TWI617459B - Gas barrier film and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film having a very high gas barrier property, which is used to the extent that it can be used as a substrate for an electronic device such as an organic EL device.

As a solution, a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide-containing layer containing an oxide of the transition metal are disposed adjacent to each other on the surface of one side of the substrate, and then they are configured to exist The oxide of the constituent material of the layer becomes a highly hypoxic region with respect to the stoichiometric composition, or after a gas barrier layer containing a metal other than a transition metal and a transition metal is disposed on one side of the substrate, the The oxygen-deficient region composed of a metal other than a transition metal and a composite oxide of the transition metal continuously exists in a thickness direction of the gas barrier layer with a thickness equal to or greater than a specific value.

Description

Gas barrier film and manufacturing method thereof

The present invention relates to a gas barrier film and a method for manufacturing the same.

In a flexible electronic device, especially a flexible organic EL device, a gas barrier film is used as a substrate film or a sealing film. High barrier properties are required for the gas barrier film used in these.

Generally, a gas barrier film is manufactured by forming an inorganic gas barrier layer on a base film by a vapor-phase film formation method such as a vapor deposition method, a sputtering method, or a CVD method. On the other hand, in recent years, a method of forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate to form a gas barrier layer has also been discussed. In particular, the use of a polysilazane compound as a precursor has been widely investigated, and a technique for achieving both high productivity and barrier properties due to coating has been gradually explored. In particular, the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.

Furthermore, from the viewpoint of improving productivity, as a technology for manufacturing a gas barrier film using a roll-to-roll method, for example, a physical vapor deposition (PVD) film forming apparatus using sputtering or the like has been discussed, and A roll-to-roll method is used to produce a gas barrier film (for example, refer to Japanese Patent Application Laid-Open No. 2005-035128). However, in the conventional technology, for example, it has been difficult to obtain a gas barrier property to the extent that it can be used as a substrate for an electronic device such as an organic EL device (as WVTR10 ^-5 to 10 ^-6 ).

In addition, in the past, the formation of inorganic films obtained by the PVD method such as sputtering has been widely discussed in the field of optical films such as lens coatings (for example, refer to Japanese Patent Application Laid-Open No. 2005-298833 and Patent No. 4178190). Bulletin). However, these technologies are specific to the improvement of optical properties, so the technology that can be used for gas barrier films is relatively scarce, especially the technology of high gas barrier properties based on the laminated structure of PVD film formation is completely absent. Being explored.

Furthermore, conventionally, regarding the film formation of an inorganic film obtained by a PVD method such as sputtering, there have been extensive reviews of the formation of high barriers using a composite compound of a plurality of metals. For example, Japanese Patent Publication No. 2010-524732 discloses a technology in which a transparent barrier film including a transparent barrier film on a transparent thermoplastic film is made of a compound of elements of zinc, tin, and oxygen. And control the mass ratio of zinc to a value within a specific range. In the example of Japanese Patent Publication No. 2010-524732, although a ZnSnO _x layer having a thickness of 200 nm is formed by a sputtering method using a Zn-Sn alloy target, the gas barrier property (WVTR) is 2 × 10 ^-2 (g / m ² / day), sufficient gas barrier properties cannot be obtained.

Furthermore, Japanese Patent Application Laid-Open No. 2011-213102 discloses a technique for forming a mixture containing ZnS and SiO ₂ as a main component on one or both sides of a polymer film substrate having a specific surface roughness. In the mixed thin film layer of components, when ZnS is expressed as M and oxide is expressed as L, the composition of the mixed thin film layer is set to "M _X L _(1-X) (0.7 ≦ X ≦ 0.9)”. In the example of Japanese Patent Application Laid-Open No. 2011-213102, although a ZnS-SiO ₂ layer having a thickness of 50 nm is formed by a sputtering method using a target of a ZnS-SiO ₂ mixed sintered material, it is a gas barrier (WVTR) At a level of 4 × 10 ^-2 (g / m ² / day) (40 ° C 90% RH), sufficient gas barrier properties cannot be obtained.

As described above, although conventionally, various technologies have been proposed for producing gas barrier films using a vapor-phase film formation method, the current situation is that a film exhibiting very high gas barrier properties has not yet been realized, and it can be used as an organic EL device or the like. The degree to which a substrate for an electronic device is used.

In view of the foregoing circumstances, an object of the present invention is to provide a gas barrier film exhibiting a very high gas barrier property, and the film can be used as a substrate for an electronic device such as an organic EL device.

The present inventors conducted intensive studies in order to solve the above problems. As a result, it was found that a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide-containing layer containing an oxide of a transition metal were disposed adjacent to each other on the side of the substrate, and then they were constituted so as to exist Areas where the oxide of the constituent material of the layer becomes a highly anoxic composition relative to the stoichiometric composition, or will contain metals other than transition metals and After the gas barrier layer of the transition metal is disposed on one surface of the base material, it is constituted as an oxygen-deficient region of a metal other than the transition metal and a compound oxide of the transition metal in the thickness direction of the gas barrier layer continuously by a certain value or more. The present invention has such a thickness that the above-mentioned problems can be solved and the present invention can be completed.

That is, one aspect of the present invention relates to a gas barrier film having a layer structure including a gas barrier layer containing an oxide of a metal other than a transition metal and a transition metal oxide containing an oxide of a transition metal. The containing layers are arranged adjacent to each other on the surface of one side of the substrate (hereinafter, the gas barrier film having such a layer structure is referred to as a "first aspect"). According to an embodiment of this first aspect, it is possible to provide a gas barrier film having a substrate and a surface disposed on at least one side of the substrate, and containing an oxide of a metal (M1) other than a transition metal. The first gas barrier layer is a transition metal oxide-containing layer arranged adjacent to the first gas barrier layer and containing an oxide of a transition metal (M2). The gas barrier film is characterized by satisfying at least one of the following (1), (2), or (3): (1) In the first gas barrier layer, the transition metal is other than the transition metal. The maximum valence of metal (M1) is set to a, oxygen is set to O, nitrogen is set to N, carbon is set to C, and the composition of the oxide of the aforementioned metal (M1) is set to (M1) O _u N _v C _{At w} , at least a part of the thickness direction of the gas barrier layer has a region satisfying the following formula: u> 0, and v ≧ 0, and w ≧ 0, and (2u + 3v + 2w) / a <0.85; (2) In the transition metal oxide-containing layer, the maximum valence of the transition metal (M2) is set to b, oxygen is set to O, and nitrogen is set to N. When the composition is (M2) O _x N _y , at least a part of the thickness direction of the transition metal oxide layer has a region satisfying the following formula: x> 0, and y ≧ 0, and (2x + 3y) / b <0.85; (3) When the oxides contained in the first gas barrier layer and the transition metal oxide-containing layer are represented by the compositions shown in the above (1) and (2), respectively , In the aforementioned first gas barrier A combination of at least a part of the thickness direction of the layer and at least a part of the thickness direction of the transition metal oxide containing layer satisfies the following formula: (2u + 3v + 2w) / a + (2x + 3y) / b <1.85.

According to another embodiment of the first aspect of the present invention, there is also provided a gas barrier film having the same layer structure as described above, wherein the laminated body of the first gas barrier layer and the transition metal oxide-containing layer is satisfied The following (4): (4) The mixed region where the aforementioned metal (M1) and the aforementioned transition metal (M2) coexist, and the maximum valence of the aforementioned (M1) is set to a, and the maximum valence of the aforementioned (M2) is set B, oxygen is O, nitrogen is N, carbon is C, and when the composition of the mixed region is (M1) (M2) _p O _q N _r C _s , at least a part of the thickness direction of the mixed region Has a region that satisfies the following formula: 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) < 0.85.

According to another aspect of the present invention, a gas barrier film having a layer structure in which a gas barrier layer containing a metal other than a transition metal and a transition metal is disposed on one side of a substrate (hereinafter, referred to as A gas barrier film having such a layer structure is referred to as a "second aspect"). According to this aspect, it is possible to provide a gas barrier film having a base material and a surface disposed on at least one side of the base material and containing a metal (M1) other than a transition metal and a first transition metal (M2). Gas barrier layer. The gas barrier film is characterized in that the first gas barrier layer satisfies the following (5): (5) The maximum valence of the metal (M1) is set to a, and the transition metal (M2) is described above. The maximum valence is set to b, oxygen is set to O, nitrogen is set to N, and carbon is set to C. When the composition of the first gas barrier layer is set to (M1) (M2) _p O _q N _r C _s , The region where the thickness direction of the first gas barrier layer is 5 nm or more is a region [a] that satisfies the following formula.

0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <1.

Furthermore, according to another aspect of the present invention, a method for manufacturing a gas barrier film related to each of the aspects is also provided. Here, the manufacturing method related to the first aspect includes forming a film by a gas phase on a surface of the first gas barrier layer that is a laminate of the substrate and the first gas barrier layer on the side opposite to the substrate. The step of forming the transition metal oxide-containing layer by a method is that in the step of forming the transition metal oxide-containing layer, a ratio of the transition metal (M2) to oxygen selected from a film-forming raw material, and inertness during film formation are selected. The ratio of gas to reactive gas, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power in the group formed by film formation It is characteristic that one or more conditions are adjusted to satisfy the above (2).

In addition, the manufacturing method related to the second aspect includes a step of forming the first gas barrier layer on at least one side of the substrate, and the step of forming the first gas barrier layer includes including the metal (M1) and The composite oxide of the transition metal (M2) is co-evaporated on at least one side of the substrate, so that the formed first gas barrier layer satisfies the above point (5).

10‧‧‧Gas barrier film

11‧‧‧ Substrate

12‧‧‧ 1st gas barrier

13‧‧‧ transition metal oxide containing layer

101‧‧‧Vacuum Plasma CVD Device

102‧‧‧Vacuum tank

103‧‧‧ cathode electrode

105‧‧‧ Acceptor

106‧‧‧Heat medium circulation system

107‧‧‧Vacuum exhaust system

108‧‧‧Gas introduction system

109‧‧‧High-frequency power supply

110‧‧‧ substrate

160‧‧‧Heating and cooling device

Fig. 1 is a schematic cross-sectional view showing a gas barrier film according to a first aspect of the present invention. In FIG. 1, 10 is a gas barrier film, 11 is a base material, 12 is a 1st gas barrier layer, and 13 is a transition metal oxide containing layer.

Fig. 2 is a schematic cross-sectional view showing a gas barrier film according to a second aspect of the present invention. In FIG. 2, 10 is a gas barrier film, 11 is a substrate, and 12 is a first gas barrier layer.

Fig. 3 is a schematic diagram showing an example of a vacuum plasma CVD apparatus. In FIG. 3, 101 is a plasma CVD apparatus, 102 is a vacuum tank, 103 is a cathode electrode, 105 is a susceptor, 106 is a heat medium circulation system, 107 is a vacuum exhaust system, 108 is a gas introduction system, 109 It is a high-frequency power supply, 110 is a substrate, and 160 is a heating and cooling device.

[Form of Implementing Invention]

Hereinafter, preferred embodiments of the present invention will be described. The present invention is not limited to the following embodiments. In addition, the size ratio of the drawing is exaggerated for convenience of explanation, and sometimes it is different from the actual ratio.

In this specification, unless otherwise stated, measurement of operation and physical properties is performed under conditions of room temperature (20-25 ° C) / relative humidity 40-50% RH.

≪First Form≫

The gas barrier film according to the first aspect of the present invention has, as its basic structure, a substrate, a surface disposed on at least one side of the substrate, and an oxide containing a metal (M1) other than a transition metal. The first gas barrier layer and a transition metal oxide-containing layer arranged adjacent to the first gas barrier layer and containing an oxide of a transition metal (M2). A detailed description of the characteristic structure of the gas barrier film according to the present invention will be described later.

FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to a first aspect of the present invention. The gas barrier film 10 shown in FIG. 1 is formed by sequentially arranging a substrate 11, a first gas barrier layer 12, and a transition metal oxide-containing layer 13. Furthermore, in the first aspect of the present invention, as long as the first gas barrier layer 12 and the transition metal oxide containing layer 13 are arranged adjacent to each other, the first gas barrier layer 12 and the transition metal oxide may be sequentially arranged from the substrate side. Contains layer 13 (Figure 1), and transitions can be arranged in sequence from the substrate side The metal oxide contains a layer 13 and a first gas barrier layer 12. In addition to the configuration in which the first gas barrier layer 12 and the transition metal oxide-containing layer 13 are disposed on one side of the substrate, the gas barrier layer 12 and the transition metal oxide-containing layer may be disposed on both sides of the substrate. 13. Further, another layer may be disposed between the substrate and each layer, or on each layer.

However, from the viewpoint of exhibiting higher gas barrier properties, as shown in FIG. 1, the first gas barrier layer 12 and the transition metal oxide containing layer 13 are preferably arranged in order from the substrate side. In this case, it is particularly preferable that the gas barrier film satisfies the above (2).

[Substrate]

Specific examples of the base material 11 related to the present invention (common to the first aspect and the second aspect) include polyester resin, methyl acrylate resin, methyl acrylate acid-maleic acid copolymer, and polybenzene. Ethylene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyimide resin, polyimide resin, polyetherimide resin, trimethylcellulose resin, polyimide Acid ester resins, polyetheretherketone resins, polycarbonate resins, alicyclic polyolefin resins, polyaromatic ester resins, polyether resins, polyfluorene resins, cyclic olefin copolymers, cyclic modified polycarbonate resins, Base material of thermoplastic resins such as alicyclic modified polycarbonate resin, fluorene modified polyester resin, and acrylic fluorene compound. This base material can be used individually or in combination of 2 or more types.

The base material is preferably made of a material having heat resistance. Specifically, a substrate having a linear expansion coefficient of 15 ppm / K or more and 100 ppm / K or less and a glass transition temperature (Tg) of 100 ° C or more and 300 ° C or less is used. The substrate meets the requirements It is a necessary condition for the application of electronic parts and display laminated films. That is, when the gas barrier film according to the present invention is used for such applications, the gas barrier film may be exposed to a step of 150 ° C or higher. At this time, if the linear expansion coefficient of the substrate in the gas barrier film exceeds 100 ppm / K, when the gas barrier film is advanced in the step of the temperature described above, the substrate size will be unstable, accompanied by thermal expansion and contraction. It is prone to adverse conditions such as deteriorating performance, or to fail to withstand thermal steps. When it is less than 15 ppm / K, the film may be cracked like glass and the flexibility may be deteriorated.

