WO2015083706A1

WO2015083706A1 - Gas barrier film and method for producing same

Info

Publication number: WO2015083706A1
Application number: PCT/JP2014/081883
Authority: WO
Inventors: 鈴木　一生; 真琴新
Original assignee: コニカミノルタ株式会社
Priority date: 2013-12-02
Filing date: 2014-12-02
Publication date: 2015-06-11
Also published as: JPWO2015083706A1

Abstract

　A gas barrier film containing a resin base material and a first gas barrier layer, wherein the first gas barrier layer contains carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms, and in a carbon distribution curve which represents the relationship between the distance from the surface in the thickness direction of the layer, and the ratio of the quantity of carbon atoms to the total content of all atoms, there is at least one extreme value, and the absolute value of the difference between the maximum value and the minimum value is at least 5at%, and in a nitrogen distribution curve representing the relationship between the distance from the surface and the ratio of the quantity of nitrogen to the total content of all atoms, the maximum value falls within the range of 0.5 to 10at%, and in regions with 90% or more of the entire layer thickness, the average atomic ratio of each of the atoms with respect to the total quantity of all atoms satisfies the relations represented by formula (A) or (B). The gas barrier film has minimal curling, excellent bend resistance and high gas barrier properties. (A): carbon atomic ratio > silicon atomic ratio > oxygen atomic ratio > nitrogen atomic ratio (B): oxygen atomic ratio > silicon atomic ratio > carbon atomic ratio > nitrogen atomic ratio

Description

Gas barrier film and method for producing the same

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

Conventionally, a gas barrier film formed by laminating a plurality of layers including a thin film (gas barrier layer) of a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide on the surface of a plastic substrate or film is made of water vapor or oxygen. It is widely used for packaging of articles that need to block various gases, for example, packaging for preventing deterioration of food, industrial goods, pharmaceuticals, and the like.

In recent years, for such gas barrier films that prevent permeation of water vapor, oxygen, etc., in addition to packaging applications, flexible electronics such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display (LCD) elements, etc. Many devices have been studied for the development of devices. However, in these flexible electronic devices, a gas barrier property having a very high glass substrate level is required, so that a gas barrier film having sufficient performance has not been obtained yet.

As a method for manufacturing such a gas barrier film, an organic silicon compound typified by tetraethoxysilane (hereinafter abbreviated as TEOS) is used to form a film on a substrate while being oxidized with oxygen plasma under reduced pressure. Gas phase methods such as chemical deposition methods (plasma CVD method: Chemical Vapor Deposition), and physical deposition methods (vacuum deposition and sputtering) in which metal Si is evaporated using a semiconductor laser and deposited on a substrate in the presence of oxygen It has been known.

Examples of the inorganic film forming (gas barrier layer forming) method by the physical deposition method include a PVD method (PVD: Physical Vapor Deposition: physical vapor deposition method, physical vapor deposition method). However, the PVD method tends to generate particles in the gas phase system. In addition, when the PVD method is used, it is common to perform columnar growth or island-like growth in the thin film growth process, so that grain boundaries are generated in the film and high barrier properties are exhibited. Have difficulty.

On the other hand, a CVD method (Chemical Vapor Deposition) is used as an inorganic film formation (gas barrier layer formation) method by a chemical deposition method. For example, in Patent Document 1, gas barrier performance and bending performance are improved by a carbon-containing silicon oxide film formed by a plasma CVD method (plasma chemical vapor deposition method) in which plasma is generated by discharging between a pair of film forming rolls. If so.

JP 2011-73430 A

However, the gas barrier film described in the above-mentioned patent document is excellent in flexibility that does not deteriorate the gas barrier performance even when bent, but the problem that the curl becomes large when the film is thickened to improve the gas barrier performance. was there.

Accordingly, the object of the present invention has been made in view of the above-mentioned problems, and the solution is to provide a gas barrier film having less curl, excellent bending resistance, and high gas barrier properties, and a method for producing the same. It is.

As a result of studying the above problems, the present inventors have determined that the carbon-containing oxidation in which the carbon and oxygen contents in the carbon-containing silicon oxide film formed by the plasma CVD method continuously change in the depth direction. A gas barrier film comprising a silicon film (gradient SiOC barrier film; gas barrier layer) is expected to be a barrier substrate member for flexible devices because of its excellent flexibility and resistance to cracking even when bent. When the film thickness is increased, the film curl becomes large, and the substrate for electronic devices has a problem in handling property during the process. Therefore, a carbon-containing silicon oxynitride film (SiOCN barrier film; gas barrier layer) in which nitrogen is contained in a carbon-containing silicon oxide film (gradient SiOC barrier film) formed by a plasma CVD method, which has a maximum carbon atom ratio. The absolute value of the difference between the extreme value and the minimum extreme value is 5 at% or more, the maximum nitrogen atom ratio is in the range of 0.5 to 10 at%, and the film composition (silicon, oxygen, Carbon, nitrogen) is continuously changed to have oxygen> silicon> carbon> nitrogen or carbon> silicon> oxygen> nitrogen in order to reduce curl and excel in bending resistance. The present inventors have found that a gas barrier film having a high gas barrier property for blocking gas can be obtained.

Furthermore, as a result of intensive studies without satisfying the above invention, the present inventors applied a liquid containing polysilazane (polysilazane containing liquid) on the carbon-containing silicon oxynitride film (SiOCN barrier film), and after excimer The barrier film formed (laminated) with the SiON barrier film (polysilazane modified film; silicon oxynitride film) by the treatment (modification process) is not only compatible with low curling property and bending resistance, but also has the above-mentioned SiOCN barrier. Nitrogen contained in both the film (first gas barrier layer) and the SiON barrier film (second gas barrier layer) is formed by interaction between the layers, so that structural defects between the layers are reduced, and barrier performance at the time of stacking The inventors have also found that a gas barrier film having a large improvement effect can be obtained, and have reached the present invention.

That is, the above-mentioned problem according to the present invention is solved by the following means.

1. A gas barrier film comprising a resin substrate and a first gas barrier layer formed on at least one surface side of the resin substrate,
The first gas barrier layer contains silicon atoms, oxygen atoms, carbon atoms, and nitrogen atoms, the composition continuously changes in the layer thickness direction, and satisfies the following requirements (1) and (2): Gas barrier film;
(1) Of the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, the first gas barrier layer in the layer thickness direction of the first gas barrier layer Carbon showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”). The distribution curve has at least one extreme value, and an absolute value of a difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more, and the first The distance from the surface of the first gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (“nitrogen atom ratio That at%) ".) In a nitrogen distribution curve showing the relationship between the maximum value of the nitrogen atomic ratio is in the range of 0.5 ~ 10at%,
(2) In the region of 90% or more of the total thickness of the first gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms is expressed by the following formula ( It has an order of magnitude relationship represented by A) or (B).

2. 2. The gas barrier film according to item 1, further comprising a second gas barrier layer containing a polysilazane modified product formed on the first gas barrier layer.

3. 3. The gas barrier film according to item 2, wherein the second gas barrier layer is obtained by applying an excimer modification treatment to a coating film formed by applying and drying a liquid containing polysilazane.

