WO2015008708A1

WO2015008708A1 - Electronic device

Info

Publication number: WO2015008708A1
Application number: PCT/JP2014/068607
Authority: WO
Inventors: 昌ニ西尾
Original assignee: コニカミノルタ株式会社
Priority date: 2013-07-17
Filing date: 2014-07-11
Publication date: 2015-01-22
Also published as: JPWO2015008708A1

Abstract

Provided is an electronic device in which the adhesiveness of a gas barrier film is maintained even under high-temperature, high-humidity conditions, and in which good barrier characteristics are maintained. This electronic device comprises a gas barrier film including, in the following order: a base material; a first layer having gas barrier performance; and a second layer obtained by applying a modification treatment to a coating film obtained by coating with a coating liquid including a polysilazane compound. The average oxygen content rate to the sum of silicon, oxygen, and nitrogen in a region from the outermost surface of the second layer opposing the base material to 35 nm from the outermost surface is greater than the average oxygen content rate to the sum of silicon, oxygen, and nitrogen in a region that is 35 nm or farther from the outermost surface.

Description

Electronic devices

The present invention relates to an electronic device.

So-called gas barrier films having the property of blocking the permeation of water vapor gas and oxygen gas have been studied.

In recent years, in addition to demands for weight reduction and size increase, long-term reliability, high degree of freedom in shape, and the ability to display curved surfaces have been added, resulting in a glass substrate that is heavy, easily broken, and difficult to increase in area. Instead, film substrates such as transparent plastics have begun to be adopted.

However, film substrates such as transparent plastics have a problem that gas barrier properties are inferior to general glass substrates. For this reason, there exists a subject that water vapor | steam and air osmose | permeate and will degrade the function in an electronic device, for example.

In order to enhance the gas barrier function of a film made of a plastic film as a base material, an inorganic film is formed on the base material by a vapor phase film forming method such as sputtering or plasma CVD (for example, see JP-A-HEI No. 8-165368).

As such an inorganic film, a silicon oxide film or an aluminum oxide film is known, but these techniques only have a water vapor barrier property of about 1 g / m ² / day at most. In recent years, with the development of large-sized liquid crystal displays, high-definition displays, etc., the gas barrier performance for film substrates is about 0.1 g / m ² / day for water vapor barriers, and further water vapor barrier performance is required for organic electroluminescence. It is the present situation.

For the purpose of improving gas barrier performance, US Pat. No. 5,260,095 discloses a polymer multilayer (PML) technique. In this technique, a coating consisting of a polymer layer and an aluminum oxide layer is applied to a flexible substrate and the substrate is sealed. Both the polymer layer and the aluminum oxide layer can be operated at very high speeds in the deposition process using web processing equipment. It is disclosed that the resistance to water and oxygen permeability is improved by 3 to 4 orders of magnitude compared to uncoated PET membranes. In such a polymer multilayer technique, the polymer layer obscures any defects in the adjacent ceramic layer so as to reduce the diffusion rate of oxygen and / or water vapor through the channels that can be created by these defects in the barrier layer. Suggested to work.

However, the interface between the polymer layer and the aluminum oxide layer is generally weak due to the incompatibility of the adjacent materials. Therefore, these layers are easy to peel off and the gas barrier property deteriorates after long-term storage. It was.

On the other hand, there is a technique for forming a gas barrier layer by a wet method using a coating liquid containing polysilazane instead of the above-described vapor phase method for forming an inorganic film on a substrate (for example, JP 2007-237588 A, International Publication). 2011/007543 (U.S. Patent Application No. 2012/107607). In Japanese Patent Application Laid-Open No. 2007-237588, a coating film obtained by applying a polysilazane-containing liquid on a substrate is subjected to plasma irradiation treatment in the presence of oxygen gas to be converted into silicon dioxide. In International Publication No. 2011/007543, the silicon dioxide film obtained by the silica conversion of polysilazane is considered to have insufficient gas barrier performance. Irradiation is performed to form a silicon dioxide film having a high nitrogen concentration region.

However, when the gas barrier film described above is applied to an electronic device, the gas barrier film is peeled off under a high temperature and high humidity condition, that is, there is a problem that the adhesion between the gas barrier film and the lower layer is lowered.

Accordingly, an object of the present invention is to provide an electronic device in which the adhesion of a gas barrier film is maintained even under high temperature and high humidity conditions, and high barrier properties are maintained.

Another object of the present invention is to provide an electronic device that maintains device performance even after long-term use.

The present invention provides a base material, a first layer having gas barrier performance, and a second layer obtained by modifying a coating film obtained by applying a coating liquid containing a polysilazane compound in this order. A region having an average oxygen content ratio of 35 nm or more from the outermost surface (region excluding the outermost surface to 35 nm region) having a gas barrier film containing and having an average oxygen content in the region of the outermost surface to 35 nm facing the substrate of the second layer It is an electronic device larger than the average oxygen content ratio.

It is a schematic diagram which shows an example of the manufacturing apparatus used for formation of the 1st layer concerning this invention. 1 is a gas barrier film, 2 is a base material, 3 is a first layer, 31 is a manufacturing apparatus, 32 is a delivery roller, 33, 34, 35 and 36 are transport rollers, 39 and 40 are film forming rollers, 41 Is a gas supply pipe, 42 is a plasma generating power source, 43 and 44 are magnetic field generators, 45 is a winding roller, A and B are points where the maximum value of the carbon distribution curve is formed, C1, C2, C3 and C4 Indicates the point where the minimum value of the carbon distribution curve is formed. It is an example of the organic electroluminescent panel which is an electronic device using the gas barrier film which concerns on this invention as a sealing film. 4 is a transparent electrode, 5 is an organic EL element, 6 is an adhesive layer, 7 is a counter film, 9 is an organic EL panel, and 10 is a gas barrier film. Gas barrier film No. which is an example. 4 is a diagram showing a film thickness composition of a second layer in FIG.

Hereinafter, preferred embodiments of the present invention will be described. In addition, this invention is not limited only to the following embodiment.

In this specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

The present invention provides a base material, a first layer having gas barrier performance, and a second layer obtained by modifying a coating film obtained by applying a coating liquid containing a polysilazane compound in this order. Silicon, oxygen in a region having an average oxygen content ratio of 35 nm or more from the outermost surface to the total of silicon, oxygen and nitrogen in the region of the outermost surface to 35 nm opposed to the base material of the second layer. And an electronic device greater than the average oxygen content relative to the sum of nitrogen.

As described above, International Publication No. 2011/007543 discloses that a polysilazane film formed on a substrate is irradiated with energy rays in an atmosphere substantially free of oxygen or water vapor, and at least a part of the polysilazane film. To form a high nitrogen concentration region. At the same time, oxidation behavior presumed to be caused by moisture from the substrate side occurs, the inside of the barrier layer changes to an oxide film (silicon oxide layer), and the silicon-containing film is composed of a high nitrogen concentration region and a silicon oxide region. (WO 2011/007543, paragraph “0075”).

Also, Example 10 of International Publication No. 2011/007543 describes a form in which a silicon-containing film including a high nitrogen concentration region is formed on an alumina-deposited PET film. And when a vapor deposition film is formed between the base material and the silicon-containing film, the silicon-containing film can compensate for a defect site such as a pinhole in the vapor deposition film, and further than the silicon-containing film or the vapor deposition film carrier. It is also described that a high gas barrier property can be expressed (International Publication No. 2011/007543, paragraph “0146”).

However, in the electronic device using the gas barrier film described in the above International Publication No. 2011/007543, the present inventor indicates that deterioration due to invasion of water vapor or the like occurs particularly during storage under high temperature and high humidity conditions. I found it.

In the gas barrier film described in International Publication No. 2011/007543, the oxygen element content in the high nitrogen concentration region on the surface side is small, and the oxygen element content increases as it becomes deeper (International Publication No. 2011/007543). , See FIG. It is estimated that the cause of the deterioration of the electronic device under the high temperature and high humidity condition is that the adhesion with the lower layer is deteriorated by such a film composition.

According to the configuration of the present invention, the gas barrier performance of the gas barrier film is maintained even under high temperature and high humidity conditions, and deterioration due to water vapor or the like of the electronic device can be suppressed. In addition, since high gas barrier performance is maintained even after long-term use, device performance is maintained.

The mechanism by which the present invention has such an effect is estimated as follows.

The gas barrier film used in the electronic device of the present invention has a first layer having gas barrier performance between the substrate and the second layer. The water vapor permeability of the first layer is preferably 0.1 g / m ² · day or less. By providing the first layer having a low water vapor transmission rate in the lower layer of the second layer in this way, the water vapor transmitted from the substrate side does not reach the second layer. This is a technical means different from International Publication No. 2011/007543 that allows water vapor permeation from the substrate side as described in paragraph “0075” of International Publication No. 2011/007543. Such technical means has found that the inventor has increased the deterioration of electronic devices under high-temperature and high-humidity conditions as the oxygen content in the substrate-side region increases as described above. It depends.