The Tg or linear expansion coefficient of the substrate can be adjusted in accordance with additives and the like. As further specific examples of the thermoplastic resin that can be used as the base material, examples include polyethylene terephthalate (PET: 70 ° C), polyethylene naphthalate (PEN: 120 ° C), polymer Carbonate (PC: 140 ° C), alicyclic polyolefin (for example, made by Japan Zeon Corporation, ZEONOR (registered trademark) 1600: 160 ° C), polyaromatic ester (PAr: 210 ° C), polyether fluorene (PES: 220 ° C), polyfluorene (PSF: 190 ° C), cyclic olefin copolymer (COC: Compound described in Japanese Patent Laid-Open No. 2001-150584: 162 ° C), polyimide (for example, manufactured by Mitsubishi Gas Chemical Co., Ltd., NEOPULIM (registered trademark): 260 ° C), fluorene modified polycarbonate (BCF-PC: Compound described in JP 2000-227603: 225 ° C), alicyclic modified polycarbonate (IP-PC: Compounds described in Japanese Patent Application Laid-Open No. 2000-227603: 205 ° C), acrylhydrazone compounds (compounds described in Japanese Patent Application Laid-Open No. 2002-80616: 300 ° C or higher), and the like (Tg is shown in parentheses).

Since the gas barrier film according to the present invention can be used in an electronic device such as an organic EL element, the substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance can be calculated using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device to measure the total light transmittance and the amount of scattered light, and subtracting the diffuse transmittance from the total light transmittance.

However, even when the gas barrier film according to the present invention is used in a display application, transparency is not necessarily required if it is not provided on the observation side or the like. Therefore, at this time, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and a known liquid crystal polymer.

In addition, the substrates listed above may be unstretched films or stretched films. This base material can be manufactured by the conventionally well-known general method. Regarding the manufacturing method of these base materials, the matters described in paragraphs "0051" to "0055" of International Publication No. 2013/002026 can be appropriately adopted.

The surface of the substrate may be subjected to various known treatments for improving adhesion, such as a corona discharge treatment, a flame treatment, an oxidation treatment, or a plasma treatment, etc., or a combination of the above treatments may be performed as necessary. In addition, the substrate may be subjected to easy adhesion treatment.

The substrate may be a single layer or a laminated structure of two or more layers. When the substrate has a laminated structure of two or more layers, each substrate may be the same type or a different type.

The thickness of the substrate according to the present invention (in the case of a laminated structure of two or more layers) The total thickness) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

[First gas barrier layer]

In the present invention, the first gas barrier layer 12 must contain a metal (M1) other than a transition metal (preferably an oxide of the metal (M1)). As a result, the first gas barrier layer exhibits gas barrier properties. When the gas barrier property of the first gas barrier layer is calculated as a laminate in which the first gas barrier layer is formed on a substrate, the water vapor transmission rate (WVTR) is preferably 0.1 g / (m ² ‧day) or less . Here, in the first aspect, the first gas barrier layer 12 must contain an oxide of a metal (M1) other than a transition metal.

The metal (M1) other than the transition metal is not particularly limited, and any metal or combination of the transition metals can be used. The metal (M1) other than the transition metal includes Group 12 selected from the long-period periodic table ~ Metals in the group consisting of metals of group 14 are preferred. Examples of the metal (M1) other than the transition metal include Si, Al, In, Sn, Zn, and the like. Furthermore, in the first aspect, the first gas barrier layer may include, in addition to the oxide of the metal (M1), nitrides and carbides of the metal (M1) (that is, oxynitride or carbon) Oxide form). Among them, M1 preferably includes Si, Sn, or Zn, and even more preferably Si, and particularly preferably Si alone. In addition, in the first aspect, when M1 contains Si, it is preferable that the first gas barrier layer contains an oxide of Si and / or a nitride of Si as a main component. In addition, "the first gas barrier layer contains an oxide of Si and / or a nitride of Si as a main component" means the amount of the oxide of Si and / or nitride of Si in the first gas barrier layer (when both sides are included) (The total amount) is 50% by mass or more, and this value is more than It is more preferably 80% by mass or more, more preferably 95% by mass or more, particularly preferably 98% by mass or more, and most preferably 100% by mass. In addition, there is no particular limitation on the content of the transition metal in the first gas barrier layer constituting the gas barrier film according to the first aspect, but the meaning of the transition metal oxide-containing layer provided later will not be impaired From a viewpoint, it is preferable that it is less than 2 atomic% with respect to the whole metal element contained in the 1st gas barrier layer which comprises the gas barrier film of 1st aspect.

The film thickness of the first gas barrier layer is not particularly limited, but it is preferably 5 to 1000 nm. If it is in this range, it has high gas barrier performance, bending resistance, and excellent cutting processability. The first gas barrier layer may be composed of two or more adjacent layers.

In the first aspect, the method for forming the first gas barrier layer is not particularly limited, and for example, a conventionally known vapor-phase film-forming method using an existing film deposition technique can be used. As an example, a conventionally known vapor deposition method such as a vapor deposition method, a reactive vapor deposition method, a sputtering method, a reactive sputtering method, a chemical vapor deposition method (Chemical Vapor Deposition, CVD method), or the like can be used. These vapor-phase film-forming methods can be used by a well-known method.

Here, for example, the CVD method is a method in which a raw material gas including a component of a target thin film is supplied to a substrate, and a film is deposited by a chemical reaction on the surface of the substrate or a gas phase. In addition, for the purpose of activating chemical reactions, there are methods for generating plasma, etc., and examples include thermal CVD method, catalytic chemical vapor growth method, photo CVD method, and plasma CVD method using plasma as an excitation source ( PECVD method) a well-known CVD method such as a vacuum plasma CVD method, an atmospheric piezoelectric plasma CVD method, and the like. Especially PECVD method is the better method law. This method will be described in detail below.

(Vacuum plasma CVD method)

The vacuum plasma CVD method allows a material gas to flow into a vacuum container equipped with a plasma source, and supplies electric power to the plasma source from a power source to generate a discharge plasma in the vacuum container and decompose the material gas with the plasma. A method for reacting and accumulating the generated reactive species on a substrate. The vapor-phase film-forming barrier layer obtained by the vacuum plasma CVD method can be used for manufacturing a desired compound by selecting conditions such as a metal compound of a raw material, a decomposition gas, a decomposition temperature, and an input of electric power.

As the compound of the raw material, a compound containing a metal (M1) other than a transition metal such as a silicon compound or an aluminum compound is preferably used. The compounds of these raw materials may be used alone or in combination of two or more.

As these silicon compounds and aluminum compounds, conventionally known compounds can be used. For example, known compounds include compounds described in paragraphs "0028" to "0031" of Japanese Patent Application Laid-Open No. 2013-063658, and paragraphs "0078" to "0081" of Japanese Patent Laid-Open No. 2013-047002. Preferable examples include silane, tetramethoxysilane, tetraethoxysilane, and hexamethyldisiloxane.

In addition, examples of the decomposition gas used to decompose a raw material gas containing these metals and obtain an inorganic substance such as an oxide include hydrogen, methane, acetylene, carbon monoxide, carbon dioxide, nitrogen, ammonia, and monoxide. Dinitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen, water vapor, etc. In addition, the above-mentioned decomposition gas may be combined with argon gas and helium gas. Mixed with inert gas. By appropriately selecting a raw material gas and a decomposition gas containing a compound of a raw material, a desired vapor-phase film-forming barrier layer can be obtained. Hereinafter, a more suitable form of the vacuum plasma CVD method will be specifically described.

FIG. 3 is a schematic diagram showing an example of a vacuum plasma CVD apparatus. In FIG. 3, the vacuum plasma CVD apparatus 101 includes a vacuum tank 102, and a receiver 105 is disposed on the bottom surface side inside the vacuum tank 102. A cathode electrode 103 is disposed on the zenith side inside the vacuum chamber 102 at a position facing the receiver 105. A heat medium circulation system 106, a vacuum exhaust system 107, a gas introduction system 108, and a high-frequency power source 109 are arranged outside the vacuum tank 102. A heat medium is arranged in the heat medium circulation system 106. The heating medium circulation system 106 is provided with a heating and cooling device 160 having a pump for moving the heating medium, a heating device for heating the heating medium, a cooling device for cooling, and a temperature sensor for measuring the temperature of the heating medium. , And a memory device that stores the set temperature of the thermal medium. The heating and cooling device 160 is configured to measure the temperature of the heat medium, and heat or cool the heat medium to a set temperature in memory, and supply the heat medium to the receiver 105. The details of the device shown in FIG. 3 can be referred to paragraphs "0080" to "0098" of International Publication No. 2012/090644.

[Transition metal oxide containing layer]

The transition metal oxide-containing layer 13 is a layer which must be provided in the first aspect of the present invention. The transition metal oxide-containing layer 13 must contain an oxide of a transition metal (M2), and a layer substantially free of a metal (M1) other than a transition metal (but Except mixed zone area). When the transition metal oxide-containing layer is formed in contact with the first gas barrier layer, a composite oxide of the metal (M1) and the transition metal (M2) contained in the first gas barrier layer is formed at the interface between the two. At this time, it is considered that by setting the ratio of oxygen or nitrogen within the scope of the present invention, a dense structure in which the metal (M1) and the transition metal (M2) are directly bonded is formed, thereby improving barrier properties. Further, in the first aspect, a region formed by the composite oxide as described above is also referred to as a "mixed region".

The transition metal (M2) is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal means a long-period periodic table from Group 3 elements to Group 11 elements. Examples of transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn. , Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.

Among them, examples of transition metals (M2) capable of obtaining good barrier properties include Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce. Among these, from the results of various investigations, it is considered that the bonding of the metal (M1) contained in the first gas barrier layer, especially Nb, Ta, and V of the Group 5 element, is more likely to occur, so it can be better. To use. If the transition metal (M2) is a Group 5 element (especially Nb) and the above-mentioned metal (M1) is Si, a significant effect of improving gas barrier properties can be obtained. This is considered to be because the bond between Si and a Group 5 element (especially Nb) is particularly easy to occur. Furthermore, from the viewpoint of optical characteristics, transition metals (M2) are particularly preferably Nb and Ta that can obtain compounds with good transparency.

In addition, the transition metal oxide-containing layer may include a nitride of the transition metal (M2) in addition to the oxide of the transition metal (M2) (that is, it may also be in the form of an oxynitride).

The content of the transition metal oxide in the transition metal oxide-containing layer is not particularly limited as long as it can achieve the effects of the present invention, but the content of the transition metal oxide is 50 masses relative to the total mass of the transition metal oxide-containing layer. It is preferably at least 80% by mass, more preferably at least 80% by mass, more preferably at least 95% by mass, particularly preferably at least 98% by mass, and 100% by mass (that is, the transition metal oxide-containing layer is oxidized by the transition metal From the best). In addition, the content of metals other than transition metals in the transition metal oxide-containing layer is not particularly limited, but from the viewpoint of not impairing the significance of providing the above-mentioned first gas barrier layer, compared to transition metals The total amount of metal elements contained in the oxide-containing layer is preferably less than 2 atomic%.

The transition metal oxide-containing layer is preferably formed by a vapor-phase film formation method from the viewpoint that the composition ratio of the metal element and oxygen can be easily adjusted. The vapor-phase film formation method is not particularly limited, and examples thereof include a physical vapor phase growth (PVD) method such as a sputtering method, a vapor deposition method, an ion plating method, and an ion-assisted vapor deposition method, and a plasma CVD (chemical vapordeposition) method. And CVD (Atomic Layer Deposition) methods. Among them, in terms of being able to form a film without causing damage to the lower layer and having high productivity, it is better to form it by a physical vapor phase growth (PVD) method, and it is more preferable to form it by a sputtering method.

Film formation by sputtering method, can use 2 pole sputtering, magnetron sputtering alone Plating, dual magnetron (DMS) sputtering in the middle frequency range, ion beam sputtering, ECR sputtering, or a combination of two or more of them is used. In addition, the target application method can be appropriately selected according to the type of target, and either DC (direct current) sputtering or RF (high frequency) sputtering is used. Also, a reactive sputtering method may be used, which uses a transition phase between a metal phase and an oxide phase. By controlling the sputtering phenomenon to make it a transition region, a metal oxide can be formed at a higher film forming speed, which is preferable. When performing DC sputtering or DMS sputtering, a thin film of a transition metal oxide can be formed by using a transition metal in the target and further introducing oxygen into the processing gas. When forming a film by RF (high frequency) sputtering, a target of an oxide of a transition metal can be used. As the inert gas used for the processing gas, He, Ne, Ar, Kr, Xe, etc. can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the processing gas, a thin film of a transition metal compound such as a transition metal oxide, a nitrogen oxide, or a carbon oxide can be produced. Examples of film forming conditions in the sputtering method include application of electric power, discharge current, discharge voltage, time, and the like, but these can be appropriately selected depending on the sputtering apparatus, the material of the film, the film thickness, and the like.

Among them, a sputtering method using an oxide of a transition metal as a target is preferable in view of a higher film formation rate and higher productivity.

The transition metal oxide-containing layer may be a single layer or a laminated structure of two or more layers. When the transition metal oxide-containing layer has a laminated structure of two or more layers, the transition metal oxides contained in the transition metal oxide-containing layer may be the same or different.

Since the transition metal oxide-containing layer is considered to have a suppression of the first gas The barrier layer is oxidized and maintains the function of gas barrier properties, so it is not necessary to have gas barrier properties. Therefore, the transition metal oxide-containing layer is effective even if it is a relatively thin layer. Specifically, the thickness of the transition metal oxide-containing layer (the total thickness in the case of a laminated structure of two or more layers) is preferably 1 to 200 nm from the viewpoint of in-plane uniformity of gas barrier properties, and is 2 to 200 nm. 100 nm is more preferable, and 3 to 50 nm is more preferable. Especially if it is 50 nm or less, the productivity of film formation of a transition metal oxide containing layer will be further improved.

[Area of hypoxia]

The gas barrier film according to the first aspect of the present invention having the above-mentioned basic structure is characterized in that it satisfies at least any one of the following (1), (2), or (3): (1) the first gas barrier layer Let the maximum valence of a metal (M1) other than the transition metal be a, oxygen be O, nitrogen be N, carbon be C, and the composition of the oxide of the metal (M1) be (M1) O _{When u} N _v C _w , at least a part of the thickness direction of the gas barrier layer has a region satisfying the following formula, u> 0, and v ≧ 0, and w ≧ 0, and (2u + 3v + 2w) / a <0.85; (2) In the transition metal oxide containing layer, set the maximum valence of the transition metal (M2) to b, oxygen to O, nitrogen to N, and oxidation of the transition metal. When the composition of the material is (M2) O _x N _y , at least a part of the thickness direction of the transition metal oxide layer has a region satisfying the following formula, x> 0, and y ≧ 0, and (2x + 3y) / b <0.85; (3) the oxides contained in the first gas barrier layer and the transition metal oxide-containing layer are represented by the compositions shown in the above (1) and (2), respectively At The combination of the at least a part of the thickness direction of the first gas barrier layer and the at least a part of the thickness direction of the transition metal oxide containing layer satisfies the following formula: (2u + 3v + 2w) / a + (2x + 3y) / b <1.85.

