inorganic film formed by an atomic phase growth method or an atomic layer deposition method (hereinafter also referred to as an ALD (Atomic Layer Deposition) method) has few defects and is good. Gas barrier properties are expected to be obtained.

  Further, as one of the methods for forming a gas barrier layer that does not depend on the gas phase method as described above, a coating layer formed by applying a solution of an inorganic precursor compound on a substrate and drying it is modified by heat or light. Studies have been made to improve the gas barrier property by improving the quality, and in particular, studies have been made to develop a high gas barrier property by using polysilazane as the inorganic precursor compound (see Patent Document 6).

International Publication No. 2009/086095 JP 2009-101548 A International Publication No. 2012/003198 International Publication No. 2011-013341 JP 2007-73332 A JP 2011-194319 A

  When an electronic device is sealed using such a conventional barrier film, an adhesive or a sealant is used. However, since the barrier layer of the barrier film has a very dense structure, the electronic device There is a problem that the durability of the bonded portion between the film and the barrier film is low, and the durability of the electronic device is lowered. In particular, in the case of a flexible barrier film, there is a problem that the durability of the bonded portion against repeated bending is low.

  Further, when the crosslink density of the adhesive is increased and the added amount of filler or the like is increased in order to reduce the permeability of oxygen or moisture, the tendency becomes remarkable.

  This invention is made | formed in view of the said subject, and it aims at providing the organic electronics device excellent in durability.

  The present inventor has intensively studied to solve the above problems. As a result, a sealing agent layer containing a first sealing agent having a Shore D hardness of 80 or more after curing and a second sealing agent having a Shore D hardness of less than 80 after curing is provided with a gas barrier property. It has been found that the above problem can be solved by providing the film between the film and the sealing member, and the present invention has been completed.

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

  1. A gas barrier film having a base material and a barrier layer, a sealing member, an organic element and a sealing agent layer located between the gas barrier film and the sealing member, and the sealing agent. The organic electronic device, wherein the layer includes a first sealant having a Shore D hardness of 80 or more after curing, and a second sealant having a Shore D hardness of less than 80 after curing.

2. The water vapor permeability after curing of the first sealant is 20 g / m ² · day or less, and the water vapor permeability after curing of the second sealant is 50 g / m ² · day or less, Above 1. Organic electronic devices as described in 1.

  3. The second sealing agent is disposed in a central portion in the surface direction, and the first sealing agent is disposed in an outer peripheral portion surrounding the central portion. Or 2. Organic electronic devices as described in 1.

  4). 2. The second sealing agent is further disposed outside the outer peripheral portion. Organic electronic devices as described in 1.

  5. The sealing member contains a metal or a metal compound. ~ 4. Organic electronic device as described in any one of these.

  6). The barrier layer is formed by modifying a layer containing polysilazane. ~ 5. Organic electronic device as described in any one of these.

  7). The barrier layer is a laminate of an inorganic layer and an organic layer. ~ 5. Organic electronic device as described in any one of these.

  8). The first sealing agent includes at least one of an epoxy resin and an acrylic resin. ~ 7. Organic electronic device as described in any one of these.

  9. The second sealing agent includes at least one selected from the group consisting of a polyolefin resin, a fluororesin, and a polyvinylidene chloride resin. ~ 8. Organic electronic device as described in any one of these.

  10. The sealing agent layer is formed by a liquid crystal dropping method. ~ 9. Organic electronic device as described in any one of these.

  ADVANTAGE OF THE INVENTION According to this invention, the organic electronics device excellent in durability is provided.

1 is a schematic cross-sectional view illustrating an organic electronic device according to an embodiment of the present invention. It is a schematic diagram which shows an example of the arrangement | positioning form of the surface direction of sealing agent. It is a cross-sectional schematic diagram of a vacuum ultraviolet irradiation device.

  The present invention has a gas barrier film having a base material and a barrier layer, a sealing member, and an organic element and a sealing agent layer located between the gas barrier film and the sealing member, The said sealing agent layer contains the 1st sealing agent whose Shore D hardness after hardening is 80 or more, and the 2nd sealing agent whose Shore D hardness after hardening is less than 80, Organic electronics Regarding devices.

  FIG. 1 is a schematic cross-sectional view illustrating an organic electronic device according to an embodiment of the present invention. An organic electronic device 10 shown in FIG. 1 includes an organic element 13 and a sealant layer 14 between a gas barrier film having a base material 11 and a barrier layer 12 and a sealing member 15.

  The sealant layer 14 includes a first sealant having a Shore D hardness of 80 or more after curing, and a second sealant having a Shore D hardness of less than 80 after curing. The first sealing agent having a high Shore D hardness after curing mainly plays a role of improving gas barrier properties, and the second sealing agent having a low Shore D hardness after curing mainly has an adhesive property. Play a role to improve. By setting it as such a structure, the gas barrier property and adhesiveness of a sealing agent layer improve, and the organic electronics device excellent in durability can be obtained.

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

[Gas barrier film]
The gas barrier film according to the present invention has a base material and a barrier layer, and has other layers as necessary.

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

<Base material>
The base material used in the gas barrier film according to the present invention is a long support, and can hold a barrier layer having a gas barrier property described later (also simply referred to as “barrier property”), Although formed with the following materials, it is not limited to these.

  Examples of the substrate 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), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide, etc. Heat-resistant transparent films having a silsesquioxane having a hybrid structure as a basic skeleton (for example, product name Sila-DEC; manufactured by Chisso Corporation, and product name Silplus (registered trademark); manufactured by Nippon Steel Chemical Co., Ltd.); It can is mentioned consists resin film by laminating the resin two or more layers.

  In terms of cost and availability, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used, and optical transparency, heat resistance, and barrier layer In terms of adhesion, a heat-resistant transparent film having a basic skeleton of silsesquioxane having an organic-inorganic hybrid structure 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 substrate, when the substrate is placed at a high temperature and the substrate temperature rises, the substrate temperature becomes the glass transition temperature. If it exceeds 1, the elastic modulus of the base material is drastically reduced, and the base material is stretched by tension, which may cause damage to the barrier layer. 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 base material. 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 base material due to humidity becomes larger, so that it becomes a barrier layer. There is a concern of damage. However, even when these heat-resistant materials are used as a base material, by forming a barrier layer on both sides, dimensional changes due to moisture absorption and desorption of the base film itself under severe conditions of high temperature and high humidity are suppressed. And damage to the barrier layer can be suppressed. Therefore, it is one of the more preferable embodiments to use a heat resistant material as a base material and to form a barrier layer on both surfaces.

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

  Moreover, it is preferable that a base material is transparent. Here, the base material is transparent means that the light transmittance of visible light (400 to 700 nm) is 80% or more.

  Since the base material is transparent and the barrier layer formed on the base material 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 base material using the above-described resins or the like may be an unstretched film or a stretched film.

  The base material according to the present invention can be produced by a conventionally known general method. For example, an unstretched substrate 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 base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis).

  The draw ratio in this case can be appropriately selected according to the resin as the raw material of the base material, 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 base material which concerns on this invention, before forming a barrier layer, you may give a corona treatment to the surface.

  As the surface roughness of the substrate 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.

  Moreover, it is preferable that the centerline average surface roughness (Ra) prescribed | regulated by JISB0601: 2001 is in the range of 0.5-12 nm in the base-material surface, and it is more preferable that it exists in the range of 1-8 nm.

<Barrier layer>
The material of the 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 ), Metal oxides such as boron carbide, tungsten carbide, 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 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 barrier layer is not particularly limited, and includes, for example, a sputtering method (for example, magnetron cathode sputtering, flat plate magnetron sputtering, two-pole AC flat plate magnetron sputtering, two-pole AC rotary magnetron sputtering), a vapor deposition method (for example, resistance heating). Vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD method, catalytic chemical vapor deposition (Cat-CVD), capacitively coupled plasma CVD method (CCP-CVD), photo CVD method, plasma CVD method And chemical vapor deposition methods such as an epitaxial growth method, an atomic layer growth method, and a reactive sputtering method.

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

  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 organic oligomer to the substrate to form a 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 substrate. 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 solution containing an inorganic precursor such as polysilazane, tetraethyl orthosilicate (TEOS), etc., is wet-coated on a substrate and then subjected to a modification treatment by irradiation with vacuum ultraviolet light, etc. The barrier layer is also formed by film metallization techniques such as metal plating on the base material and adhesion of the metal foil and the resin base material.

