JP2012240358A - Barrier film for electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new and improved barrier film for an electronic device, capable of improving a barrier performance more than before.SOLUTION: The barrier film for the electronic device includes: an alternately stacked part for which an inorganic planar particle layer containing charged inorganic planar particles and a binder layer charged oppositely to the inorganic planar particles are alternately stacked; and a filling part formed at a defective part which is a part in which the inorganic planar particles are not present in the inorganic planar particle layer.

Description

  The present invention relates to a barrier film for electronic devices.

  As a flexible substrate for an electronic device, a barrier film in which a barrier layer is formed on a resin film is used. Conventionally, these barrier films have been used for packaging foods, but in recent years, they have been used in electronic devices, and there has been a demand for dramatic improvement in barrier performance.

  Patent Document 1 discloses such a barrier film. The barrier film described in Patent Document 1 is obtained by laminating a clay layer made of clay particles and a cationic resin by an alternating adsorption method.

US Patent Application Publication No. 2004/053037

However, in the barrier film described in Patent Document 1, the density (adsorption density) of the clay particles is not uniform (unstable) in the clay layer, and a large number of defect portions where the clay particles are not adsorbed to the resin film are formed. This defective portion becomes a passage for gas such as moisture. For this reason, the barrier film described in Patent Document 1 has a problem that the barrier performance of each clay layer tends to be insufficient. As a method of solving this problem, a method of increasing the number of laminated clay layers is also conceivable, but this method complicates the process and increases the thickness of the barrier film.
Therefore, the present invention has been made in view of the above problems, and an object of the present invention is to provide a new and improved barrier film for electronic devices capable of improving the barrier performance as compared with the prior art. It is to provide.

  In order to solve the above problems, according to one aspect of the present invention, an inorganic plate-like particle layer containing charged inorganic plate-like particles on a resin film, and a binder layer charged to a charge opposite to that of the inorganic plate-like particles, An electronic device comprising: alternately stacked portions alternately stacked; and a filling portion formed in a defective portion of the inorganic plate-like particle layer where the inorganic plate-like particles are missing. A barrier film is provided.

  In the barrier film for electronic devices according to this aspect, since the filling portion is formed in the defective portion, the filling portion can prevent gas permeation through the defective portion. Therefore, the barrier film for electronic devices according to this aspect can improve the barrier performance as compared with the conventional case.

  Here, the filling portion may include a metal oxide.

  Thereby, the barrier film for electronic devices can prevent the permeation | transmission of the gas in a defective part more reliably.

  Further, the metal constituting the metal oxide may be at least one of vanadium, tungsten, and molybdenum.

  Thereby, the barrier film for electronic devices can prevent the permeation | transmission of the gas in a defective part more reliably.

  Further, the element constituting the metal oxide may include phosphorus.

  Thereby, the barrier film for electronic devices can prevent the permeation | transmission of the gas in a defective part more reliably.

  Further, the inorganic plate-like particles may be negatively charged, and the binder layer may be positively charged.

  Thereby, since the layers which comprise the barrier film for electronic devices adsorb | suck firmly by Coulomb force, barrier performance improves more.

  Moreover, the inorganic plate-like particle may be obtained by layer-separating at least one of clay mineral and zirconium phosphate.

  Thereby, since inorganic plate-like particles prevent gas permeation, the barrier performance is further improved.

  The clay mineral may be at least one of mica, vermulite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, and stevensite.

  Thereby, since inorganic plate-like particles prevent gas permeation, the barrier performance is further improved.

  The clay mineral may be montmorillonite.

  Since montmorillonite is easily separated into layers, according to this aspect, inorganic plate-like particles are easily generated.

  Further, the inorganic plate-like particles may be obtained by layer separation of zirconium phosphate.

  Since zirconium phosphate is easily separated into layers, according to this aspect, inorganic plate-like particles are easily generated.

  Moreover, you may make it provide the adsorption layer which is formed in a resin film and makes a resin film adsorb | suck to an alternating lamination part strongly.

  Thereby, since an alternating lamination part and a resin film adsorb | suck strongly, barrier performance improves more. Furthermore, since the adsorption layer prevents gas permeation, the barrier performance is further improved.

  Further, the adsorption layer may include at least one of silica and alumina.

  Thereby, since an alternating lamination part and a resin film adsorb | suck strongly, barrier performance improves more.

  In addition, the adsorption layer may be charged to a charge opposite to the outermost layer, which is the outermost layer of the alternately laminated portion.

  Thereby, since an alternating lamination part and a resin film adsorb | suck strongly, barrier performance improves more.

  Further, the treatment for charging the adsorption layer may be performed by using a silane coupling agent.

  Thereby, the adsorption layer can be more reliably charged.

  As described above, according to the present invention, since the filling portion is formed in the defective portion, the permeation of the gas in the defective portion can be prevented by this filling portion. Therefore, the barrier film for electronic devices according to the present invention can improve the barrier performance as compared with the conventional case.

It is sectional drawing which shows the barrier film which concerns on embodiment of this invention. It is a schematic diagram which shows a mode that a filling part is formed (filling) in the defect part which is a location where the inorganic plate-shaped particle | grain was missing. It is a pool diagram of Tungsten (Pourbaix Diagram). It is sectional drawing which shows the manufacturing method of the barrier film concerning the embodiment.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

[Problems of conventional barrier films]
The inventor has scrutinized the conventional barrier film and its problems, and has completed the barrier film according to the present embodiment based on this result. First, the conventional barrier film and its problems will be described.

As a flexible substrate for an electronic device, a barrier film in which a barrier layer is formed is used. Conventionally, these barrier films have been used for packaging foods, but in recent years, they have been used in electronic devices, and there has been a demand for dramatic improvement in barrier performance. For example, in the case of an organic electroluminescence element which is an all-solid-state light-emitting element, which is said to be suitable for a flexible display, the required barrier performance is a moisture permeability (WVTR) of 1E-6 (g / m ² / day).

Various companies have proposed barrier films that satisfy such high performance. For example, the US company Vitex discloses a barrier film composed of an alternately laminated structure of a resin film and an alumina layer (http://www.vitexsys.com/barix_how_made.html). According to Vitex, this barrier film has high performance applicable to organic light emitting devices. According to a press release on February 20, 2008 by Mitsubishi Plastics Co., Ltd. (http://www.mpi.co.jp/info/360/index.html), the WVTR is 0.05 (g / m ² / day) barrier film is on the market.