(1) to (3) of the characteristics of the gas barrier film according to the first aspect of the present invention share the same technical characteristics in the following points: At least a part of the first gas barrier layer and / or the transition metal oxide-containing layer Contains a certain level of hypoxia composition.

Here, if the first gas barrier layer and the transition metal oxide-containing layer are disposed so as to satisfy at least any one of the above (1) to (3) (that is, at least a part of these layers is defective to a certain degree or more). Oxygen loss composition), the metal (M1) and the transition metal (M2) will coexist, and, as will be described later, a region where a direct bond between the metal (M1) and the transition metal (M2) is supposed to exist (i.e., Mixed area). The composition of this mixed region is represented by (M1) (M2) _p O _q N _r C _s . Here, the maximum valence of the metal (M1) is set to a, the maximum valence of the transition metal (M2) is set to b, the valence of O is set to 2, the valence of N is set to 3, and the valence of C was originally It is 4, but among the above-mentioned layers formed in the present invention, C is considered to be bonded in a state including a hydrogen atom like -CH _2- , so the valence of C is set to 2. When the mixed region has a stoichiometric composition, it becomes (2q + 3r + 2s) / (a + bp) = 1.0. This formula means that the total of the bonds of the metal (M1) and the transition metal (M2) and the total of the bonds of O, N, and C are the same number. At this time, the metal (M1) and the transition metal (M2) will be together. It is bonded to any one of O, N, and C. Moreover, in the present invention, when two or more kinds are used as the metal (M1) or two or more kinds are used as the transition metal (M2), the maximum valence of each element is weighted and averaged by the existence ratio of each element. The calculated compound valence is taken as the value of a and b of the "maximum valence" (refer to the production columns of the gas barrier film 3-16 described later).

On the other hand, when (2q + 3r + 2s) / (a + bp) <1.0, it means that O, N, and C are bonded to the total of the bonds of the metal (M1) and the transition metal (M2). The total is insufficient, this state is "hypoxia" in the mixed area. In the hypoxic state, there is a possibility that the extra bonding of the metal (M1) and the transition metal (M2) will be bonded to each other. If the metals of the metal (M1) or the transition metal (M2) are directly bonded to each other, the phase will be Compared with the case where metals are bonded via O, N, or C, a denser and higher-density structure is formed. As a result, gas barrier properties are considered to be improved.

The above description is that when the first gas barrier layer and the transition metal oxide-containing layer have a specific oxygen-depleted composition, the mixed region also becomes an oxygen-deficient state, which can improve the gas barrier properties. Here, the inventors have further studied and found that, in the gas barrier film having a layer structure related to the first aspect of the present invention, it is not necessary to specify that the first gas barrier layer and the transition metal oxide-containing layer have specific characteristics. An anoxic composition (that is, satisfying at least any one of (1) to (3) above) is a composition capable of improving the gas barrier property. From such a point of view, the gas barrier film according to another aspect of the first aspect of the present invention that has been defined has the basic structure described above, and the first gas barrier layer and the transition metal oxide-containing layer are layers. The combination has the following characteristics (4): (4) It has a mixed region in which the aforementioned metal (M1) and the aforementioned transition metal (M2) coexist, and the maximum valence of the aforementioned (M1) is set to a, and the aforementioned (M2) When the maximum valence is set to b, oxygen is set to O, nitrogen is set to N, carbon is set to C, and when the composition of the aforementioned mixed region is set to (M1) (M2) _p O _q N _r C _s , At least a part of the thickness direction has a region satisfying the following formula: 0.02 ≦ p ≦ 98, and q> 0, r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / ( a + bp) <0.85.

It is considered that in the mixed region, if 0.02 ≦ p ≦ 98 is satisfied, both the metal (M1) and the transition metal (M2) will have a direct bond with the metal, and will contribute to the improvement of gas barrier properties. Here, p is preferably 0.05 ≦ p ≦ 95, more preferably 0.10 ≦ p ≦ 90, and still more preferably 0.20 ≦ p ≦ 80. In this way, (4) related to the first aspect of the present invention also shares the same technical characteristics as the above (1) to (3) in the following points: it indicates that the metal (M1) and / or the transition metal (M2) coexist in the region At least part of it contains a certain degree of anoxic composition.

And, as described above, if there is a mixed region satisfying (2q + 3r + 2s) / (a + bp) <0.85, it can be confirmed that the improvement effect of the gas barrier property will be exerted, but (2q + 3r + 2s) is preferred /(a+bp)<0.80, more preferably (2q + 3r + 2s) / (a + bp) <0.70, more preferably (2q + 3r + 2s) / (a + bp) <0.65. On the other hand, from the viewpoint of optical characteristics such as transparency, it is preferably (2q + 3r + 2s) / (a + bp)> 0.40, and more preferably (2q + 3r + 2s) / (a + bp)> 0.50.

In addition, in the present invention, the thickness of the mixed region having a composition that satisfies the relationship described in (4) above, which has good gas barrier properties, is not particularly limited as long as the thickness can be detected by the XPS analysis described later. However, specifically, the sputtering thickness in terms of SiO ₂ is preferably 1 nm or more, more preferably 2 nm or more, and even more preferably 4 nm or more. From the viewpoint of optical characteristics such as transparency, when the laminate of the first gas barrier layer and the transition metal oxide-containing layer satisfies the above (4), the thickness of the region of p> 98 of the laminate is smaller than It is preferably 5 nm or less.

The gas barrier film having the above-mentioned structure exhibits a very high gas barrier property, and it is such that it can be used as a substrate for an electronic device such as an organic EL device.

Here, as a result of various investigations made by the present inventors, if an oxygen-deficient composition film of a compound (oxide) of a metal (M1) other than a transition metal is used alone to form a gas barrier layer, or a transition metal (M2) is used alone Compounds (oxides) form an oxygen-deficient film to form a gas barrier layer. As the degree of oxygen deficiency increases, although a tendency to increase the gas barrier properties is observed, it has not been related to a significant improvement in gas barrier properties. On the other hand, it was found that, as in the configuration related to the first aspect of the present invention described above, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a transition metal (M2) as a main component were laminated. The layer of the compound (oxide) of the main component forms a mixed region where a metal other than the transition metal (M1) and a transition metal (M2) coexist. When the mixed region is further set to an anoxic composition, the degree of anoxic becomes larger , Gas barrier properties will be significantly improved. This is presumably due to the fact that the bond between a metal other than the transition metal (M1) and the transition metal (M2) is higher than that between the metal other than the transition metal (M1) or the bond between the transition metal (M2) as shown above. Knots are easier to produce, and by making the structure relevant to the present invention, The reason why the mixed region forms a dense and high-density structure.

In order to manufacture the gas barrier film according to the first aspect of the present invention, the first gas barrier layer and the transition metal oxide-containing layer are formed so as to satisfy at least any one of (1) to (3) (and further exist as described in (4) above. ) To form a mixed region in a state of anoxic conditions), it is only necessary to appropriately adjust conditions for forming each layer.

For example, as a method for forming the first gas barrier layer to satisfy the above (1), when the first gas barrier layer is formed by a vapor-phase film formation method, the metal (M1 1 or 2 of the ratio of oxygen to oxygen, the ratio of inert gas to reactive gas during film formation, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power during film formation The above conditions can control the degree of oxidation (the oxide composition of the metal (M1) in the first gas barrier layer is set to the value of u when (M1) O _u N _v C _w ).

Similarly, as a method for forming a transition metal oxide-containing layer to satisfy the above (2), when a transition metal oxide-containing layer is formed by a vapor-phase film-forming method, the material selected from the film-forming raw materials is adjusted by adjustment. The ratio of transition metal (M2) to oxygen, the ratio of inert gas to reactive gas during film formation, the amount of gas supplied during film formation, the degree of vacuum during film formation, and the power at the time of film formation One or two or more conditions can control the degree of oxidation (the oxide composition of the transition metal (M2) in the transition metal oxide-containing layer is the value of x when (M2) O _x N _y ). That is, according to still another aspect of the present invention, there is also provided a method for producing a gas barrier film according to the first aspect of the present invention. This manufacturing method includes the steps of forming a transition metal by a vapor-phase film-forming method on a surface of the first gas barrier layer that is a laminate of the substrate and the first gas barrier layer on the side opposite to the substrate. The oxide contains a layer. In addition, in the step of forming the transition metal oxide-containing layer, the ratio is selected from the ratio of the aforementioned transition metal (M2) and oxygen in the film-forming raw material, the ratio of the inert gas and the reactive gas during film formation, and One or two or more of the conditions of the amount of gas supplied during the film formation, the degree of vacuum during the film formation, and the electric power during the film formation satisfy the above (2). In addition, when both the first gas barrier layer and the transition metal oxide-containing layer are formed by a vapor-phase film-forming method, by adjusting the above-mentioned conditions, neither of the above (1) and (2) can be satisfied, and It is controlled so that it satisfies the above (3).

In the method for producing a gas barrier film according to the first aspect of the present invention, the first gas barrier layer and the transition metal oxide-containing layer may be formed on the substrate in order to form the first gas barrier layer and the transition metal oxide-containing layer necessary for the first aspect. It is performed batchwise, but it is preferably performed continuously. As a method for continuously forming these layers, there is a method using a roll-to-roll method. By using the roll-to-roll method to continuously form a film, it is not necessary to roll into a roll from the formation of one layer to the formation of the next layer, so the productivity is improved, and it is possible to further prevent the layer from being wound when winding into a roll Deterioration of the gas barrier layer and the like caused by surface damage. That is, the above-mentioned preferred embodiment of the manufacturing method related to the first aspect of the present invention further includes the steps of forming a first gas barrier layer on a surface of at least one side of the substrate in a roll-to-roll manner, and The step of forming a transition metal oxide-containing layer on a surface of the first gas barrier layer on the side opposite to the substrate by a roll-to-roll method. At this time, after the step of forming the first gas barrier layer, it is not necessary to roll a film, that is, Can form Step of transition metal oxide containing layer.

In addition, when the manufacturing method related to the first aspect of the present invention includes the step of forming a second gas barrier layer (described in detail later), the formation of a transition metal oxide-containing layer under the second gas barrier layer is continuously performed. And formation of the second gas barrier layer is preferred. That is, the preferred embodiment of the manufacturing method related to the first aspect of the present invention further includes: forming a transition metal oxide on a surface of the first gas barrier layer on the side opposite to the base material by a roll-to-roll method. A step of containing a layer, and a step of forming a second gas barrier layer containing a metal oxide on a surface of the transition metal oxide containing layer on the side opposite to the first gas barrier layer, and in this case, After the step of forming the transition metal oxide-containing layer, the step of forming the second gas barrier layer can be performed without winding the film.

Furthermore, when the manufacturing method related to the first aspect of the present invention includes the step of forming the second gas barrier layer, the first gas barrier layer is formed, the transition metal oxide-containing layer is formed, and the second gas barrier layer is formed. All are carried out continuously in a roll-to-roll manner, thereby improving the productivity of the gas barrier film. That is, a preferred embodiment of the manufacturing method related to the first aspect of the present invention described above further includes a step of forming a first gas barrier layer on a surface of at least one side of the substrate in a roll-to-roll manner, 1 a step of forming a transition metal oxide-containing layer on a surface of the gas barrier layer on the side opposite to the substrate, and a surface of the transition metal oxide-containing layer on the side opposite to the first gas barrier layer, The step of forming a second gas barrier layer containing a metal oxide in a roll-to-roll manner, and at this time, after the step of forming the first gas barrier layer, it is not necessary to roll thin The film can perform the step of forming the transition metal oxide-containing layer, and after the step of forming the transition metal oxide-containing layer, the step of forming the second gas barrier layer can be performed without winding the film.

Moreover, in the continuous film formation using the above-mentioned roll-to-roll method, the specific configuration of the continuous film formation device is not particularly limited, and conventionally known knowledge can be appropriately referred to. For example, in a continuous film forming apparatus, the environment of an adjacent film forming apparatus may be atmospheric pressing film → vacuum film forming, and conversely may be vacuum film forming → air pressing film.

For example, the formation of a first gas barrier layer, the formation of a transition metal oxide containing layer, the formation of a second gas barrier layer, and the formation of a transition metal oxide containing layer and a third gas barrier containing a metal oxide may be further formed. The layer formation is all performed continuously in a roll-to-roll manner, and the formation of the same layered structure can also be repeated, and all of the layer formation can be continuously performed in a roll-to-roll manner. In addition, the formation of the first gas barrier layer, the formation of the transition metal oxide-containing layer, and the formation of the second gas barrier layer may all be continuously performed in a roll-to-roll manner and wound, and then rolled out, and Above it, the formation of the first gas barrier layer, the formation of the transition metal oxide-containing layer, and the formation of the second gas barrier layer were all continuously carried out by a roll-to-roll method and wound up to form a multilayer laminate structure.

≪Second Form≫

The gas barrier film according to the second aspect of the present invention has a base material and a gas barrier layer disposed on at least one side of the base material as its basic structure. The gas barrier layer related to the second aspect must contain a transition A metal (M1) and a transition metal (M2) other than metal are different from the gas barrier layer of the first embodiment described above. However, for convenience of explanation, the gas barrier layer in the gas barrier film related to the second aspect is also referred to as a "first gas barrier layer", unless otherwise noted, the article of the first aspect and the second aspect is not distinguished. The concept of "the first gas barrier layer" in "2" also includes the "(1) gas barrier layer" related to the second aspect.

2 is a schematic cross-sectional view showing a gas barrier film according to a second aspect of the present invention. The gas barrier film 10 shown in FIG. 2 is obtained by disposing a first gas barrier layer 12 on a substrate 11. In addition, the first gas barrier layer 12 is not limited to the configuration in which the first gas barrier layer 12 is disposed on one surface of the substrate, and the first gas barrier layer 12 may be disposed on both surfaces of the substrate. Further, another layer may be disposed between the substrate and the first gas barrier layer, or on the first gas barrier layer.

[First gas barrier layer]

As described above, the first gas barrier layer 12 is a layer exhibiting gas barrier properties, and is provided on at least one side of the substrate 11 and must contain a metal (M1) other than a transition metal (preferably the metal (M1) ) Of oxide). Here, in the second aspect, the first gas barrier layer must contain a metal (M1) other than a transition metal and a transition metal (M2).