By making it difficult for water vapor to reach the second layer, the formation of silanol formed by bonding oxygen to polysilazane in the region on the substrate side is suppressed, and the adhesion between the second layer and the first layer is improved. Estimated to improve. For this reason, it is thought that deterioration of the electronic device resulting from peeling of a gas barrier film is suppressed.

Hereinafter, the gas barrier film constituting the electronic device of the present invention will be described.

In the gas barrier film used in the electronic device of the present invention, the base material, the first layer, and the second layer are in this order, but a preferred embodiment is a base material, In this embodiment, the first layer and the second layer formed (directly) on the first layer are arranged in this order.

In addition, the gas barrier unit having the first layer and the second layer may be formed on one surface of the base material, or may be formed on both surfaces of the base material. The gas barrier unit may further include a layer that does not necessarily have a gas barrier property.

In addition, the gas barrier film used in the electronic device of the present invention preferably has a permeated water amount of 1 × 10 ⁻³ g / (m ² · 24 h) or less as measured by the method described in Examples below. More preferably, it is 1 × 10 ⁻⁴ g / (m ² · 24 h) or less. In addition, since the permeated water amount in the gas barrier film is preferably as low as possible, the lower limit is not specified, but it is usually about 1 × 10 ⁻⁷ g / (m ² · 24 h) or more.

[Base material]
Examples of the base material used for the gas barrier film include a metal substrate such as silicon, a glass substrate, a ceramic substrate, and a plastic film, and a plastic film is preferably used. The plastic film to be used is not particularly limited in material, thickness and the like as long as it can hold a barrier layer, a hard coat layer, and the like, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification Examples thereof include thermoplastic resins such as polycarbonate resin, fluorene ring-modified polyester resin, and acryloyl compound.

The base material of the gas barrier film used in the electronic device of the present invention is preferably made of a material having heat resistance. Specifically, a resin base material having a linear expansion coefficient of 15 volume ppm / K or more and 100 volume ppm / K or less and a glass transition temperature (Tg) of 100 ° C. or more and 300 ° C. or less is used. The base material satisfies the requirements for use as a laminated film for electronic parts and displays. Specific examples include those described in paragraphs “0115” to “0116” of JP2013-226757A.

Since the gas barrier film is used as an electronic device such as an organic EL element, the plastic film is preferably transparent. Suitable ranges, measurement methods, and the like are as described in paragraphs “0120” and “0121” of JP2013-226757A.

The thickness of the plastic film used for the gas barrier film is appropriately selected depending on the application and is not particularly limited, but is typically 1 to 800 μm, preferably 10 to 200 μm. These plastic films may have functional layers such as a transparent conductive layer and a primer layer. As the functional layer, in addition to those described above, those described in paragraph numbers 0036 to 0038 of JP-A-2006-289627 can be preferably employed.

The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the barrier layer is provided, may be polished to improve smoothness.

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 used in the present invention can be produced by a conventionally known general method. A specific manufacturing method and the like are as described in paragraph “0125” of JP2013-226757A.

It is preferable to perform various known treatments for improving adhesion, for example, corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, at least on the side on which the barrier layer is provided. More preferably, the treatment is performed in combination.

[First layer]
The first layer has gas barrier performance. Here, the gas barrier performance is not limited, but the water vapor permeability of the first layer is preferably 0.1 g / m ² · day or less. When the water vapor transmission rate of the first layer is 0.1 g / m ² · day or less, the second layer has an average oxygen content ratio in the region of the outermost surface to 35 nm facing the substrate of 35 nm from the outermost surface. It can satisfy the configuration that it is larger than the average oxygen content ratio in the above region. Further, from the viewpoint of the effect of defect repair of the second layer, the water vapor permeability of the first layer is more preferably 0.01 g / m ² · day or less. Here, when the water vapor transmission rate of the first layer was calculated with a laminate in which the first layer was formed on the base material, from the water vapor transmission rate measured by the method described in Examples below, It is assumed that the water vapor transmission rate of the base material measured by the method described in Examples below is subtracted. The lower the water vapor transmission rate of the first layer, the better the effect of the present invention. However, it is usually 0.00001 g / m ² · day or more.

The first layer satisfying the water vapor transmission rate can be obtained by appropriately selecting the constituent material, manufacturing method, manufacturing conditions, and the like.

The thickness per layer of the first layer is not particularly limited, but is usually in the range of 30 to 500 nm, preferably 50 to 300 nm, from the viewpoint of gas barrier performance and the likelihood of defects. The first layer may have a stacked structure including a plurality of sublayers. In this case, the number of sublayers is preferably 2 to 10 layers. Moreover, each sublayer may have the same composition or a different composition. Note that the preferable range of the film thickness is the total of the plurality of sublayers when the first layer is composed of the plurality of sublayers. Here, as the thickness of the first layer, a value measured by a film thickness measurement method by observation with a transmission microscope (TEM) described below is adopted at the time of production and after the production.

<Method of measuring film thickness by observation with transmission microscope (TEM)>
The film thickness of each layer was measured at 10 locations by cross-sectional observation with a transmission electron microscope (TEM), and the average value was taken as the film thickness.

(TEM image of cross section in film thickness direction)
As a cross-sectional TEM observation, the observation sample was made into a thin piece by the following FIB processing apparatus, and then subjected to TEM observation.

(FIB processing)
Device: SII SMI2050
Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm (TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)
The first layer is made of silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon carbide, silicon oxynitride carbide (SiONC), and aluminum silicate from the viewpoint of gas barrier performance. It is preferable to include at least one selected from the group consisting of (SiAlO), including at least one selected from the group consisting of silicon oxynitride (SiON), silicon oxycarbide (SiOC), and aluminum silicate (SiAlO). More preferred. Among them, the first layer preferably contains silicon oxycarbide because adhesion to the second layer under high temperature and high humidity conditions is improved and deterioration of gas barrier performance is suppressed. Since silicon oxycarbide has carbon atoms, an organic bond is formed between the elements of the second layer, so that it is considered that the adhesion with the second layer is improved.

The formation method of the first layer is not particularly limited, but is preferably formed by a vapor deposition method because high gas barrier performance is obtained. As the vapor deposition method, there are a chemical vapor deposition method and a physical vapor deposition method.

Chemical vapor deposition (chemical vapor deposition, Chemical Vapor Deposition) is a method of depositing a film on a substrate by supplying a raw material gas containing a target thin film component and performing a chemical reaction on the substrate surface or in the gas phase. It is. In addition, for the purpose of activating the chemical reaction, there is a method of generating plasma or the like. Known CVD such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, vacuum plasma CVD method, atmospheric pressure plasma CVD method, etc. The method etc. are mentioned. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of film forming speed and processing area.

The gas barrier layer obtained by the vacuum plasma CVD method, or the plasma CVD method under atmospheric pressure or near atmospheric pressure, selects conditions such as the raw material (also referred to as raw material) metal compound, decomposition gas, decomposition temperature, input power, etc. Therefore, the target compound can be produced, which is preferable.

For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, silicon oxide is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.

As the silicon compound that can be used as the raw material compound, conventionally known compounds such as those described in US Patent Application Publication No. 2013/236710 [0056] can be used. In addition, a silicon compound which is a raw material compound used in forming a layer satisfying the requirements (i) to (ii), which are preferred forms described later, can be used.

Also, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, there are gases described in US Patent Application Publication No. 2013/236710 [0063]. Further, the decomposition gas may be mixed with an inert gas such as argon gas or helium gas.

A desired barrier layer can be obtained by appropriately selecting a source gas containing a source compound and a decomposition gas.

As an apparatus used for the vacuum plasma CVD method, there is an apparatus as shown in FIG. 1 of JP 2012-131194 A.

The physical vapor deposition method is a method of depositing a thin film of a target substance on the surface of the substance by a physical method in a gas phase, and can be roughly classified into an evaporation system and a sputtering system. It is preferable to use a system. Film formation by sputtering can be performed using bipolar sputtering, magnetron sputtering, dual magnetron (DMS) sputtering using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used. When sputtering an Si oxide film, a nitride film, a nitrided oxide film, a carbonated film, or the like, Si can be used as the target. As the inert gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film of Si oxide, nitride, nitride oxide, carbonate or the like can be formed. When the film is formed by RF (high frequency) sputtering, a ceramic target such as SiO ₂ or Si ₃ N ₄ can also be used. Examples of film forming conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, and these can be appropriately selected according to the sputtering apparatus, the material of the film, the film thickness, and the like. In addition, vacuum evaporation (heating method: resistance heating, electron beam, high frequency induction, laser, etc.), molecular beam evaporation (MBE), ion plating, ion beam evaporation etc. It may be used.