  Many high performance barrier films, including these two technologies, are made using a vacuum process. The vacuum process is generally a process in which a substance constituting the barrier film is attached on a film substrate placed in a vacuum chamber. Since the vacuum process requires a huge vacuum chamber, there is a problem that the capital investment is increased. In addition, since the vacuum process requires an excessive running cost for maintaining the vacuum chamber, there is also a problem that the manufacturing cost of the barrier film increases. Further, the vacuum process has a problem in that the step coverage of the barrier film is poor, and therefore pinholes are likely to occur due to foreign matters on the film substrate.

  On the other hand, a film forming method using a wet process is also known as a method for forming a barrier film. This film forming method can avoid these problems of the vacuum process, and can form a barrier film with few pinholes at low cost. As the wet process, a sol-gel method or a method using clay particles having almost no gas permeation can be considered. In addition to the above-mentioned Patent Document 1, a method for producing a barrier film using these techniques is disclosed in JP 2007-22075 A (hereinafter also referred to as “Reference Document 1”) and JP 2003-41153 A (hereinafter referred to as “Patent Document 1”). , Also referred to as “reference document 2”). The technique disclosed in Patent Document 1 and problems related to the technique are as described above.

  Reference 1 discloses a barrier film in which clay layers made of clay particles (particles of inorganic layered compounds described later) and inorganic layers formed by a sol-gel method are alternately laminated. In the technique disclosed in Reference 1, a clay layer is formed by allowing a dispersion in which clay particles are dispersed to stand. However, the clay layer formed by such a method has a problem of low adhesion to other layers, that is, inorganic layers. Further, since the clay layer is simply a layer in which clay particles are deposited, the bond between the clay particles in the clay layer is very weak. For example, when moisture enters the clay layer through the inorganic layer, water molecules easily enter between the clay particles, the clay layer swells, and the barrier performance of the barrier film is significantly reduced. In order to solve this problem, it is conceivable to reduce the moisture permeability of the inorganic layer, but for this purpose, the inorganic layer needs to be baked at a high temperature (100 to 500 ° C.), so the process becomes complicated. There was a problem.

  Reference 2 discloses a barrier film made of a mixture of a sol-gel material and clay particles. In this technique, it is important to disperse clay particles at a high concentration in the sol-gel material in order to improve the barrier performance of the barrier film. For how much the barrier film can improve the barrier performance when a layered compound such as clay particles is dispersed in a sol-gel material, see J. Org. MACROMOL. SCI. (CHEM.), A1 (5), 929-942 (1967). According to the calculation method of the literature, for example, when clay particles having a diameter of 1 μm and a thickness of 1 nm are used, in order to lower the WVTR of the sol-gel material to be mixed, that is, the WVTR of the barrier film by two orders of magnitude, About 20% by mass of clay particles must be dispersed in the sol-gel material with respect to the total mass of the sol-gel. A dispersion in which particles having a very flat shape such as clay particles are dispersed in a sol-gel material exhibits thixotropy and has a very high viscosity upon standing. Due to such high viscosity, there has been a problem that it is practically difficult to disperse 20% by mass of clay particles in the sol-gel material. Further, even if it can be dispersed, there is a problem that it is very difficult to apply the dispersion in the form of a film because the viscosity of the dispersion is high.

  In view of the above problems, the present inventor has developed the barrier film described in the present embodiment. Hereinafter, the barrier film according to the present embodiment will be described.

[Barrier film structure]
First, the structure of the barrier film according to the present embodiment will be described with reference to FIG. The barrier film 1 according to the present embodiment is formed on the resin film 2, the alternately laminated portion 8 in which the inorganic plate-like particle layer 3 and the binder layer 5 are alternately laminated, and the defective portion 7 of the inorganic plate-like particle layer 3. The filling part 4 is provided. In the following description, a film manufactured in the course of manufacturing the barrier film 1, that is, a film in which at least one of the inorganic plate-like particle layer 3 and the binder layer 5 is laminated on the surface of the resin film 2 is “ Also referred to as “intermediate film”.

[Configuration of resin film]
First, the configuration of the resin film 2 will be described. The resin film 2 may be made of any resin as long as it is a known resin. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), and polyimide (PI) ) Etc. The resin film 2 may be composed of only one of these substances, or may be composed of two or more substances among these substances.

The surface of the resin film 2 is positively or negatively charged. In FIG. 1, the resin film 2 is positively charged. The treatment for charging the resin film 2 is not particularly limited. For example, physical treatment (for example, corona treatment, UV / O ₃ treatment, etc.), EB treatment (electron beam treatment), and a chemical solution such as a silane coupling agent. Chemical treatment or the like can be used. By corona-treating the surface of the resin film 2, the surface of the resin film 2 is negatively charged. Further, when the surface of the resin film 2 is treated with a silane coupling agent, the surface of the resin film 2 is positively charged. Furthermore, in order to enhance the effect of these charging treatments, an adsorption layer may be formed on the resin film 2 and the adsorption treatment may be performed on the adsorption layer. The adsorption layer strongly adsorbs the resin film 2 to the inorganic plate-like particle layer 3 or the binder layer 5 and is composed of a metal oxide such as silica and alumina. Since these metal oxides have an OH group on the surface in the atmosphere, when the metal oxide is subjected to corona treatment or UV / O ₃ treatment, the surface is strongly and uniformly charged. Similarly, when the surface of the metal oxide is charged with a silane coupling agent, the surface is strongly and uniformly charged as a result of the silane coupling agent binding to the OH group on the surface of the metal oxide.

  Which of the inorganic plate-like particle layer 3 and the binder layer 5 is laminated on the resin film 2 is determined by the electric charge of the resin film 2, the inorganic plate-like particle layer 3, and the binder layer 5. For example, when the surface of the resin film 2 is positive and the inorganic plate-like particle layer 3 is negatively charged, the inorganic plate-like particle layer 3 is laminated on the resin film 2 and the binder layer 5 is made of the inorganic plate-like particle. Laminate on layer 3.

[Configuration of inorganic plate-like particle layer]
Next, the inorganic plate-like particle layer 3 constituting the barrier film 1 will be described. The inorganic plate-like particle layer 3 is composed of inorganic plate-like particles.

  The inorganic plate-like particles are layered with inorganic layered compounds, for example, clay minerals such as mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, zirconium phosphate, and layered double hydroxide (LDH). It can be obtained by separation (delamination, Exfoliate).