4). A method for producing a gas barrier film comprising at least a first gas barrier layer on at least one surface side of a resin substrate,
A step of forming a first gas barrier layer containing a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom, the composition continuously changing in the layer thickness direction, and satisfying the following requirements (1) and (2): A method for producing a gas barrier film,
(1) Of the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, the first gas barrier layer in the layer thickness direction of the first gas barrier layer Carbon showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”). The distribution curve has at least one extreme value, and an absolute value of a difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more, and the first The distance from the surface of the first gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (“nitrogen atom ratio ( In nitrogen distribution curve showing the relationship between the called.) And t%) ", the maximum value of the nitrogen atomic ratio is in the range of 0.5 ~ 10at%,
(2) In the region of 90% or more of the total thickness of the first gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms is expressed by the following formula ( It has an order of magnitude relationship represented by A) or (B).

5. The first gas barrier layer is formed by a discharge plasma chemical vapor deposition method using a source gas containing a nitrogen-containing organosilicon compound and an oxygen gas and having a discharge space between rollers to which a magnetic field is applied. The method for producing a gas barrier film according to the above item 4.

6. The first gas barrier layer is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, using a source gas containing an organic silicon compound, oxygen gas, and nitrogen gas. The manufacturing method of the gas-barrier film of the said 4th item.

7. The method further includes forming a coating film by applying and drying a liquid containing polysilazane on the first gas barrier layer, and forming a second gas barrier layer by subjecting the coating film to an excimer modification treatment. 7. The method for producing a gas barrier film according to any one of the above items 4 to 6, wherein:

8. 8. The method for producing a gas barrier film according to the above item 7, wherein the modification treatment means used for forming the second gas barrier layer is a method of irradiating vacuum ultraviolet light having a wavelength of 200 nm or less.

By the above means of the present invention, it is possible to provide a gas barrier film having little film curl, excellent bending resistance and high gas barrier properties, and a method for producing the same.

As for the technical reason why the intended effect of the present invention can be obtained by the configuration defined in the present invention, the details of the mechanism have not been elucidated, but are presumed as follows.

The gas barrier film according to the present invention is mainly composed of a resin base material and a first gas barrier layer (carbon-containing silicon oxynitride film) which is an inclined SiOCN barrier film formed on at least one surface side of the resin base material. It consists of and. The gas barrier film of a preferred embodiment of the present invention is mainly composed of a resin base material and a first gas barrier layer (carbon-containing acid) which is an inclined SiOCN barrier film formed on at least one surface side of the resin base material. A silicon nitride film) and a second gas barrier layer which is a polysilazane modified film formed on the first gas barrier layer.

As in Patent Document 1, a gas barrier is a tilted SiOC barrier film in which the carbon and oxygen contents in the carbon-containing silicon oxide film are continuously changed in the film thickness (depth) direction by a plasma CVD method on the substrate. When a layer (carbon-containing silicon oxide film) is formed, a gas barrier film having a gas barrier layer that is excellent in flexibility and hardly broken even when bent can be formed. However, there has been a problem that the film curl becomes large when the film thickness is increased in order to improve the gas barrier property. Furthermore, it has been found that the substrate for electronic devices provided with the gas barrier film has a problem in handling properties during the process.

In order to solve such a problem, the present inventors surprisingly have a gradient SiOCN in which nitrogen is contained in the gas barrier layer (carbon-containing silicon oxide film) which is the above-described gradient SiOC barrier film constituting the gas barrier film. It is a first gas barrier layer (carbon-containing silicon oxynitride film) that is a barrier film, and the film composition (silicon, oxygen, carbon, nitrogen) is continuously changed in the film thickness direction, and oxygen> silicon> carbon> Nitrogen or carbon> silicon> oxygen> nitrogen in order to achieve a gas barrier film with small film curl, excellent flex resistance, and high gas barrier properties that block various gases such as water vapor and oxygen I guess.

Further, a second gas barrier layer (polysilazane modified film) obtained by further applying a polysilazane-containing liquid on the first gas barrier layer (carbon-containing silicon oxynitride film) that is the above-described inclined SiOCN barrier film and performing an excimer modifying treatment ( When the SiON barrier film) is laminated, not only the low curling property and the bending resistance are compatible, but also the first gas barrier layer that is the inclined SiOCN barrier film and the second gas barrier layer that is the polysilazane modified film. In the hybrid gas barrier film, since the nitrogen contained in both the first and second gas barrier layers is formed by the interaction between the layers, the structural defect between the layers is reduced, and the gas barrier having a large effect of improving the barrier performance at the time of lamination. It is speculated that the film could be realized.

It is a schematic sectional drawing which shows the basic composition which shows an example of the gas barrier film which concerns on this invention. In the method for producing a gas barrier film according to the present invention, an example of a method for producing a first gas barrier layer, which is a tilted SiOCN barrier film constituting the gas barrier film, is shown using an inter-roller discharge plasma CVD apparatus to which a magnetic field is applied. FIG. It is a graph which shows an example of the silicon distribution curve of the 1st gas barrier layer which is the inclination SiOCN barrier film which comprises the gas barrier film of this invention (sample 1), an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve. It is a graph which shows an example of the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve of the 1st gas barrier layer which is a non-inclined SiOCN barrier film which comprises the gas barrier film of a comparative example (sample 8). It is a schematic diagram of the electronic device provided with the gas barrier film according to the present invention.

The gas barrier film of the present invention is a gas barrier film comprising a resin base material and a first gas barrier layer formed on at least one surface side of the resin base material, wherein the first gas barrier layer is formed of carbon. It contains an atom, a silicon atom, an oxygen atom and a nitrogen atom, the composition continuously changes in the layer thickness direction, and satisfies the following requirements (1) and (2).

(1) Of the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, the first gas barrier layer in the layer thickness direction of the first gas barrier layer Carbon showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”). The distribution curve has at least one extreme value, and an absolute value of a difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more, and the first The distance from the surface of the first gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (“nitrogen atom ratio In nitrogen distribution curve showing the relationship between the called.) And (at%) ", the maximum value of the nitrogen atomic ratio is in the range of 0.5 ~ 10at%.

(2) In the region of 90% or more of the total thickness of the first gas barrier layer, the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms is expressed by the following formula ( It has an order of magnitude relationship represented by A) or (B).

This feature is a technical feature common to the inventions according to claims (each item) from claim 1 (the first item) to claim 9 (the ninth item).

As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, it is possible to further include a second gas barrier layer containing a modified polysilazane on the first gas barrier layer which is the inclined SiOCN barrier film. In addition to the balance between bending resistance and nitrogen, the nitrogen contained in both the first and second gas barrier layers is formed by the interaction between the layers, reducing structural defects between the layers and improving the barrier performance during lamination It is preferable from the viewpoint that a gas barrier film having a large effect can be obtained.

The second gas barrier layer is obtained by applying an excimer modification treatment to a coating film formed by applying and drying a polysilazane-containing liquid. It is preferable from the viewpoint of improving the adhesion between the two gas barrier layers and the surface smoothness, further reducing the structural defects between the layers, and obtaining a gas barrier film having a large effect of improving the barrier performance during lamination.