  From the viewpoint of obtaining high barrier properties and the effects of the present invention more effectively, the 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.

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

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

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

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

In the present invention, perhydropolysilazane, in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms, is particularly preferred from the viewpoint of the denseness of the resulting barrier layer as a film.

  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 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. (Example 1 mass%). 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 for the modification treatment, a coating liquid containing polysilazane is applied on a substrate 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.

Here, the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and becomes a specific composition of SiO _x N _y will be described by taking perhydropolysilazane as an example.

Perhydropolysilazane can be represented by a composition of “— (SiH ₂ —NH) _n —”. In the case of SiO _x N _y , x = 0 and y is 1 at maximum. Since actual perhydropolysilazane has a cyclic structure, y is less than 1 and is considered to be around 0.8. In order to satisfy x> 0, an external oxygen source is required. This is because (i) oxygen and moisture contained in the polysilazane coating solution, and (ii) oxygen taken into the coating film from the atmosphere during the coating and drying process. As an outgas from the substrate side due to oxygen, moisture, ozone, singlet oxygen taken into the coating film from the atmosphere in the vacuum ultraviolet irradiation process, (iv) heat applied in the vacuum ultraviolet irradiation process, etc. Oxygen and moisture moving into the coating film, (v) When the vacuum ultraviolet irradiation process is performed in a non-oxidizing atmosphere, when moving from the non-oxidizing atmosphere to the oxidizing atmosphere, Oxygen, moisture, etc. taken into the coating film become oxygen sources.

  On the other hand, for y, the condition under which nitriding proceeds rather than the oxidation of Si is considered to be very special, so basically 1 is the upper limit.

  Also, from the relationship of Si, O, and N bond, x and y are basically in the range of 2x + 3y ≦ 4. In the state of y = 0 where the oxidation has progressed completely, the coating film contains silanol groups, and there are cases where 2 <x <2.5.

  The reaction mechanism presumed to produce silicon oxynitride and further silicon oxide from perhydropolysilazane in the vacuum ultraviolet irradiation step will be described below.

(I) Dehydrogenation and accompanying Si—N bond formation Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation, etc., and in an inert atmosphere, Si— It is considered that they are recombined as N (a dangling bond of Si may be formed). That is, the cured as SiN _y composition without oxidizing. In this case, the polymer main chain is not broken. The breaking of Si—H bonds and N—H bonds is promoted by the presence of a catalyst and heating. The cut H is released out of the membrane as H ₂ .

(II) Formation of Si—O—Si Bonds by Hydrolysis / Dehydration Condensation Si—N bonds in perhydropolysilazane are hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. Two Si—OHs are dehydrated and condensed to form Si—O—Si bonds and harden. This is a reaction that occurs in the air, but during vacuum ultraviolet irradiation in an inert atmosphere, water vapor generated as outgas from the base material by the heat of irradiation is considered to be the main moisture source. When the water is excessive, Si—OH that cannot be dehydrated and condensed remains, and a cured film having a low gas barrier property represented by a composition of SiO _2.1 to SiO _2.3 is obtained.

(III) Direct oxidation by singlet oxygen, formation of Si—O—Si bond When a suitable amount of oxygen is present in the atmosphere during irradiation with vacuum ultraviolet rays, singlet oxygen having a very strong oxidizing power is formed. H or N in the perhydropolysilazane is replaced with O to form a Si—O—Si bond and harden. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

(IV) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation / excitation Since the energy of vacuum ultraviolet light is higher than the bond energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved, and oxygen, It is considered that when an oxygen source such as ozone or water is present, it is oxidized to form a Si—O—Si bond or a Si—O—N bond. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

When the composition of the barrier layer formed from polysilazane is expressed by SiO _x N _y , a region where 0.25 ≦ x ≦ 1.1 and 0.4 ≦ y ≦ 0.75 is formed in the thickness direction. It is one of the preferred embodiments to have 50 nm or more. The thickness of the barrier layer is preferably in the range of 50 nm to 1 μm, more preferably in the range of 100 nm to 700 nm, and even more preferably in the range of 150 nm to 500 nm.

  Here, the composition distribution in the thickness direction of the barrier layer can be obtained by measurement by the following method using XPS analysis.

Since the etching rate of the barrier layer varies depending on the composition, in the present invention, the thickness in the XPS analysis is obtained once based on the etching rate in terms of SiO ₂ , and the thickness of the barrier layer is determined from the cross-sectional TEM image of the same sample. The region corresponding to the barrier layer in the composition distribution in the thickness direction is specified while comparing this with the composition distribution in the thickness direction obtained from the XPS analysis, and the region corresponding to the barrier layer is determined from the cross-sectional TEM image. Correction in the thickness direction is performed by uniformly applying a coefficient so as to match the obtained film thickness.

  The region where the composition x, y of the barrier layer is in the above range is a region having good gas barrier properties.

If x is 0.25 or more, the modification is sufficient and sufficient gas barrier properties can be exhibited.
In the above-described modification estimation mechanism, the oxidation during modification may break the —Si—N—Si— bond, which is the main chain of polysilazane, and replace O with N. It is considered that the modified polysilazane bond is recombined as a finer structure. Therefore, it is considered that sufficient gas barrier properties can be obtained when a certain amount or more of O is present. When x is 1.1 or less, it is possible to suppress a decrease in water vapor capturing ability (capable of being oxidized), and as a result, it is possible to suppress an increase in water vapor permeability as a barrier layer.

  If y is 0.4 or more, the oxidation of polysilazane can be advanced moderately, the fall of water vapor capture ability (capability which can be oxidized) can be suppressed, and the raise of the water vapor permeability as a gas barrier layer can be controlled. When y is 0.75 or less, it is sufficiently modified to obtain a sufficient gas barrier property. The composition distribution in the thickness direction of the gas barrier layer can be obtained by measurement by a method using fulfilled underground XPS analysis.

In the vacuum ultraviolet irradiation process of the present invention, the illuminance of the vacuum ultraviolet light on the coating surface received by the polysilazane layer coating is preferably 30 mW / cm ² or more and 200 mW / cm ² or less, and 50 mW / cm ² or more and 160 mW / cm. More preferably, it is ² or less. If it is 30 mW / cm ² or more, a sufficient modification effect is obtained, and if it is 200 mW / cm ² or less, generation of ablation to the coating film and damage to the substrate can be prevented.

  Although the time of vacuum ultraviolet light irradiation changes also with a base material to be used, a composition, a density | concentration, etc. of a polysilazane layer, it is 0.1 second-10 minutes normally, Preferably it is 0.5 second-3 minutes.

Irradiation energy amount of the VUV in the polysilazane coating film surface is preferably in a range from 200 mJ / cm ² or more 5000 mJ / cm ² or less, and more preferably 500 mJ / cm ² or more 3000 mJ / cm ² or less. If 200 mJ / cm ² or more can be sufficiently reformed, if 5000 mJ / cm ² or less, it is possible to prevent thermal deformation of cracking and base barrier layer due to excessive modification.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. Atoms of noble gases such as Xe, Kr, Ar, and Ne are called inert gases because they are not chemically bonded to form molecules.

However, excited atoms of rare gases that have gained energy by discharge or the like can form molecules by combining with other atoms. When the rare gas is xenon, the following chemical formula is obtained, and when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted.

  A feature of the excimer lamp is that the radiation is concentrated at one wavelength, and only the necessary light is not emitted, so that the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

  In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge is a gas space created by placing a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. When the micro discharge streamer reaches the tube wall (dielectric), the electric discharge accumulates on the surface of the dielectric and the micro discharge disappears.

  This micro discharge spreads over the entire tube wall, and is a discharge that is repeatedly generated and extinguished. For this reason, flickering of light that can be seen with the naked eye occurs. Moreover, since a very high temperature streamer reaches a pipe wall directly locally, there is a possibility that deterioration of the pipe wall may be accelerated.

  As a method for efficiently obtaining excimer light emission, electrodeless electric field discharge is possible in addition to dielectric barrier discharge. Electrodeless electric field discharge by capacitive coupling, also called RF discharge. The lamp and electrodes and their arrangement may be basically the same as for dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless field discharge can provide a spatially and temporally uniform discharge in this way, a long-life lamp without flickering can be obtained.