  These inorganic layered compounds are obtained by laminating a plurality of positively or negatively charged inorganic plate-like particles via interlayer ions (for example, sodium ions) charged to a charge opposite to that of the inorganic plate-like particles. In order to separate the inorganic layered compound, for example, particles having a particle size larger than the interlayer ions, such as water molecules, calcium ions, and tetrabutylammonium ions may be inserted between the inorganic plate-like particles. For example, the inorganic layered compound may be added to water and stirred.

  The inorganic plate-like particle layer 3 may be composed of one kind of inorganic plate-like particle, or may be composed of two or more kinds of inorganic plate-like particles having the same charge.

  The ease of layer separation depends on the charge density of the inorganic layered compound. Examples of the inorganic layered compound that can be easily separated include montmorillonite and zirconium phosphate. Therefore, it can be said that these inorganic layered compounds are preferable in terms of easy layer separation.

  The inorganic plate-like particles have a very flat shape and are composed of an inorganic substance such as a metal oxide. Inorganic plate-like particles hardly permeate gas. Therefore, the barrier performance of the barrier film 1 is improved by arranging the inorganic plate-like particles horizontally with respect to the other layers.

  The dimensions of the inorganic tabular compound are, for example, a diameter in the plane direction of 10 nm to 10 μm and a thickness of 1 to 100 nm. The diameter in the plane direction is, for example, the value obtained by arithmetically averaging the equivalent diameter of each particle (the diameter when the shape of the particle in the plane direction is a circle), and the thickness is the arithmetic average of the thickness of each particle. Value. The planar diameter and thickness of the inorganic tabular compound particles are measured by, for example, SEM (scanning electron microscope), AFM (atomic force microscope), or laser scattering particle size distribution analyzer.

  Further, the inorganic plate-like particles are charged positively or negatively as described above. Specifically, the inorganic platy particles obtained from clay minerals such as mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, and zirconium phosphate are negatively charged.

On the other hand, the inorganic plate-like particles obtained from the layered double hydroxide are positively charged. That is, the layered double hydroxide is represented by the following chemical formula 1.
^{_{[M 2+ 1-x M 3+}} x (OH) 2] x + [B n- x / n · yH 2 O] x- ··· ( Formula 1)
In Chemical Formula 1, M ²⁺ is a divalent metal, M ³⁺ is a trivalent metal, B is an anion, n is a valence of the anion, x is a real number where 0 <x <0.4, and y is a real number greater than 0. That is, the layered double hydroxide has a structure similar to that of brucite, an anion and a layer between positively charged inorganic plate-like particles ([M 2 ⁺ _1-x M ³⁺ _x (OH) ₂ ] ^{x +} ). It is an inorganic layered compound composed of interlayer water and in which negatively charged interlayer ions ([B nx _{/ n} · yH ₂ O] ^x− ) are arranged.

Electrical neutrality is maintained in the entire layered double hydroxide crystal. As the divalent metal, Mg, Mn, Fe, Co, Ni, Cu, Zn and the like are known, and as the trivalent metal, Al, Fe, Cr, Co, In and the like are known. The anions include OH ⁻ , F ⁻ , Cl ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , Fe (CN) ₆ ⁴⁻ , CH ₃ COO ⁻ , V ₁₀ O ₂₈ ⁶⁻ , dodecyl. SO ₄ ^{− and the} like are known.

  The inorganic plate-like particle layer 3 is formed by an adsorption method. The adsorption method is a technique in which a substrate having a charged surface is immersed in a dispersion of particles charged to a charge opposite to that of the substrate. In this method, particles are adsorbed on the substrate surface by Coulomb force. In the present embodiment, the resin film 2 or the intermediate film whose surface becomes the binder layer 5 is immersed in a dispersion of inorganic plate-like particles charged to a charge opposite to the surface charge of the resin film 2 or the intermediate film. Thereby, inorganic plate-like particles are adsorbed on the surface of the resin film 2 or the intermediate film. At this time, the inorganic plate-like particles are adsorbed so as to be parallel to the surface of the resin film 2 or the intermediate film.

  The dispersion of inorganic plate-like particles is produced by adding an inorganic layered compound to water and stirring. Here, the concentration of the inorganic layered compound is preferably 0.01 to 10 (g / L), and more preferably 0.1 to 1 (g / L). When the concentration is too low, the adsorption of the inorganic plate-like particles to the resin film 2 or the intermediate film becomes insufficient. On the other hand, when the concentration is too high, the viscosity of the dispersion becomes high. The dispersion is composed of at least water and an inorganic stratiform compound (specifically, inorganic plate-like particles and interlayer ions formed by separating the inorganic stratiform compound), but in order to increase the dispersibility of the inorganic platy particles. And an intercalating agent for promoting layer separation of the inorganic layered compound may be included.

[Configuration of filling section]
Next, the configuration of the filling unit 4 will be described. As shown in FIG. 2, when the inorganic plate-like particle layer 3 is formed by the adsorption method, the inorganic plate-like particle layer 3 can be formed with a defective portion 7 that is a portion where the inorganic plate-like particles are missing. Therefore, in the present embodiment, the defective portion 7 is filled with the filling portion 4.

  The filling unit 4 is made of an inorganic material having a low gas permeability. Examples of such an inorganic material include metals and metal oxides.

Here, a method of forming the filling portion 4 in the defect portion 7 will be described by taking as an example a case where tungsten trioxide (WO ₃ ) is formed as the filling portion 4 in the defect portion 7. FIG. 3 shows a pool diagram for tungsten. The Pourbaille diagram shows the existence region of chemical species (especially metal) in water on the two-dimensional coordinates of electrode potential and pH. FIG. 3 shows a region where tungsten is present at 25 ° C. In the present embodiment, the regions A1 and A2 sandwiched between the straight line a and the straight line b are important in the pool diagram, and these regions will be described. The region A1 is a region where tungsten exists as tungstate ions (WO ₄ ²⁻ ), and the region A2 is a region where tungsten exists as tungsten trioxide. A boundary line between these regions is represented by any of straight lines L1 to L4. That is, when the concentration of tungsten in water is 1E-0 (mol / L), the boundary line is a straight line L1, and when the concentration of tungsten in water is 1E-2 (mol / L), the boundary is The line is a straight line L2, and when the concentration is 1E-4 (mol / L), the boundary line is a straight line L3. When the concentration is 1E-6 (mol / L), the boundary line is a straight line L4. It becomes. The boundary line belongs to the region A1.