The first gas barrier in the thickness direction of the first gas barrier layer among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer of the gas barrier film. The relationship between the distance from the surface of the layer and the ratio of the amount of nitrogen atoms to the total amount of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (100 at%) (referred to as “nitrogen atom ratio (at%)”). In the nitrogen distribution curve shown, the maximum value of the nitrogen atomic ratio is in the range of 0.5 to 10 at%, preferably 2 to 10 at%, more preferably 4 to 10 at%. As the number of atoms) increases, the internal stress of the first gas barrier layer, which is a tilted SiOCN barrier film, decreases, and a barrier film with excellent flatness can be obtained. On the other hand, the more N (nitrogen atoms) in the first gas barrier layer, the denser the film density becomes. Therefore, if the N gas (nitrogen atoms) is excessively contained, cracks occur in the barrier film when bent. The barrier film is inferior in flexibility. If the maximum extreme value (maximum value) of the nitrogen atom ratio is within the above range, both flexibility and flatness can be achieved. Furthermore, it is also preferable from the viewpoint of effectively exhibiting the barrier performance improving effect.

In the gas barrier film according to the present invention, the object effect of the present invention is exhibited effectively when a relatively thin resin substrate having a resin substrate thickness in the range of 40 to 150 μm is used. can do.

Moreover, the method for producing a gas barrier film of the present invention is a method for producing a gas barrier film comprising a first gas barrier layer that is a tilted SiOCN barrier film on at least one surface side of a resin base material, comprising carbon atoms, It has a step of forming a first gas barrier layer containing silicon atoms, oxygen atoms and nitrogen atoms, the composition continuously changing in the layer thickness direction and satisfying the above requirements (1) and (2). .

In the method for producing a gas barrier film of the present invention, the first gas barrier layer is a discharge having a discharge space between rollers to which a magnetic field is applied using a source gas containing a nitrogen-containing organosilicon compound and an oxygen gas. From the viewpoint of being able to realize the first gas barrier layer (carbon-containing silicon oxynitride film) that is a graded SiOCN barrier film having a desired element profile with higher accuracy by being formed by plasma enhanced chemical vapor deposition. preferable.

In the method for producing a gas barrier film of the present invention, the first gas barrier layer has a discharge space between rollers to which a magnetic field is applied using a raw material gas containing an organosilicon compound, oxygen gas, and nitrogen gas. The first gas barrier layer (carbon-containing silicon oxynitride film), which is a graded SiOCN barrier film having a desired element profile with higher accuracy, can also be realized by forming by a discharge plasma chemical vapor deposition method. It is preferable from the viewpoint.

Further, in the method for producing a gas barrier film of the present invention, a polysilazane-containing liquid is applied onto the first gas barrier layer (carbon-containing silicon oxynitride film) that is a gradient SiOCN barrier film, and dried to form a coating film. The method further includes a step of forming a second gas barrier layer (SiON barrier film; silicon oxynitride film), which is a polysilazane modified film, by subjecting the coating film to an excimer modification treatment. In addition to being compatible with flexibility, the adhesion and surface smoothness between the first and second gas barrier layers are also improved, and further, structural defects between layers are reduced, realizing a gas barrier film with a great effect of improving barrier performance during lamination. It is preferable from the viewpoint that can be performed.

In the method for producing a gas barrier film of the present invention, the excimer modification treatment means used for forming the second gas barrier layer is a method of irradiating vacuum ultraviolet light having a wavelength of 200 nm or less. It is preferable from the viewpoint that the second gas barrier layer having (interlayer structural defect repair (reduction) property, barrier performance improvement effect at the time of stacking, etc.) can be realized with high accuracy.

The “gas barrier property” as used in the present invention is the water vapor permeability measured by a method according to JIS K 7129-1992 (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%). Is 1 × 10 ⁻² g / m ² · 24 h or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻² ml / m ² · 24 h · atm or less. Means.

In the present invention, “vacuum ultraviolet light”, “vacuum ultraviolet light”, “VUV”, and “VUV light” specifically mean light having a wavelength of 100 to 200 nm.

Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In the present application, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

《Gas barrier film》
FIG. 1 is a schematic cross-sectional view showing an example of a basic configuration of a gas barrier film according to the present invention.

As shown in FIG. 1, a gas barrier film F according to the present invention contains a carbon substrate, a silicon atom, an oxygen atom, and a nitrogen atom on a resin substrate 1 as a support and a resin substrate 1, and has a layer thickness. The first gas barrier layer 2 having a composition that continuously changes in the direction and satisfying the above requirements (1) and (2) is provided, and the second gas barrier layer 3 containing the polysilazane modified product is formed on the first gas barrier layer 2. It has a stacked basic configuration. The gas barrier film F according to the present invention only needs to have a configuration in which the resin base material 1 as a support and the first gas barrier layer 2 having the above characteristics are formed on the resin substrate 1, Any other layer may be formed (other layers are not shown).

The first gas barrier layer 2 according to the present invention contains carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms, the composition continuously changes in the layer thickness direction, and the requirements specified in the above (1) and (2) It has the element distribution profile which satisfy | fills simultaneously. Moreover, the 2nd gas barrier layer 3 which concerns on this invention contains a polysilazane modified material, It is characterized by the above-mentioned. The second gas barrier layer 3 is obtained by applying a liquid containing polysilazane (polysilazane-containing liquid) and drying the coating film formed by excimer modification treatment.

[1] Resin base material As the resin base material constituting the gas barrier film according to the present invention, the first gas barrier layer having the gas barrier property according to the present invention, and further the second gas barrier layer can be retained, and it is flex-resistant. As long as it is formed of an organic material having excellent properties, it is not particularly limited.

Examples of the resin base material applicable to the present invention include methacrylate ester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polystyrene (PS), aromatic polyamide, and polyether. Examples include resin films such as ether ketone, polysulfone, polyethersulfone, polyimide, polyetherimide, and a laminated film formed by laminating two or more layers of the above resins. From the viewpoint of cost and availability, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC) and the like are preferably used.

The thickness of the resin base material is not particularly limited and can be selected within the range of 5 to 500 μm, preferably 20 to 150 μm. From the viewpoint of further manifesting the effects of the present invention, the thickness of the resin base material is 40 to It is preferable to be in the range of 150 μm.

The resin base material according to the present invention is preferably transparent. Since the resin base material is transparent and the layer formed on the base material is also transparent, a transparent gas barrier film can be obtained. Therefore, a transparent substrate such as an electronic device (for example, organic EL) It is also possible to do.

[2] First gas barrier layer The first gas barrier layer according to the present invention contains a carbon atom, a silicon atom, an oxygen atom and a nitrogen atom, the composition continuously changes in the layer thickness direction, and the above requirements (1) and It is the structure which satisfy | fills (2) simultaneously. That is, the first gas barrier layer of the present invention is a carbon-containing silicon oxynitride film, and is a graded SiOCN barrier film.

In addition, the measurement accuracy in the resin base material interface region is slightly lowered due to noise of constituent atoms of the resin base material, etc., so the region satisfying the relationship defined by the above formula (A) or formula (B) is A region within the range of 90 to 95% of the total thickness of one gas barrier layer is preferable.

Further, as a more preferable aspect, the layer thickness of the first gas barrier layer according to the present invention is preferably in the range of 50 to 1000 nm. The first gas barrier layer forming method according to the present invention is not particularly limited as long as it is a thin film forming method capable of realizing the element profile defined in the present invention, but the first element in which the element distribution is precisely controlled. From the viewpoint of being able to form one gas barrier layer, (a) a raw material gas containing a nitrogen-containing organosilicon compound and an oxygen gas, or (b) a raw material gas containing an organosilicon compound and an oxygen gas are used. A method of forming by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied is preferable.

Hereinafter, details of the first gas barrier layer according to the present invention will be described.