  In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes. Therefore, in order to cause discharge in the entire discharge space, the outer electrode covers the entire outer surface and transmits light to extract light to the outside. Must be a thing.

  For this reason, an electrode in which a fine metal wire is formed in a net shape is used. Since this electrode uses as thin a line as possible so as not to block light, it is easily damaged by ozone generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to provide an atmosphere of an inert gas such as nitrogen around the lamp, that is, the inside of the irradiation apparatus, and provide a synthetic quartz window to extract the irradiation light. Synthetic quartz windows are not only expensive consumables, but also cause light loss.

  Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in distance to the irradiation surface cannot be ignored between the position directly below the lamp axis and the side surface of the lamp, resulting in a large difference in illuminance. Therefore, even if the lamps are closely arranged, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

  When electrodeless field discharge is used, it is not necessary to make the external electrodes mesh. The glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the lamp outer surface. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is as large as in the case of the dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

  The biggest feature of the capillary excimer lamp is its simple structure. The quartz tube is closed at both ends, and only gas for excimer light emission is sealed inside.

  The outer diameter of the tube of the thin tube lamp is about 6 nm to 12 mm, and if it is too thick, a high voltage is required for starting.

  As the form of discharge, either dielectric barrier discharge or electrodeless field discharge can be used. The electrode may have a flat surface in contact with the lamp, but if the shape is matched to the curved surface of the lamp, the lamp can be firmly fixed and the discharge is more stable when the electrode is in close contact with the lamp. Also, if the curved surface is made into a mirror surface with aluminum, it also becomes a light reflector.

  The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating organic bonds has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane layer can be modified in a short time.

  Therefore, compared with low-pressure mercury lamps with wavelengths of 185 nm and 254 nm and plasma cleaning, it is possible to shorten the process time associated with high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are easily damaged by heat. .

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated with a single wavelength in the ultraviolet region, so that an increase in the surface temperature of the object to be fired is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

(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.

  The oxygen concentration at the time of irradiation with vacuum ultraviolet rays (VUV) according to the present invention is preferably 10 to 10,000 ppm by volume, more preferably 50 to 5000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

  The barrier layer may be a single layer or a multilayer structure of two or more layers.

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

  Examples of the material used for the intermediate layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl-modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. More than one species can be used in combination.

Conventionally known additives can be added to these intermediate layer forming materials. The intermediate layer is formed by coating on a support by a known method such as roll coating, die coating, gravure coating, knife coating, dip coating, spray coating, etc., and drying and removing the solvent, diluent, and the like. be able to. The coating amount of the intermediate layer is preferably about 0.1 to 5.0 g / m ² (dry state).

  The intermediate layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

(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 substrate on which the protrusions and the like exist, or to fill the unevenness and pinholes generated in the barrier layer by the protrusions existing on the substrate to flatten the surface. It is done. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specifically, as a thermosetting material, Tutprom series (Organic polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid silicone manufactured by Adeka, Unidick manufactured by DIC, Inc. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra high heat resistance epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coat, thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyamidoamine-epichlorohydrin resin, etc. It is below.

  The method for forming the smooth layer is not particularly limited, but it is formed by a wet coating method such as a spin coating method, a die coating method, a spray method, a blade coating method, a dip method or a gravure printing method, or a dry coating method such as a vapor deposition method. It is preferable.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The smoothness of the smooth layer is preferably such that the center line average roughness Ra defined by JIS B0601: 2001 is 0.5 to 12 nm. More preferably, it is 1 to 3 nm. Moreover, it is preferable in the smooth layer surface that 10 point average roughness Rz prescribed | regulated by JISB0601: 2001 is 5-50 nm. More preferably, it is 10-40 nm. When the value is smaller than this range, when the coating layer contacts the smoothing layer surface in a coating method such as a wire bar or a wireless bar at the stage of forming the coating layer described later, the coating property is impaired. There is. Moreover, when larger than this range, smoothing will become inadequate with respect to the surface roughness of a base material, and the meaning which provides a smooth layer will fade.

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm, and more preferably in the range of 2 to 7 μm.

(Bleed-out prevention layer)
The gas barrier film according to the present invention may have a bleed-out preventing layer on the base material surface opposite to the surface on which the 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 unreacted oligomers migrate from the film base material to the surface when the film having the smooth layer is heated and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.

  The unsaturated organic compound having a polymerizable unsaturated group that can be contained as a hard coat agent in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule. Or a mono-unsaturated organic compound having one polymerizable unsaturated group in the molecule can be exemplified.

  As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable. As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

  The bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator and the like as other components of the hard coat agent and the mat agent.

  The bleed-out prevention layer as described above is formulated as a coating solution with a hard coating agent, a matting agent, and other components as necessary, and appropriately prepared as a dilution solvent to support the coating solution. It can form by apply | coating to a body film surface by a conventionally well-known coating method, and then irradiating with ionizing radiation and hardening.

  Examples of the material used in the bleed-out prevention layer include a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) series manufactured by JSR Corporation.

  As a method of irradiating with ionizing radiation, ultraviolet rays having a wavelength range of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated or scanned. The irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a type or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer is in the range of 1.0 to 10 μm from the viewpoint of improving the heat resistance of the film, facilitating the balance adjustment of the optical properties of the film, and adjusting the curl of the gas barrier film. Preferably, it is more preferable to set it in the range of 2 μm to 7 μm.

(Overcoat layer)
An overcoat layer may be provided on the 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. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured. Here, the “crosslinkable group” is a group capable of crosslinking the resin by a chemical reaction that occurs in the light irradiation treatment or heat treatment. The chemical structure is not particularly limited as long as it has such a function, but examples of the functional group capable of addition polymerization include cyclic ether groups such as an ethylenically unsaturated group, an epoxy group, and an oxetanyl group. Moreover, the functional group which can become a radical by light irradiation may be sufficient, As such a crosslinkable group, a thiol group, a halogen atom, an onium salt structure etc. are mentioned, for example. Among these, an ethylenically unsaturated group is preferable and includes functional groups described in paragraphs 0130 to 0139 of JP2007-17948A.

  As the organic-inorganic composite resin, for example, an organic-inorganic composite resin described as “ORMOCER (registered trademark)” in US Pat. No. 6,503,634 can be preferably used.

  The elastic modulus of the overcoat layer can be adjusted to a desired value by appropriately adjusting the structure of the organic resin, the density of the polymerizable group, the density of the crosslinkable group, the ratio of the crosslinking agent, and the curing conditions.

  Specific examples of the organic resin composition include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, and urethane acrylate. And a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Examples of the reactive monomer having at least one photopolymerizable unsaturated bond in the molecule include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n- Pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, di Cyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, group Sidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol Diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripro Lenglycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, Propion oxide modified pentaerythritol triacrylate, propion oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanediol triacrylate, 2,2 , 4 -Trimethyl-1,3-pentadiol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, and acrylate instead of acrylate, γ-methacryloxypropyltrimethoxysilane , 1-vinyl-2-pyrrolidone and the like. Said reactive monomer can be used as a 1 type, 2 or more types of mixture, or a mixture with another compound.

  The composition of the photosensitive resin contains a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino acetophenone, 4,4-dichloro. Benzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p- tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyl acetal, benzoy Methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis (p-azide Benzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (O-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxy , Michler's ketone, 2-methyl [4- (methylthio) phenyl] -2-monoforino-1-propane, 2-benzyl-2-dimethylamino-1- (4-monoforinophenyl) -butanone-1, naphthalenesulfonyl chloride Quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabrominated, tribromophenyl sulfone, benzoin peroxide And combinations of photoreducing dyes such as eosin and methylene blue and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used alone or in combination of two or more. .

  The overcoat layer can contain an inorganic material. Inclusion of an inorganic material generally leads to an increase in the elastic modulus of the overcoat layer. The elastic modulus of the overcoat layer can also be adjusted to a desired value by appropriately adjusting the content ratio of the inorganic material.

  As the inorganic material, inorganic fine particles having a number average particle diameter of 1 to 200 nm are preferable, and inorganic fine particles having a number average particle diameter of 3 to 100 nm are more preferable. As the inorganic fine particles, metal oxides are preferable from the viewpoint of transparency.