As described later, the gas barrier layer related to the second aspect is characterized in that the oxygen-deficient region composed of a compound oxide other than a transition metal (M1) and a transition metal (M2) is in the thickness direction of the gas barrier layer Continuously exists in a thickness of a certain value or more (specifically 5 nm or more) The point is expressed in this specification as "the gas barrier layer has an area [a]"). The details of this feature will be described later, but as long as this feature is satisfied, the region other than the region [a] of the gas barrier layer can be, for example, the composite oxidation of the metal (M1) and the transition metal (M2) that do not correspond to the region [a]. Area (which may also be an anoxic area, or an area of stoichiometric composition). In addition, the area other than the area [a] of the gas barrier layer may also be an oxide, nitride, oxynitride, or carbon oxide of the metal (M1) (it may also be an anoxic area, or it may be a stoichiometric composition) Regions) and the like may also be regions such as oxides, nitrides, oxynitrides, and carbon oxides of transition metals (M2) (also hypoxic regions or regions with stoichiometric composition).

The metal (M1) other than the transition metal is not particularly limited. Specific examples of the metal (M1), and preferable types and the like are the same as those in the first embodiment described above, and thus detailed descriptions thereof are omitted here.

There is also no particular limitation on the transition metal (M2). The specific examples of the transition metal (M2), the preferred types, and the like are also the same as those in the first embodiment described above, and thus detailed descriptions thereof are omitted here.

In the second aspect, as in the above, the film thickness of the first gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. If it is in such a range, it will have high gas barrier performance, excellent bending resistance, and excellent cutting processability. The gas barrier layer may be composed of two or more adjacent layers.

[Area of hypoxia]

The gas barrier film according to the second aspect is characterized in that the first gas barrier layer satisfies the following point (5).

(5) Set the maximum valence of the metal (M1) to a, the maximum valence of the transition metal (M2) to b, oxygen to O, nitrogen to N, carbon to C, and the first gas When the composition of the barrier layer is (M1) (M2) _p O _q N _r C _s , a region continuously in the thickness direction of the gas barrier layer by 5 nm or more is a region [a] that satisfies the following formula.

0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <1

The above (5) indicates the oxygen-deficient composition of the gas barrier layer containing a composite oxide of the metal (M1) and the transition metal (M2) at a specific thickness or more.

As described above, the composition of the composite oxide of the metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) _p O _q N _r C _s . It is clear from this composition that a part of the composite oxide may include a structure of a nitride or a carbide. At this time, the maximum valence of the metal (M1) is set to a, the maximum valence of the transition metal (M2) is set to b, the valence of O is set to 2, the valence of N is set to 3, and the valence of C was originally It is 4, but in the above-mentioned layer formed by the present invention, it is considered that C is bonded in a state including a hydrogen atom like -CH _2- , so the valence of C is set to 2. In addition, when the composite oxide (a part of which includes nitrides or carbides) has a stoichiometric composition, it becomes (2q + 3r + 2s) / (a + bp) = 1.0. This formula means that the total of the bond of the metal (M1) and the transition metal (M2) and the total of the bond with O, N, and C are the same number. At this time, the metal (M1) and the transition metal (M2) will It is bonded to any one of O, N, and C together. Moreover, in the present invention, when two or more kinds are used as the metal (M1) or two or more kinds are used as the transition metal (M2), the maximum valence of each element is weighted and averaged by the existence ratio of each element. The calculated compound price is the value of a and b of the "maximum price" (refer to the column of the embodiment described later).

On the other hand, if the area [a] in the second aspect becomes (2q + 3r + 2s) / (a + bp) <1.0, it means a bond to the metal (M1) and the transition metal (M2). In total, the total of O, N, and C bond bonding is insufficient, and this state is the "oxygen deficiency" of the above-mentioned composite oxide. In the hypoxic state, there is a possibility that the extra bonding of the metal (M1) and the transition metal (M2) will be bonded to each other. If the metals of the metal (M1) or the transition metal (M2) are directly bonded to each other, the phase will be Compared with the case where metals are bonded via O, N, or C, a denser and higher-density structure is formed. As a result, gas barrier properties are considered to be improved.

In the present invention, the region [a] is a region satisfying 0.02 ≦ x ≦ 98. It is considered that in this region, both the metal (M1) and the transition metal (M2) are related to the direct bonding between the metals. Therefore, the region [a] that satisfies this condition exists in a thickness greater than a specific value (5nm). Contribute to the improvement of gas barrier properties. In addition, it is considered that the closer the existence ratio of the metal (M1) and the transition metal (M2) is, the more it will contribute to the improvement of the gas barrier property. Therefore, the area [a] with a thickness of 5nm includes a region satisfying 0.1 <x <90. It is more preferable to include a region satisfying 0.2 <x <80 with a thickness of 5nm, and it is more preferable to include a region satisfying 0.3 <x <70 with a thickness of 5nm.

Here, as described above, if there exists a region [a] satisfying (2q + 3r + 2s) / (a + bp) <1.0, it can be confirmed that the improvement effect of the gas barrier property will be exerted, but the region [a] satisfies (2q + 3r + 2s) / (a + bp) ≦ 0.9 is better, satisfying (2q + 3r + 2s) / (a + bp) ≦ 0.85 is even better, satisfying (2q + 3r + 2s) / (a + bp) ≦ 0.8 is more good. Here, the smaller the value of (2q + 3r + 2s) / (a + bp) in the region [a], the higher the effect of improving the gas barrier property will be greater in the absorption of visible light. Therefore, when using a gas barrier film in applications where transparency is desired, (2q + 3r + 2s) / (a + bp) ≧ 0.2 is preferred, and (2q + 3r + 2s) / (a + bp ) ≧ 0.3 is more preferable, and (2q + 3r + 2s) / (a + bp) ≧ 0.4 is more preferable.

In addition, in the present invention, the thickness of the region [a] where good gas barrier properties can be obtained, as the sputtering thickness in terms of SiO ₂ conversion, is 5 nm or more. The thickness is preferably 8 nm or more, more preferably 10 nm or more, and even more preferably 20 nm or more.

The gas barrier film having the above-mentioned configuration, like the gas barrier film according to the first aspect, represents a very high gas barrier property, and is used to the extent that it can be used as a substrate for an electronic device such as an organic EL device.

Here, in the column of the first aspect, as described above, as a result of various investigations by the present inventors, even if an oxygen-deficient composition film of a compound (oxide) of a metal (M1) other than a transition metal is used alone to form a gas barrier layer, Or using the oxygen-deficient composition film of the compound (oxide) of the transition metal (M2) alone to form the gas barrier layer has not been related to the significant improvement of the gas barrier property. Based on this finding, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component are laminated to form a transition When a mixed region in which a metal other than metal (M1) and a transition metal (M2) coexist, and the mixed region is further set to an anoxic composition, as the degree of anoxic becomes larger, the gas barrier properties will be further improved. This is thought to be due to the fact that The bonding between the foreign metal (M1) and the transition metal (M2) is easier to generate than the bonding between the metals other than the transition metal (M1) or the bonding between the transition metal (M2), and by setting the mixed region This is because of the anoxic composition, and a dense and high-density structure is formed in the mixed region (this is the technical significance of the "first aspect" mentioned above).

Here, as described above, a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component are laminated as described above. In the configuration, a mixed region made of a composite oxide is formed on a lamination interface ((4) in the first embodiment). However, the existence ratio of each metal element (M1 or M2) among the metal elements contained in the mixed region is inclined to a certain degree with respect to the thickness direction of the mixed region. Therefore, as a result of further review, it is known that even in the above mixed region, even if the oxygen-deficient composition of the composite oxide of the metal (M1) and the transition metal (M2) is formed, the thickness of the gas barrier layer in the oxygen-deficient region will have a thickness limit. In particular, it is known that the thickness of the region (M1) / {(M1) + (M2)} with a high improvement effect of the gas barrier property can only be formed up to about 10 nm. As a result, as described in the first aspect (4), when (2q + 3r + 2s) / (a + bp) <0.85 is satisfied, although excellent gas barrier properties can be exhibited, when the conditions are not satisfied, the above The gas barrier properties reachable by the laminated structure are limited, and even if the film thickness of each layer in the laminated structure is increased, the above-mentioned thickness is hardly seen to change.

Based on the above findings, the inventors discussed the critical thickness, which is a complex oxide of a metal (M1) and a transition metal (M2) After the thickness of the oxygen-deficient composition is changed, the improvement effect of the gas barrier property can be seen, and the thickness of the oxygen-deficient composition of the composite oxide of the metal (M1) and the transition metal (M2) is sufficient to make the metal (M1) and The condition of the relationship between the two metals of the transition metal (M2) and the direct bond between the metals is 0.02 ≦ x ≦ 98. As a result, as described above, if the thickness is 5 nm or more, it is confirmed that the gas barrier property has a very significant improvement effect, and the present invention has been completed. In this way, (5) related to the second aspect of the present invention shares the same technical features as (1) to (3) and (4) related to the first aspect described above: the metal (M1) and / or transition In the region where the metal (M2) coexists, by increasing the degree of hypoxia (here, the thickness of the hypoxia region (= presence volume)), a significant improvement in gas barrier properties can be achieved.

In addition, as described above, a lamination interface of a layer containing a compound (oxide) containing a metal (M1) other than a transition metal as a main component and a layer containing a compound (oxide) containing a transition metal (M2) as a main component. In the mixed region, the presence ratio of each metal element (M1 or M2) occupying the entire metal element is inclined with a certain degree of inclination with respect to the thickness direction of the mixed region. In this regard, the present inventors have further studied and found that, by controlling the absolute value of the above-mentioned tilt to a small value, it is possible to suppress the variation in the existence ratio of each metal element (M1 or M2) occupied in the entire metal element. Furthermore, the thickness of the region [a] in which the metal (M1) and the transition metal (M2) coexist can be made larger. Here, the existence ratio of the transition metal element (M2) in the entire metal element is expressed as (M2) / {(M1) + (M2)}, but the numerator and denominator of this score are divided by (M1), When using the relationship of x = (M2) / (M1) to convert, the existence ratio of the above transition metal element (M2) can be Expressed as x / (1 + x). And it was found that the gas barrier layer related to the present invention can further enhance the gas barrier performance by further satisfying the following (6): (6) the value of x / (1 + x) in the aforementioned region [a] (Here, x is relative to the presence ratio (atomic ratio) of the transition metal (M2) of the metal (M1)). The absolute value of the change in the thickness direction of the aforementioned gas barrier layer is 0 or more and 0.015 per 1 nm thickness [1 / nm] or less.

Here, the absolute value of the slope of the above change is preferably 0.010 [1 / nm] or less, still more preferably 0.007 [1 / nm] or less, and even more preferably 0.005 [1 / nm] or less. Moreover, as the absolute value of the above-mentioned change, as described in the column of the examples described later, the composition distribution data of the thickness direction of the gas barrier layer obtained from the XPS analysis will be equivalent to the analysis measurement point of the area [a] (required) It is necessary to have two or more measurement points, and it is better to measure under the condition that three or more measurement points can be obtained.) The absolute value of the tilt of the one-shot equation when the approximate analysis is performed by one-shot equation.

In the second aspect, the method for forming the gas barrier layer is not particularly limited, and a conventionally known gas phase film formation method using, for example, an existing thin film deposition technique can be used. As an example, a conventionally known gas phase film-forming method can be used. These vapor-phase film-forming methods can be used by a well-known method. The vapor-phase film-forming method is not particularly limited, and various vapor-phase film-forming methods exemplified as the method for forming the transition metal oxide-containing layer in the first aspect can be used in the same manner. Physical vapor phase growth (PVD) is preferred, and sputtering is even more preferred.

In particular, as a method for producing the above-mentioned area [a], the embodiment will be described later. As shown in the column description, it is preferable to use a co-evaporation method. That is, according to still another aspect of the present invention, it is possible to provide a method for manufacturing a gas barrier film according to the second aspect of the present invention. In this manufacturing method, the step of forming the first gas barrier layer includes co-evaporating a composite oxide including the metal (M1) and the transition metal (M2) on at least one side of the base material to form the formed oxide. It is characteristic that the gas barrier layer satisfies the above condition (5). As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method used in the present invention can be, for example, a composite target made of an alloy of both metal (M1) and transition metal (M2), or a composite oxide of metal (M1) and transition metal (M2) The resulting composite target is a one-element sputtering used as a sputtering target. In addition, the co-sputtering method in the present invention may also be multiple simultaneous sputtering. The multiple simultaneous sputtering uses a plurality of monomers containing metal (M1) or an oxide thereof, and a plurality of monomers containing a transition metal (M2) or an oxide thereof. Sputter target. Regarding a method for producing such a sputtering target or a method for producing a thin film made of a composite oxide using such a sputtering target, for example, Japanese Patent Application Laid-Open No. 2000-160331 and Japanese Patent Application Laid-Open No. 2004- It is described in JP 068109 and JP 2013-047361. In addition, as a film forming condition when the co-evaporation method is performed, there are exemplified a ratio selected from the aforementioned transition metal (M2) and oxygen in a film forming raw material, a ratio of an inert gas and a reactive gas during film forming, and a film forming time. The amount of gas supply, the degree of vacuum at the time of film formation, and the power at the time of film formation are one or two or more conditions, and by adjusting these film formation conditions (preferably oxygen partial pressure) , Can form a thin film of a composite oxide having an anoxic composition. That is, by forming the gas barrier layer using the co-evaporation method as described above, it is possible to form almost the gas barrier after it is formed. The areas in the thickness direction of the wall layer are all referred to as areas [a]. Therefore, by such a method, the desired gas barrier properties can be achieved by the extremely simple operation of controlling the thickness of the area [a]. In addition, when controlling the thickness of the area [a], it is only necessary to adjust the film formation time when the co-evaporation method is performed, for example.

[Second gas barrier layer]

In the gas barrier film according to the present invention, a gas barrier layer containing a metal oxide is further disposed on the surface of the layer containing the transition metal (M2) on the side opposite to the substrate (also referred to as "the second gas barrier in this specification"). Layer "). By having such a structure, it is possible to express a higher level of gas barrier properties.

When the substrate, the transition metal oxide-containing layer, and the first gas barrier layer are sequentially disposed in the gas barrier film according to the first aspect, the second gas barrier layer is not disposed on the transition metal oxide. Between the containing layer and the first gas barrier layer. In other words, in the first embodiment, as shown in FIG. 1, when the substrate 11, the first gas barrier layer 12, and the transition metal oxide-containing layer 13 are sequentially disposed, the layer containing the transition metal (M2) ( That is, it is preferable that the second gas barrier layer 13 is disposed on a surface of the transition metal oxide containing layer) on the side opposite to the first gas barrier layer 12 (that is, the exposed surface of the transition metal oxide containing layer 13). In addition, the second gas barrier layer does not have the specific oxygen-deficient region described above. That is, the second gas barrier layer may have the same configuration as the first gas barrier layer when the gas barrier film according to the first aspect of the present invention satisfies only the above (2).