In the present invention, the average value of the content ratio of carbon atoms in the first gas barrier layer according to the present invention can be obtained by measuring an XPS depth profile described later.

Hereinafter, details of the first gas barrier layer according to the present invention will be further described.

(2.1) Carbon element profile in the first gas barrier layer The first gas barrier layer according to the present invention contains carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms as constituent elements of the first gas barrier layer, and is composed in the layer thickness direction. Continuously changing and out of the distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy from the surface of the first gas barrier layer in the layer thickness direction of the first gas barrier layer. Carbon distribution curve showing the relationship between the distance and the ratio of the amount of carbon atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”) ( Hereinafter, the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5a. One of the characteristics is that it is t% or more.

In addition, the first gas barrier layer according to the present invention has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region of the first gas barrier layer. This is a preferred embodiment from the viewpoint of providing a gas barrier film having both properties and high gas barrier properties. Here, the “configuration in which the carbon atom ratio varies continuously” means that the carbon distribution curve does not include a portion in which the carbon atom ratio varies discontinuously. Specifically, the etching rate and the etching rate are not included. In the relationship between the distance (x, unit: nm) from the surface in the film thickness direction calculated from the time and the atomic ratio of carbon (C, unit: at%), the condition represented by the following formula (1) Satisfying.

The first gas barrier layer according to the present invention is characterized in that the carbon distribution curve has at least one extreme value, more preferably at least two extreme values, and at least three extreme values. It is particularly preferred. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained gas barrier film is bent is insufficient. Further, in the case of having at least two or three extreme values as described above, the one in the carbon distribution curve and the extreme value adjacent to the extreme value in the thickness direction of the first gas barrier layer. The absolute value of the difference in distance from the surface of the first gas barrier layer is preferably 200 nm or less, and more preferably 100 nm or less.

In the present invention, the extreme value of the distribution curve means a measured value of the maximum value or the minimum value of the atomic ratio of the element to the distance from the surface of the first gas barrier layer in the thickness direction of the first gas barrier layer. .

In the present invention, the maximum value is a point where the value of the atomic ratio of an element changes from increasing to decreasing when the distance from the surface of the first gas barrier layer is changed, and the value of the atomic ratio of the element at that point. Rather, the atomic ratio value of the element at a position where the distance from the surface of the first gas barrier layer in the layer thickness direction of the first gas barrier layer is further changed by 20 nm from this point is reduced by 3 at% or more.

Further, in the present invention, the minimum value is a point where the value of the atomic ratio of an element changes from decreasing to increasing when the distance from the surface of the first gas barrier layer is changed, and the atomic ratio of the element at that point is changed. The value of the atomic ratio of the element at a position where the distance from the surface of the first gas barrier layer in the layer thickness direction of the first gas barrier layer from the point is further changed by 20 nm from the point increases by 3 at% or more. .

In the first gas barrier layer according to the present invention, the carbon distribution curve has at least one extreme value, and has a maximum extreme value (maximum value) and a minimum extreme value (minimum value) of the carbon atom ratio. The absolute value of the difference is 5 at% or more.

(2.2) Element profiles in the first gas barrier layer The first gas barrier layer according to the present invention is characterized by containing carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms as constituent elements. Preferred embodiments of the atomic ratio, maximum value, and minimum value (maximum value for nitrogen atoms) will be described below.

<2.2.1> Relationship between maximum value and minimum value of carbon atom ratio In the first gas barrier layer according to the present invention, the maximum extreme value (maximum value) and the minimum extreme value of the carbon atom ratio in the carbon distribution curve. One of the characteristics is that the absolute value of the difference of (minimum value) is 5 at% or more. Moreover, in such a 1st gas barrier layer, it is more preferable that the absolute value of the difference of the maximum value of carbon atom ratio and minimum value is 6 at% or more, and it is especially preferable that it is 7 at% or more. By setting the absolute value of the difference between the maximum value and the minimum value of the carbon atom ratio to 5 at% or more, the gas barrier property when the produced gas barrier film is bent is sufficient.

<2.2.2> Relationship of Maximum Value of Nitrogen Atom Ratio In the first gas barrier layer according to the present invention, the maximum value of nitrogen atom ratio (not necessarily the maximum extreme value) in the nitrogen distribution curve is 0. One of the characteristics is that it is in the range of 5 to 10 at%. In such a first gas barrier layer, the maximum value of the nitrogen atom ratio is more preferably in the range of 2 to 10 at%, and more preferably in the range of 4 to 10 at%. If it is in the said range, the low curl property and bending resistance of the gas barrier film obtained will be compatible, and gas barrier property and planarity as an electronic device member will become enough. In particular, when the maximum value of the nitrogen atom ratio is 10 at% or less, it is possible to effectively prevent the barrier performance from being deteriorated during bending. Further, when the maximum value of the nitrogen atom ratio is 0.5% or more, particularly 2 at% or more, the film curl becomes smaller and the barrier film is more excellent in flatness, and when it is 4 at% or more, the film curl is particularly suppressed small. Furthermore, it is excellent in that a barrier film having excellent flatness can be obtained. The nitrogen distribution curve here is the distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, in the thickness direction of the first gas barrier layer. The distance from the surface of the first gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “nitrogen atom ratio (at%)”). Refers to a nitrogen element distribution curve. Further, in the first gas barrier layer according to the present invention, the maximum value of the nitrogen atomic ratio in the nitrogen distribution curve is the maximum value of the atomic ratio of the nitrogen element when the distance from the surface of the first gas barrier layer is changed. This is the point.

<2.2.3> Relationship between Maximum Value and Minimum Value of Oxygen Atomic Ratio In the first gas barrier layer according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the oxygen distribution curve is 5 at% or more. Is preferably 6 at% or more, and more preferably 7 at% or more. When the absolute value is 5 at% or more, the gas barrier property when the obtained gas barrier film is bent is sufficient. The oxygen distribution curve here is the distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, in the thickness direction of the first gas barrier layer. The distance from the surface of the first gas barrier layer and the ratio of the amount of oxygen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “oxygen atom ratio (at%)”). The oxygen element distribution curve indicating the relationship between

<2.2.4> Relationship between maximum value and minimum value of silicon atomic ratio In the first gas barrier layer according to the present invention, the absolute value of the difference between the maximum value and the minimum value in the silicon distribution curve is less than 5 at%. Is preferably less than 4 at%, more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property and mechanical strength of the obtained gas barrier film are sufficient. The silicon distribution curve here is the distribution curve of each constituent element based on the element distribution measurement in the depth direction by the X-ray photoelectron spectroscopy for the first gas barrier layer, in the thickness direction of the first gas barrier layer. The distance from the surface of the first gas barrier layer and the ratio of the amount of silicon atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “silicon atom ratio (at%)”). The distribution curve of silicon element showing the relationship between

In the above description regarding the carbon atom distribution profile (carbon distribution curve, silicon distribution curve, oxygen distribution curve and nitrogen distribution curve) as shown in FIG. 3 and FIG. 4 described later, “carbon atom, silicon atom, oxygen atom and nitrogen”. “Total amount of atoms” means the total at% of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms, and “amount of carbon atoms” means the number of carbon atoms. The term “at%” in the present invention means the atomic ratio of each atom when the total number of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms is 100%. The same applies to “amount of silicon atoms” and “amount of nitrogen atoms” for the carbon distribution curve, silicon distribution curve, oxygen distribution curve and nitrogen distribution curve as shown in FIGS.