  According to this pool diagram, under a constant electrode potential and pH, the higher the concentration of tungsten, the wider the region A2 (that is, tungsten tends to precipitate as tungsten trioxide). For example, the point C (electrode potential = 0, pH = 6.0) belongs to the region A1 if the tungsten concentration is 1E-2 or less. Therefore, when the electrode potential of the aqueous tungsten solution is 0, the pH is 6.0, and the concentration is 1E-2 or less, tungsten exists as tungstate ions. On the other hand, the point C belongs to the region A2 if the tungsten concentration is higher than 1E-2. Therefore, when the electrode potential of the tungsten aqueous solution is 0, the pH is 6.0, and the concentration is higher than 1E-2, tungsten exists as tungsten trioxide.

In this embodiment, the filling portion 4 is formed in the defective portion 7 by utilizing this principle. That is, first, a tungsten trioxide aqueous solution, for example, an ammonium tungstate ((NH ₄ ) WO ₄ ) aqueous solution is prepared. At this time, the electrode potential of the tungsten trioxide aqueous solution (essentially becomes zero) so that the point indicating the electrode potential and pH belongs to the region A1 and is in the vicinity of the boundary line between the region A1 and the region A2. Adjust pH and concentration. Next, as shown in FIG. 2, an intermediate film whose surface is the inorganic plate-like particle layer 3 (that is, a film in which the inorganic plate-like particle layer 3 is laminated on the surface of the resin film 2 or the binder layer 5) in an aqueous solution of tungsten trioxide. Soak). Here, the resin film 2 or the binder layer 5 is positively charged, and the inorganic plate-like particle layer 3 is negatively charged.

  The tungstate ion 10 in the tungsten aqueous solution is attracted to the defect portion 7 by the Coulomb force and aggregates. As a result, the concentration of tungsten is increased in the defect portion 7, so that tungsten trioxide 11, that is, the filling portion 4 is deposited in the defect portion 7. In addition, the tungstate ion 10 does not aggregate on the portion of the surface of the resin film 2 or the binder layer 5 where the inorganic plate-like particle layer 3 is formed. This is because the inorganic plate-like particle layer 3 is negatively charged.

  Examples of the metal constituting the filling portion 4 include aluminum, iron, magnesium, and potassium. The method of forming the filling portion 4 with a metal is roughly as follows. That is, first, an aqueous metal solution is prepared by dissolving a water-soluble metal compound such as sulfate, chloride, hydroxide, etc. in water. In the aqueous metal solution, the metal exists as a cation (metal ion). Next, an intermediate film whose surface is the inorganic plate-like particle layer 3 is immersed in this aqueous metal solution. At this time, the inorganic plate-like particle layer 3 is positively charged, and the resin film 2 or the binder layer 5 is negatively charged. The metal ions are attracted to the defective portion 7 by the Coulomb force and aggregate in the defective portion 7. As a result, the concentration of metal ions is increased in the defect portion 7, so that metal, that is, the filling portion 4 is deposited in the defect portion 7.

  Therefore, the inorganic material constituting the filling portion 4 is selected according to the charge of the resin film 2 or the binder layer 5. That is, when the resin film 2 or the binder layer 5 is positively charged, a metal oxide is selected as an inorganic material constituting the filling portion 4. This is because the metal oxide exists as an anion (oxo acid ion) in the aqueous solution, and thus the metal oxide ion is attracted to the defect portion 7 by the Coulomb force. On the other hand, when the resin film 2 or the binder layer 5 is negatively charged, a metal is selected as the inorganic material constituting the filling portion 4. This is because the metal exists as a cation (metal ion) in the aqueous solution, so that the metal ion is attracted to the defect portion 7 by the Coulomb force.

When the filling part 4 is made of aluminum, examples of the metal compound include AlK (SO ₄ ) ₂ and AlNH ₄ (SO ₄ ) ₂ . When the filling part 4 is made of iron, examples of the metal compound include FeK (SO ₄ ) ₂ . When the filling part 4 is made of magnesium, examples of the metal compound include MgCl ₂ and Mg (NO ₃ ) ₂ . When the filling part 4 is composed of potassium, examples of the metal compound include KOH, K ₂ SO ₄ , and KCl.

On the other hand, as a metal oxide which comprises the filling part 4, the oxide of vanadium and molybdenum other than tungsten mentioned above is mentioned. The aqueous metal oxide solution is prepared by dissolving a metal oxoacid salt in water. Examples of such oxo acid salts include NaVO ₃ , (NH ₄ ) ₂ MoO ₄ , (NH ₄ ) ₂ WO _{4 and the} like. Such a metal oxide may be a heteropoly acid containing phosphorus or silicon. The metal oxide containing phosphorus, for _{example, H 3 PMo 12 O 40 ·} nH 2 O , and examples of the metal oxide containing silicon _{include H 4 SiMo 12 O 40 · nH} 2 O.

[Binder layer configuration]
The binder layer 5 is composed of binder particles that can be charged to a charge opposite to that of the inorganic plate-like particle layer 3. Examples of such binder particles include polymer electrolyte ions, metal ions, metal compound ions, and inorganic plate-like particles. The binder layer 5 may be composed of only one of these substances, or may be composed of two or more substances having the same charge among these substances.

Examples of the polymer electrolyte ions include polymer electrolyte ions in which protons are coordinated to nitrogen atoms of polyallylamine and polyacrylamide. Examples of metal ions include ions of aluminum, magnesium, potassium, and polyvalent transition metals. Examples of the polyvalent transition metal include iron, cobalt, and manganese. Examples of the metal compound ions include metal oxoacid ions such as VO ₃ ⁻ , MoO ₄ ²⁻ , WO ₄ ²⁻ , TiO ^{2+ and the} like. The inorganic plate-like particles are obtained by separating the inorganic layered compound described above. That is, when the inorganic plate-like particle layer 3 is made of inorganic plate-like particles obtained from clay mineral, the binder layer 5 is made of inorganic plate-like particles obtained from layered double hydroxide. Conversely, when the inorganic plate-like particle layer 3 is composed of inorganic plate-like particles obtained from layered double hydroxide, the binder layer 5 is composed of inorganic plate-like particles obtained from clay mineral.