_{There is} no particular restriction as the metal _{oxide, SiO 2, Al 2 O 3} , TiO 2, ZrO 2, ZnO, SnO 2, In 2 O 3, BaO, SrO, CaO, MgO, VO 2, V 2 O 5, _{CrO 2, MoO 2, MoO 3} , MnO 2, Mn 2 O 3, WO 3, LiMn 2 O 4, Cd 2 SnO 4, CdIn 2 O 4, Zn 2 SnO 4, ZnSnO 3, Zn 2 In 2 O 5, Examples thereof include Cd ₂ SnO ₄ , CdIn ₂ O ₄ , Zn ₂ SnO ₄ , ZnSnO ₃ , and Zn ₂ In ₂ O ₅ . These may be used alone or in combination of two or more.

  It may be adjusted to obtain a dispersion of inorganic fine particles, or a commercially available inorganic fine particle dispersion may be used.

  Specifically, for example, Snowtex (registered trademark) series and organosilica sol manufactured by Nissan Chemical Industries, Ltd., NANOBYK (registered trademark) series manufactured by Big Chemie Japan Co., Ltd., NanoDur (registered trademark) manufactured by Nanophase Technologies, etc. And a dispersion of various metal oxides.

  These inorganic fine particles may be subjected to surface treatment.

Other inorganic materials include mica groups such as natural mica and synthetic mica, and tabular fine particles such as talc, teniolite, montmorillonite, saponite, hectorite, and zirconium phosphate represented by 3MgO.4SiO.H ₂ O. it can.

More specifically, examples of the natural mica include muscovite, soda mica, phlogopite, biotite, sericite, and the like. Further, as the synthetic mica, non-swelling mica such as fluorine phlogopite mCM ₃ (AlSi ₃ O ₁₀ ) F ₂ , potassium tetrasilicon mica KMg _2.5 (Si ₄ O ₁₀ ) F ₂ , and Na tetrasilic mica NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ , Na or Li Teniolite (Na, Li) Mg ₂ Li (Si ₄ O ₁₀ ) F ₂ , Montmorillonite Na or Li Hectorite (Na, Li) _1/8 Examples thereof include swellable mica such as Mg _2/5 Li _1/8 (Si ₄ O ₁₀ ) F ₂ . Synthetic smectite is also useful.

  The ratio of the inorganic material in the overcoat layer is preferably in the range of 10 to 95% by mass, and more preferably in the range of 20 to 90% by mass with respect to the entire overcoat layer.

  In the overcoat layer, a so-called coupling agent can be used alone or mixed with other materials. The coupling agent is not particularly limited, such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, but a silane coupling agent is preferable from the viewpoint of the stability of the coating solution.

  Specific examples of the silane coupling agent include halogen-containing silane coupling agents (2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane). Etc.), epoxy group-containing silane coupling agent [2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) ) Propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane], amino group Silane coupling agents (2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane, etc.) , Mercapto group-containing silane coupling agents (2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents (vinyltrimethoxysilane, vinyltrimethoxysilane, Ethoxysilane), ( ) Acryloyl group-containing silane coupling agent (2-methacryloyloxyethyltrimethoxysilane, 2-methacryloyloxyethyltriethoxysilane, 2-acryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxy Propyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, etc.). These silane coupling agents can be used alone or in combination of two or more.

  The overcoat layer is blended with the above organic resin and inorganic material, and other components as necessary, and prepared as a coating solution with a diluting solvent used as necessary, and the coating solution is conventionally known on the substrate surface. It is preferable to form the film by applying the ionizing radiation and curing it by irradiating with ionizing radiation. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The overcoat layer can also be cured by irradiation with the above-described excimer lamp. When the barrier layer and the overcoat layer are applied and formed on the same line, the overcoat layer is preferably cured by irradiation with an excimer lamp.

[Sealing member]
The sealing member according to the present invention is the same as the gas barrier film. That is, it preferably contains a metal or metal compound. Further examples of specific materials used as the sealing member include silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), titanium (Ti), and copper (Cu). , At least one metal selected from the group consisting of cerium (Ce) and tantalum (Ta), or a metal compound such as an oxide, nitride, carbide, oxynitride or oxycarbide of the above metal. .

  Further, the sealing member may be a member composed only of a barrier layer having no base material among the gas barrier films. 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 gas barrier film, the description thereof is omitted here. When the sealing substrate is a gas barrier film, the sealing substrate 11 and the gas barrier film 15 may have the same configuration or different configurations (materials, layer configurations).

[Sealing agent layer]
The sealant layer according to the present invention is located between the gas barrier film and the sealing member. The encapsulant that forms the encapsulant layer has sufficient barrier properties and delays the entry of oxygen and / or moisture into the device. The sealing agent layer includes a first sealing agent having a Shore D hardness of 80 or more after curing, and a second sealing agent having a Shore D hardness of less than 80 after curing. Thereby, both a gas barrier property and adhesiveness improve, and the sealing agent layer with which durability improved is formed. Therefore, the organic electronic device of the present invention having such a sealant layer is excellent in durability.

  Examples of the resin (crosslinked resin) contained in the first sealant include, for example, an epoxy resin, an acrylic resin, an ionomer resin, a urethane resin, an ethylene-vinyl acetate copolymer resin, and the like. Especially, it is more preferable that at least one of an epoxy resin and an acrylic resin is included.

  Examples of the resin (crosslinked resin) contained in the second sealing agent include, for example, an epoxy resin, an acrylic resin, a polyolefin resin, a fluororesin, and a polyvinylidene chloride resin. Among these, it is more preferable to include at least one selected from the group consisting of polyolefin resins, fluororesins, and polyvinylidene chloride resins.

  In addition, you may use these resin individually or in combination of 2 or more types.

  The content of the resin in the sealant is preferably 20 to 80 parts by mass with the total amount of the sealant being 100 parts by mass in both the first sealant and the second sealant.

  The first sealing agent and the second sealing agent may include a curing agent. 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 is preferably 20 to 60 parts by mass with the total amount of the sealant being 100 parts by mass for both the first sealant and the second sealant. .

  The first sealant and the second sealant 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- ( Curing catalyst such as 2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, silane coupling agent, curing accelerator, ionic liquid, lithium salt, inorganic Fillers, softeners, antioxidants, anti-aging agents, stabilizers, tackifier resins, leveling agents, antifoaming agents, plasticizers, dyes, pigments (colored pigments, extender pigments, etc.), processing agents, UV blockers, fluorescence Examples include brighteners, dispersants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, and lubricants.

  The viscosity of the first sealant and the second sealant at 25 ° C. before curing is preferably 100 to 300,000 mPa · s. The viscosity can be measured by the method described in the examples.

  The curing method of the first sealing agent and the second sealing agent is not particularly limited, and examples thereof include heating, ultraviolet irradiation, and electron beam irradiation.

  The Shore D hardness after curing of the first sealant is preferably 83 or more, more preferably 85 or more. Further, the Shore D hardness after curing of the second sealant is preferably 75 or less, and more preferably 70 or less.

  The Shore D hardness after curing of the sealant can be adjusted by appropriately selecting the resin of the sealant to be used, but it is adjusted by a method of introducing a polymer having a flexible structure into the sealant. You may go. Examples of flexible structures include polyolefin structures such as polyethylene, polyisobutylene, and polybutadiene, (meth) acrylic acid ester polymer chains having a glass transition point (Tg) of 30 ° C. or less, such as polybutyl acrylate, and (meth) acrylonitrile-butadiene. A structure such as a copolymer is preferably used. Such a flexible structure is obtained by adding a polymer (elastomer or resin) exemplified above to the sealant, or by adding a reactive functional group such as an amino group, a carboxyl group, or a hydroxyl group at the terminal or inside of the polymer. It can also be introduced by a method of adding and reacting with a reactive group of the resin of the sealant.

  The addition amount in the case of adding such a polymer is preferably 5 to 30 parts by mass with the total amount of the sealant being 100 parts by mass for both the first sealant and the second sealant. .

The water vapor permeability after curing of the sealant can be appropriately adjusted depending on the type of resin to be used, the crosslinking density, the amount of inorganic filler, and the like. However, there is a tendency that the water vapor permeability is reduced by the crosslinking density, inorganic filler, etc., the hardness of the sealant is increased, and the adhesiveness is decreased. Therefore, the water vapor permeability after curing of the first sealant is preferably 30 g / m ² · day or less, and more preferably 20 g / m ² · day or less. Further, the water vapor permeability after curing of the second sealant is preferably 60 g / m ² · day or less, and more preferably 50 g / m ² · day or less. In addition, the water vapor permeability after hardening of sealing agent can be measured by the method as described in an Example.