<2.2.6> Element distribution in the entire layer thickness region from the surface in the layer thickness direction In the first gas barrier layer according to the present invention, carbon atoms are present in a region of 90% or more of the total layer thickness of the first gas barrier layer. One of the features is that the average atomic ratio of each atom with respect to the total amount (100 at%) of silicon atom, oxygen atom and nitrogen atom has an order of magnitude represented by the following formula (A) or (B): To do. By satisfying such conditions, it is possible to provide a gas barrier film that has both a low curling property and a high bending resistance and a high gas barrier property.

(2.3) Element distribution measurement in the depth direction by X-ray photoelectron spectroscopy Carbon distribution curve, silicon distribution curve, oxygen distribution curve, nitrogen distribution curve, and oxygen-carbon total distribution in the layer thickness direction of the first gas barrier layer Curves and the like are so-called XPS depth profiles in which X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon are used in combination to perform surface composition analysis sequentially while exposing the inside of the sample. It can be created by measurement. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface of the first gas barrier layer in the layer thickness direction of the first gas barrier layer in the layer thickness direction. Therefore, the “distance from the surface of the first gas barrier layer in the layer thickness direction of the first gas barrier layer” is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. The distance from the surface can be employed (applied in FIGS. 3 and 4). In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

In the present invention, from the viewpoint of forming a first gas barrier layer that is uniform over the entire film surface and has excellent gas barrier properties, the first gas barrier layer is in the film surface direction (parallel to the surface of the first gas barrier layer). (Direction) is preferably substantially uniform. In the present invention, the fact that the first gas barrier layer is substantially uniform in the film surface direction means that the carbon distribution curve and the silicon distribution at any two measurement points on the film surface of the first gas barrier layer by XPS depth profile measurement. When the curve, the oxygen distribution curve, the nitrogen distribution curve, and the oxygen-carbon total distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same. The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same or within 5 at%.

The gas barrier film according to the present invention is indispensable to have at least one first gas barrier layer that simultaneously satisfies the requirements (1) and (2) defined in the present invention. Two or more layers may be provided. Further, when two or more such first gas barrier layers are provided, the materials of the plurality of first gas barrier layers may be the same or different. Further, when two or more such first gas barrier layers are provided, such a first gas barrier layer may be formed on one surface of the substrate, and on both surfaces of the substrate. It may be formed. Further, the plurality of first gas barrier layers may include a first gas barrier layer that does not necessarily have gas barrier properties.

In the carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the nitrogen distribution curve in the first gas barrier layer, the silicon atom ratio to the total amount of carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms is: A range of 19 to 40 at% is preferable, and a range of 30 to 40 at% is more preferable. In the carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the nitrogen distribution curve in the first gas barrier layer, the oxygen atom ratio relative to the total amount of carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms is: It is preferably in the range of 25 to 67 at%, more preferably in the range of 25 to 40 at%. Furthermore, in the carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the nitrogen distribution curve in the first gas barrier layer, the carbon atom ratio to the total amount of carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms is: The range is preferably 1 to 38 at%, more preferably 10 to 38 at%. Furthermore, in the carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the nitrogen distribution curve in the first gas barrier layer, the nitrogen atom ratio with respect to the total amount of carbon atoms, silicon atoms, oxygen atoms, and nitrogen atoms is The range is preferably 0.2 to 10 at%, more preferably 2 to 10 at%, and particularly preferably 4 to 10 at%.

(2.4) Thickness of the First Gas Barrier Layer The thickness of the first gas barrier layer according to the present invention is preferably in the range of 5 to 1000 nm, more preferably in the range of 10 to 1000 nm. Particularly preferably, it is in the range of ˜1000 nm. When the thickness of the first gas barrier layer is within the above range, curling is small, gas barrier properties against various gases such as water vapor and oxygen are excellent, and no deterioration of the gas barrier properties due to bending is observed. In particular, even when the thickness of the first gas barrier layer is increased within the above range, it is excellent in that the increase in film curl can be effectively suppressed.

Even when there are two or more first gas barrier layers, the total thickness of the first gas barrier layers is preferably within a range of 5 to 1000 nm, more preferably within a range of 10 to 1000 nm, It is particularly preferable that it is in the range of 1000 nm. If the total thickness of the first gas barrier layers is within the above range, desired flatness can be realized, curl is small, gas barrier properties against various gases such as water vapor and oxygen, etc. are excellent, and the gas barrier by bending There is no decline in sex. In particular, even when the total thickness of the first gas barrier layer is increased within the above range, the film curl is excellent in that the increase in film curl can be effectively suppressed.

(2.5) Forming method of the first gas barrier layer The forming method of the first gas barrier layer according to the present invention is not particularly limited as long as it is a thin film forming method capable of realizing the element profile defined in the present invention. From the viewpoint that the first gas barrier layer in which the element distribution is precisely controlled can be formed, (a) using a source gas containing nitrogen-containing organosilicon compound and oxygen gas, or (b) organosilicon compound It is preferable to use a source gas containing oxygen and oxygen gas to form by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied.

More specifically, the first gas barrier layer according to the present invention uses an inter-roller discharge plasma processing apparatus to which a magnetic field is applied, winds a resin substrate around a pair of film forming rollers, and forms a film forming gas between the pair of film forming rollers. This is a layer formed by plasma chemical vapor deposition by plasma discharge while supplying. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable to reverse the polarity between the pair of film forming rollers alternately. Furthermore, as a film forming gas used in such a plasma chemical vapor deposition method, (a) a source gas containing a nitrogen-containing organosilicon compound and an oxygen gas are used, or (b) a source gas containing an organosilicon compound is used. The oxygen gas content in the deposition gas is less than or equal to the theoretical oxygen amount necessary to completely oxidize the nitrogen-containing organosilicon compound or the entire organosilicon compound in the deposition gas. It is preferable. In the gas barrier film according to the present invention, the first gas barrier layer is preferably a layer formed by a continuous film forming process.

Next, a specific method for forming the first gas barrier layer according to the present invention will be described.

The first gas barrier layer constituting the gas barrier film according to the present invention uses an inter-roller discharge plasma treatment apparatus to which a magnetic field is applied, and is formed on the surface of the resin base material (an intermediate layer may be provided if necessary). 1 gas barrier layer is formed by forming.

In the first gas barrier layer according to the present invention, in order to form a layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer, an inter-roller discharge plasma chemical vapor deposition method using a magnetic field is applied. It is a preferable aspect to use.

In the inter-roller discharge plasma chemical vapor deposition method (hereinafter also referred to as plasma CVD method or roller CVD method) to which a magnetic field is applied according to the present invention, a magnetic field is generated between a plurality of film forming rollers when generating plasma. In the present invention, a pair of film forming rollers is used, and a resin substrate is wound around each of the pair of film forming rollers, and the pair of film forming rollers is used. It is preferable to generate plasma by discharging in a state where a magnetic field is applied between the film forming rollers. Thus, by using a pair of film forming rollers, winding the resin base material on the pair of film forming rollers, and performing plasma discharge between the pair of film forming rollers, the resin base material and the film forming roller By changing the distance between the first gas barrier layer and the first gas barrier layer, the carbon atomic ratio has a concentration gradient and continuously changes in the layer.