Reactive sputtering is preferably used as the physical vapor deposition method. The reactive sputtering method is a technique in which a reactive gas such as oxygen or nitrogen is allowed to flow in a chamber during sputtering to deposit a product of components and gases contained in a target constituent material as a thin film. The reactive sputtering method is preferable because the film composition becomes uniform and the gas barrier property becomes high. As the inert gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Further, oxygen, nitrogen, carbon dioxide, carbon monoxide, ammonia, H ₂ O, and acetylene can be used as the reaction gas.

The first layer may be formed using a roll-to-roll film forming apparatus. When the first layer is produced by the roll-to-roll method, the film can be continuously produced by the roll-to-roll method. Therefore, when the first layer is formed by using a roll-to-roll film forming apparatus, productivity is improved. Improved and preferred. Examples of the roll-to-roll plasma CVD apparatus include the apparatus shown in FIG. 1 described below, and a roll-to-roll sputtering apparatus is disclosed in Japanese Patent Application Laid-Open No. 2012-237047 (roll-two equipped with a magnetron sputtering cathode). A known apparatus such as a roll-type sputtering apparatus or an apparatus described in FIG. 5 of JP-A-2006-334909 can be used.

(Appropriate apparatus and suitable film composition for forming the first layer)
Hereinafter, the apparatus shown in FIG. 1, which is an apparatus suitable for forming the first layer, will be described. The apparatus illustrated in FIG. 1 is an apparatus that includes at least a pair of film forming rollers and a plasma power source, and that can discharge between the pair of film forming rollers. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus that can be suitably used for manufacturing the first layer. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

1 includes a feed roller 32,

transport rollers

33, 34, 35, and 36,

film forming rollers

39 and 40, a gas supply pipe 41, a plasma generating power source 42, and a film forming roller 39. And

magnetic field generators

43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the

film forming rollers

39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic

field generating apparatuses

43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge into the space between the film forming roller 39 and the film forming roller 40 by supplying electric power from the plasma generating power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form the 1st layer 3 on the surface of the base material 2 by CVD method, and it is 1st on the surface of the base material 2 on the film-forming roller 39. In addition, the first layer component can be deposited on the surface of the substrate 2 even on the film forming roller 40, so that the first layer is efficiently deposited on the surface of the substrate 2. Can be formed.

In the film forming roller 39 and the film forming roller 40,

magnetic field generators

43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

The

magnetic field generators

43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the

magnetic field generators

43 and 44 form a substantially closed magnetic circuit. By providing such

magnetic field generators

43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each

film forming roller

39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

The

magnetic field generators

43 and 44 provided on the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such

magnetic field generators

43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the

magnetic field generators

43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the first layer 3 that is a vapor deposition film can be efficiently formed.

As the film formation roller 39 and the film formation roller 40, known rollers can be used as appropriate. As such

film forming rollers

39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the

film forming rollers

39 and 40 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

In such a manufacturing apparatus 31, the base material 2 is disposed on a pair of film forming rollers (the film forming roller 39 and the film forming roller 40) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, when the plasma is generated by performing discharge in the facing space between the film formation roller 39 and the film formation roller 40, the base existing between the pair of film formation rollers is present. Each surface of the material 2 can be formed simultaneously. That is, according to such a manufacturing apparatus, the first layer component is deposited on the surface of the base material 2 on the film forming roller 39 by the plasma CVD method, and the first layer component is further formed on the film forming roller 40. Since the layer component can be deposited, the first layer can be efficiently formed on the surface of the substrate 2.

As the feed roller 32 and the

transport rollers

33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the winding roller 45 is not particularly limited as long as it can wind the gas barrier film 1 having the first layer 3 formed on the substrate 2, and a known roller is appropriately used. be able to.

As the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be used as appropriate.

The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 42 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. It is preferable to do. As the

magnetic field generators

43 and 44, known magnetic field generators can be used as appropriate.

In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The power applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed, and if it is 10 kW or less, the amount of heat generated during film formation can be suppressed, and the substrate during film formation can be suppressed. An increase in surface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

As the film forming gas (source gas etc.) supplied from the gas supply pipe 41 to the facing space, the source gas containing the source compound, the reaction gas, the carrier gas, and the discharge gas may be used alone or in combination of two or more. it can. The source gas in the film-forming gas used for forming the first layer 3 can be appropriately selected and used depending on the material of the first layer 3 to be formed.

It is preferable to use an organosilicon compound as the source gas. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane are preferable from the viewpoint of handling properties of the compound and gas barrier properties of the obtained first layer. These organosilicon compounds can be used alone or in combination of two or more.

Further, as the film forming gas, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. By making the ratio of the reaction gas not excessive, the first layer 3 to be formed is excellent in that excellent barrier properties and bending resistance can be obtained. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Using the manufacturing apparatus 31 shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film transport speed are adjusted as appropriate. By doing so, the first layer formed by the CVD method can be manufactured. That is, using the manufacturing apparatus 31 shown in FIG. 1, a discharge is generated between a pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film formation gas (raw material gas or the like) is decomposed by plasma, and the first layer 3 is formed on the surface of the substrate 2 on the film formation roller 39 and on the surface of the substrate 2 on the film formation roller 40. It is formed by the plasma CVD method.

The pressure in the vacuum chamber (degree of vacuum) can be adjusted as appropriate according to the type of raw material gas, but is preferably in the range of 0.5 Pa to 50 Pa.

The conveyance speed (line speed) of the base material 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, the range is from 5 to 20 m / min, and even more preferably from 0.5 to 1.2 m / min. If the line speed is 0.25 m / min or more, generation of wrinkles due to heat in the substrate can be effectively suppressed. On the other hand, if it is 100 m / min or less, it is excellent at the point which can ensure sufficient thickness as a 1st layer, without impairing productivity.

Here, in a preferred embodiment of the present invention, as in the apparatus shown in FIG. 1, at least a pair of film forming rollers and a plasma power source are provided, and plasma discharge is performed between the pair of film forming rollers. It is the form which forms the 1st layer containing silicon oxycarbide using the apparatus which can do.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reactive gas is reacted by plasma CVD to form a silicon-oxygen-based system When the thin film is prepared, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane as a raw material is a stoichiometric ratio of 12 times or less (more preferably 10 times or less). It is preferable that By including hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are incorporated into the first layer, and silicon oxycarbide containing silicon oxycarbide is contained. 1 layer can be formed, and excellent gas barrier properties and bending resistance can be exhibited in the obtained gas barrier film. From the viewpoint of use as a flexible substrate for devices that require transparency, such as organic EL elements and solar cells, the molar amount of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the deposition gas The lower limit of (flow rate) is preferably greater than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably greater than 0.5 times.

As described above, as a more preferable aspect of this embodiment, the first layer is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. This is excellent in flexibility (flexibility) and mechanical strength, especially when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because it is possible to efficiently manufacture the first layer in which the barrier performance is compatible. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in electronic devices.

In the apparatus of FIG. 1, a racetrack-like magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller shafts of the

film forming rollers

39 and 40, and plasma is generated in the magnetic field. Converge. Here, with the apparatus of FIG. 1, the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the carbon atoms relative to the total amount of L, silicon atoms, oxygen atoms, and carbon atoms. In the carbon distribution curve showing the relationship with the quantity ratio (carbon atomic ratio), there will be extreme values. Specifically, when the substrate 2 passes through the point A of the film forming roller 39 and the point B of the film forming roller 40 in FIG. 1, the maximum value of the carbon distribution curve is formed. On the other hand, when the base material 2 passes the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. 1, the carbon distribution curve is minimized in the first layer. A value is formed. Therefore, theoretically, five extreme values are generated for the two film forming rollers. Similarly, when the number of opposite rolls (TR number, number of two opposite roll sets) is n (n is an integer of 1 or more), the theoretical number of extreme values is about (5 + 4 × (n− 1)) It becomes a piece. However, the actual number of extreme values is not always the theoretical number of extreme values depending on the conveyance speed of the substrate, and may increase or decrease.

Here, the “extreme value” in the carbon distribution curve means the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the maximum or minimum value of carbon atoms in the carbon distribution curve. That means. In addition, the maximum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms decreases from an increase. This is a change. Furthermore, the minimum value in the carbon distribution curve means that when the distance from the surface of the first layer is changed, the value of the carbon atom ratio with respect to the total amount of silicon atoms, oxygen atoms, and carbon atoms increases from a decrease. It refers to a changing point.

Therefore, a more preferred embodiment of the first layer is a layer that satisfies the following requirement (i).

(I) The distance (L) from the surface of the first layer in the film thickness direction of the first layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (silicon atomic ratio) A distribution curve showing the relationship between L and the oxygen distribution curve showing the relationship between the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen); In the carbon distribution curve showing the relationship between the ratio of the amount of carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of carbon), the carbon distribution curve has at least two extreme values.