In the gas barrier film according to the second aspect, the second gas barrier The wall layer can be a metal containing material different from the first gas barrier layer on the surface of the gas barrier layer 12 opposite to the substrate 11 (that is, the exposed surface of the gas barrier layer 12) as shown in FIG. 2. An oxide gas barrier layer is arranged.

The second gas barrier layer is not particularly limited as long as it is a layer containing a metal oxide and exhibiting gas barrier properties. Here, the gas barrier properties of the second gas barrier layer are also the same as those of the first gas barrier layer, and when the second gas barrier layer is formed on a substrate to calculate the laminate, the water vapor transmission rate (WVTR) is It is preferably less than 0.1 g / (m ² ‧day). In addition, the second gas barrier layer may be a single layer or a laminated structure of two or more layers.

The second gas barrier layer is preferably a layer formed by applying and drying a coating film obtained by coating and drying a coating liquid containing a silicon compound such as polysilazane (that is, "polysilazane modification Floor"). With such a configuration, a gas barrier film having excellent optical properties such as transmittance can be obtained. The modification treatment is preferably a vacuum ultraviolet irradiation treatment. By this modification treatment by irradiation of vacuum ultraviolet rays, the second gas barrier layer exhibits gas barrier properties. That is, it is preferable that the second gas barrier layer is a polysilazane vacuum ultraviolet irradiation modification layer.

The thickness of each layer of the second gas barrier layer is preferably 10 to 300 nm from the viewpoint of the performance of the gas barrier. In the case of a laminated structure of two or more layers, the total thickness is preferably 10 to 1000 nm from the viewpoint of suppressing cracking.

Here, the case where the silicon compound is polysilazane is taken as an example. An example of a method for forming the second gas barrier layer will be described.

The coating liquid containing polysilazane is applied by a known wet coating method and modified, thereby forming a second gas barrier layer.

The "polysilazane" used in the present invention means a polymer having a silicon-nitrogen bond in the structure and a polymer that will become a precursor of silicon oxynitride. A polymer having the following general formula (1) is used. Constructors are better.

In the formula, R ¹ , R ² , and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

In the present invention, a highly hydrogenated polysilazane in which all of R ¹ , R ^2, and R ³ are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the obtained film as the gas barrier layer.

Polysilazane is commercially available in a state of being dissolved in a solution in an organic solvent, and a commercially available product can be used as a coating liquid containing polysilazane as it is. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by Merck.

In addition, for the details of the polysilazane, paragraphs "0024" to "0040" of JP 2013-255910, and paragraphs "0037" to "0043" of JP 2013-188942 can be referred to and used. , Paragraphs "0014" to "0021" of JP 2013-151123, paragraphs "0033" of JP 2013-052569, "0045", paragraphs "0062" to "0075" of JP 2013-129557, paragraphs "0037" to "0064" of JP 2013-226758, and the like.

As a method of applying the coating liquid containing polysilazane, any appropriate method can be adopted. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, cast film method, bar coating method, and gravure printing. Law, etc. It is preferable to dry the coating film after applying the coating liquid. By drying the coating film, the organic solvent contained in the coating film can be removed. Regarding the formation method, the paragraphs "0058" to "0064" of JP-A-2014-151571 and the paragraphs "0052" to "0056" of JP-A-2011-183773 can be referred to and used.

Modification treatment means the conversion reaction of polysilazane silicon oxide or silicon oxynitride. The modification treatment in the present invention can select a known method based on a polysilazane conversion reaction. In the present invention, a conversion reaction using plasma or ozone or ultraviolet rays that can be converted at a low temperature is preferred. As the plasma or ozone, a conventionally known method can be used. In the present invention, it is preferable to form a second gas barrier layer by providing a coating film of a polysilazane-containing liquid and irradiating vacuum ultraviolet rays (VUV) with a wavelength of 200 nm or less to perform the modification treatment.

The thickness of the second gas barrier layer is preferably in a range of 1 to 500 nm, and more preferably in a range of 10 to 300 nm. In the second gas barrier layer, the entire second gas barrier layer may also be a modified layer, but the thickness of the modified layer after the modification process is preferably 1 to 50 nm, and more preferably 1 to 10 nm.

In the second gas barrier layer related to the present invention, it is preferable that at least a part of the polysilazane is modified into silicon oxynitride in the step of irradiating the layer containing the polysilazane with VUV. The present invention VUV irradiation step, the poly silicon layer polysilazane coating film accepted the VUV coated surface illuminance at 30 ~ 200mW / cm ² preferably within a range of, in 50 ~ 160mW / cm longer than the range of ² good. By setting the irradiance of VUV to 30mW / cm ² or more, the modification efficiency can be sufficiently improved. When the UVV is 200mW / cm ² or less, the incidence of damage to the coating film can be extremely suppressed, and the damage to the substrate can also be reduced. , So it is better.

The irradiation energy of VUV in the coating surface of the polysilazane layer is preferably in the range of 200 to 10,000 mJ / cm ² , and more preferably in the range of 500 to 5000 mJ / cm ² . By setting the irradiation energy of VUV to 200mJ / cm ² or more, the modification of the polysilazane layer can be sufficiently performed. If it is 10000mJ / cm ² or less, excessive modification can be suppressed, and polysilicon can be suppressed as much as possible. Rupture of the azane layer, or thermal deformation of the substrate.

Moreover, as a vacuum ultraviolet light source, it is preferable to use a rare gas excimer lamp. Since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation step is easily reduced, so it is better to perform the irradiation of VUV in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during VUV irradiation is preferably set in a range of 10 to 10,000 ppm, more preferably in a range of 50 to 5000 ppm, more preferably in a range of 80 to 4500 ppm, and most preferably in a range of 100 to 1000 ppm.

As the gas that is used to fill the irradiation environment during VUV irradiation, a dry inert gas is preferred, and from a cost standpoint, dry nitrogen is preferred. The oxygen concentration can be adjusted by measuring the oxygen, Adjust the flow rate of inert gas and change the flow ratio.

In these modification processes, for example, paragraphs "0055" to "0091" of JP 2012-086394, paragraphs "0049" to "0085" of JP 2012-006154 can be referred to, and JP 2011- Contents described in paragraphs "0046" to "0074" in 251460.

Furthermore, the second gas barrier layer may be formed by a vapor-phase film formation method (that is, a “gas-phase film-formed gas barrier layer”). In such a form, the second gas barrier layer can be formed by the same gas-phase film-forming method as described in the column of the first gas barrier layer.

[The protective layer]

In the gas barrier film according to the present invention, a protective layer such as a polysiloxane modified layer may be formed on the outermost layer of the substrate on the side where the gas barrier layer is formed. The polysiloxane modified layer can be coated with a polysiloxane-containing coating liquid by a wet coating method and dried, and then the dried coating film can be subjected to heating modification treatment or ultraviolet light. It is formed by modification treatment such as irradiation of radiation and irradiation of vacuum ultraviolet light. As the vacuum ultraviolet light, VUV used in the modification treatment using the above polysilazane is preferred.

For details of the polysiloxane, reference can be made to the paragraphs "0028" to "0032" of JP 2013-151123, and the paragraphs "0050" to "0064" of JP 2013-086501. Paragraphs "0063" to "0081" of JP 2013-059927, Paragraphs "0119" of JP 2013-226673 ~ "0139" and so on.

[Various functional layers]

In addition to the above-mentioned second gas barrier layer, the gas barrier film of the present invention can be provided with various functional layers.

(Fixed coating)

On the surface of the base material forming the side of the first gas barrier layer (which is further a transition metal oxide-containing layer in the first aspect) according to the present invention, the base material and the first gas barrier layer (or For the purpose of improving the adhesion of the layer), a fixed coating layer may be disposed.

As the fixing coating agent used for the fixing coating layer, two or more types of polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, ethylene modified resin, Epoxy resin, modified styrene resin, modified silicone resin, and alkyl titanate are used.

Conventionally known additives can be added to these fixing coating agents. The fixed coating agent can be applied to a support by a known method such as roll coating, gravure coating, doctor blade coating, dip coating, and spray coating, and the solvent can be removed by drying and diluted. Agent and the like for fixed coating. The application amount of the fixed coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

In addition, the fixed coating layer can also be formed by a vapor deposition method such as a physical vapor deposition method or a chemical vapor deposition method. For example, JP 2008-142941 As described, it is possible to form an inorganic film mainly composed of silicon oxide for the purpose of improving adhesion and the like. Alternatively, as described in Japanese Patent Application Laid-Open No. 2004-314626, when a fixed coating layer is formed and an inorganic thin film is formed by a vapor-phase film-forming method thereon, a gas generated from the substrate side can be shielded from a certain gas. The purpose is to control the composition of the inorganic thin film to form a fixed coating layer.

In addition, the thickness of the fixed coating layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Hard coating)

A hard coat layer may be arranged on the surface (single or both sides) of the substrate. Examples of the material included in the hard coat layer include thermosetting resins and active energy ray-curable resins, but in terms of ease of molding, active energy ray-curable resins are preferred. Such a curable resin can be used individually or in combination of 2 or more types.

The active energy ray-curable resin means a resin which is hardened by irradiation with active energy rays such as ultraviolet rays or electron beams and undergoes a crosslinking reaction or the like. As the active energy ray-curable resin, it is preferable to use a component containing a monomer having an ethylenically unsaturated double bond. The active energy ray-curable resin is hardened by irradiating an active energy ray such as ultraviolet rays or an electron beam to form an active energy ray-curable resin The hardened layer, that is, the hard coating. Examples of the active energy ray-curable resin include a UV-curable resin and an electron beam-curable resin, but a UV-curable resin cured by ultraviolet irradiation is preferred. A commercially available substrate having a hard coat layer formed in advance may also be used.

From the viewpoint of smoothness and bending resistance, the thickness of the hard coating layer, It is preferably 0.1 to 15 μm, and more preferably 1 to 5 μm.

(Smooth layer)

A smooth layer may be disposed on the surface of the substrate on the side where the first gas barrier layer (the first embodiment further contains a transition metal oxide-containing layer) according to the present invention is formed. The smoothing layer used in the present invention is provided for flattening the rough surface of a substrate having protrusions or the like or burying and flattening unevenness or pinholes on the upper layer due to the protrusions existing on the substrate. Such a smoothing layer is basically made of a photosensitive material or a thermosetting material.

Examples of the photosensitive material of the smooth layer include a resin composition containing an acrylate compound having a radically reactive unsaturated compound, a resin composition containing an acrylate compound and a thiol compound having a thiol group, and an epoxy acrylate. , A resin composition in which polyfunctional acrylate monomers such as urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methyl acrylate are dissolved. Specifically, the UV-curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. In addition, any mixture such as the above-mentioned resin composition can be used, and it is not particularly limited as long as it is a photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule.

Examples of the thermosetting material include Tutto prom series (organic polysilazane) manufactured by Clariant, SP COAT heat-resistant transparent coating manufactured by Ceramic coat Co., Ltd., and nano-mixed silicon manufactured by ADEKA Co., Ltd. Oxygen, made by DIC Corporation UNIDIC (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra high heat resistance epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Industry Co., Ltd., and inorganics made by Nitto Textile Co., Ltd. Organic nanocomposite material SSG Coat, acrylic polyol and isocyanate prepolymer, thermosetting urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, etc. Among them, the material of the epoxy resin substrate having heat resistance is particularly preferable.

The method for forming the smooth layer is not particularly limited, and it is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, a dipping method, or a dry coating method such as an evaporation method.

In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the photosensitive resin as necessary. Moreover, regardless of the lamination position of the smoothing layer, in any smoothing layer, an appropriate resin or additive can be used to improve film formation and prevent pinholes of the film from occurring.

The thickness of the smoothing layer is preferably in the range of 1 to 10 μm, and more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and making it easy to adjust the balance of the optical characteristics of the film.

The smoothness of the smoothing layer is represented by the value of the surface roughness specified by JIS B 0601: 2001. The ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. As long as it is within this range, even when the barrier layer is applied in a coating form, or when the coating means is contacted on the surface of the smooth layer by a coating method such as a wire rod or a wireless rod, the coating property is less likely to be damaged, It is also easy to smooth unevenness after coating.

[Electronic device]

The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated due to chemical components (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) in the air. That is, the present invention provides an electronic device including the gas barrier film of the present invention and an electronic device body.

As examples of the electronic device body used in the electronic device of the present invention, there can be exemplified electromechanical light-emitting elements (organic EL elements), liquid crystal display elements (LCD), thin-film transistors, touch panels, electronic paper, and solar cells ( PV) and so on. From the viewpoint of obtaining the effect of the present invention more efficiently, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

[Example]

The effect of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments.

≫Fabrication of gas barrier film≫ [Example 1]

The gas barrier film of Example 1 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 1 are shown in Table 1 below.

<Production of Gas Barrier Film 1-1> [Fabrication of substrate]

A 100 μm-thick polyethylene terephthalate film (made by Toray Co., Ltd., LUMIRROR (registered trademark) (U48)) on both sides was formed on the side opposite to the side on which the gas barrier layer was formed. Transparent hard coating with anti-blocking function. Specifically, after applying a UV-curable resin (manufactured by Aica Industry Co., Ltd., product number: Z731L) to a dry film thickness of 0.5 μm, drying at 80 ° C., and then using a high-pressure mercury lamp in the air to irradiate energy Hardening was performed under the conditions of 0.5 J / cm ² .

Next, a transparent hard coat layer having a thickness of 2 μm was formed on the surface on the side where the gas barrier layer was formed. Specifically, a UV-curable resin OPSTAR (registered trademark) Z7527 made by JSR Co., Ltd. was coated to a dry film thickness of 2 μm, and then dried at 80 ° C. Then, a high-pressure mercury lamp was used in the air to irradiate the energy of 0.5. J / cm ² is used for hardening. A base material was produced in this manner (the same base material is used for all production examples below).

[Formation of the first gas barrier layer]

The first gas barrier was formed on the surface of one side of the substrate by a vapor phase method, sputtering (magnetron sputtering device, made by Canon-anelva: type EB1100 (hereinafter, the same device is used for sputtering)). Layer film. The sputtering device used can set a plurality of targets, and can continuously form a plurality of layers of different types of metals while maintaining a specific vacuum state.