  The binder layer 5 is formed by an adsorption method in the same manner as the inorganic plate-like particle layer 3. In the present embodiment, the resin film 2 or the intermediate film whose surface is the inorganic plate-like particle layer 3 is converted into an aqueous solution (or dispersion) of an inorganic material charged to a charge opposite to the surface charge of the resin film 2 or the intermediate film. Immerse. Thereby, an inorganic material adsorb | sucks to the surface of the resin film 2 or an intermediate | middle film. That is, the binder layer 5 is formed on the surface of the resin film 2 or the intermediate film. At this time, when the inorganic material becomes inorganic plate-like particles, the inorganic plate-like particles are adsorbed so as to be parallel to the surface of the resin film 2 or the intermediate film.

  The binder particle aqueous solution (or dispersion liquid) is obtained by dissolving or dispersing various water-soluble compounds or the above-described inorganic layered compounds in water. Here, the concentration of the water-soluble compound or the inorganic stratiform compound is preferably 100 (nmol / L) to 1 (mol / L), and more preferably 1 (μmol / L) to 100 (μmol / L). When the concentration is too low, the adsorption of the binder particles to the resin film 2 or the intermediate film becomes insufficient. On the other hand, if the concentration is too high, the viscosity of the aqueous binder particle solution (or dispersion) becomes high. The binder particle aqueous solution (or dispersion liquid) is composed of at least water and binder particles. When the binder particles are inorganic plate particles, a dispersant for increasing the dispersibility of the inorganic plate particles or an inorganic layered compound is used. An intercalating agent for promoting layer separation may be included.

In the case where the binder layer 5 is composed of polymer electrolyte ions, examples of the water-soluble compound include ionic polymers such as polyallylamine hydroxide and polyacrylic acid. When the binder layer 5 is composed of metal ions, examples of water-soluble compounds include metal sulfates, chlorides, and hydroxides such as AlK (SO ₄ ) ₂ , AlNH ₄ (SO ₄ ) ₂ , MgCl ₂ , Mg (NO ₃ ) ₂ , KOH, K ₂ SO ₄ , KCl, FeK (SO ₄ ) ₂ , CoCl ₂ , Co (NO ₃ ) ₂ , MnCl ₂ , Mn (NO ₃ ) ₂ , NiCl ₂ , Ni (NO ₃ ) ₂ , CuCl ₂ , Cu (NO ₃ ) ₂ , ZnCl ₂ , Zn (NO ₃ ) ₂ , and the like. When the binder layer 5 is composed of metal compound ions, examples of water-soluble compounds include sodium salts and ammonium salts of oxo acids such as NaVO ₃ , (NH ₄ ) ₂ MoO ₄ , (NH ₄ ) ₂ WO ₄ , and TiOSO. ₄ etc. are mentioned.

[Method for producing barrier film]
Next, the manufacturing method of the barrier film 1 is demonstrated based on FIG. Here, as an example of the manufacturing method, a manufacturing method in which the inorganic plate-like particle layer 3 is laminated on the resin film 2 and then the binder layer 5 is laminated on the inorganic plate-like particle layer 3 will be described. Of course, the binder layer 5 may be laminated.

[First Stage: Charging Treatment for Resin Film 2]
First, as shown in FIG. 4A, the surface of the resin film 2 is positively charged. Alternatively, an adsorption layer is formed on the surface of the resin film 2 and the adsorption layer is positively charged. As a method for charging the resin film 2 or the adsorption layer, for example, corona treatment, UV / O ₃ treatment, EB treatment (electron beam treatment), chemical treatment with a chemical solution such as a silane coupling agent, or the like can be used. .

[Second stage: treatment for forming inorganic plate-like particle layer]
Next, as shown in FIG. 4B, a negatively charged inorganic plate-like particle layer 3 is formed on the surface of the resin film 2. Specifically, first, at least one of clay mineral and zirconium phosphate is put into water and stirred to produce a dispersion of inorganic plate-like particles. The clay mineral and zirconium phosphate are obtained by laminating negatively charged inorganic plate-like particles via interlayer ions. Next, the resin film 2 is immersed in a dispersion of inorganic plate-like particles. Thereby, inorganic plate-like particles are adsorbed on the surface of the resin film 2. That is, the inorganic plate-like particle layer 3 is formed on the surface of the resin film 2. However, in the inorganic plate-like particle layer 3, a defective portion 7 which is a portion where the inorganic plate-like particles are missing is formed.

[Third stage: treatment for forming the filling portion]
Next, as shown in FIG. 4C, the filling portion 4 is formed (filled) in the defective portion 7. Specifically, first, a metal oxide aqueous solution is generated by dissolving a metal oxide in water. Oxoic acid ions (anions) are present in this metal oxide aqueous solution. Here, in the pool diagram corresponding to the metal oxide, the points indicating the electrode potential and pH belong to the ion region (the region corresponding to the region A1 in FIG. 3), and the ion region and the solid region (the region in FIG. 3). The electrode potential (essentially zero), pH, and concentration of the aqueous metal oxide solution are adjusted so that they are close to the boundary line with the region corresponding to A2.

  Next, an intermediate film whose surface is the inorganic plate-like particle layer 3 is immersed in the aqueous metal oxide solution. As a result, oxo acid ions in the metal oxide aqueous solution are attracted to the defective portion 7 by the Coulomb force and aggregate. As a result, the concentration of the oxo acid ion is increased in the defect portion 7, so that the metal oxide, that is, the filling portion 4 is deposited in the defect portion 7. In the surface of the resin film 2, oxo acid ions do not aggregate on the portion where the inorganic plate-like particle layer 3 is formed. This is because the inorganic plate-like particle layer 3 is negatively charged.

[Fourth stage: treatment for forming binder layer]
Next, as shown in FIG. 4 (d), a binder layer 5 is formed on the inorganic plate-like particle layer 3. Specifically, first, an aqueous binder particle solution in which at least one of positively charged polymer electrolyte ions, metal ions, metal compound ions, and positively charged inorganic plate-like particles is dissolved (or dispersed) (or Prepare a dispersion. Next, the intermediate film whose surface is the inorganic plate-like particle layer 3 is immersed in the aqueous binder particle solution (or dispersion). Thereby, binder particles are adsorbed on the surface of the intermediate film. That is, the binder layer 5 is formed on the surface of the intermediate film. At this time, when the binder particles are inorganic plate-like particles, the inorganic plate-like particles are adsorbed so as to be parallel to the surface of the intermediate film.