Furthermore, the carbon distribution curve preferably has at least three extreme values, more preferably at least four extreme values, but may have five or more extreme values. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier performance during bending is enhanced. Since the number of extreme values is also caused by the film thickness of the barrier layer, it cannot be specified unconditionally.

Here, in the case of having at least three extreme values, one extreme value of the carbon distribution curve and an extreme value adjacent to the extreme value of the first layer in the film thickness direction of the first layer. The absolute value of the difference in distance (L) from the surface (hereinafter also simply referred to as “distance between extreme values”) is preferably 200 nm or less, more preferably 100 nm or less, and 75 nm or less. It is particularly preferred. If it is such a distance between extreme values, since the site | part (maximum value) with many carbon atom ratios exists in a suitable period in a 1st layer, moderate flexibility is provided to a 1st layer, Generation of cracks during bending of the gas barrier film can be more effectively suppressed / prevented.

The distance between the extreme values of the barrier layer (the absolute value of the difference between the one extreme value of the carbon distribution curve and the distance (L) from the surface of the barrier layer in the thickness direction of the barrier layer at the extreme value adjacent to the extreme value) ) Can be adjusted by the rotation speed of the film forming rollers 39 and 40 (base material transport speed). In such film formation, the substrate 2 is conveyed by the delivery roller 32, the film formation roller 39, and the like, respectively, so that the surface of the substrate 2 is formed by a roll-to-roll continuous film formation process. The first layer 3 is formed.

In the first layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is preferably 3 at% or more, more preferably 5 at% or more, and 7 at%. More preferably, it is the above. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 3 at% or more, the gas barrier performance during bending is enhanced. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values.

Further, in the region of 90% or more (upper limit: 100%) of the film thickness of the first layer, (atomic ratio of oxygen), (atomic ratio of silicon), and (atomic ratio of carbon) increase in this order (atomic ratio) Is preferably O> Si> C). Here, at least 90% or more of the film thickness of the first layer does not have to be continuous in the barrier layer, and it is only necessary to satisfy the above-described relationship in a portion of 90% or more. By satisfying such conditions, the resulting gas barrier film has sufficient gas barrier properties and flexibility. In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the first layer, When this condition is satisfied, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 25 to 45 at%, and preferably 30 to 40 at%. More preferably. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the first layer is preferably 33 to 67 at%, and preferably 45 to 67 at%. More preferred. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms, and carbon atoms in the layer is preferably 3 to 33 at%, and more preferably 3 to 25 at%.

The oxygen distribution curve of the first layer preferably has at least one extreme value, more preferably has at least two extreme values, and more preferably has at least three extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the barrier layer, and it cannot be defined unconditionally. In the case of having at least three extreme values, from the surface of the first layer in the film thickness direction of the first layer at one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value. The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less. With such a distance between extreme values, the occurrence of cracks during bending of the gas barrier film can be more effectively suppressed / prevented.

In addition, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the first layer (hereinafter also simply referred to as “O _max −O _min difference”) is 3 at% or more. Is preferably 5 at% or more, more preferably 6 at% or more, and even more preferably 7 at% or more. When the absolute value is 3 at% or more, the gas barrier property when the obtained gas barrier film is bent is further improved.

Furthermore, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the first layer (hereinafter, also simply referred to as “Si _max −Si _min difference”) is less than 5 at%. Preferably, it is less than 4 at%, more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property and mechanical strength of the obtained gas barrier film are further improved. The _lower limit of Si max _{-Si min} _difference, since Si max improvement of cracking suppressing / preventing flexion enough gas barrier film _{-Si min} difference is small is high, not particularly limited.

Moreover, it is preferable that the total amount of carbon and oxygen atoms in the film thickness direction of the first layer is substantially constant. Thereby, the 1st layer exhibits moderate flexibility, and the crack generation at the time of bending of a gas barrier film can be controlled and prevented more effectively. More specifically, the sum of oxygen atoms and carbon atoms with respect to the distance (L) from the surface of the first layer in the film thickness direction of the first layer and the total amount of silicon atoms, oxygen atoms, and carbon atoms In the oxygen carbon distribution curve showing the relationship with the ratio of the amount (atomic ratio of oxygen and carbon), the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen carbon distribution curve (hereinafter, (Also simply referred to as “OC _max −OC _min difference”) is preferably less than 5 at%, more preferably less than 4 at%, and even more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is the distance (L) from the surface of the first layer in the film thickness direction of the first layer in the film thickness direction. Since there is a general correlation, the “distance from the surface of the first layer in the film thickness direction of the first layer” is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface of one layer can be employed. The silicon distribution curve, oxygen distribution curve, carbon distribution curve and oxygen carbon distribution curve were prepared under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific;
Irradiation X-ray: Single crystal spectroscopic AlKα X-ray spot and size: 800 × 400 μm ellipse.

From the viewpoint of forming the first layer having a uniform and excellent gas barrier property over the entire film surface, the first layer is substantially uniform in the film surface direction (direction parallel to the surface of the first layer). It is preferable that Here, the fact that the first layer is substantially uniform in the film surface direction means that the oxygen distribution curve and the carbon distribution curve are measured at any two measurement points on the film surface of the first layer by XPS depth profile measurement. When the oxygen carbon distribution curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the maximum value of the atomic ratio of carbon in each carbon distribution curve And the absolute value of the difference between the minimum values is the same as each other or within 5 at%.

Furthermore, it is preferable that the carbon distribution curve is substantially continuous. Here, the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. The distance (x, unit: nm) from the surface of the first layer in the film thickness direction of at least one of the first layers to be used, and the atomic ratio of carbon (C, unit: at%) In the relationship, the condition expressed by the following formula (1) is satisfied.

Also, in the carbon distribution curve, the carbon atom ratio of the first layer is preferably in the range of 8 to 20 at%, more preferably in the range of 10 to 20 at%, as an average value of the entire layer. By setting it within this range, it is possible to form the gas first layer that sufficiently satisfies the gas barrier property and the flexibility.

[Second layer]
The second layer is obtained by modifying a coating film obtained by applying a coating liquid containing a polysilazane compound. The average oxygen content ratio of the region of the outermost surface to 35 nm (hereinafter also referred to as a surface region) facing the substrate of the second layer is 35 nm or more from the outermost surface (hereinafter also referred to as the substrate side region). It is larger than the average oxygen content ratio (that is, the average oxygen content ratio in the surface region / the average oxygen content ratio in the substrate side region exceeds 1). From the viewpoint of improving the adhesion to the lower layer, the average oxygen content ratio of the surface region / average oxygen content ratio of the base material side region is preferably 1.10 or more, and more preferably 1.35 or more. The larger the average oxygen content ratio in the surface region / the average oxygen content ratio on the substrate side, the better. However, from the viewpoint of production, it is usually about 1.90 or less.

Here, the oxygen content ratio is the oxygen content ratio relative to the total of silicon, oxygen, and nitrogen.

Note that the oxygen content ratio in the film thickness direction (composition ratio of oxygen element (at%)) is obtained by using both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Further, it can be measured by so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created with the vertical axis representing the composition ratio (at%) of the oxygen element and the horizontal axis representing the etching time (sputtering time). FIG. 3 shows a gas barrier film No. in Examples described later. 4 shows a distribution curve.

In the present invention, it was created under the following measurement conditions.

[Measurement condition]
Etching ion species: Argon (Ar ⁺ )
Etching rate: 0.05 nm / sec (SiO ₂ thermal oxide equivalent value)
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

In the measurement by the XPS depth profile, the interface between the first layer and the second layer, or the interface between the second layer and the other layer when another layer is stacked on the second layer, The film thickness at the time of manufacture or the film thickness obtained by the film thickness measurement method by observation with a transmission microscope (TEM) = the SiO ₂ equivalent film thickness. That is, for example, in FIG. 3 to be described later, the manufacturing thickness and the TEM observation film thickness of the second layer are 100 nm. Therefore, the point of SiO ₂ equivalent film thickness = 0 nm is the outermost layer, and the SiO ₂ equivalent film thickness = The second layer is up to 100 nm. The film thickness measurement method by transmission microscope (TEM) observation is as described in the first layer.

Further, the average oxygen content ratio within 35 nm from the outermost surface is a value obtained by measuring the oxygen content ratio in the film thickness direction, integrating in the film thickness direction, and dividing the integrated value by the integrated film thickness. The same applies to a region of 35 nm or more.