Here, a polycrystalline Si target is used as the target, and the processing gas is Ar and O ₂ , and a layer with a thickness of 30 nm is formed by DC sputtering. Film formation is performed by adjusting the oxygen partial pressure so that the composition of the layer becomes SiO ₂ . In addition, a condition search for the composition was performed by forming a film using a glass substrate in advance and adjusting the oxygen partial pressure to find out the conditions where the composition from the surface layer to a depth of about 10 nm became SiO _{2 and} the conditions were applied. In addition, regarding the film thickness, data on the film thickness change with respect to the film formation time in the range of 100 nm to 300 nm are obtained. After calculating the film thickness per unit time, the film formation time is set to a set thickness, and This adjusts the film thickness. Hereinafter, the conditions for forming a film from the surface layer to a depth of about 10 nm are the same as those for the film formation by sputtering, and the film thickness per unit time is calculated, and the conditions are applied.

A first gas barrier layer (composition: SiO ₂ , film thickness: 30 nm) was formed on the surface on one side of the substrate by the above-mentioned method, and a gas barrier film 1-1 was produced.

<Production of Gas Barrier Film 1-3>

Except that the composition of the first gas barrier layer was SiO _1.7 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier film 1-3 was produced in the same manner as in the production of the gas barrier film 1-1.

<Production of Gas Barrier Film 1-5>

Except that the composition of the first gas barrier layer was SiO _1.6 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier film 1-5 was produced in the same manner as in the production of the gas barrier film 1-1.

<Production of Gas Barrier Film 1-2>

On the exposed surface of the first gas barrier layer of the gas barrier film 1-1, a transition metal oxide-containing layer was formed by the following method to produce a gas barrier film 1-2.

[Formation of a transition metal oxide-containing layer (sputtering)]

Here, an oxygen-deficient Nb ₂ O ₅ target is used as a target, and Ar and O _{2 are} used as a process gas, and a transition metal oxide-containing layer is formed by DC sputtering (composition: NbO _2.5 , film thickness: 15 nm) .

<Production of Gas Barrier Film 1-4>

Instead of using the gas barrier film 1-3 instead of the gas barrier film 1-1, the gas barrier film 1-4 was produced in the same manner as in the production of the gas barrier film 1-2.

<Production of Gas Barrier Film 1-6>

Instead of using the gas barrier film 1-5 instead of the gas barrier film 1-1, the gas barrier film 1-6 was produced in the same manner as in the production of the gas barrier film 1-2.

<Production of Gas Barrier Films 1-7>

Except that the composition of the transition metal oxide-containing layer was changed to NbO _2.2 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier films 1 to 7 were produced in the same manner as in the production of the gas barrier film 1-2.

<Production of Gas Barrier Films 1-8>

Except that the composition of the first gas barrier layer was SiO _1.9 and the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier films 1-7 were produced in the same manner as in the production of the gas barrier films 1-7.

[Example 2]

The gas barrier film of Example 2 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 2 are shown in Table 2 below.

<Production of Gas Barrier Film 2-1>

A gas barrier film 2-1 was produced in the same manner as in the production of the gas barrier film 1-2, except that the first gas barrier layer was not formed.

<Production of Gas Barrier Film 2-2>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-1, a first gas barrier layer was formed in the same manner as in the gas barrier film 1-3, and a gas barrier film 2- was produced. 2.

<Production of Gas Barrier Film 2-3>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-1, a first gas barrier layer was formed by the same method as in the gas barrier film 1-5, and a gas barrier film 2- was produced. 3.

<Production of Gas Barrier Film 2-4>

Except that the composition of the transition metal oxide-containing layer was NbO _1.5 and the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier film 2-4 was produced in the same manner as in the production of the gas barrier film 2-1.

<Production of Gas Barrier Film 2-5>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-4, a first gas barrier layer was formed by the same method as in the gas barrier film 1-1, and a gas barrier film 2-5 was produced. .

<Production of Gas Barrier Film 2-6>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 2-4, a transition metal oxide-containing layer was further formed by the same method as that in the gas barrier film 2-4 to produce a gas barrier. Sex film 2-6.

[Example 3]

The gas barrier film of Example 3 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 3 are shown in Table 3 below.

<Production of Gas Barrier Film 3-1>

The first surface was made on one side of the substrate by vacuum plasma CVD. Gas barrier layer. Specifically, the vacuum plasma CVD apparatus shown in FIG. 3 was used to form the first gas barrier layer on the surface on one side of the substrate. At this time, the high-frequency power used is a 27.12MHz high-frequency power, and the distance between the electrodes is 20mm. In addition, as a raw material gas, hexamethyldisilazane gas was introduced into the vacuum chamber under a condition of a flow rate of 10 sccm, and oxygen was introduced under a condition of a flow rate of 100 sccm. At the beginning of film formation, an inorganic layer containing silicon oxide containing carbon as a main component was formed by setting the temperature of the substrate to 100 ° C. and the gas pressure during film formation to 30 Pa.

By the above method, a first gas barrier layer (composition: SiO _1.6 C _0.4 , film thickness: 200 nm) was formed on a surface on one side of the base material, and a gas barrier film 3-1 was produced.

<Production of Gas Barrier Film 3-2>

On the exposed surface of the first gas barrier layer 3-1 of the gas barrier film 3-1, a gas barrier layer was sputtered by the same gas phase method as in the gas barrier film 2-2, and a gas barrier layer was formed to produce a gas. Barrier film 3-2. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

<Production of Gas Barrier Film 3-3>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-1, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 1-2 to produce a gas barrier film 3- 3. In addition, the formation of the two layers will not be performed continuously, and the first layer is temporarily exposed after the formation After being exposed to the atmosphere, a second layer is formed.

<Production of Gas Barrier Film 3-4>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-1, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 2-6 to produce a gas barrier film 3- 4. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

<Production of Gas Barrier Film 3-5>

Except that the film thickness of the first gas barrier layer was set to 200 nm and the film formation time during DC sputtering was adjusted, the rest of the gas barrier film 3-5 was produced in the same manner as in the production of the gas barrier film 1-1.

<Production of Gas Barrier Film 3-6>

Except that the composition of the first gas barrier layer was SiO _1.8 and the oxygen partial pressure during DC sputtering was adjusted, the rest of the gas barrier films 3-6 were produced in the same manner as in the above-mentioned production of the gas barrier films 3-5.

<Production of Gas Barrier Film 3-7>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 3-3 to produce a gas barrier film 3- 7. In addition, the formation of the two layers will not be performed continuously, and the first layer is temporarily exposed after the formation After being exposed to the atmosphere, a second layer is formed.

<Production of Gas Barrier Film 3-8>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the same method as that of the gas barrier film 3-4 to produce a gas barrier film 3- 8. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

<Production of Gas Barrier Films 3-9>

The formation of the two layers was continuously performed inside the same magnetron sputtering device, and was not exposed to the atmosphere between the formation of the two layers. The rest was the same as the production of the gas barrier film 3-8. Make a gas barrier film 3-9.

<Production of Gas Barrier Film 3-10>

The composition of the transition metal oxide-containing layer was changed to NbO _2.1 , except that the oxygen partial pressure at the time of DC sputtering was adjusted, the rest of the gas barrier film 3-9 was produced in the same manner as in the production of the gas barrier film 3-9.

<Production of Gas Barrier Film 3-11>

The composition of the transition metal oxide-containing layer was set to TaO _1.5 , and a Ta ₂ O ₅ target was used as a target during DC sputtering. The rest of the gas barrier properties were produced in the same manner as in the production of the gas barrier film 3-8. Film 3--11.

<Production of Gas Barrier Film 3-12>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-5, a transition metal oxide-containing layer was formed by the following ion-assisted evaporation method to produce a gas barrier film 3-12. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

[Formation of transition metal oxide-containing layer (ion assisted evaporation)]

The device described in Japanese Patent Application Laid-Open No. 2011-39218, paragraph "0035" or later, uses an ion assisted (ion source assisted) method that ionizes and discharges argon and oxygen, and deposits a niobium metal film to a thickness of 15 nm. Conditions for film formation. In addition, from the prior discussion, the composition of the vapor deposition film was changed to NbO _1.8 to adjust the oxygen partial pressure. And, the conditions of the ion source assistance are as follows: Acceleration voltage: 1000V

Acceleration current: 200mA.

<Production of Gas Barrier Film 3-13>

A first gas barrier layer was produced on a surface on one side of the substrate by a vacuum plasma CVD method. Specifically, the vacuum plasma CVD apparatus shown in FIG. 3 was used to form the first gas barrier layer on the surface on one side of the substrate. At this time, the high-frequency power used is a high-frequency power of 27.12MHz. The distance is 20mm. In addition, as the raw material gas, a silane gas was introduced into the vacuum chamber under a condition of a flow rate of 7.5 sccm, an ammonia gas was used under a condition of a flow rate of 50 sccm, and a hydrogen gas was used at a flow rate of 200 sccm. At the beginning of film formation, an inorganic layer containing silicon nitride as a main component was formed by setting the temperature of the substrate to 100 ° C. and the gas pressure during film formation to 30 Pa.

By the above method, a first gas barrier layer (composition: SiO _0.05 N _0.8 , film thickness: 100 nm) was formed on a surface on one side of the base material, and a gas barrier film 3-13 was produced.

<Production of Gas Barrier Film 3-14>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-13, a gas barrier layer was sputtered by the same gas phase method as that of the gas barrier film 3-2, and a gas barrier layer was formed to produce a gas. Barrier film 3-14. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

<Production of Gas Barrier Film 3-15>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-13, a transition metal oxide-containing layer was formed in the same manner as in the gas barrier film 3-4, and a gas barrier film 3- was produced. 15. In addition, the formation of these two layers does not proceed continuously, and the formation of the second layer is performed after being temporarily exposed to the atmosphere after the formation of the first layer.

<Production of Gas Barrier Film 3-16>

A first gas barrier layer (composition: ZnSn _0.7 O _1.82 , film thickness: 200 nm) was formed on the surface of one side of the substrate by a vapor phase method and sputtering under the following film formation conditions to produce a gas barrier property Film 3-16. In addition, the "maximum valence of (M1)" described in Table 3 is the maximum valence of 2 from Zn and the maximum valence of 6 from Sn, and the molar ratio (1: 0.7) to Zn: Sn, as Zn and Sn The theoretical maximum valence for a total of 1 mole is calculated as (2 × 1 + 6 × 0.7) / (1 + 0.7) = 3.65.

[Film forming conditions]

A ZnSn alloy target was used as a target, and Ar and O _{2 were} used as a process gas, and a DC gas sputtering was used to form a first gas barrier layer.

<Production of Gas Barrier Film 3-17>

On the exposed surface of the first gas barrier layer 3-16 of the gas barrier film 3-16, a gas barrier layer was sputtered in the same manner as in the gas barrier film 3-2, and a gas barrier layer was further formed to produce a gas. Barrier film 3-17. Moreover, the formation of the two layers is continuously performed in the same interior of the magnetron sputtering device, and it is not necessary to be exposed to the atmosphere between the formation of the two layers.

<Production of Gas Barrier Film 3-18>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-16, a transition metal oxide-containing layer was formed by the same method as in the gas barrier film 3-4, and a gas barrier film 3 was produced 3- 18. In addition, the formation of these two layers is continuous in the interior of the same magnetron sputtering device. It does not need to be exposed to the atmosphere between the two layers.

<Production of Gas Barrier Film 3-19>

On the exposed surface of the first gas barrier layer of the gas barrier film 3-6, a protective layer made of a polysiloxane modified layer was formed by the following coating modification method to produce a gas barrier film 3 -19.

[Formation of protective layer (coating modification method)]

Polymethylsilsesquioxane (SR-13, manufactured by Konishi Chemical Industry Co., Ltd.) was dissolved in methyl ethyl ketone and filtered to obtain a coating solution of 5 mass%. This was applied by spin coating to a dry film thickness of 100 nm, and dried at 100 ° C for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 4 J / cm ² . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C.

<Production of Gas Barrier Film 3-20>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier layer was formed by the following coating modification method to produce a gas barrier film 3-20. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are not continuously performed. After the formation of the transition metal oxide-containing layer, the second gas barrier layer is formed after being temporarily exposed to the atmosphere. .

[Formation of the second gas barrier layer (coating modification method)]

A 20% by mass solution of dibutyl ether containing highly hydrogenated polysilazane (NN120-20, manufactured by Merck) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6- Diamine hexane (TMDAH)) high hydrogenated polysilazane 20% by mass dibutyl ether solution (Merck, NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and the thickness of the dried film was adjusted further. Dibutyl ether was appropriately diluted to prepare a coating solution.

On the exposed surface of the transition metal oxide-containing layer, the coating liquid was applied by a spin coating method so as to have a dry film thickness of 100 nm, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 4 J / cm ² . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C.

<Production of Gas Barrier Film 3-21>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier layer was formed by the same method as in the production of the gas barrier film 3-19, and a gas barrier film was produced. 3-21. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are not continuously performed. After the formation of the transition metal oxide-containing layer, the second gas barrier layer is formed after being temporarily exposed to the atmosphere. .

<Production of Gas Barrier Film 3-22>

On the exposed surface of the transition metal oxide-containing layer of the gas barrier film 3-9, a second gas barrier was formed in the same manner as the formation of the first gas barrier layer in the production of the gas barrier film 1-1. Layer to make a gas barrier film 3-22. At this time, the film thickness of the second gas barrier layer was set to 100 nm to adjust the film formation time during DC sputtering. In addition, the formation of the transition metal oxide-containing layer and the formation of the second gas barrier layer are continuously performed in the same magnetron sputtering apparatus, and there is no need to be exposed to the atmosphere between the formation of the two layers. .

[Example 4]

The gas barrier film of Example 4 was produced by the following method. The structure and manufacturing conditions of each thin film produced in Example 4 are shown in Table 4 below.

<Production of Gas Barrier Film 4-1>

A gas barrier film 4-1 was produced in the same manner as in the above-mentioned production of the gas barrier film 1-1 except that the film thickness of the first gas barrier layer was set to 150 nm to adjust the film formation time during DC sputtering.

<Production of Gas Barrier Film 4-2>

On the exposed surface of the first gas barrier layer of the gas barrier film 4-1, a transition metal oxide-containing layer was formed by the following method to produce a gas barrier film 4-2.

[Formation of a transition metal oxide-containing layer (sputtering)]

Here, an oxygen-deficient Nb ₂ O ₅ target is used as a target, and Ar and O _{2 are} used as a process gas, and a transition metal oxide-containing layer is formed by DC sputtering (composition: NbO _2.2 , film thickness: 15 nm) .

<Production of Gas Barrier Film 4-3>

The composition of the transition metal oxide-containing layer was changed to NbO _2.1 , except that the oxygen partial pressure at the time of DC sputtering was adjusted, and the rest of the gas barrier film 4-2 was produced in the same manner as in the production of the gas barrier film 4-2.