It is also possible to form a film on the surface part of the resin substrate that exists on the other film forming roller while forming a film on the surface part of the resin substrate that exists on one film formation roller. In addition to efficiently producing a thin film, the film formation rate can be doubled, and a film having the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form the first gas barrier layer that satisfies the requirements (1) and (2) at the same time.

Further, the first gas barrier layer constituting the gas barrier film according to the present invention is preferably formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity.

An apparatus that can be used for producing the first gas barrier layer constituting the gas barrier film by such a plasma chemical vapor deposition method is not particularly limited, but an apparatus that applies at least a pair of magnetic fields. It is preferable that the apparatus includes a film-forming roller provided with a plasma power source and is configured to be capable of discharging between a pair of film-forming rollers. For example, the manufacturing apparatus illustrated in FIG. In such a case, a gas barrier film can be produced by a roll-to-roll method using a plasma chemical vapor deposition method.

Hereinafter, the manufacturing method of the first gas barrier layer constituting the gas barrier film according to the present invention will be described in more detail with reference to FIG. FIG. 2 is a schematic view showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used in the production of the first gas barrier layer constituting the gas barrier film according to the present invention is applied.

An inter-roller discharge plasma CVD apparatus (hereinafter also referred to as a plasma CVD apparatus) to which a magnetic field shown in FIG. 2 is applied mainly includes a delivery roller 11,

transport rollers

21, 22, 23 and 24, and a film formation roller 31. And 32, a film forming gas supply pipe 41, a plasma generation power source 51,

magnetic field generators

61 and 62 installed inside the

film forming rollers

31 and 32, and a winding roller 71. Further, in such a plasma CVD manufacturing apparatus, at least the

film forming rollers

31 and 32, the film forming gas supply pipe 41, the plasma generating power source 51, and the magnetic

field generating apparatuses

61 and 62 are not shown in a vacuum. Located in the chamber. Further, in such a plasma CVD manufacturing apparatus, a vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump. Yes.

In such a plasma CVD manufacturing apparatus, each film forming roller generates plasma so that a pair of film forming rollers (the film forming roller 31 and the film forming roller 32) can function as a pair of counter electrodes. It is connected to the power source 51 for use. By supplying electric power to the pair of film forming rollers (the film forming roller 31 and the film forming roller 32) from the power source 51 for generating plasma, the space between the film forming roller 31 and the film forming roller 32 can be discharged. Thus, plasma can be generated in a space (also referred to as a discharge space) between the film formation roller 31 and the film formation roller 32. In addition, since the film-forming roller 31 and the film-forming roller 32 are used as electrodes in this way, materials and designs that can be used as electrodes may be changed as appropriate. In such a plasma CVD manufacturing apparatus, it is preferable that the pair of film forming rollers (film forming rollers 31 and 32) be arranged so that their central axes are substantially parallel on the same plane. By arranging a pair of film forming rollers (film forming rollers 31 and 32) in this way, the film forming rate can be doubled, and a film having the same structure can be formed. Can be at least doubled.

Further, the film forming roller 31 and the film forming roller 32 are characterized in that

magnetic field generators

61 and 62 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

The

magnetic field generators

61 and 62 provided on the film forming roller 31 and the film forming roller 32 respectively are a magnetic field generating device 61 provided on one film forming roller 31 and a magnetic field generating device provided on the other film forming roller 32. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between the magnetic field generator 62 and the

magnetic field generators

61 and 62 form a substantially closed magnetic circuit. By providing such

magnetic field generators

61 and 62, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each

film forming roller

31 and 32, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

The

magnetic field generators

61 and 62 provided on the film forming roller 31 and the film forming roller 32 respectively include racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generating device 61 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 62 have the same polarity. For example, in the

magnetic field generators

61 and 62 of FIG. 2, the racetrack-shaped magnetic poles (one for each film-forming roller, two in total) are provided on the long protrusion at the center of the mountain-shaped cross section. It is arranged so as to be polar (N pole or S pole), and the racetrack-shaped magnetic poles (two for each film-forming roller, four in total) are also provided on the short protrusions on both sides of the center of the mountain-shaped cross section. All of these magnetic poles are arranged so as to have the same polarity (S pole or N pole) as the counter pole of the magnetic pole of the central long protrusion. However, the magnetic poles (N pole and S pole) may be arranged in reverse. By providing the

magnetic field generators

61 and 62, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the lines of magnetic force of each of the

magnetic field generators

61 and 62 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 1 is excellent in that a first gas barrier layer (not shown) that is a vapor deposition film can be efficiently formed.

Furthermore, as the film forming roller 31 and the film forming roller 32, known rollers can be used as appropriate. As the

film forming rollers

31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. The diameters of the

film forming rollers

31 and 32 are preferably in the range of 100 to 1000 mmφ, particularly in the range of 100 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter is 100 mmφ or more, the plasma discharge space does not become small, so there is no deterioration in productivity, and it is possible to avoid that the total heat of plasma discharge is applied to the film (resin substrate 1) in a short time, and the residual stress Is preferable because it is difficult to increase. On the other hand, a diameter of 1000 mmφ or less is preferable because practicality can be maintained in terms of device design including uniformity of the plasma discharge space.

Also, as the feed roller 11 and the

transport rollers

21, 22, 23, and 24 used in such a plasma CVD manufacturing apparatus, known rollers can be appropriately selected and used. The winding roller 71 is not particularly limited as long as it can wind up the resin base material 1 on which the first gas barrier layer is formed, and a known roller can be used as appropriate.

As the film forming gas supply pipe 41, a material gas and oxygen gas, or a material capable of supplying or discharging the material gas, oxygen gas and nitrogen gas at a predetermined rate can be appropriately used. Furthermore, as the plasma generating power source 51, a conventionally known power source for a plasma generating apparatus can be used. Such a power source 51 for generating plasma supplies power to the film forming roller 31 and the film forming roller 32 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generating power source 51, it is possible to more efficiently carry out the plasma CVD method, so that the polarity of the pair of film forming rollers can be alternately reversed (AC power source or the like). Is preferably used. In addition, since such a plasma generating power source 51 can perform the plasma CVD method more efficiently, the applied power can be in the range of 100 W to 10 kW, and the AC frequency is 50 Hz. More preferably, it can be in the range of -500 kHz. As the

magnetic field generators

61 and 62, known magnetic field generators can be used as appropriate.

Using the plasma CVD apparatus as shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the strength of the magnetic field generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the resin The gas barrier film according to the present invention can be produced by appropriately adjusting the conveyance speed of the substrate. That is, using the plasma CVD apparatus shown in FIG. 2, a magnetic field is generated between a pair of film forming rollers (film forming rollers 31 and 32) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. By performing plasma discharge, the film forming gas (raw material gas or the like) is decomposed by plasma, and on the surface of the resin base material 1 on the film forming roller 31 and on the surface of the resin base material 1 on the film forming roller 32. The first gas barrier layer according to the present invention is formed by a plasma CVD method. In such film formation, the resin base material 1 is conveyed by the delivery roller 11 and the film formation roller 31, respectively, so that the resin base material 1 is formed by a roll-to-roll continuous film formation process. The first gas barrier layer is formed on the surface.

<2.5.1> Source gas The film forming gas used for forming the first gas barrier layer according to the present invention contains (a) a source gas containing a nitrogen-containing organosilicon compound and an oxygen gas, or (b). A source gas containing an organosilicon compound, oxygen gas and nitrogen gas can be used. In the case of the film forming gas (a) described above, the source gas constituting the film forming gas used for forming the first gas barrier layer according to the present invention is a nitrogen-containing organosilicon compound containing at least nitrogen and silicon, (b) In the case of the film forming gas, it is preferable to use an organosilicon compound containing at least silicon.