[Fifth stage: repetitive processing]
Next, as shown in FIG. 4 (e), the inorganic plate-like particle layer 3 and the binder layer 5 are alternately laminated on the resin film 2 by repeatedly performing the second to fourth steps. . A set of the inorganic plate-like particle layer 3 and the binder layer 5 forms one unit 6. Thereby, the barrier film 1 is manufactured.

[Function of barrier film]
Next, based on FIG. 1 etc., the effect | action (operation | movement) of the barrier film 1 is demonstrated. Gases such as moisture and oxygen that have entered the inorganic plate-like particle layer 3 through the resin film 2 cannot pass through the inorganic plate-like particles constituting the inorganic plate-like particle layer 3, so that the permeation path 100 as shown in FIG. May diffuse through. The gas permeation of the barrier film 1 is divided into permeation through the binder layer 5 and permeation through the filling portion 4 as shown in the following formula (1).

1 / T = 1 / Tb + 1 / Tp (1)
T: Gas permeability of the entire barrier film Tb: Gas permeability of the entire binder layer 5 Tp: Gas permeability of the entire filling portion 4

  The gas permeability of the entire binder layer 5 is proportional to the length of the gas permeation path, the gas permeability of the binder layer 5, and the area of the permeation cross section (cross section perpendicular to the permeation path 100) of the binder layer 5. Since the area of the transmission cross section of the binder layer 5 is proportional to the film thickness of the binder layer 5, the gas permeability can be expressed as in equation (2).

Tb∝L * Tb0 * Db (2)
Tb: gas permeability of the entire binder layer 5 L: length of a permeation path in the binder layer 5 Tb0: gas permeability per unit length (unit thickness) of the binder layer 5 Db: film thickness of the binder layer 5 ( For example, a value obtained by arithmetically averaging the film thickness of each binder layer 5. The film thickness is measured by, for example, an ellipsometer, AFM, etc. The same applies hereinafter)

  On the other hand, the gas permeability of the entire filling portion 4 is the thickness of the filling portion, the gas permeability per unit length (unit thickness) of the filling portion 4, the permeation section of the defect portion 7 (the section perpendicular to the permeation path 100) ) Is proportional to the area, respectively, and can be expressed as in equation (3).

Tp∝Dp * Tp0 * Sc (3)
Tp: gas permeability of the entire filling portion 4 Dp: film thickness of the filling portion 4 (for example, a value obtained by arithmetically averaging the film thickness of each filling portion 4)
Tp0: gas permeability Sc of filling portion 4 per unit length (unit thickness) Sc: area of permeation cross section of defect portion 7

  In the technique disclosed in Patent Document 1 described above, nothing is applied to the defective portion of the clay layer, and thus Tp0 in Expression (3) is a very large value. That is, Tp becomes a very large value, and as a result, the value of T also becomes large. On the other hand, since the defect part 7 of the inorganic plate-like particle layer 3 is filled with the filling portion 4, that is, the inorganic material, the barrier film 1 can reduce the value of Tp0, and as a result, the value of Tp is also reduced. The gas permeability T of the entire barrier film 1 can be reduced. Therefore, the barrier film 1 can reduce the gas permeability (that is, improve the barrier performance) as compared with the technique disclosed in Patent Document 1. Furthermore, since the barrier film 1 can significantly reduce the number of alternating adsorptions (the number of units 6) as compared with the prior art, the process becomes simple.

  Moreover, in this Embodiment, since the binder layer 5 is formed by the adsorption method, Db becomes very small compared with the technique disclosed in Reference Document 2. For example, in Example 2 of Reference Document 2, an inorganic layered compound composed of a swellable synthetic mica is dispersed in 10% by mass in a 3 μm sol-gel material. In Example 2, the interval between the arithmetic average inorganic layered compounds is estimated to be about 300 nm. On the other hand, since the film thickness of the binder layer 5 according to the present embodiment is estimated to be 1 nm or less, Db is two digits or more smaller. On the other hand, when the same inorganic layered compound as that in Reference 2 is used for the binder layer 5, Tb is approximately the same, so that the barrier film 1 can obtain higher barrier performance than the technique disclosed in Reference 2. .

  Furthermore, in the barrier film 1, the inorganic layered compound that is weak to moisture (that is, swelled by moisture) is not used as it is in the inorganic tabular particle layer 3, but the inorganic layered compound is generated by separating the layers. The inorganic plate-like particle layer 3 is formed using the inorganic plate-like particles. Specifically, in the present embodiment, the inorganic layered compound is separated into layers by adding the inorganic layered compound to water and stirring. Then, the inorganic plate-like particle layer 3 is formed by adsorbing the resulting inorganic plate-like particles to the resin film 2 or the binder layer 5 by an ion adsorption method. Thereby, the barrier film 1 which concerns on this Embodiment can prevent gas, such as a water | moisture content, permeating the inside of the inorganic plate-like particle layer 3, and swelling the inorganic plate-like particle layer 3. FIG. In addition, since the inorganic plate-like particles are adsorbed to other layers by Coulomb force, the barrier film 1 also prevents gas such as moisture from entering between the inorganic plate-like particle layer 3 and the other layers. be able to. Therefore, the barrier film 1 can improve the barrier performance as compared with the technique disclosed in Reference Document 1.

  Next, examples of the present embodiment will be described.

  In Example 1, the resin film 2 is positively charged, and the negatively charged inorganic plate-like particle layer 3 and the positively charged binder layer 5 are alternately laminated on the resin film 2.

1) Cleaning of Resin Film 2 As the resin film 2, a 0.1 mm thick PET film was prepared. The resin film 2 was washed with detergent and pure water and dried by air blow.

2) Preparation of inorganic plate-like particle dispersion liquid As montmorillonite (MMT), 0.5 g of Kunimine Industries Kunifil-D36 is put in 1 L of pure water, and a commercially available stirrer (Aswan KNS-T1) is used for 1 day. Stir. Thereby, the inorganic plate-like particle dispersion liquid in which the inorganic plate-like particles were dispersed was prepared.

3) Preparation of binder particle aqueous solution A 30 mmol / L aqueous solution of polyallylamine hydroxide (PAH) was prepared.

Preparation of Filling Part Aqueous Solution 4) A 1 mmol / L aqueous solution of NaVO _{3 was} prepared and the pH was measured and found to be 5.9. To this aqueous solution, 100 mmol / L NaOH was used to adjust the pH to 6.5 to prepare a packed portion aqueous solution.