<Production of Gas Barrier Film 4-4>

The composition of the transition metal oxide containing layer was changed to NbO _1.5 and the oxygen partial pressure at the time of DC sputtering was adjusted. The rest of the gas barrier film 4-4 was produced in the same manner as in the production of the gas barrier film 4-2.

<Production of Gas Barrier Film 4-5>

Except that the film thickness of the transition metal oxide-containing layer was adjusted to 9 nm and the film-forming time during DC sputtering was adjusted, the rest of the gas barrier film 4-4 was produced in the same manner as in the production of the gas barrier film 4-4.

<Production of Gas Barrier Film 4-6>

The film thickness of the transition metal oxide-containing layer was set to 5 nm, and the film formation time during DC sputtering was adjusted, and the rest was the same as that of the gas barrier film 4-4. In the same manner, the gas barrier film 4-6 was produced.

<Production of Gas Barrier Film 4-7>

Except that the film thickness of the transition metal oxide-containing layer was adjusted to 3 nm to adjust the film formation time at the time of DC sputtering, the gas barrier film 4-7 was produced in the same manner as in the production of the gas barrier film 4-4.

[Example 5]

A gas barrier film was produced by the following method. The composition (thickness, average composition of the gas barrier layer (average composition of the region [a] when the gas barrier layer has the region [a])) of each produced film is shown in Table 5 below.

<Production of Gas Barrier Film 5-1> [Fabrication of substrate]

A 100 μm-thick polyethylene terephthalate film (manufactured by Toray Co., Ltd., LUMIRROR (registered trademark) (U48)) on both sides was formed on the side opposite to the side on which the gas barrier layer was formed. Transparent hard coating with anti-blocking function. Specifically, after applying a UV-curable resin (manufactured by Aica Industry Co., Ltd., product number: Z731L) to a dry film thickness of 0.5 μm, drying at 80 ° C., and then using a high-pressure mercury lamp under air to irradiate energy Hardening was performed under the conditions of 0.5 J / cm ² .

Next, a transparent hard coat layer having a thickness of 2 μm was formed on the surface on the side where the gas barrier layer was formed. Specifically, a UV-curable resin OPSTAR (registered trademark) Z7527 made by JSR Co., Ltd. was coated to a dry film thickness of 2 μm, and then dried at 80 ° C. Then, a high-pressure mercury lamp was used in the air to irradiate the energy of 0.5. J / cm ² is used for hardening. A base material was produced in this manner (the same base material is used for all production examples below).

[Formation of gas barrier layer (SiO ₂ layer)]

A gas barrier layer was formed on a surface of one side of the substrate by a gas phase method, sputtering (magnetron sputtering device, manufactured by Canon-anelva: type EB1100 (hereinafter, the same device is used for sputtering)). membrane. The sputtering equipment used is one capable of simultaneous sputtering of 2 yuan.

Here, a polycrystalline Si target is used as a target, Ar and O _{2 are} used as a processing gas, and a layer having a thickness of 30 nm is formed by DC sputtering. Film formation is performed by adjusting the oxygen partial pressure so that the composition of the layer becomes SiO ₂ . In addition, a condition search for the composition was performed by forming a film using a glass substrate in advance and adjusting the oxygen partial pressure to find out the conditions where the composition from the surface layer to a depth of about 10 nm became SiO _{2 and} the conditions were applied. In addition, regarding the film thickness, data on the film thickness change with respect to the film formation time in the range of 100 nm to 300 nm are obtained. After calculating the film thickness per unit time, the film formation time is set to a set thickness, and This adjusts the film thickness. Hereinafter, the conditions for forming a film from the surface layer to a depth of about 10 nm are the same as those for the film formation by sputtering, and the film thickness per unit time is calculated, and the conditions are applied.

By the above-mentioned method, a gas barrier layer (composition: SiO ₂ , film thickness: 30 nm) was formed on a surface on one side of the base material, and a gas barrier film 5-1 was produced.

<Production of Gas Barrier Film 5-2>

The composition of the gas barrier layer was changed to SiO _1.8 to adjust the oxygen partial pressure during DC sputtering, and the rest of the gas barrier film 5-2 was produced in the same manner as in the production of the gas barrier film 5-1.

<Production of Gas Barrier Film 5-3>

A gas barrier layer was formed on the surface on one side of the substrate by the following method to produce a gas barrier film 5-3.

[Formation of gas barrier layer (NbO _2.5 layer)]

An oxygen-deficient Nb ₂ O ₅ target was used as a target, Ar and O _{2 were} used as a process gas, and a gas barrier layer (composition: NbO _2.5 , film thickness: 30 nm) containing Nb was formed by DC sputtering.

<Production of Gas Barrier Film 5-4>

The composition of the gas barrier layer was changed to NbO _1.7 to adjust the oxygen partial pressure during DC sputtering, and the rest of the gas barrier film 5-4 was produced in the same manner as in the production of the gas barrier film 5-3.

<Production of Gas Barrier Film 5-5>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-5 was produced.

[Formation of gas barrier layer (Si-Nb composite oxide layer)]

The pulverized Si and Nb powder were mixed so that Si was 80 atomic% and Nb was 20 atomic%, and they were hot-pressed in an Ar environment to sinter. After the sintered mixed material is mechanically formed, it is joined on a copper back plate and used as a target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.

<Production of Gas Barrier Film 5-6>

Using a composition with 50 atomic% of Si and 50 atomic% of Nb as the sputtering target, the composition of the gas barrier layer is shown in Table 5, and the rest of the oxygen barrier pressure during DC sputtering is adjusted with the above gas barrier. Production of the flexible film 5 In the same manner, a gas barrier film 5-6 was produced.

<Production of Gas Barrier Film 5-7>

The composition of the gas barrier layer is shown in Table 5. The gas barrier film 5-7 was produced in the same manner as in the production of the gas barrier film 5-6 except that the oxygen partial pressure during DC sputtering was adjusted.

<Production of Gas Barrier Film 5-8>

The composition of the gas barrier layer is shown in Table 5. The gas barrier film 5-8 was produced in the same manner as in the production of the gas barrier film 5-6 except that the oxygen partial pressure during DC sputtering was adjusted.

<Production of Gas Barrier Film 5-9>

The gas barrier film 9 was produced in the same manner as in the above-mentioned production of the gas barrier film 8 except that the film thickness of the gas barrier layer was set to 20 nm and the film formation time during the DC sputtering was adjusted.

<Production of Gas Barrier Film 5-10>

A gas barrier film 5-10 was produced in the same manner as in the above-mentioned production of the gas barrier film 5-8 except that the film thickness of the gas barrier layer was set to 10 nm to adjust the film formation time during DC sputtering.

<Production of Gas Barrier Film 5-11>

The gas barrier film 11 was produced in the same manner as in the production of the gas barrier film 5-8 except that the film thickness of the gas barrier layer was set to 4 nm to adjust the film formation time during DC sputtering.

<Production of Gas Barrier Film 5-12>

Except that the film thickness of the gas barrier layer was adjusted to 100 nm and the film formation time during the DC sputtering was adjusted, the rest of the gas barrier film 5-12 was produced in the same manner as in the production of the gas barrier film 5-8.

<Production of Gas Barrier Film 5-13>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-13 was produced.

[Formation of gas barrier layer (Si-Nb composite oxide layer)]

Nb ₂ O ₅ powder was 50% by mass and SiO ₂ powder was 50% by mass. Distilled water was used as a dispersant and mixed with a ball mill. The obtained slurry was granulated using a spray dryer to obtain secondary particles. An oxide mixed powder having a particle size of 20 to 100 μm.

On the other hand, a copper backing plate with a diameter of 6 inches was used as the target holder. In addition, the surface portion of the backing plate on which the above oxide mixed powder should be sprayed is roughened by sandblasting using Al ₂ O ₃ particles, and becomes a rough surface state.

Next, the alloy powder of Ni-Al (mass ratio 8: 2) was subjected to plasma spraying (using a Metco dissolver) in a reducing environment to form a base made of Ni-Al (mass ratio 8: 2) with a thickness of 50 μm After coating, the above oxide mixed powder is plasma-sprayed on the undercoat layer under a reducing environment to produce a target. The obtained target was an anaerobic target containing Si at a ratio of 40 atomic% and Nb at a ratio of 60 atomic%. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.

<Production of Gas Barrier Film 5-14>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-14 was produced.

[Formation of gas barrier layer (Si-Nb composite oxide layer)]

A polycrystalline Si target and a metal Nb target were used as targets, and Ar and O _{2 were} used as a processing gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set as shown in Table 5 to adjust the sputtering conditions in the polycrystalline Si target during DC sputtering, the sputtering conditions in the metal Nb target, and the oxygen partial pressure.

<Production of Gas Barrier Film 5-15>

The composition of the gas barrier layer is shown in Table 5. The sputtering conditions in the polycrystalline Si target during DC sputtering, the sputtering conditions in the metal Nb target, and the oxygen partial pressure were adjusted. Production of Film 5-14 Similarly, a gas barrier film 5-15 was produced.

<Production of Gas Barrier Film 5-16>

On one side of the substrate, a gas barrier layer (composition: shown in Table 51, film thickness: 30 nm) was formed by the following method to produce a gas barrier film 5-16.

[Formation of gas barrier layer (Si-Ta composite oxide layer)]

A polycrystalline Si target and a metal Ta target were used as targets, and Ar and O _{2 were} used as a process gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set as shown in Table 5 to adjust the sputtering conditions in the polycrystalline Si target, the sputtering conditions in the metal Ta target, and the oxygen partial pressure during DC sputtering.

<Production of Gas Barrier Film 5-17>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-17 was produced.

[Formation of gas barrier layer (Zn-Sn composite oxide layer)]

A high-purity ZnO powder, a high-purity SnO ₂ powder, a PVB resin as a binder, ethanol as an organic solvent, and acetone were prepared separately.

Next, ZnO powder, SnO ₂ powder, a binder, and an organic solvent were mixed at a specific ratio by wet mixing of a ball mill to prepare a slurry having a concentration of 40% by mass. In addition, the mixing amount of the ZnO powder and the SnO ₂ powder was adjusted so that Zn contained in the formed sputtering target was 50 atomic% and Sn was 50 atomic%.

Next, the prepared slurry is spray-dried using a spray dryer to obtain a mixed granulated powder having an average particle size of 200 μm. This granulated powder is placed in a specific model and pressurized by a uniaxial press. Forming. After demolding, the obtained compact was sintered at 1000 ° C. for 5 hours in an atmospheric environment to obtain a ZnO-SnO ₂ target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.

<Production of Gas Barrier Film 5-18>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the base material by the following method to produce a gas barrier film 5-18.

[Formation of gas barrier layer (Zn-Sn-Nb composite oxide layer)]

ZnO-SnO ₂ targets and metal Nb targets used for the production of the gas barrier thin films 5-17 were used as targets. Ar and O _{2 were} used as a process gas, and two-dimensional simultaneous sputtering was performed by a DC method to form a gas barrier layer. In addition, the composition of the gas barrier layer was set to Table 5 to adjust the sputtering conditions in the ZnO-SnO ₂ target, the sputtering conditions in the metal Nb target, and the oxygen partial pressure during DC sputtering.

<Production of Gas Barrier Film 5-19>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-19 was produced.

[Formation of a gas barrier layer (Zn-Si composite oxide layer)]

A SiO ₂ powder having a purity of 99.99% or more is mixed with ZnS so that the ratio of Zn is 80 atomic% and Si is 20 atomic%. 0.1% by mass of Na ₂ O is added to 100% by mass of the mixed powder and mixed. This mixed powder was filled in a graphite mold, and hot-pressed under conditions of an Ar environment, a surface pressure of 150 kg / cm ² , and a temperature of 1000 ° C. to obtain a ZnS-SiO ₂ target. Using the obtained target, a film was formed by the same sputtering as described above to form a gas barrier layer.

<Production of Gas Barrier Film 5-20>

A gas barrier layer (composition: shown in Table 5, film thickness: 30 nm) was formed on the surface on one side of the substrate by the following method, and a gas barrier film 5-20 was produced.

[Formation of a gas barrier layer (Zn-Si-Nb composite oxide layer)]

ZnS-SiO ₂ target and metal Nb target used for the production of the gas barrier thin film 5-19 are used as targets, and Ar and O _{2 are} used as the processing gas, and two-dimensional simultaneous sputtering is performed by DC method to form a gas barrier. Floor. In addition, the composition of the gas barrier layer was set to Table 5 to adjust the sputtering conditions in the ZnS-SiO ₂ target, the sputtering conditions in the metal Nb target, and the oxygen partial pressure during DC sputtering.

≫Evaluation of gas barrier films 薄膜

The following evaluation was performed on the gas barrier film produced in the above Examples 1 to 5. The results are shown in Tables 1 to 5 below. Moreover, the slash marks in the squares of Tables 1 to 5 mean that the composition does not exist or no corresponding evaluation has been performed.

<Composition and Measurement of Oxidation Degree of Gas Barrier Layer and Transition Metal Oxide Containing Layer>

By XPS analysis, compositional distribution data of the gas barrier layer and the transition metal oxide-containing layer in the thickness direction were measured. The XPS analysis conditions are as follows.

[XPS analysis conditions]

‧Equipment: QUANTERASXM manufactured by ULVAC-PHI Co., Ltd.

‧X-ray source: Monochromatic Al-Kα

‧Sputtered ions: Ar (2keV)

‧Depth analysis: Sputter thickness converted in SiO ₂ and repeated measurement at specific thickness intervals to obtain depth analysis in the depth direction. This thickness interval is set to 2 nm during the measurement of the thin films produced in Examples 1 to 3 (data can be obtained in the depth direction every 2 nm), and is set to 1 nm during the measurement of the thin films produced in Example 4 (allowable at depth Direction to get data per 1nm).

‧ Quantification: The background was obtained by the Shirley method, and the obtained peak area was quantified using the relative sensitivity coefficient method. For data processing, MultiPak manufactured by ULVAC-PHI Co., Ltd. was used.

<Evaluation of Gas Barrier Property by Mocon Method>

The water vapor transmission rate (unit: g / m ² / day) was measured using a water vapor transmission rate measuring device AQUATRAN made by MOCON under the conditions of 38 ° C and 100% RH.

<Evaluation of Gas Barrier Property by Ca Method>

The Ca method evaluation sample prepared as described below was stored in a 40 ° C 90% RH environment for 500 hours. At this time, the permeation concentration (average of 4 arbitrary points) was measured before and after storage, and the water vapor transmission rate after storage (unit: g / m ² / day) was calculated from the change.

[Creation of the Ca method evaluation sample]

After the surface of the gas barrier layer on which the gas barrier film was formed was UV-washed, a thermosetting sheet-like adhesive (epoxy resin) with a thickness of 20 μm was laminated on the same surface as a sealing resin layer. After punching this into a size of 50mm × 50mm, put it into a hand box and dry it for 24 hours.