  The placement of the sealant in the sealant layer is not particularly limited, but the second sealant having a small Shore D hardness after curing is placed in the center portion (portion C in FIG. 2) in the surface direction. It is preferable to arrange | position the 1st sealing agent with high Shore D hardness after hardening to the outer peripheral part (B part of FIG. 2) surrounding the said center part. Thus, the effect of this invention can be acquired more efficiently by arrange | positioning a 1st sealing agent and a 2nd sealing agent.

  In addition, by further disposing the second sealant on the outside of the outer peripheral portion (portion A in FIG. 2), the adhesion of the gas barrier film, the organic element, and the sealing member is further improved. It is preferable because an organic electronic device having higher durability can be obtained. At this time, the second sealant disposed in the center portion and the second sealant disposed outside the outer peripheral portion may be of the same type or different types.

  Particularly preferably, the second sealing agent is arranged on the upper part of the organic element (upper part 13 in FIG. 1), and the first sealing agent is placed on the upper part of the barrier layer on which the organic element is not mounted (FIG. 1). And the second sealing agent is further arranged outside the first sealing agent.

  As the sealant, a commercial product or a synthetic product (prepared product) may be used. Examples of commercially available products include, for example, Nukurel (registered trademark) AN4214C, AN4225C, AN4228C (above, Mitsui DuPont Polychemical Co., Ltd.), TB1655, TB3124, TB3125 (above, made by ThreeBond Co., Ltd.), DS6000 (above, Henkel Co., Ltd.), LP655, LP415 (manufactured by Dero Co., Ltd.).

  When preparing the sealing agent, for example, a method of stirring and mixing the resin, the curing agent, and other components as necessary at -20 to 40 ° C. for 1 to 24 hours is applied. The

  The formation method in particular of a sealing agent layer is not restrict | limited, For example, the method of apply | coating a liquid sealing agent and drying, the method of arrange | positioning a sheet-like sealing agent, etc. are mentioned.

  Examples of the liquid sealing agent coating method include a micro gravure coating method, a gravure coating method, a bar coating method, a wire bar coating method, a roll coating method, a dip coating method, a flexographic printing method, an offset printing method, and a screen printing method. Etc. A liquid crystal dropping method (ODF, One Drop Filling) in which a liquid sealant is applied with a dispenser is preferably used because of the ease of controlling the amount of sealant.

[Organic element]
The organic element according to the present invention is not particularly limited, and examples thereof include an organic photoelectric conversion element, an organic EL element, electronic paper, a liquid crystal display element, a thin film transistor, and a touch panel.

(Organic EL device)
Hereinafter, an organic EL element is demonstrated as an example about the structure of a specific organic element.

  The organic EL device according to the present invention is an organic EL structure (also referred to as a light emitting portion) having at least a first electrode, an organic functional layer including a light emitting layer, and a second electrode on a gas barrier film. As a specific example, an organic layer composed of a first electrode (anode), a hole transport layer, a light emitting layer, an electron transport layer, and a cathode buffer layer (electron injection layer) sequentially on the gas barrier film; An organic EL structure having a structure in which a second electrode (cathode) is laminated is adhered to a sealing substrate via the sealing agent layer of the present invention to form a sealed sealing structure.

Furthermore, typical layer constitution examples of the organic EL structure according to the present invention are shown below.
(1) Gas barrier film / first electrode (anode) / organic layer (light emitting layer) / second electrode (cathode) / sealing agent layer / sealing member;
(2) Gas barrier film / first electrode (anode) / organic layer (light emitting layer) / electron transport layer / second electrode (cathode) / sheet adhesive / gas barrier substrate 2;
(3) Gas barrier film / first electrode (anode) / hole transport layer / organic layer (light emitting layer) / hole blocking layer / electron transport layer / second electrode (cathode) / sealing agent layer / sealing member ;
(4) Gas barrier film / first electrode (anode) / hole transport layer (hole injection layer) / organic layer (light emitting layer) / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / Second electrode (cathode) / sealing agent layer / sealing member;
(5) Gas barrier film / first electrode (anode) / anode buffer layer (hole injection layer) / hole transport layer / organic layer (light emitting layer) / hole blocking layer / electron transport layer / cathode buffer layer (electrons) Injection layer) / second electrode (cathode) / sealing agent layer / sealing member;
(6) Gas barrier film / first electrode (anode) / anode buffer layer (hole injection layer) / hole transport layer / organic layer (light emitting layer) / hole blocking layer / electron transport layer / cathode buffer layer (electrons) Injection layer) / second electrode (cathode) / protective layer / sealing agent layer / sealing member.

[Organic EL structure]
Subsequently, the base material and each component layer which comprise the organic EL element which concerns on this invention are demonstrated (except the above-mentioned gas barrier film, a sealing agent layer, and a sealing member).

(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. Specific examples of such an electrode substance include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO2, and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ .ZnO) that can form a transparent conductive film may be used. Alternatively, a coatable substance such as an organic conductive compound can be used. In the case of taking out light emission from the first electrode (anode), it is desirable that the transmittance is larger than 10%, and the sheet resistance as the first electrode (anode) is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(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. The details are described in the second volume, Chapter 2, “Electrode Materials” (pages 123 to 166) of The details of the anode buffer layer (hole injection layer) are described in JP-A Nos. 9-45479, 9-260062, and 8-288069. Specific examples thereof include copper phthalocyanine. Examples thereof include a phthalocyanine buffer layer, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

(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. The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N′-diphenyl-N, N ′ Di (4-methoxyphenyl) -4,4′-diaminobiphenyl; N, N, N ′, N′-tetraphenyl-4,4′-diaminodiphenyl ether; 4,4′-bis (diphenylamino) quadriphenyl N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 ′-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino -(2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two described in US Pat. No. 5,061,569 Having a condensed aromatic ring of, for example, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-30 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 688 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  Alternatively, for example, as the hole transport layer, PEDOT / PSS (poly-3,4-ethylenedioxythiophene / polystyrene sulfonate) such as Baytron (trade name) Baytron (registered trademark) P, polyaniline and its doping material, The cyanide compounds described in International Publication No. 2006/019270 and the like can also be used.

(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. In the present invention, it is preferable that at least one blue light emitting layer is provided at a position closest to the anode among all the light emitting layers. When four or more light emitting layers are provided, for example, from the order close to the anode, for example, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting. Layered / green light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer / green light emitting layer / red light emitting layer, etc. It is preferable for improving luminance stability. A white element can be manufactured by forming a light emitting layer in multiple layers. The light emitting layer can also have the function of an electron transport layer.

  The total thickness of the light-emitting layer (thickness after drying) is not particularly limited, but is usually selected in the range of 2 nm to 5 μm, preferably 2 to 200 nm in consideration of film homogeneity, voltage necessary for light emission, and the like. It is. Furthermore, it is preferable that it exists in the range of 10-50 nm. A film thickness of 50 nm or less is preferable because it has the effect of improving the stability of the emission color with respect to the drive current as well as the voltage aspect. The film thickness (film thickness after drying) of each light emitting layer is preferably selected in the range of 2 to 100 nm, and more preferably in the range of 2 to 50 nm. Although there is no restriction | limiting in particular about the film thickness relationship of each light emitting layer of blue, green, and red, It is preferable that a blue light emitting layer (the sum total when there are multiple layers) is the thickest among three color light emitting layers.

  The light emitting layer includes at least three layers having different emission spectra, each having an emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm. If it is three or more layers, there will be no restriction | limiting in particular. When there are more than four layers, there may be a plurality of layers having the same emission spectrum. A layer having an emission maximum wavelength of 430 to 480 nm is referred to as a blue light emitting layer, a layer having a wavelength of 510 to 550 nm is referred to as a green light emitting layer, and a layer in the range of 600 to 640 nm is referred to as a red light emitting layer. Moreover, in the range which maintains the said maximum wavelength, you may mix a several luminescent compound in each light emitting layer. For example, a blue light emitting layer having a maximum wavelength of 430 to 480 nm and a green light emitting compound having the same wavelength of 510 to 550 nm may be mixed and used.