The average oxygen content in the region of the outermost surface to 35 nm is preferably 25 to 55 at%, more preferably 30 to 45 at%. Within the above range, the modification of the polysilazane compound on the surface layer side proceeds to some extent and the hardness is ensured to some extent, and the scratch resistance of the second layer can be improved, while the bending resistance and high temperature and high humidity are improved. It is preferable because gas barrier properties under conditions are also secured. And within a suitable range of the average oxygen content ratio of the surface region of the second layer, the average oxygen content ratio of the surface region / average oxygen content ratio of the base material side region is taken into account, and the average of the base material side region It is preferable to set the oxygen content ratio. By setting as such, a soft region having a lower hardness than the surface layer side exists in the second layer on the base material side, and the generated stress is dispersed in the base material side region in the horizontal direction. Therefore, it is preferable because the bending resistance of the film is improved. However, since it is necessary to contain oxygen to some extent in order to maintain the hardness on the substrate side, the average oxygen content ratio in the region of 35 nm or more from the outermost surface is preferably 10 at% or more, and 15 at% or more. It is more preferable. More specifically, the average oxygen content ratio in the region of 35 nm or more from the outermost surface is preferably 10 to 40 at%, and more preferably 15 to 30 at%.

In the present invention, the thickness of the second layer exceeds 35 nm. Since the high gas barrier performance can be maintained in the long term, the thickness of the second layer is preferably 40 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. Although the upper limit of a 2nd layer is not specifically limited, From a viewpoint of the applicability | paintability at the time of layer formation and light transmittance, it is preferable that it is 500 nm or less.

(Polysilazane)
Polysilazane is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, and ceramics such as both intermediate solid solutions SiO _x N _y. It is a precursor inorganic polymer.

Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different. Here, examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. Examples of the aryl group include aryl groups having 6 to 30 carbon atoms. More specifically, alkyl groups described in U.S. Patent Application Publication No. 2013/236710 [0117] and [0120] can be given. The (trialkoxysilyl) alkyl group includes an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group. The substituent optionally present in R ₁ to R ₃ is not particularly limited, and examples thereof include an alkyl group, a halogen atom, a hydroxyl group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxyl group (—COOH), a nitro group (—NO ₂ ) and the like. Note that the optionally present substituent is not the same as R ₁ to R ₃ to be substituted. For example, when R ₁ to R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group in the above is the same as the definition of the general formula (I), and thus the description is omitted.

In the general formula (I), (II) or (III), n, n ′, p, n ″, p ″ and q are integers, and the general formula (I), (II) or (III) It is preferable that the polysilazane having a structure represented by formula (1) is determined so as to have a number average molecular weight of 150 to 150,000 g / mol. Note that n ′ and p may be the same or different. Further, n ″, p ″ and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

On the other hand, organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an improved adhesion to the lower layer due to having an alkyl group such as a methyl group, and is hard and brittle polysilazane. The ceramic film can be provided with toughness, and there is an advantage that generation of cracks can be suppressed even when the (average) film thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The number average molecular weight (Mn) is about 600 to 2000 (polystyrene conversion), and there are liquid or solid substances, and the state 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. Examples of commercially available polysilazane solutions include those described in paragraph “0051” of JP2013-226757A.

Other examples of polysilazanes that can be used in the present invention include, but are not limited to, those described in [0128] of US Patent Application Publication No. 2013/236710.

The content of polysilazane in the second layer can be 100% by weight when the total weight of the second layer is 100% by weight. When the second layer contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by weight or more and 99% by weight or less, and 40% by weight or more and 95% by weight or less. More preferably, it is 70 to 95 weight%.

The method for forming the second layer is not particularly limited, and a known method can be applied. A coating solution containing polysilazane and, if necessary, a catalyst in an organic solvent is applied by a known wet coating method. A method of removing by evaporation and then performing a reforming treatment is preferable.

(Coating liquid containing polysilazane)
The solvent for preparing the coating liquid containing polysilazane is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups that easily react with polysilazane (for example, hydroxyl group, amine group, etc.) ) And an inert organic solvent with respect to polysilazane is preferred, and an aprotic organic solvent is more preferred. Specific examples include those described in [0129] of US Patent Application Publication No. 2013/236710. 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 coating solution is not particularly limited and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by weight, more preferably 5 to 50% by weight, and particularly preferably 10 to 10%. 40% by weight.

The coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, a metal catalyst such as an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, or an Rh compound such as Rh acetylacetonate. , N-heterocyclic compounds. Examples of the amine catalyst include those described in paragraph “0057” of JP2013-226757A. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10 mol%, more preferably 0.5 to 7 mol%, based on polysilazane. 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.

The following additives can be used in the polysilazane modified layer forming coating solution as necessary. Specifically, those described in paragraph “0058” of JP2013-226757A.

(Method of applying a coating liquid containing polysilazane)
As a method for applying the coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

The coating thickness can be appropriately set according to the purpose.

After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable gas barrier layer can be obtained. The remaining solvent can be removed later.

It is preferable to dry the coating film in a low oxygen / low water vapor concentration atmosphere. Specifically, the oxygen concentration is preferably in the range of 20% by volume (200,000 ppm) or less, more preferably 2% by volume (20,000 ppm), and still more preferably 0.5% by volume (5,000 ppm) or less. . Further, the water vapor concentration is preferably in the range of 0.1% by volume (1000 ppm) or less, more preferably 0.01% by volume (100 ppm) or less, and still more preferably 0.001% by volume (10 ppm) or less. In addition, the minimum of oxygen concentration and water vapor | steam density | concentration is 0 ppm. By performing the drying treatment in such a low water vapor concentration atmosphere, the formation of silicon oxynitride can proceed more favorably than the formation of silicon dioxide, and the gas barrier performance of the second layer can be improved.

The drying temperature of the coating film varies depending on the substrate to be applied, but is preferably 50 to 200 ° C. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere is preferably performed under an inert atmosphere such as a nitrogen atmosphere or an argon atmosphere.

(Modification process)
The second layer is formed by irradiating the coating film obtained by applying a coating liquid containing a polysilazane compound with energy rays in an atmosphere having an oxygen concentration of 1000 ppm by volume or less and a water vapor concentration of 150 ppm by volume or less. It is preferable. That is, the reforming treatment is preferably performed by irradiating energy rays in an atmosphere having an oxygen concentration of 1000 volume ppm or less and a water vapor concentration of 150 volume ppm or less.

In the reforming treatment performed in a region where the oxygen concentration and / or the water vapor concentration is high (region where the oxygen concentration exceeds 1000 volume ppm / the water vapor concentration exceeds 150 volume ppm), silicon dioxide is mainly formed by the reforming treatment. The mechanism by which silicon dioxide is formed is estimated as follows. When an appropriate amount of oxygen is present in the atmosphere, 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. In addition, since the energy of vacuum ultraviolet rays is higher than the bond energy of Si—N in perhydropolysilazane, the Si—N bond is broken and oxidized when there are oxygen sources such as oxygen, ozone, water, etc. It is considered that O—Si bond and Si—O—N bond are generated. It is thought that recombination of the bond may occur due to cleavage of the polymer main chain.

On the other hand, in an atmosphere with very low oxygen and water vapor concentrations (oxygen concentration of 1000 ppm by volume or less / water vapor concentration of 150 ppm by volume or less), Si—N bonds in polysilazane are cleaved by energy irradiation. Since the content is very small, conversion to silicon oxynitride or silicon nitride proceeds more efficiently than formation of silicon dioxide. The presence of silicon oxynitride or silicon nitride mainly in the film is considered to improve the gas barrier performance of the second layer. Also, in an atmosphere having a high oxygen and water vapor concentration, the oxygen concentration in the surface region is lower than the oxygen concentration in the substrate side region, and the average oxygen content ratio on the surface side of the second layer is on the substrate side. It is difficult to obtain a composition having a larger average oxygen content ratio. On the other hand, after the first layer is formed on the substrate, the content of oxygen and water vapor concentration is very low, or the energy beam irradiation is modified in an atmosphere in which oxygen and water vapor are not present. It becomes possible to set it as the composition that the average oxygen content ratio of the surface side of 2 layers is larger than the average oxygen content ratio of the base material side.

The modification treatment in the present invention refers to modification of polysilazane, specifically, a conversion reaction to silicon nitride or silicon oxynitride, and specifically, the gas barrier film as a whole has gas barrier properties (water vapor permeation). This refers to a process for forming an inorganic thin film at a level that can contribute to the development of a rate of 1 × 10 ⁻³ g / (m ² · 24 h) or less.

Specific examples of the energy ray irradiation treatment include plasma treatment and ultraviolet irradiation treatment, and these may be performed in combination. The energy ray irradiation treatment can be applied to a plastic substrate that can undergo a conversion reaction at a lower temperature than a heat treatment that requires a treatment at 450 ° C. or higher, and is difficult to treat at a high temperature. In addition to these treatments, heat treatment may be performed.

(Heat treatment)
By subjecting the coating film containing polysilazane to heat treatment in combination with other modification treatment, preferably energy ray irradiation treatment, the modification treatment can be performed efficiently.