<2.5.1.1> Nitrogen-containing organosilicon compound Examples of the nitrogen-containing organosilicon compound applicable to the present invention include triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, and hexaethyldisilazane. Hexapropyldisilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, octaethylcyclotetrasilazane, hexaphenylcyclotrisilazane and the like. Among these nitrogen-containing organosilicon compounds, hexamethyldisilazane, hexaethyldisilazane, and the like are preferable from the viewpoints of handling in film formation and low curling properties, bending resistance, gas barrier properties, and the like of the obtained first gas barrier layer. . Moreover, these nitrogen-containing organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

<2.5.1.2> Organosilicon compound Examples of the organosilicon compound applicable to the present invention include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, and methyltrimethyl. Silane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane , Octamethylcyclotetrasiloxane, and further nitrogen-containing organosilicon compounds such as triethylsilazane, tripropylsilazane, triphenylsilazane, hexamethyldisilazane, hexaethyldisilazane, hexapropyl Examples include disilazane, hexaphenyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexaethylcyclotrisilazane, and octaethylcyclotetrasilazane. Among these organosilicon compounds, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, hexamethyldisilazane, hexamethyldisiloxane are used from the viewpoints of handling in film formation and gas barrier properties of the obtained gas barrier layer. Ethyl disilazane and the like are preferable. In addition, the above-described nitrogen-containing organosilicon compound may be used as the organosilicon compound. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

The film forming gas is characterized in that (a) when a nitrogen-containing organosilicon compound is used as the source gas, oxygen gas is contained as a reaction gas in addition to the source gas. Alternatively, (b) when an organosilicon compound is used as the source gas, oxygen gas and nitrogen gas are contained as reaction gases in addition to the source gas. The oxygen gas used in the above (a) and (b) is a gas that reacts with the raw material gas (nitrogen-containing organosilicon compound or organosilicon compound) to become an inorganic compound such as an oxide. The nitrogen gas used in the above (b) is a gas that reacts with the raw material gas (organosilicon compound) to become an inorganic compound such as a nitride.

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

When such a film forming gas contains (a) a source gas containing a nitrogen-containing organosilicon compound containing nitrogen and silicon and an oxygen gas, the ratio of the source gas to the oxygen gas is as follows: It is preferable that the ratio of oxygen gas is not excessively larger than the ratio of the amount of oxygen gas that is theoretically necessary for completely reacting. If the ratio of oxygen gas is excessive, it is difficult to obtain the first gas barrier layer intended in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the nitrogen-containing organosilicon compound in the film-forming gas is less than or equal to the theoretical oxygen amount necessary for complete oxidation. Similarly, when the film forming gas contains (b) a raw material gas containing an organosilicon compound containing silicon, an oxygen gas, and a nitrogen gas, the ratio of the raw material gas, the oxygen gas, and the nitrogen gas is as follows. It is preferable that the ratio of oxygen gas and nitrogen gas is not excessively larger than the ratio of the amount of oxygen gas and nitrogen gas that is theoretically necessary for completely reacting the gas and nitrogen gas. If the ratio of oxygen gas and nitrogen gas is excessive, it is difficult to obtain the first gas barrier layer intended in the present invention. Therefore, in order to obtain the desired performance as a barrier film, it is preferable that the total amount of the organosilicon compound in the film-forming gas is less than or equal to the theoretical oxygen amount and the theoretical nitrogen amount necessary for complete oxynitriding.

<2.5.2> Degree of vacuum The pressure (degree of vacuum) in the vacuum chamber can be adjusted as appropriate according to the type of the raw material gas, but is preferably in the range of 0.5 Pa to 100 Pa.

<2.5.3> Roller Film Formation In the plasma CVD method using a plasma CVD apparatus or the like as shown in FIG. 2, it is connected to a plasma generation power source 51 in order to discharge between the

film formation rollers

31 and 32. The power applied to the electrode drum (installed in the

film forming rollers

31 and 32 in FIG. 2) can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, and the like. Although it cannot be generally stated, it is preferably within a range of 0.1 to 10 kW. If the applied power is in such a range, no generation of particles (illegal particles) is observed, and the amount of heat generated during film formation is within the control range. There is no thermal deformation of the base material, performance deterioration due to heat, and no wrinkles during film formation. In addition, damage to the film forming roller due to melting of the resin base material by heat and generation of a large current discharge between the bare film forming rollers can be prevented.

The conveyance speed (line speed) of the resin base material 1 can be appropriately adjusted according to the type of raw material gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. More preferably, it is within the range of 0.5 to 20 m / min. When the line speed is within the above range, wrinkles due to the heat of the resin base material hardly occur, and the thickness of the formed first gas barrier layer can be sufficiently controlled.

FIG. 3 shows an example of each element profile in the layer thickness direction based on the XPS depth profile of the first gas barrier layer of the present invention formed as described above.

FIG. 3 is a graph showing an example of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve of the first gas barrier layer that is the inclined SiOCN barrier film according to the present invention.

In FIG. 3, symbols A to D represent A as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as a nitrogen distribution curve. As shown in the graph of FIG. 3, the first gas barrier layer according to the present invention has at least one extreme value in the carbon distribution curve, and the difference between the maximum maximum value and the minimum maximum value of the carbon atom ratio. The average value of each atom with respect to the total amount (100 at%) of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms in a region where the absolute value of is 5 at% or more and 90% or more of the total thickness of the first gas barrier layer It can be seen that the atomic ratio satisfies the order relationship defined by the previous formula (A) or (B).

FIG. 4 is a graph showing an example of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve of a gas barrier layer that is a non-tilted SiOCN barrier film of a comparative example. In FIG. 4, symbols A to D represent A as a carbon distribution curve, B as a silicon distribution curve, C as an oxygen distribution curve, and D as a nitrogen distribution curve.

The first gas barrier layer of the comparative example (sample 8) includes a carbon atom profile A, a silicon atom profile B, an oxygen atom profile C in the first gas barrier layer formed by a flat electrode (horizontal conveyance) type plasma CVD discharge method, and The nitrogen atom profile D is shown, and in particular, it can be seen that the non-gradient SiOCN barrier film configuration does not cause a continuous change in the concentration gradient of the carbon atom component A, and has no extreme value.

[3] Second Gas Barrier Layer The gas barrier film according to the present invention preferably further includes a second gas barrier layer formed on the first gas barrier layer described above. The second gas barrier layer may be any layer having gas barrier properties, and among them, a polysilazane modified film containing a polysilazane modified product is preferable. As a gas barrier layer other than the polysilazane modified film, a conventionally used barrier layer can be used.

Hereinafter, a polysilazane modified film containing a polysilazane modified material suitable as the second gas barrier layer will be described as an example, but the present invention is not limited to these. The second gas barrier layer as the polysilazane modified film is obtained by applying an excimer modifying treatment to a coating film formed by applying and drying a liquid containing polysilazane (polysilazane-containing liquid). At this time, the contraction rate in the layer thickness direction before and after the excimer modification treatment is within the range of 10 to 30%, preferably within the range of 15 to 20%, to the coating film formed by applying and drying the polysilazane-containing liquid. The second gas barrier layer (polysilazane modified film) may be formed by performing an excimer modification process under the following conditions. That is, the second gas barrier layer, which is a polysilazane modified film, is obtained by applying a liquid containing polysilazane on the first gas barrier layer and drying it to form a coating film, and subjecting the coating film to an excimer modification treatment. It can be manufactured by the step of forming the second gas barrier layer. In addition, about gas barrier layers other than a polysilazane modified film | membrane, a 2nd gas barrier layer can be manufactured by using the manufacturing method of the barrier layer generally used conventionally.