5) Charge treatment of resin film 2 The resin film 2 washed in 1) was immersed in a 10 mmol / L ethanol solution of 3-aminopropyltriethoxysilane (APTES) for 30 minutes. Thereafter, the resin film 2 was washed away with ethanol and pure water and then dried by air blow. Thereby, the resin film 2 was positively charged.

6) Formation of inorganic plate-like particle layer The resin film 2 electrified in 5) was immersed in the inorganic plate-like particle dispersion prepared in 2) for 15 minutes, washed thoroughly with pure water, and dried by air blow. Thereby, the inorganic plate-like particle layer 3 was formed on the surface of the resin film 2.

7) Filling portion formation The resin film 2 on which the inorganic plate-like particle layer 3 was formed in 6) was immersed in the filling portion aqueous solution prepared in 4) for 15 minutes, and then thoroughly washed with pure water and dried by air blow. Thereby, the filling part 4 was formed in the defect part 7 of the inorganic plate-like particle layer 3.

8) Binder layer formation After immersing the resin film 2 in which the inorganic plate-like particle layer 3 and the filling portion 4 are formed in 7) in the binder particle aqueous solution prepared in 3) for 15 minutes, the resin film 2 is thoroughly washed with pure water and air blown. Dried. Thereby, the binder layer 5 was formed on the inorganic plate-like particle layer 3.

9) Alternating adsorption The steps 6) to 8) are repeated 5, 10, and 20 times, and the unit 6 (the combination of the inorganic plate-like particle layer 3 and the binder layer 5) is 5, 10, and 20 layers on the resin film 2, respectively. The formed barrier film 1 was obtained.

10) WVTR measurement WVTR was measured for the three barrier films 1 prepared in 9) using a water vapor transmission rate measuring apparatus AQUATRAN manufactured by MOCON.

  Next, Example 2 will be described. In the second embodiment, the filling unit 4 is changed from the first embodiment. That is, in Example 2, three barrier films 1 were produced and WVTR was measured in the same process as Example 1 except that the process of 4) of Example 1 was performed as follows.

4) Measurement of the adjusted pH prepare (1 mmol / L aqueous solution of _{NH 4)} 2 WO ₄ of the filling unit solution was 5.5. To this solution, 100 mmol / L NaOH was used to adjust the pH to 6.0 to prepare a filling portion aqueous solution.

  Next, Example 3 will be described. In the third embodiment, the filling unit 4 is changed in the first embodiment. That is, in Example 3, except that the process of 4) of Example 1 was performed as follows, three barrier films 1 were prepared and WVTR was measured in the same process as in Example 1.

4) Measurement of the adjusted pH prepare (1 mmol / L aqueous solution of _{NH 4)} 2 MoO ₄ of the filling unit solution was 5.0. To this solution, 100 mmol / L HCl was used to adjust the pH to 4.0 to prepare an aqueous filling portion solution.

  Next, Example 4 will be described. In Example 4, the resin film 2 is negatively charged, and the positively charged inorganic plate-like particle layer 3 and the negatively charged binder layer 5 are alternately laminated on the resin film 2.

1) Washing of Resin Film 2 A 0.1 mm thick PET film was prepared as the resin film 2, and the resin film 2 was washed with a detergent and pure water and dried by air blow.

2) Preparation of inorganic plate-like particle dispersion M ²⁺ _x M ³⁺ _y (OH) _n CO ₃ .nH ₂ O (M ²⁺ : Mg, M ³⁺ : Al, B: CO ₃ ²⁻ , x = 4.5, A layered double hydroxide (LDH) composed of y = 2, n = 13) was added 20 mL of a mixed aqueous solution of 1 mol / L sodium chloride, 0.01 mol / L acetic acid and 0.09 mol / L sodium acetate per 20 mg LDH. commercial shaker (SH-B type, Terasawa) by stirring for 2 days using _{^{a, M 2+ x M 3+ y (}} OH) n Cl 2 · nH 2 O (M 2+: Mg, M 3+: Al, B: An inorganic plate-like particle dispersion liquid in which LDH composed of CO ₃ ²⁻ , x = 4.5, y = 2, n = 13) was dispersed was prepared.

3) Preparation of binder particle aqueous solution A binder particle aqueous solution was prepared by adjusting a 30 mmol / L aqueous solution of polyacrylic acid (PAA).

4) Preparation of filling portion aqueous solution A 30 mmol / L aqueous solution of AlK (SO4) 2 was prepared to prepare a binder layer solution.

5) Charging treatment of resin film 2 The resin film 2 washed in 1) was subjected to corona treatment for 10 minutes using HPS-101 manufactured by Nihon Statech.

6) Formation of inorganic plate-like particle layer The resin film 2 charged in 5) was dipped in the inorganic plate-like particle dispersion prepared in 2) for 15 minutes, then thoroughly washed with pure water and dried by air blow. Thereby, the inorganic plate-like particle layer 3 was formed.

7) Filling portion formation The resin film 2 on which the inorganic plate-like particle layer 3 was formed in 6) was immersed in the filling portion aqueous solution prepared in 4) for 15 minutes, and then thoroughly washed with pure water and dried by air blow. Thereby, the filling part 4 was formed in the defect part 7 of the inorganic plate-like particle layer 3.

8) Binder layer formation After immersing the resin film 2 in which the inorganic plate-like particle layer 3 and the filling portion 4 are formed in 7) in the binder particle aqueous solution prepared in 3) for 15 minutes, the resin film 2 is thoroughly washed with pure water and air blown. Dried. Thereby, the binder layer 5 was formed.

9) Alternating adsorption The steps 6) to 8) are repeated 5, 10, and 20 times, and the unit 6 (the combination of the inorganic plate-like particle layer 3 and the binder layer 5) is 5, 10, and 20 layers on the resin film 2, respectively. The formed barrier film 1 was obtained.

10) WVTR measurement WVTR was measured for the three barrier films 1 prepared in 9) using a water vapor transmission rate measuring apparatus AQUATRAN manufactured by MOCON.

  Next, Example 5 will be described. In Example 5, an adsorption layer is added to Example 1. Specifically, in Example 5, three barrier films 1 were produced in the same process as Example 2 except that the process of 5) of Example 1 was performed as follows, and WVTR was measured. .