As the heat treatment, for example, a method of heating a coating film by contacting a substrate with a heating element such as a heat block, a method of heating an atmosphere by an external heater such as a resistance wire, an infrared region such as an IR heater, etc. A method using light can be raised, but is not particularly limited. Moreover, you may select suitably the method which can maintain the smoothness of the coating film containing a silicon compound.

The temperature of the coating film during the heat treatment is preferably adjusted appropriately in the range of 50 to 250 ° C, more preferably in the range of 50 to 120 ° C.

Further, the heating time is preferably in the range of 1 second to 10 hours, more preferably in the range of 10 seconds to 1 hour.

(Oxygen concentration and water vapor concentration during reforming treatment)
As described above, the oxygen concentration in the atmosphere during the reforming treatment is preferably 1000 ppm by volume or less, more preferably 500 ppm by volume or less, and even more preferably 100 ppm by volume or less. Although the lower limit of the oxygen concentration is 0 ppm by volume, it is difficult to control the atmosphere to contain no oxygen at all, and practically, it is 8 ppm by volume or more. Further, the water vapor concentration in the atmosphere during the reforming treatment is preferably 150 ppm by volume or less, more preferably 100 ppm by volume or less, and still more preferably 75 ppm by volume or less. In addition, although the minimum of water vapor | steam density | concentration is 0 volume ppm, it is difficult to control to the atmosphere which does not contain water vapor | steam at all, and actually becomes 10 volume ppm or more. The water vapor concentration refers to water vapor partial pressure / atmospheric pressure at a room temperature of 23 ° C.

Examples of a method for carrying out the reforming treatment in an atmosphere of such oxygen or water vapor concentration include a method for reducing the pressure in the apparatus during the reforming treatment, a method for performing a gas flow with an inert gas or the like under normal pressure, and the like. . In the method of reducing the pressure, the pressure in the apparatus is reduced from atmospheric pressure to preferably 100 Pa or less, more preferably 20 Pa or less using a vacuum pump, and then a predetermined gas is introduced to obtain a predetermined pressure. Create an atmosphere.

(Plasma treatment)
As the plasma treatment that can be used as the modification treatment, a known method can be used, and examples thereof include low-pressure plasma treatment and atmospheric pressure plasma treatment.

Examples of the discharge gas used in the plasma treatment include nitrogen gas and 18th group atoms of the periodic table, and specifically, those described in US Patent Application Publication No. 2013/236710 [0091] are used.

Low-pressure plasma treatment refers to treatment performed under a pressure condition of 100 Pa or less, preferably 10 Pa or less. In the vacuum state in the apparatus, the pressure in the apparatus is reduced from atmospheric pressure (101325 Pa) to a pressure of 100 Pa or less, preferably 10 Pa or less using a vacuum pump, and then the gas described below is introduced to a pressure of 100 Pa or less. Can be obtained. The pressure of the low-pressure plasma treatment is preferably 1 Pa to 1000 Pa, more preferably 1 Pa to 500 Pa.

The oxygen concentration and water vapor concentration under low pressure are generally evaluated by oxygen partial pressure and water vapor partial pressure. The low-pressure plasma treatment is performed under the above pressure, with an oxygen partial pressure of 10 Pa or less (oxygen concentration 0.001% (10 ppm)) or less, preferably an oxygen partial pressure of 2 Pa or less (oxygen concentration 0.0002% (2 ppm)) or less, a water vapor concentration It is carried out at 10 ppm or less, preferably 1 ppm or less.

For low-pressure plasma, a known electrode or waveguide is placed in a vacuum closed system, and power such as direct current, alternating current, radio wave, or microwave is applied via the electrode or waveguide. Plasma can be generated. Power applied to the plasma treatment (W), the unit area of the electrode (cm ²⁾ per preferably ^{0.0001W / cm 2 ~ 100W / cm} 2, more preferably ^{0.001W / cm 2 ~ 50W / cm} 2 is there.

For atmospheric pressure plasma treatment, gas is passed between two electrodes, this gas is turned into plasma and then irradiated onto the substrate, or a polysilazane film that is irradiated between the two electrodes is placed, and gas is passed through it. The method to do. In order to lower the oxygen / water vapor gas concentration in the processing atmosphere, the gas flow rate in the atmospheric pressure plasma treatment is preferably as high as possible, preferably 0.01 to 1000 L / min, more preferably 0.1 to 500 L / min. is there.

In the atmospheric pressure plasma treatment, the applied power (W), the unit area of the electrode (cm ²⁾ per preferably ^{0.0001W / cm 2 ~ 100W / cm} 2, more preferably 0.001W ^/ cm 2 ~ 50W ^/ cm ² .

(UV irradiation treatment)
As one of the modification treatment methods, treatment by ultraviolet irradiation is also preferable. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and it is possible to form a film containing silicon oxynitride having high density and insulation at low temperature. .

In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

The ultraviolet ray referred to in the present invention generally refers to an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of an ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later, it is preferably 210 to 375 nm. Use ultraviolet light.

In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range in which the substrate carrying the second layer to be irradiated is not damaged.

Taking the case of using a plastic film as a base material, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the base material surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / cm. The distance between the base material and the ultraviolet irradiation lamp is set so as to be ^2, and irradiation can be performed for 0.1 seconds to 10 minutes.

There is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.

Examples of such means for generating ultraviolet rays include those described in paragraph “0054” of JP2012-228859A, but are not particularly limited.

UV irradiation can be applied to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate used.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the present invention, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by the vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and bonds atoms with only photons called photon processes. In this method, a film is formed at a relatively low temperature (about 200 ° C. or less) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by action. In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as having mentioned above.

The radiation source in the present invention may be any radiation source that emits light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and has an emission line at about 185 nm. Low pressure mercury vapor lamps, and medium and high pressure mercury vapor lamps having a wavelength component of 230 nm or less, and excimer lamps having maximum emission at about 222 nm.

Among these, 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.

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

¡Excimer lamps have high light generation efficiency and can be lit 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 in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

The gas satisfying the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays is preferably a dry inert gas, and particularly preferably dry nitrogen gas 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.

In vacuum ultraviolet irradiation step, it is preferable that the illuminance of the vacuum ultraviolet rays in the coated surface of the coating film is subjected is 30 ~ 200mW / cm ^2, and more preferably 50 ~ 160mW / cm ^2. If it is less than 30 mW / cm ^2, there is a concern that the reforming efficiency is greatly reduced, and if it exceeds 200 mW / cm ² , there is a concern that the coating film may be ablated or the substrate may be damaged.

Irradiation energy amount of the VUV in the coated surface is preferably 10 ~ 1000J / cm ^2, more preferably from 50 ~ 500J / cm ^2, further preferably 80 ~ 500J / cm ^2. If it is less than 10 J / cm ² , the reforming does not proceed, and there is a possibility that the average oxygen content ratio in the surface region / the average oxygen content ratio on the substrate side becomes 1 or less. The performance of the system may be degraded. On the other hand, if it exceeds 1000 J / cm ² , there are concerns about cracking due to excessive reforming and thermal deformation of the substrate. The amount of irradiation energy is calculated as illuminance (mW / cm ² ) × time (s) of excimer light.

Further, the vacuum ultraviolet light used for reforming, CO, may be generated by plasma formed in a gas containing at least one of CO ₂ and CH _4. Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

[Middle layer]
An intermediate layer may be separately provided between the above-described base material, first layer, and second layer as long as the effects of the present invention are not impaired.

[Anchor coat layer]
On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). As the constituent material and formation method of the anchor coat layer, the materials and methods disclosed in paragraphs “0229” to “0232” of JP2013-52561A are appropriately employed.

[Smooth layer]
The gas barrier film may have a smooth layer between the surface of the base material having the barrier layer, preferably between the base material and the base layer. The smooth layer is provided for flattening the rough surface of the substrate on which protrusions and the like are present, or for filling the unevenness and pinholes generated in the barrier layer with the protrusions existing on the resin base material. . The materials, methods, etc. disclosed in paragraphs “0233” to “0248” of JP2013-52561A are appropriately employed as the constituent material, forming method, surface roughness, film thickness, etc. of the smooth layer.

[Bleed-out prevention layer]
The gas barrier film may further have a bleed-out preventing layer. The bleed-out prevention layer is used for the purpose of suppressing a phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the resin base material to the surface 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. As the constituent material, forming method, film thickness and the like of the bleed-out prevention layer, the materials, methods and the like disclosed in paragraphs “0249” to “0262” of JP2013-52561A are appropriately employed.

[Electronic device]
(Electronic element body)
The electronic element main body is the main body of the electronic device, and is disposed on the gas barrier film side. As the electronic element body, a known electronic device body to which sealing with a gas barrier film can be applied can be used. For example, an organic EL element, a solar cell (PV), a liquid crystal display element (LCD), electronic paper, a thin film transistor, a touch panel, and the like can be given. From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic element body is preferably an organic EL element or a solar cell, and more preferably an organic EL element. There is no restriction | limiting in particular also about the structure of these electronic element main bodies, It can have a conventionally well-known structure.