  The organic light emitting material used as the material of the light emitting layer is (a) charge injection function, that is, holes can be injected from the anode or hole injection layer when an electric field is applied, and electrons are injected from the cathode or electron injection layer. (B) a transport function, ie, a function of moving injected holes and electrons by the force of an electric field, and (c) a light emission function, ie, a recombination field of electrons and holes. However, there is no particular limitation as long as it has the three functions of connecting these to light emission. For example, fluorescent whitening agents such as benzothiazole, benzimidazole, and benzoxazole, and styrylbenzene compounds can be used. Specific examples of the above-mentioned optical brightener include 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) -1,3,4-thiadiazole in the benzoxazole series, 4 , 4′-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 4,4′-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxa Zoolyl] stilbene, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene, 2,5-bis [5-α, α-dimethylbenzyl-2-benzoxazoli Ru] thiophene, 2,5-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene, 2,5-bis (5-methyl) -2-benzoxazolyl) thiophene, 4,4′-bis (2 -Benzoxazolyl) biphenyl, 5-methyl-2- [2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazole, 2- [2- (4-chlorophenyl) vinyl Naphtho [1,2-d] oxazole and the like. Examples of the benzothiazole type include 2,2 ′-(p-phenylenedivinylene) -bisbenzothiazole, and examples of the benzimidazole type include 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole. 2- [2- (4-carboxyphenyl) vinyl] benzimidazole and the like. In addition, other useful compounds are listed in Chemistry of Synthetic Soybean (1971), pages 628-637 and 640. Specific examples of the styrylbenzene compound include 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl). ) Benzene, distyrylbenzene, 1,4-bis (2-ethylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene, 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like can be mentioned.

  Further, in addition to the above-described optical brightener and styrylbenzene compound, for example, 12-phthaloperinone, 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3- Butadiene, naphthalimide derivatives, perylene derivatives, oxadiazole derivatives, aldazine derivatives, pyrazirine derivatives, cyclopentadiene derivatives, pyrrolopyrrole derivatives, styrylamine derivatives, coumarin compounds, International Publication No. 90/13148, Appl. Phys. Lett. , Vol 58, 18, P1982 (1991), and aromatic dimethylidin compounds. Specific examples of the aromatic dimethylidin compounds include 1,4-phenylene dimethylidin, 4,4′-phenylene dimethylidin, 2,5-xylylene dimethylidin, 2,6-naphthylene dimethylidin, 1,4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 4,4′-bis (2,2-di-t-butylphenylvinyl) biphenyl, 4,4′-bis (2 , 2-diphenylvinyl) biphenyl and the like, and derivatives thereof. Specific examples of the compound represented by the general formula (I) include bis (2-methyl-8-quinolinolato) (p-phenylphenolate) aluminum (III), bis (2-methyl-8-quinolinolato). ) (1-naphtholate) aluminum (III) and the like.

  In addition, a compound in which the above-described organic light-emitting material is used as a host and the host is doped with a strong fluorescent dye from blue to green, for example, coumarin-based or the same fluorescent dye as the host, is also suitable as the organic light-emitting material. When the above-described compound is used as the organic light-emitting material, blue to green light emission (the emission color varies depending on the type of dopant) can be obtained with high efficiency. Specific examples of the host that is the material of the compound include organic light-emitting materials having a distyrylarylene skeleton (particularly preferably, 4,4′-bis (2,2-diphenylvinyl) biphenyl). Specific examples of the dopant of the material are diphenylaminovinylarylene (particularly preferably, for example, N, N-diphenylaminobiphenylbenzene and 4,4′-bis [2- [4- (N, N-di- -P-tolyl) phenyl] vinyl] biphenyl).

  The light emitting layer preferably contains a known host compound and a known phosphorescent compound (also referred to as a phosphorescent compound) in order to increase the light emission efficiency of the light emitting layer.

  The host compound is a compound contained in the light-emitting layer, the mass ratio in the layer is 20% or more, and the phosphorescence quantum yield of phosphorescence emission is 0.1 at room temperature (25 ° C.). Is defined as less than a compound. The phosphorescence quantum yield is preferably less than 0.01. A plurality of host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As these host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) are preferable. Known host compounds include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, Examples thereof include compounds described in 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837 and the like.

  In the case of having a plurality of light emitting layers, it is preferable that 50% by mass or more of the host compound in each layer is the same compound because it is easy to obtain a uniform film property over the entire organic layer. It is more preferable that the light emission energy is 2.9 eV or more because it is advantageous in efficiently suppressing energy transfer from the dopant and obtaining high luminance. Phosphorescence emission energy means the peak energy of the 0-0 band of phosphorescence emission when the photoluminescence of a deposited film of 100 nm is measured on a substrate with a host compound.

  The host compound has a phosphorescence emission energy of 2.9 eV or more and a Tg of 90 ° C. or more in consideration of deterioration of the organic EL device over time (decrease in luminance and film properties), market needs as a light source, and the like. Preferably there is. That is, in order to satisfy both luminance and durability, it is preferable that phosphorescence emission energy is 2.9 eV or more and Tg is 90 ° C. or more. Tg is more preferably 100 ° C. or higher.

  A phosphorescent compound (phosphorescent compound) is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. The compound is 0.01 or more at ° C. When used in combination with the host compound described above, an organic EL device with higher luminous efficiency can be obtained.

  The phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more. The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen), 4th edition, Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the phosphorescence quantum yield in any solvent.

  There are two types of light emission of the phosphorescent compound in principle. One is the recombination of the carrier on the host compound to which the carrier is transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound. The energy transfer type is to obtain light emission from the phosphorescent compound by moving to the other, and the other is that the phosphorescent compound becomes a carrier trap, and carrier recombination occurs on the phosphorescent compound, and the phosphorescent compound emits light. Although it is a carrier trap type in which light emission can be obtained, in any case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device. The phosphorescent compound is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), rare earth Of these, iridium compounds are the most preferred.

  In the present invention, the phosphorescence emission maximum wavelength of the phosphorescent compound is not particularly limited, and can be obtained in principle by selecting a central metal, a ligand, a ligand substituent, and the like. The emission wavelength can be changed.

  The light emission color of the organic EL device according to the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (Edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with a luminance meter CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

The white element referred to in the present invention means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X = 0.33 ± 0.07 when the front luminance at 2 ° viewing angle is measured by the above method. It is in the region of Y = 0.33 ± 0.07.

(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. The electron injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of the light emission. “Organic EL element and its forefront of industrialization (NST 30, November 30, 1998) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166). Details of the electron injection layer (cathode buffer layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. A metal buffer layer typified by lithium fluoride, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, an oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, as an electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the light emitting layer side, it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. As a material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodisides. Examples include methane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metal of these metal complexes is In, Mg, A metal complex replaced with Cu, Ca, Sn, Ga, or Pb can also be used as an electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. A distyrylpyrazine derivative can also be used as an electron transport material. Similarly to the hole injection layer and the hole transport layer, inorganic semiconductors such as n-type-Si and n-type-SiC are also used as an electron transport material. I can do it. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

Further, an electron transport layer having a high n property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such an electron transport layer having a high n property because an element with lower power consumption can be manufactured.
The external extraction efficiency at room temperature of light emission of the organic EL device according to the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

(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. The electron injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of the light emission. “Organic EL element and its forefront of industrialization (NST 30, November 30, 1998) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166). Details of the electron injection layer (cathode buffer layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. A metal buffer layer typified by lithium fluoride, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, an oxide buffer layer typified by aluminum oxide, etc. .

(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. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

  In order to transmit the emitted light, if either one of the first electrode (anode) or the second electrode (cathode) of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the said electrode substance (metal) with a film thickness of 1-100 nm as a 2nd electrode, by producing the electroconductive transparent material quoted by description of the 1st electrode on it, it is transparent or translucent A second electrode (cathode) can be produced, and by applying this, an element in which both the first electrode (anode) and the second electrode (cathode) are transmissive can be produced.

(Protective layer)
The organic electronic device 10 may have a protective layer on the organic element as necessary. The protective layer has a function of preventing deterioration of the organic element such as moisture and oxygen from entering the element, a function of making the organic element disposed on the sealing substrate 12 insulative, or It has a function to eliminate steps due to organic elements.