5) Charge treatment of resin film 2 The resin film 2 washed in 1) was spin-coated with AQUAMICA NL100A manufactured by AZ Electronic Materials using MS-A150 manufactured by Mikasa. Next, the resin film 2 was cured at 120 ° C. for 1 hour, and then in an atmosphere of 95 ° C.-80% humidity for 3 hours. Thus, a silica layer having a thickness of about 0.2 μm was formed on the surface of the resin film 2 as an adsorption layer. This resin film 2 was immersed in a 10 mmol / L ethanol solution of 3-aminopropyltriethoxysilane (APTES) for 30 minutes. Thereafter, the resin film 2 was washed away with ethanol and pure water and then dried by air blow. Thereby, the silica layer was positively charged.

[Comparative Example 1]
Except for not performing the steps 4) and 7) of Example 1, the same steps as in Example 1 were performed to produce three comparative films in which the filling portion 4 was not formed, and the WVTR was measured. did.

[Measurement result of WVTR]
Table 1 shows the results of WVTR measurement of the barrier film 1 and the comparative film prepared in Examples 1 to 5 and Comparative Example 1 in an environment of 40 ° C. and 90% RH (humidity) (unit: g / m ^2). / Day).

In any of the Examples, the value of WVTR is smaller than that of Comparative Example 1, and it can be seen that the barrier film 1 according to the present embodiment has a high barrier performance. For example, in order to obtain 10 −2 (g / m ² / day) WVTR, 20 pairs in the comparative example (that is, 20 units) is impossible in the comparative example, but 5 pairs in the example. (Ie 5 units 6) is sufficient. That is, it was confirmed that the barrier film 1 using the alternate adsorption according to the present embodiment can achieve high performance with a smaller number of layers than the conventional barrier film using the alternate adsorption.

  Note that the WVTR of the barrier film 1 according to Example 5 is lower than that of Example 1 because the effect of charging treatment is improved by the silica layer formed in Example 5, and the inorganic plate-like particle layer 3 is more completely made of a resin film. This is probably due to adsorbed to 2.

  As described above, according to the present embodiment, since the filling portion 4 is formed in the defective portion 7 of the barrier film 1, the filling portion 4 can prevent gas from being transmitted through the defective portion 7. Therefore, the barrier film 1 can improve the barrier performance as compared with the conventional case.

  Here, since the filling part 4 can contain a metal oxide, the barrier film 1 can prevent the permeation | transmission of the gas in the defective part 7 more reliably.

  Furthermore, since the metal which comprises a metal oxide may be at least 1 sort (s) among vanadium, tungsten, and molybdenum, the barrier film 1 can prevent the permeation | transmission of the gas in the defect part 7 more reliably.

  Furthermore, since the element which comprises a metal oxide can contain phosphorus, the barrier film 1 can prevent more reliably the permeation | transmission of the gas in the defect part 7. FIG.

  Further, since the inorganic plate-like particle layer 3 can be negatively charged and the binder layer 5 can be positively charged, the layers constituting the barrier film 1 are firmly adsorbed by Coulomb force. Therefore, the barrier performance is further improved.

  Furthermore, the inorganic plate-like particles can be obtained by layer separation of at least one of clay mineral and zirconium phosphate. Therefore, since the inorganic plate-like particles prevent gas permeation, the barrier performance is further improved.

  Furthermore, since the clay mineral can be at least one of mica, vermulite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, and stevensite, the inorganic plate-like particles prevent gas permeation. Therefore, the barrier performance is further improved.

  Further, the clay mineral can be montmorillonite. In this case, since montmorillonite is easily separated into layers, inorganic plate-like particles are easily generated.

  Furthermore, inorganic plate-like particles can be obtained by layer separation of zirconium phosphate. In this case, since the zirconium phosphate is easily separated into layers, inorganic plate-like particles are easily generated.

  Moreover, the adsorption layer formed on the resin film 2 and adsorb | sucking the resin film 2 to an alternating lamination part strongly can be provided. In this case, since the alternately laminated portions and the resin film 2 are firmly adsorbed, the barrier performance is further improved. Furthermore, since the adsorption layer prevents gas permeation, the barrier performance is further improved.

  Moreover, the adsorption layer can include at least one of silica and alumina. In this case, since the alternately laminated portions and the resin film 2 are firmly adsorbed, the barrier performance is further improved.

  Further, the adsorption layer can be charged to the opposite charge to the outermost layer of the alternately laminated portion. Thereby, since an alternately laminated part and the resin film 2 adsorb | suck firmly, barrier performance improves more.

  Moreover, the process which charges an adsorption layer can be performed by using a silane coupling agent. Thereby, the adsorption layer can be more reliably charged.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Barrier film 2 Resin film 3 Inorganic plate-like particle layer 4 Filling part 5 Binder layer 6 Unit 7 Defect part

Claims (13)

An alternating laminate part in which an inorganic plate-like particle layer containing charged inorganic plate-like particles and a binder layer charged to a charge opposite to that of the inorganic plate-like particles are alternately laminated on the resin film;
A barrier film for an electronic device, comprising: a filler portion formed in a defective portion of the inorganic plate-like particle layer where the inorganic plate-like particle is missing.   The barrier film for electronic devices according to claim 1, wherein the filling portion includes a metal oxide.   The barrier film for electronic devices according to claim 2, wherein the metal constituting the metal oxide is at least one of vanadium, tungsten, and molybdenum.   4. The barrier film for electronic devices according to claim 2, wherein the element constituting the metal oxide contains phosphorus.   The barrier film for an electronic device according to any one of claims 1 to 4, wherein the inorganic plate-like particles are negatively charged and the binder layer is positively charged.   6. The barrier film for electronic devices according to claim 5, wherein the inorganic plate-like particles are obtained by layer-separating at least one of a clay mineral and zirconium phosphate.   The barrier film for electronic devices according to claim 6, wherein the clay mineral is at least one of mica, vermulite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, and stevensite.   The barrier film for electronic devices according to claim 7, wherein the clay mineral is montmorillonite.   The barrier film for electronic devices according to claim 6, wherein the inorganic plate-like particles are obtained by layer separation of zirconium phosphate.   The barrier film for an electronic device according to claim 1, further comprising an adsorption layer that is formed on the resin film and adsorbs the resin film to the alternately laminated portion.   The barrier film for electronic devices according to claim 10, wherein the adsorption layer contains at least one of silica and alumina.   The barrier film for electronic devices according to claim 10, wherein the adsorption layer is charged with a charge opposite to that of the outermost layer, which is the outermost layer of the alternate laminated portion. The barrier film for electronic devices according to claim 12, wherein the treatment for charging the adsorption layer is performed by using a silane coupling agent.

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