Next, one side of an alkali-free glass plate (thickness: 0.7 mm) having a size of 50 mm × 50 mm was subjected to UV cleaning. Using a vacuum vapor deposition device manufactured by ALS Technology Co., Ltd., Ca was vapor-deposited in a size of 20 mm × 20 mm through a mask in the center of the glass plate. The thickness of Ca is set at 80 nm. Take out the glass plate after Ca vapor deposition into a hand-held work box, arrange the sealing resin layer of the gas barrier film bonded with the sealing resin layer and the Ca vapor deposition surface of the glass plate, and arrange it by vacuum lamination. . At this time, heating was performed at 110 ° C. Furthermore, the next sample was placed on a hot plate set at 110 ° C. with the glass plate facing downward, and was cured for 30 minutes to prepare a Ca method evaluation sample.

<Evaluation of dark spots in organic EL devices>

The dark spot was evaluated using an organic EL device produced as described below.

[Manufacture of organic EL device]

On the surface of the gas barrier film formed on the side where the gas barrier layer was formed in Example 3, two gas barrier layers were further formed by the following coating modification method, and corresponding gas barrier properties for device evaluation were produced. film.

[Formation of gas barrier layer (coating modification method)]

A 20% by mass solution of dibutyl ether containing highly hydrogenated polysilazane (NN120-20, manufactured by Merck) and an amine catalyst (N, N, N ', N'-tetramethyl-1,6- Diamine hexane (TMDAH)) high hydrogenated polysilazane 20% by mass dibutyl ether solution (Merck, NAX120-20) was mixed at a ratio of 4: 1 (mass ratio), and the thickness of the dried film was adjusted further. Dibutyl ether was appropriately diluted to prepare a coating solution.

On the surface of the gas barrier film on the side where the gas barrier layer is formed, the coating solution was applied by a spin coating method to a dry film thickness of 250 nm, and dried at 80 ° C. for 2 minutes. Next, the dried coating film was subjected to vacuum ultraviolet irradiation treatment using a vacuum ultraviolet irradiation device having an Xe excimer lamp with a wavelength of 172 nm under the condition of irradiation energy of 6 J / cm ² . At this time, the irradiation environment was replaced with nitrogen, and the oxygen concentration was set to 0.1% by volume. The stage temperature at which the sample was set was set to 80 ° C. This operation was repeated once more to form two layers of a gas barrier layer formed by the coating modification method.

The thus prepared gas barrier film for device evaluation was used as a base material, and the area of the light-emitting region was 5 cm × 5 cm by the method described below to produce a bottom-emission type organic electroluminescence element (organic EL element).

(Formation of base layer and first electrode)

The gas barrier film for device evaluation was fixed to a substrate holder of a commercially available vacuum evaporation device, and the following compound 118 was placed in a resistance heating plate made of tungsten. Inside the first vacuum chamber of the vacuum deposition apparatus. In addition, silver (Ag) was put into a resistance heating plate made of tungsten and installed in a second vacuum tank of a vacuum evaporation device.

Next, the first vacuum chamber of the vacuum evaporation device was depressurized to 4 × 10 ^-4 Pa, and then heated to a heating plate having Compound 118 and heated at a deposition rate of 0.1 nm / second to 0.2 nm / second and a thickness of A base layer of the first electrode was provided at 10 nm.

Next, the base material formed on the base layer was moved to a second vacuum tank under a vacuum state, the second vacuum tank was decompressed to 4 × 10 ^-4 Pa, and then a heating plate with silver was applied and heated. Thereby, a first electrode having a thickness of 8 nm of silver was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(Organic function layer ~ 2nd electrode)

Next, using a commercially available vacuum evaporation device, after decompressing to a vacuum degree of 1 × 10 ^-4 Pa, while moving the substrate, the compound HT-1 was evaporated at a deposition rate of 0.1 nm / sec. Positive Hole Transport Layer (HTL).

Next, the following compound A-3 (blue light emitting dopant) and the following compound H-1 (host compound) were co-evaporated so that the compound A-3 linearly changed from 35% by mass to the film thickness. The method of 5% by mass changes the deposition rate depending on the location, and changes the compound H-1 from 65% by mass to 95% by mass. In the method of%, the deposition rate is changed depending on the location, so that the thickness is 70 nm, and a light-emitting layer is formed.

Thereafter, the following compound ET-1 was evaporated to a film thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum was deposited at 110 nm to form a second electrode.

(Solid seal)

Next, a sealing member using a 25 μm-thick aluminum foil, and a 20 μm-thick thermosetting sheet adhesive (epoxy resin) as a sealing resin layer bonded to one side of the aluminum foil, and The samples prepared to the second electrode are overlapped. At this time, the end of the extraction electrode of the first electrode and the second electrode is exposed to the outside by continuously overlapping the adhesive formation surface of the sealing member and the organic functional layer of the element.

Next, the sample was placed in a decompression device, and the pressure was applied to the overlapped substrate and the sealing member under a reduced pressure condition of 90 ° C. and 0.1 MPa for 5 minutes. Next, the sample was returned to the atmospheric pressure environment, and further heated at 120 ° C for 30 minutes to harden the adhesive.

The above sealing step is under atmospheric pressure and in a nitrogen environment with a moisture content of 1 ppm or less, according to JIS B 9920: 2002, and the cleanliness after the measurement is rated as 100, and the dew point temperature is -80 ° C or lower, and the oxygen concentration is 0.8 ppm or lower. To atmospheric pressure. In addition, description of formation of extraction wiring from an anode and a cathode is omitted.

In this manner, an organic EL device having a light emitting area having a size of 5 cm × 5 cm was produced.

[Dark Spot Evaluation of Organic EL Devices]

The organic EL device manufactured as described above was kept in an environment of 85 ° C and 85% RH for 300 hours, and then allowed to emit light. The number of dark dots having a circle-equivalent diameter of 200 μm or more was obtained, and evaluated in the following classification: 5: 0 to 4 Each

4: 5 ~ 9

3: 10 ~ 19

2: 20 ~ 49

1: 50 or more.

<Evaluation of optical characteristics>

Regarding the gas barrier film produced in Examples 3 and 4, the light transmittance at a wavelength of 450 nm was measured as an optical characteristic index.

<Winding prediction evaluation>

As an index of resistance to deterioration when the gas barrier film is wound into a roll, the following surface contact and fold processing is applied, and the surface contact and fold treatment is a process of simulating winding into a roll, The water vapor transmission rate was calculated in the same manner as in the above "Evaluation of Gas Barrier Property by Ca Method".

From the above results, it can be understood that the present invention can provide a gas barrier film which exhibits a very high gas barrier property and can be used as a substrate for an electronic device such as an organic EL device.

This application is based on Japanese Patent Application No. 2015-104904 and Japanese Patent Application No. 2015-104908, filed on May 22, 2015, and the entire disclosure thereof is incorporated herein by reference.

10‧‧‧Gas barrier film

11‧‧‧ Substrate

12‧‧‧ 1st gas barrier

13‧‧‧ transition metal oxide containing layer

Claims (21)

A gas barrier film comprising: a substrate; and a first gas barrier layer, which are arranged on at least one side of the substrate, and contain an oxide of a metal (M1) other than a transition metal, and The transition metal oxide-containing layer is arranged adjacent to the first gas barrier layer and contains an oxide of a transition metal (M2), and the gas barrier film is on at least one side of the substrate. The first gas barrier layer and the transition metal oxide-containing layer are arranged in this order, and satisfy the following (2): (2) In the transition metal oxide-containing layer, one of the transition metal (M2) When the maximum valence is b, oxygen is O, nitrogen is N, and when the composition of the transition metal oxide is (M2) O _x N _y , at least a part of the thickness direction of the transition metal oxide layer, There exists a region satisfying the following formula, x> 0, and y ≧ 0, and (2x + 3y) / b <0.85. A gas barrier film comprising: a substrate; and a first gas barrier layer, which are arranged on at least one side of the substrate, and contain an oxide of a metal (M1) other than a transition metal, and The transition metal oxide-containing layer is disposed adjacent to a surface of the first gas barrier layer on the side opposite to the substrate, and contains an oxide of a transition metal (M2), and the first gas barrier layer and the foregoing The laminated body of the transition metal oxide-containing layer satisfies the following (4): (4) A mixed region in which the aforementioned metal (M1) and the aforementioned transition metal (M2) coexist, and the maximum valence of the aforementioned (M1) is set to a When the maximum valence of (M2) is set to b, oxygen is set to O, nitrogen is set to N, carbon is set to C, and the composition of the mixed region is set to (M1) (M2) _p O _q N _r C _s , At least a part of the mixed region in the thickness direction has a region satisfying the following formula: 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <0.85. For example, the gas barrier film of claim 2, wherein the thickness of the region of p> 98 that the laminate has is 5 nm or less. The gas barrier film according to any one of claims 1 to 3, wherein the transition metal oxide-containing layer is formed by a physical vapor phase growth (PVD) method. A gas barrier film, comprising a substrate and a first gas barrier layer, which are arranged on at least one side of the substrate, and contain a metal (M1) other than a transition metal and a transition metal (M2) ), And the first gas barrier layer satisfies the following (5): (5) The maximum valence of the metal (M1) is set to a, the maximum valence of the transition metal (M2) is set to b, and the oxygen setting When it is O, nitrogen is N, carbon is C, and when the composition of the first gas barrier layer is (M1) (M2) _p O _q N _r C _s , the thickness direction of the first gas barrier layer is 5 nm continuously. The above area is an area satisfying the following formula [a] 0.02 ≦ p ≦ 98, and q> 0, and r ≧ 0, and s ≧ 0, and (2q + 3r + 2s) / (a + bp) <1. For example, the gas barrier film of claim 5, wherein the first gas barrier layer further satisfies the following (6): (6) In the aforementioned area [a], the value x / (1 + x) (here, x is The absolute value of the change in the thickness direction of the aforementioned gas barrier layer in the presence ratio (atomic ratio) of the transition metal (M2) to the metal (M1) is 0 to 0.015 [1 / nm] or less per 1nm thickness. For example, the gas barrier film of claim 5 or 6, wherein the area [a] satisfies (2q + 3r + 2s) / (a + bp) ≦ 0.9. The gas barrier film according to any one of claims 1 to 3, wherein the metal (M1) includes a metal selected from the group consisting of metals of groups 12 to 14 of the long-period periodic table. The gas barrier film according to any one of claims 1 to 3, wherein the metal (M1) includes a metal selected from the group consisting of Si, Al, Zn, In, and Sn. The gas barrier film according to any one of claims 1 to 3, wherein the metal (M1) contains Si as a main component. The gas barrier film according to any one of claims 1 to 3, wherein the transition metal (M2) includes a metal selected from the group consisting of Nb, Ta, V, Zr, Ti, Hf, Y, La, and Ce . The gas barrier film according to any one of claims 1 to 3, wherein the transition metal (M2) is a metal element of Group 5 of the long-period periodic table. If the gas barrier film of any one of claims 1 to 3, And further includes a second gas barrier layer disposed on a surface of the layer containing the transition metal (M2) on the side opposite to the substrate (however, the substrate and the transition are sequentially disposed The metal oxide-containing layer and the transition metal oxide-containing layer in the case of the first gas barrier layer are excluded (between the first gas barrier layer and the first gas barrier layer), and a metal oxide is contained. The gas barrier film according to claim 13, wherein the second gas barrier layer is a polysilazane modified layer. The gas barrier film according to claim 14, wherein the polysilazane modifying layer is a polysilazane vacuum ultraviolet irradiation modifying layer. The gas barrier film according to claim 13, wherein the second gas barrier layer is a gas barrier film-formed gas barrier layer. A method for manufacturing a gas barrier film, which is the method for manufacturing a gas barrier film according to any one of claims 1 to 4, which is characterized by comprising: a laminate of the substrate and the first gas barrier layer; The step of forming the transition metal oxide-containing layer on the surface of the first gas barrier layer on the side opposite to the substrate by a vapor-phase film formation method, and in the step of forming the transition metal oxide-containing layer, It is selected from the ratio of the aforementioned transition metal (M2) and oxygen in the film-forming raw materials, the ratio of the inert gas and the reactive gas during the film formation, the amount of gas supplied during the film formation, the degree of vacuum during the film formation, and the film formation One or two or more conditions in the group of current power are adjusted to satisfy the following (2): (2) In the transition metal oxide-containing layer, the maximum valence of the transition metal (M2) is set to b, oxygen is O, nitrogen is N, and when the composition of the transition metal oxide is (M2) O _x N _y , at least a part of the thickness direction of the transition metal oxide layer satisfies the following number The area of the formula, x> 0, and y ≧ 0, and (2x + 3y) / b <0.85. The method for manufacturing a gas barrier film according to claim 17, further comprising: a step of forming the first gas barrier layer by a roll-to-roll method on at least one side of the substrate, And a step of forming the transition metal oxide-containing layer on a surface of the first gas barrier layer on a side opposite to the base material by a roll-to-roll method, at this time, after the step of forming the first gas barrier layer Without the need to wind the film, the step of forming the transition metal oxide containing layer is performed. The method for manufacturing a gas barrier film according to claim 17, further comprising: forming the transition metal oxide-containing layer on a surface of the first gas barrier layer on a side opposite to the substrate by a roll-to-roll method. A step of forming a second gas barrier layer containing a metal oxide on a surface of the transition metal oxide-containing layer on the side opposite to the first gas barrier layer by a roll-to-roll method. After the step of forming the transition metal oxide-containing layer, the step of forming the second gas barrier layer is performed without winding the film. A method for manufacturing a gas barrier film according to claim 17, which The method further includes a step of forming the first gas barrier layer on a surface of at least one side of the substrate by a roll-to-roll method, and a surface of the first gas barrier layer on a side opposite to the substrate. Forming the transition metal oxide-containing layer in a roll-to-roll manner, and forming the transition metal oxide-containing layer in a roll-to-roll manner on the surface of the transition metal oxide-containing layer on the side opposite to the first gas barrier layer In the step of forming the second gas barrier layer of the oxide, in this case, after the step of forming the first gas barrier layer, the step of forming the transition metal oxide-containing layer is performed without winding a film, and the step of forming the foregoing After the step of containing the transition metal oxide layer, the step of forming the aforementioned second gas barrier layer is performed without winding the film. A method for manufacturing a gas barrier film, which is the method for manufacturing a gas barrier film according to any one of claims 5 to 7, characterized in that the first gas is formed on at least one side of the substrate. The step of forming a barrier layer and forming the first gas barrier layer includes co-evaporating a composite oxide including the metal (M1) and the transition metal (M2) on at least one side of the substrate, The formed first gas barrier layer satisfies the above (5).