  The material for forming the protective layer is not particularly limited as long as it has the above function. For example, aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel ( Ni), cobalt (Co), copper (Cu), or alloys such as these, silicon oxide such as silica, aluminum oxide such as alumina, titanium oxide such as titania, indium oxide, tin oxide, indium tin oxide ( ITO), metal oxides such as tantalum oxide, zirconium oxide and niobium oxide; metal nitrides such as aluminum nitride, silicon nitride and boron nitride; metal carbides such as boron carbide, tungsten carbide and silicon carbide; aluminum oxynitride and oxynitride Metal oxynitrides such as silicon and boron oxynitride; metal oxide such as zirconium boride and titanium boride Monster, and a diamond-like carbon, and combinations of these.

  The method for forming the protective layer is not particularly limited. For example, sputtering; evaporation; chemical vapor deposition (CVD); plasma enhanced chemical vapor deposition (plasma CVD); inorganic oxide or nitride precursor (eg, sol-like polysilazane). Film metallization such as plating, spraying, spin coating, etc., by heating after wet coating and / or irradiation with vacuum ultraviolet light, etc .; plating; spraying; spin coating, etc. Formed using the technology used in the technology.

  Although the thickness of a protective layer is not specifically limited, For example, it is preferable that it is 10 nm-1 micrometer, and it is more preferable that it is 50-500 nm.

[Method for manufacturing organic electronic devices]
The method for producing the organic electronic device of the present invention is not particularly limited. For example, (1) after forming an organic element on a gas barrier film, a sealing agent layer on the gas barrier film and / or on the organic element. (2) After forming an organic element on the sealing member, a sealing agent layer is formed on the sealing member and / or the organic element. Then, a method of laminating and adhering a gas barrier film;

  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 sealant)
The components and composition ratios shown in Table 2 below were stirred at 10 ° C. for 4 hours to prepare sealants AD-1 to 10. In addition, the detail of each component shown in following Table 2 is as following Table 1, and the number of each component in following Table 2 represents a mass part. Moreover, as sealing agent AD-11, the Mitsui DuPont polychemical Co., Ltd. make and Nucrel (trademark) AN4228C (20-micrometer-thick sheet form) were prepared.

  The viscosity before curing, the water vapor permeability after curing (“WVTR” in Table 2), and the Shore D hardness after curing of each sealant were measured by the following methods.

Viscosity For AD-1 to AD-10, the viscosity was measured by a method according to ISO3219 at 25 ° C. using a rotational viscometer Viscomaster VT550 manufactured by Harke.

About water vapor permeability AD-1-AD-10, it apply | coated so that it might become thickness of 100 micrometers on a cellophane base material, the hardening process was performed, and the sealing agent sheet was obtained. For AD-11, a 20 μm sealant sheet was used as it was. About the obtained sealing agent sheet | seat, the water vapor transmission rate was measured by the cup method according to JISZ0208: 1976 in the environment of 60 degreeC and 90% RH. In addition, about AD-11, in order to make it the water-vapor permeability per 100 micrometers, 1/5 of the obtained value was computed.

For Shore D hardness AD-1 to AD-10, a sealant having a thickness of 5 mm was repeatedly applied by applying a sealant on a glass substrate to a thickness of about 100 μm and then being cured under the curing conditions described in Table 1. A stopper layer was formed. AD-11 was made to have a thickness of 5 mm by stacking a plurality of sheets having a thickness of 20 μm. About the sealing agent layer obtained in this way, according to the method of JIS K6253: 1997, the Shore D hardness after hardening at 25 degreeC was measured using the durometer made from TQC.

  In the above curing treatment, the product name HLR100T-2 manufactured by Sen Special Light Source Co., Ltd. was used as the ultraviolet curing device, and the PU-2 type manufactured by Espec Corp. was used as the heating device.

Example 1
<Production of base material>
As a base material (support), a 125 μm thick polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films Ltd.) processed to be easily bonded on both sides, a bleed-out prevention layer on one side as shown below, A substrate having a smooth layer formed on the opposite surface was used.

<Formation of bleed-out prevention layer>
The UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Co., Ltd. is applied to one surface side of the thermoplastic resin base material under the condition that the film thickness after drying is 4.0 μm. After that, as a curing condition, an irradiation energy amount of 1.0 J / cm ² was used, a high pressure mercury lamp was used in an air atmosphere, and a curing process was performed at 80 ° C. for 3 minutes to form a bleed-out prevention layer. .

<Formation of smooth layer>
Next, a 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 substrate opposite to the surface on which the bleedout prevention layer is formed. After coating under the condition that the film thickness after that becomes 4.0 μm, after drying at 80 ° C. for 3 minutes, using a high-pressure mercury lamp in an air atmosphere, the irradiation energy amount is 1.0 J / cm ² as curing conditions. The film was irradiated and cured with 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 B0601: 2001. Rz was 20 nm.

  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.

[Production of gas barrier film]
On the smooth layer of the base material, the following polysilazane-containing coating solution was applied using a spin coater under the condition that the film thickness after drying was 150 nm. The drying conditions were 100 ° C. and 2 minutes.

<Preparation of polysilazane-containing coating solution>
Dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20), and N, N, N ′, N′-tetramethyl-as an amine catalyst 1% by weight of 1,6-diaminohexane and 19% by weight of dihydrolether solution (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NAX120-20) mixed at a ratio of 4: 1 Then, the content of the amine catalyst was adjusted to 1% by mass with respect to the solid content of the coating solution. Further, a coating solution was prepared by appropriately diluting with dibutyl ether according to the set film thickness.

(Vacuum ultraviolet irradiation treatment)
After forming a coating film containing polysilazane as described above, a barrier layer was formed by performing irradiation with vacuum ultraviolet rays at an irradiation energy of 3000 mJ / cm ² according to the following method.

<Measurement of vacuum ultraviolet irradiation conditions and irradiation energy>
The vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic cross-sectional view of FIG.

  In FIG. 3, reference numeral 21 denotes an apparatus chamber, which supplies appropriate amounts of nitrogen and oxygen from a gas supply port (not shown) to the inside and exhausts gas from a gas discharge port (not shown), thereby substantially removing water vapor from the inside of the chamber. The oxygen concentration can be maintained at a predetermined concentration. Reference numeral 22 denotes an Xe excimer lamp having a double tube structure that irradiates vacuum ultraviolet rays of 172 nm, and reference numeral 23 denotes an excimer lamp holder that also serves as an external electrode. Reference numeral 24 denotes a sample stage. The sample stage 24 can be reciprocated horizontally at a predetermined speed V in the apparatus chamber 21 by a moving means (not shown). The sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 25 denotes a sample on which a polysilazane coating layer is formed. When the sample stage 24 moves horizontally, the height of the sample stage 24 is adjusted so that the shortest distance between the sample coating layer surface and the excimer lamp tube surface is 3 mm. Reference numeral 26 denotes a light shielding plate, which prevents the application layer of the sample from being irradiated with vacuum ultraviolet light during aging of the Xe excimer lamp 22.

  The energy applied to the surface of the sample coating layer in the vacuum ultraviolet irradiation process was measured using a 172 nm sensor head using a UV integrating light meter: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics Co., Ltd. In the measurement, the sensor head is installed in the center of the sample stage 4 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head is 3 mm, and the atmosphere in the apparatus chamber 21 is irradiated with vacuum ultraviolet rays. Nitrogen and oxygen were supplied so that the oxygen concentration was the same as that in the process, and the sample stage 24 was moved at a speed of 0.5 m / min for measurement. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 22, an aging time of 10 minutes was provided after the Xe excimer lamp 22 was turned on, and then the measurement was started by moving the sample stage.

  Based on the irradiation energy obtained by this measurement, the moving speed of the sample stage 24 was adjusted so that the predetermined irradiation energy was obtained. The vacuum ultraviolet irradiation was performed after aging for 10 minutes as in the case of irradiation energy measurement.

Thus, the gas barrier film 1 was produced. Moreover, the water vapor permeability of the gas barrier film 1 measured at 60 ° C. and 90% RH using the Ca method disclosed in Japanese Patent Application Laid-Open No. 2006-119069 is 3 × 10 ⁻⁵ g / m ² · day. there were.

<< Production of organic electronics devices >>
Using the gas barrier film 1 as a sealing film, an organic EL element 6 which is a 20 cm square organic electronic device was produced by the following procedure.

[Production of organic EL elements]
(Formation of first electrode layer)
On the 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 solution for forming the hole transport layer, the gas barrier film was subjected to cleaning surface modification 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 at 25 ° C. and a relative humidity of 50%.