Hereinafter, an organic EL element and an organic EL panel using the same will be described as an example of a specific electronic element body.

FIG. 5 shows an example of an organic EL panel 9 which is an electronic device using the gas barrier film 10 according to the present invention as a sealing film. As shown in FIG. 5, the organic EL panel 9 includes a gas barrier film 10, a transparent electrode 4 such as ITO formed on the gas barrier film 10, and an organic EL formed on the gas barrier film 10 via the transparent electrode 4. An element 5 and a counter film 7 disposed via an adhesive layer 6 so as to cover the organic EL element 5 are provided. It can be said that the transparent electrode 4 forms part of the organic EL element 5. The transparent electrode 4 and the organic EL element 5 are formed on the surface of the gas barrier film 10 on which the gas barrier layer is formed. The counter film 7 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 7, the surface on which the gas barrier layer is formed may be attached to the organic EL element 5 with the adhesive layer 6.

(Organic EL device)
The organic EL element 5 sealed with the gas barrier film 10 in the organic EL panel 9 will be described.

Although the preferable specific example of the layer structure of the organic EL element 5 is shown below, this invention is not limited to these.

(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (anode)
As the anode (transparent electrode 4) in the organic EL element 5, 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 electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.

The formation method and film thickness of the anode are the same as those described in paragraph “0056” of JP2012-106421A.

(cathode)
As the cathode in the organic EL element 5, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples and preferred examples of such electrode materials are the same as those described in paragraph “0058” of JP2012-106421A.

The formation method and film thickness of the cathode are the same as those described in paragraph “0058” of JP2012-106421A.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer, and an electron injection layer and a hole injection layer are provided as necessary, between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.

An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).

The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, 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.

Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Examples thereof include those described in paragraph “0059” of Kai 2012-106421. The buffer layer (injection layer) is preferably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Light emitting layer)
The light emitting layer in the organic EL element 5 is a layer that emits light by recombination of electrons and holes injected from an electrode (cathode, anode) or an electron transport layer or a hole transport layer, and the light emitting portion is a light emitting layer. The interface between the light emitting layer and the adjacent layer may be used.

The light emitting layer of the organic EL element 5 preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.

(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.

Examples of fluorescent dopants include those described in paragraph “0060” of JP2012-106421A.

Examples of phosphorescent dopants include those described in paragraph “0060” of JP2012-106421A.

(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more kinds of compounds. It is also simply called a dopant). For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Further, if the light emitting layer is composed of three types of compound A, compound B and compound C and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, and compound C is a host compound.

The light emitting host is not particularly limited in terms of structure, but includes those described in paragraph “0060” of JP2012-106421A.

The formation method and film thickness of the light emitting layer are the same as those described in paragraph “0060” of JP2012-106421A.

(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 either hole injection or transport or electron barrier properties, and may be either organic or inorganic. Examples thereof include those described in paragraph “0061” of JP2012-106421A.

The formation method and film thickness of the hole transport layer are the same as those described in paragraph “0061” of JP2012-106421A.

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

The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples thereof include those described in paragraph “0062” of JP2012-106421A.

The formation method and film thickness of the electron transport layer are the same as those described in paragraph “0062” of JP2012-106421A.

As a method for producing an organic EL element, a conventionally known method can be used, and specifically, a method described in paragraph “0063” of JP2012-106421A can be used.

The effect of the present invention will be described using the following examples and comparative examples. In the examples, “part” or “%” may be used, but “part by weight” or “% by weight” is expressed unless otherwise specified. Unless otherwise specified, each operation is performed at room temperature (25 ° C.).

<Production of gas barrier films 1 to 5>
1. Preparation of Underlayer A biaxially stretched PEN film (manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) having a thickness of 100 μm was used as a base material.

After applying UV curable organic / inorganic hybrid hard coating material OPSTAR Z7501 manufactured by JSR Co., Ltd. on the easy-adhesive surface of the base material and applying it with a wire bar so that the film thickness after drying becomes 4 μm, drying conditions; 80 After drying at 3 ° C. for 3 minutes, a high pressure mercury lamp was used in an air atmosphere, curing conditions: 1.0 J / cm ² curing was performed, and an underlayer was formed.

2. Formation of First Layer Using the vacuum plasma CVD apparatus shown in FIG. 1, a 300 nm first layer was formed on the underlayer under the following film formation conditions.
[Plasma deposition conditions]
<Film forming conditions>
-Film transport speed: 0.5 m / min
・ Supply amount of source gas (HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
・ Supply amount of oxygen gas (O ₂ ): 500 sccm
・ Degree of vacuum in the vacuum chamber: 3Pa
・ Applied power from the power source for plasma generation: 0.8 kW
-Frequency of power source for plasma generation: 80 kHz.

3. Formation of second layer (Preparation of polysilazane coating solution)
A xylene (dehydrated) solution (Aquamica NL110A: manufactured by AZ Electronic Materials Co., Ltd.) containing 20% by mass of a palladium-based catalyst (palladium propionate) and 20% by mass of perhydropolysilazane is further added with xylene to give a solid content of 2 A polysilazane coating solution was prepared by diluting to a weight percent.

(Application of polysilazane coating solution, drying)
The polysilazane coating solution prepared above was spin-coated (10 s, 3000 rpm) on the first layer and dried at 120 ° C. for 10 minutes in a nitrogen atmosphere to prepare a polysilazane film having a thickness of 100 nm. Drying was performed in an atmosphere having a water vapor concentration of about 500 ppm.

(Modification process)
In the above film, using an excimer lamp in a nitrogen atmosphere, under the oxygen and water vapor environment conditions shown in Table 1, the irradiation time of vacuum ultraviolet rays (172 nm) is set as the exposure time shown in Table 1, and the modification treatment is performed. As a result, gas barrier films 1 to 5 were obtained.

《Reforming treatment equipment》
Apparatus: Ex D-irradiator MODEL manufactured by M.D. Com: MECL-M-1-200
Wavelength: 172 nm
Lamp filled gas: Xe
<Reforming treatment conditions>
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Film transport speed: 0.6 m / min
Pass number: 1 time The ratio of oxygen element in the film thickness direction from the surface of the polysilazane modified film is measured by XPS, and the ratio of the average oxygen content ratio up to 35 nm to the average oxygen content ratio after 35 nm is shown in Table 1 as the oxygen element ratio. It was shown to. Further, in FIG. 4 shows the oxygen distribution curve of No. 4 second layer.

<Evaluation method of water vapor transmission rate>
In accordance with the following measurement method, the permeated moisture amount of each gas barrier film was measured, and the water vapor barrier property was evaluated according to the following criteria.

(apparatus)
Vapor deposition device: JEOL Ltd., vacuum vapor deposition device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Using a vacuum deposition device (manufactured by JEOL Ltd., vacuum deposition device JEE-400) on the surface of the barrier layer of the sample, the portion of the gas barrier film sample to be deposited before attaching the transparent conductive film (9 locations of 12 mm x 12 mm) The metal calcium (granular form) was vapor-deposited (deposition film thickness 80 nm). Thereafter, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample is stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of moisture permeated into the cell is calculated from the corrosion amount of metallic calcium based on the method described in Japanese Patent Application Laid-Open No. 2005-283561. did.

In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 60 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 1000 hours.

The permeated water amount (g / m ² · day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method and ranked as follows. In addition, if it is rank 3 or more, there is no problem in actual use and it is a pass product.

(Rank evaluation)
Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 5 × 10 ⁻⁴ g / m ² / day 3: 5 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more <Production of organic light-emitting elements (organic EL elements) 1 to 5>
A transparent conductive film was produced on the gas barrier layers of the produced gas barrier films 1 to 5 by the following method. The gas barrier film was ashed with oxygen plasma (2 kW output, substrate temperature 200 ° C.) for 10 minutes. By this treatment, the surface of the gas barrier film is further cleaned and becomes a flatter layer.

An ITO transparent electrode (hole injection electrode) was formed and patterned so as to constitute a pixel of 64 dots × 7 lines (100 × 100 μm per pixel) with a film thickness of 85 nm. And the board | substrate with which the patterned hole injection electrode was formed was ultrasonically cleaned using neutral detergent, acetone, and ethanol, and it pulled up from boiling ethanol and dried. Thereafter, UV / O ₃ cleaning was performed.