<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 as described above, a mask pattern is formed by vapor deposition using aluminum as the 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, except for the portion to be the extraction portion of the first electrode and the second electrode, SiO ₂ was laminated with a thickness of 200 nm by a CVD method, and a protective layer was formed on the second electrode layer.

(Cutting)
The gas barrier film formed up to the protective layer was moved again to a nitrogen atmosphere and cut into a prescribed size using an ultraviolet laser.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the cut element, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm, surface Treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
Dry lamination (adhesion) of polyethylene terephthalate (PET) film (12 μm thickness) to 30 μm thick aluminum foil (Toyo Aluminum Co., Ltd.) using an adhesive for dry lamination (two-component reaction type urethane adhesive) The thickness of the agent layer is 1.5 μm) On the sealing member, AD-1 and AD-6, which are liquid sealants, are dispensed by Musashi Engineering Co., Ltd., using the ODF method, as shown below. Applied. AD-1 is applied to B part of FIG. 2 in a size of 195 mm × 195 mm and R = 2 mm at right angle part, and AD-6 is applied to C part inside B of FIG. It was dripped in divided places. The sealing member was bonded onto an element to which an electrode lead (flexible printed circuit board) was connected using a vacuum bonding apparatus manufactured by Run Technical Service Co., Ltd. so that the sealant layer had a thickness of 20 μm. . The application amount of AD-1 was adjusted so that the width of AD-1 was 1.0 mm when the gap between the element and the sealing member was 20 μm. The application amount of AD-6 was adjusted so that no gap was formed between the element and the sealing member when the gap between the element and the sealing member was 20 μm.

  After coating, the sealing agent was cured under the curing conditions described in Table 3 below, and an organic EL element 6 was produced. In the curing process, HLR 100T-2 manufactured by Sen Special Light Source Co., Ltd. was used as the ultraviolet curing device, and PU-2 type manufactured by Espec Co., Ltd. was used as the heating device.

(Examples 2-13, Comparative Examples 1-12)
The same as in Example 1 except that the sealant shown in Table 2 was arranged in the arrangement shown in Table 3 below and the sealant was cured under the curing conditions shown in Table 3 below. Thus, organic EL elements 1 to 5 and 7 to 25 were produced. In addition, when arrange | positioning sealing agent in the part of A of FIG. 2, it apply | coats with a space | interval of 2.0 mm from the part of B of FIG. 2, and it is 20 micrometers in thickness at the part of B and A at the time of sealing. The coating amount was adjusted so that there was no gap.

  For AD-1 to AD-10, which are liquid sealing agents, a dispenser made by Musashi Engineering Co., Ltd. is used for the elements connected with electrode leads (flexible printed circuit boards), and the sealing patterns shown in Tables 3 and 4 are used. Then, the sealant layer was installed so that the thickness after spreading was 20 μm. Moreover, about AD-11 which is a sheet-like sealing agent, it punched and installed in the predetermined magnitude | size.

<< Evaluation of organic EL elements >>
About the produced said organic EL elements 1-25, durability was evaluated in accordance with the following method.

[Durability evaluation]
(Accelerated deterioration processing)
Each of the produced organic EL elements was subjected to an accelerated deterioration treatment for 1000 hours in an environment of 60 ° C. and 90% RH, and then evaluated for the following black spots together with the organic EL elements not subjected to the accelerated deterioration treatment. .

(Evaluation of sunspots)
A current of 1 mA / cm ² was applied to the organic EL element subjected to the accelerated deterioration treatment and the organic EL element not subjected to the accelerated deterioration treatment to emit light continuously for 24 hours. Part of the panel was enlarged with Moritex MS-804 and lens MP-ZE25-200), and photographs were taken toward the organic EL element at two locations, the central part and the peripheral part of the organic EL element. The photographed image was cut out to 5 mm square, the black spot generation area ratio was determined, the element deterioration resistance rate was calculated according to the following formula, and the durability was evaluated according to the following criteria. If the evaluation rank was ◎ or ◯, it was determined that the characteristic was practically preferable.

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%. Deterioration resistance rate is less than 20%. Also, after the organic EL element thus prepared was wound around a cylinder having a diameter of 10 cm and left for 5 minutes, and then spread out in a flat shape and left for 5 minutes, the same operation as described above was performed. The durability test was conducted ("Durability after bending" in the table).

  The evaluation results are shown in Tables 3 and 4 below.

  As is apparent from the results shown in Table 3 and Table 4, the organic EL elements 6 to 11, 13 to 15, 17 to 20, and 24 to 25 (Examples 1 to 15) of the present invention are durable. It turns out that it is excellent.

(Examples 16 to 18, Comparative Example 11)
[Production of gas barrier film]
As a base material (support), on a polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films, Inc.) having a thickness of 125 μm that is easily bonded on both surfaces, the method described in Example 1 of International Publication No. 2012/003198 A gas barrier film 2 was prepared by providing a barrier layer in which three inorganic layers and three organic layers were laminated in the same manner as the above method. The three inorganic layers were SiAlO _x layers, and the thickness of all three layers was 30 nm. Further, the water vapor permeability of the gas barrier film 2 measured under the conditions of 60 ° C. and 90% RH using the Ca method disclosed in Japanese Patent Application Laid-Open No. 2006-119069 is 4 × 10 ⁻⁵ g / m ² · day. there were.

  Using the gas barrier film 2 thus produced, the sealing agent shown in Table 2 was arranged in the arrangement shown in Table 5 below, and the sealing agent was cured under the curing conditions shown in Table 5 below. Organic EL elements 201 to 204 were produced in the same manner as in Example 1 except that the treatment was performed.

(Examples 19 to 21)
[Production of gas barrier film]
As a substrate (support), on a polyethylene naphthalate film (Q65FWA, manufactured by Teijin DuPont Films Co., Ltd., 125 μm thick) which is easily bonded on both sides, described in Example E2 of International Publication No. 2011/013341 Three gas barrier films produced by the same method as above were bonded together to produce a gas barrier film 3 in which an organic layer and an inorganic layer were laminated. The three inorganic layers were SiO ₂ layers, and the thickness of all three layers was 30 nm. Further, the water vapor permeability of the gas barrier film 3 measured at 60 ° C. and 90% RH using the Ca method disclosed in Japanese Patent Application Laid-Open No. 2006-119069 is 5 × 10 ⁻⁵ g / m ² · day. there were.

  Using the gas barrier film 3 thus produced, the sealing agent shown in Table 2 was arranged in the arrangement shown in Table 5 below, and the sealing agent was cured under the curing conditions shown in Table 5 below. Organic EL elements 205 to 207 were produced in the same manner as in Example 1 except that the treatment was performed.

  The durability evaluation results of the organic EL elements 201 to 207 are shown in Table 5 below.

  As is apparent from the results shown in Table 5, the organic EL elements 202 to 207 (Examples 16 to 21) of the present invention are excellent in durability.

10 Organic electronics devices,
11 Base material 12 Barrier layer,
13 Organic elements,
14 sealant layer,
15 sealing member,
21 equipment chamber,
22 Xe excimer lamp,
23 holder,
24 Sample stage,
25 samples,
26 Shading plate.

Claims (8)

A gas barrier film having a substrate and a barrier layer;
A sealing member;
An organic element and a sealant layer located between the gas barrier film and the sealing member;
Have
The sealant layer includes a first sealant having a Shore D hardness of 80 or more after curing, and a second sealant having a Shore D hardness of 56 or more and less than 80 after curing. Organic electronics devices. The water vapor permeability after curing of the first sealant is 20 g / m ² · day or less, and the water vapor permeability after curing of the second sealant is 50 g / m ² · day or less, The organic electronics device according to claim 1.   3. The organic electronic device according to claim 1, wherein the second sealant is disposed at a center portion in a plane direction, and the first sealant is disposed at an outer peripheral portion surrounding the center portion.   The organic electronics device according to claim 3, wherein the second sealant is further disposed outside the outer peripheral portion.   The organic electronic device according to claim 1, wherein the sealing member includes a metal or a metal compound.   The organic barrier device according to claim 1, wherein the barrier layer is a laminate of an inorganic layer and an organic layer. It said first sealant comprises at least one of epoxy resins and acrylic resins, organic electronic device according to any one of claims 1-6. The organic electronic device according to any one of claims 1 to 7 , wherein the second sealant includes at least one selected from the group consisting of a polyolefin resin, a fluororesin, and a polyvinylidene chloride resin.