Next, the substrate was moved to the film formation chamber, fixed to the substrate holder of the vacuum deposition apparatus, and the inside of the tank was depressurized to 1 × 10 ⁻⁴ Pa or less. Then, poly (thiophene-2,5-diyl) as a hole injection layer is formed to a thickness of 10 nm, and TPD doped with 1% by mass of rubrene as a hole transport layer and a yellow light-emitting layer is co-evaporated to 5 nm. The film was formed to a film thickness. The concentration may be determined based on the color balance of the emission color, and depends on the light intensity and wavelength spectrum of the blue light emitting layer to be formed thereafter. Further, 4′-bis [(1,2,2-triphenyl) ethenyl] biphenyl was grown to 50 nm as the blue light emitting layer, and Alq ₃ was grown to 10 nm as the electron transport layer.

Next, AlLi (Li: 7 at%) was deposited to a thickness of 1 nm, and an Al electrode layer was formed to a thickness of 200 nm to form an organic light emitting element. Before sealing as an organic light-emitting device, a desiccant (CaH ₂ ) mixed with silicon rubber and fixed was sealed, and finally sealed with a 100 μm thick PCTFE film coated with EVA. Thus, an organic light emitting device was obtained.

The compounds used were as follows: Silane coupling agent: (CH ₃ O) Si (CH ₂ ) ₃ NH ₂
TPD: N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine rubrene: 5,6,11,12-tetraphenylnaphtha Sen PCTFE: Polychlorotrifluoroethylene EVA: Ethylene-vinyl acetate copolymer <Adhesion evaluation method>
About the evaluation element produced above, the element was made to emit light and the adhesion was visually observed (immediate evaluation element). Further, after storing for 100 hours in a temperature of 60 ° C. and a humidity of 90% RH, the device was allowed to emit light and the adhesion was visually observed (deteriorated device). Rank 3 or higher is an acceptable product. The results are shown in Table 1.

5: There is no non-light emitting part due to barrier film peeling in the immediate evaluation element and the deteriorated element 4: There is no non-light emitting part in the immediate evaluation element. There is a non-light emitting part due to barrier film peeling in the deteriorated element. 3: There is a non-light emitting part due to barrier film peeling only in the deteriorated element. Deteriorating element has non-light emitting part due to barrier film peeling 1: Immediate evaluation element and deteriorating element has non-light emitting part due to barrier film peeling <Evaluation method of luminance half time and dark spot>
A direct current voltage was applied to each organic light emitting device, and the device was continuously driven at a constant current density of 50 mA / cm ² to evaluate the luminance half time. In addition, the dark spot was evaluated by continuously driving up to 1000 hours under the same conditions. The results are shown in Table 1.

<Production of Gas Barrier Films 6 to 11 and Organic Light-Emitting Elements 6 to 11>
In the production of the gas barrier film 5, the gas barrier films 6 to 11 are the same as the gas barrier film 5 except that the transport speed of the film when forming the first layer is changed as shown in Table 2. Was made. Further, organic light emitting devices 6 to 11 were produced in the same manner as in Example 1. Table 2 shows the oxygen element ratio of the film, WVTR, and organic element adhesion, luminance half-life, and dark spot results.

<Production of Gas Barrier Films 12-25, 38, 39 and Organic Light-Emitting Elements 12-25, 38, 39>
In the production of the gas barrier film 5, the gas barrier films 12 to 25, 38, 39 are the same as the gas barrier film 5 except that the environmental conditions for the modification treatment are performed in the atmosphere shown in Table 3. Was made. Further, organic light emitting devices 12 to 25, 38 and 39 were produced in the same manner as in Example 1. Table 3 shows the oxygen element ratio of the film, WVTR, organic element adhesion, luminance half time, and dark spot.

<Production of Gas Barrier Films 26-29 and Organic Light-Emitting Elements 26-29>
(1) Production of gas barrier film 26 A gas barrier film 26 was produced in the same manner as the gas barrier film 5 except that the first layer was formed as follows.

Using the vacuum plasma CVD apparatus shown in FIG. 1 of JP 2012-131194 A, the first layer was formed on the base layer.

The high frequency power source used at this time was a 27.12 MHz high frequency power source, and the distance between the electrodes was 20 mm. The source gas was introduced into the vacuum chamber at a silane gas flow rate of 7.5 sccm, an ammonia gas flow rate of 100 sccm, and a nitrous oxide gas flow rate of 50 sccm. At the start of film formation, the temperature of the film substrate was set to 100 ° C., the gas pressure during film formation was set to 100 Pa, and a silicon oxynitride layer (SiON layer) mainly composed of silicon nitride was formed as a first layer having a thickness of 300 nm. .

(2) Production of Gas Barrier Film 27 A gas barrier film 27 was produced in the same manner as the gas barrier film 5 except that the first layer was formed as follows.

The splice roll was loaded into a roll-to-roll sputter coater. The pressure in the deposition chamber was reduced to 2 × 10 ⁻⁶ Torr with a pump. Using a gas mixture containing 51 sccm argon (inert gas) and 30 sccm oxygen (reactive gas) at a pressure of 2 kW and 600 V, 1 millitorr, with a substrate transport speed of 0.43 meters / min, Si—Al (Research sputtering of 95/5 (element composition ratio)) target (available as a commercial product from Academy Precision Materials) deposits a 300-nm-thick SiAlO inorganic oxide layer on the underlying layer I let you.

(3) Production of gas barrier film 28 A gas barrier film 28 was produced in the same manner as the gas barrier film 5 except that the first layer was formed as follows.

A silicon oxide film was formed on the substrate using an atmospheric pressure plasma CVD apparatus (manufactured by Sekisui Chemical Co., Ltd.). Hexamethyldisilazane is used as the silicon source, and a carrier gas (nitrogen) is passed through the hexamethyldisilazane heated to 60 ° C. at a flow rate of 15 mL / min. , 50 mL / min) was introduced into the plasma. The plasma generation conditions were a pulse voltage of 95 V and a pulse frequency of 20 KHz, and the electrode, gas piping, and substrate temperature were heated to 80 ° C. The reaction was performed while introducing nitrogen gas as an atmospheric gas into the apparatus at a flow rate of 81 mL / min. The thickness of the silicon oxide film was 300 nm.

(4) Production of gas barrier film 29 Using an alumina-deposited PET film (trade name: TL-PET H, manufactured by Mitsui Chemicals, Inc., thickness 12 μm) as in Example 10 of International Publication No. 2011/007543. A gas barrier film 29 was produced in the same manner as the gas barrier film 5 except that the second layer was formed on the alumina deposition surface.

Organic light emitting devices 26 to 29 were produced in the same manner as in Example 1 except that the gas barrier films 26 to 29 were used. Table 4 shows the oxygen element ratio of the film, WVTR, organic element adhesion, luminance half time, and dark spot.

<Production of Gas Barrier Films 31-37 and Organic Light-Emitting Elements 31-37>
Except that the second layer was formed by adjusting the solid concentration so that the coating thickness of the polysilazane layer was as shown in Table 5, the gas barrier film No. In the same manner as in Example 5, gas barrier films 31 to 37 were prepared. Further, organic light emitting devices 31 to 37 were produced in the same manner as in Example 1. Table 5 shows the oxygen element ratio of the film, WVTR, and organic element adhesion, luminance half-life, and dark spot results.

From the above results, the organic light emitting devices 3 to 5, 9 to 11, 14 to 18, 20 to 28, and 31 to 37 of the present invention have high adhesion, long luminance half-life, and generation of dark spots up to at least 350 hours. There was no.

Further, when comparing the organic light emitting devices 13 to 17 with the organic light emitting devices 38 and 39, the organic light emitting devices 13 to 17 having an average oxygen content ratio of 25 to 55 at% in the region of the outermost surface to 35 nm are dark spots. It was excellent.

This application is based on Japanese Patent Application No. 2013-148656 filed on July 17, 2013, the disclosure of which is referenced and incorporated as a whole.

Claims

A substrate;
A first layer having gas barrier performance;
A second layer obtained by modifying a coating film obtained by applying a coating liquid containing a polysilazane compound, and a gas barrier film containing in this order,
Average oxygen content relative to the sum of silicon, oxygen and nitrogen in the region of 35 nm or more from the outermost surface with respect to the sum of silicon, oxygen and nitrogen in the region of the outermost surface to 35 nm facing the substrate of the second layer An electronic device larger than the ratio.
2. The electronic device according to claim 1, wherein the water vapor permeability of the first layer is 0.1 g / m 2 · day or less.
The second layer is formed by irradiating a coating film obtained by applying a coating liquid containing a polysilazane compound with energy rays in an atmosphere having an oxygen concentration of 1000 ppm by volume or less and a water vapor concentration of 150 ppm by volume or less. The electronic device according to claim 1 or 2.
The electronic device according to any one of claims 1 to 3, wherein the first layer includes silicon oxycarbide (SiOC).
The electronic device according to any one of claims 1 to 4, wherein an average oxygen content ratio in a region of the outermost surface to 35 nm is 25 to 55 at%.
The electronic device according to any one of claims 1 to 5, which is an organic EL element.