As the second gas barrier layer which is the polysilazane modified film according to the present invention, the layer thickness after the excimer modification treatment is preferably in the range of 50 to 500 nm, and the second gas barrier layer is formed. In, the polysilazane-containing liquid is applied and dried on the first gas barrier layer according to the present invention by a wet coating method, and the formed coating film is irradiated with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. Then, it is preferable that the formed gas film is subjected to an excimer modification treatment to form the second gas barrier layer.

In the present invention, the second gas barrier layer, which is a polysilazane modified film, is formed on the first gas barrier layer, which is a tilted SiOCN barrier film provided by, for example, an inter-roller discharge plasma CVD method to which a magnetic field is applied. In the hybrid gas barrier film of the first gas barrier layer, which is a tilted SiOCN barrier film, and the second gas barrier layer, which is a polysilazane modified film, in addition to the compatibility between the first and second gas barrier layers. Since nitrogen contained in both layers is formed by interaction between layers, structural defects between the layers are reduced, and a gas barrier film having a large effect of improving barrier performance during lamination can be realized. Specifically, when the second gas barrier layer that is the polysilazane modified film is formed on the first gas barrier layer that is the inclined SiOCN barrier film, the second gas barrier layer has a similar structure because nitrogen is contained in the first gas barrier layer. Film particles are formed (the film particles are formed by the interaction of nitrogen between the above-mentioned layers), and the effect of protecting and repairing structural defects of the first gas barrier layer is great, and barrier performance during lamination A gas barrier film having a large improvement effect can be realized. Furthermore, it is possible to obtain excellent planarity even after being left under certain conditions such as high-temperature and high-humidity treatment, and to provide a minute defect portion generated during the formation of the already formed first gas barrier layer from the top. It can be filled with the second gas barrier layer component constituted, and gas purge and the like can be efficiently prevented, and further gas barrier properties and bending resistance can be improved. From the viewpoint of effectively expressing the above-described effects, the thickness of the second gas barrier layer is in the range of 50 nm to 500 nm, preferably 50 nm to 400 nm, more preferably 50 nm to 300 nm. If the thickness of the second gas barrier layer is 50 nm or more, it is possible to protect and repair minute defects generated during the formation of the first gas barrier layer, and to achieve desired gas barrier properties and planarity, and at 500 nm or less. If there is, it is possible to suppress defects caused by concentration of film stress between the barrier layers, and to achieve desired gas barrier properties and flatness, and a dense silicon oxynitride film (SiON barrier film) Film quality deterioration such as generation of cracks in the second gas barrier layer) can be prevented. The thickness of the gas barrier layer (second gas barrier layer) other than the polysilazane modified film is preferably in the same range as the thickness of the second gas barrier layer that is the polysilazane modified film.

<3.1> Polysilazane The polysilazane according to the present invention is a polymer having a silicon-nitrogen bond in the molecular structure, and is a polymer that is a precursor of silicon oxynitride. The polysilazane to be applied is not particularly limited. A compound having a structure represented by the following general formula (1) is preferable.

In the general formula (1), 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, perhydropolysilazane in which all of R ¹ , R ^2, and R ³ are composed of hydrogen atoms is particularly preferred from the viewpoint of denseness as the obtained second gas barrier layer (polysilazane modified film).

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6-membered and 8-membered rings, and its molecular weight is about 600 to 2000 in terms of number average molecular weight (Mn) (gel Polystyrene conversion by permeation chromatography), which is a liquid or solid substance.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and a commercially available product can be used as it is as a polysilazane-containing liquid. Examples of commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

The second gas barrier layer that is a modified polysilazane film is, for example, after applying and drying a liquid containing polysilazane (polysilazane-containing liquid) on the first gas barrier layer formed by the inter-roller discharge plasma CVD method to which a magnetic field is applied. It can be formed by irradiating with vacuum ultraviolet rays.

As an organic solvent for preparing a liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. As an applicable organic solvent, for example, organic solvents described in paragraph “0055” of JP2013-226757A and paragraph “0118” of WO2012 / 077753 can be used. The organic solvent may be selected according to purposes such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

The concentration of polysilazane in the liquid containing polysilazane (the coating liquid for forming the second gas barrier layer) varies depending on the layer thickness of the second gas barrier layer and the pot life of the coating liquid, but is preferably 0.2 to 35% by mass. Within range.

In order to promote modification to silicon oxynitride, a catalyst can be added to a liquid containing polysilazane (a coating liquid for forming a second gas barrier layer). Examples of the catalyst that can be added to the liquid containing polysilazane (second gas barrier layer forming coating liquid) include, for example, paragraph “0057” of JP2013-226757A and paragraph “0103” of JP2013-226732A. , “0105” and paragraph “0120” of International Publication No. 2012/077753 can be used. In the present invention, among the catalysts described in the above publications, it is particularly preferable to use an amine catalyst.

The amount of these catalysts added to the polysilazane is preferably in the range of 0.1 to 10% by mass with respect to the total mass of the polysilazane-containing liquid (second gas barrier layer forming coating liquid), and preferably 0.2 to 5%. It is more preferably in the range of mass%, and still more preferably in the range of 0.5 to 2 mass%. By setting the addition amount of the catalyst within the range specified above, excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like can be avoided.

With respect to a method of applying a liquid containing polysilazane (second gas barrier layer forming coating liquid), for example, paragraphs “0060” of JP2013-226757A and paragraph “0092” of JP2013-226732A are disclosed. The described coating method can be employed.

The thickness of the coating film after applying and drying a liquid containing polysilazane (second gas barrier layer forming coating liquid) can be appropriately set according to the purpose. For example, the thickness of the coating film is preferably in the range of 50 nm to 2 μm as the thickness after drying, more preferably in the range of 70 nm to 1.5 μm, and in the range of 100 nm to 1 μm. Is more preferable.

<3.2> Excimer Modification Treatment The second gas barrier layer, which is a polysilazane modification film according to the present invention, is a step of irradiating a layer (coating film) containing polysilazane with vacuum ultraviolet rays (VUV), and at least a part of the polysilazane. Is modified to silicon oxynitride.

Here, regarding the presumed mechanism in which the coating film containing polysilazane is modified in the vacuum ultraviolet irradiation step and the specific composition of SiO _x N _y is assumed, for example, perhydropolysilazane is exemplified, for example, JP-A-2013-226757 Perhydropolysilazane disclosed in paragraphs “0075” to “0083” of the publication is as described as an example.

Regarding the adjustment of the composition of silicon oxynitride in the layer (second gas barrier layer) subjected to vacuum ultraviolet ray irradiation on the polysilazane-containing layer (coating film), the (I) described in paragraphs “0080” to “0083” of the above-mentioned publication ) To (IV) can be performed by appropriately combining the oxidation mechanisms of (IV) to control the oxidation state.

In the vacuum ultraviolet irradiation process of the present invention, the vacuum ultraviolet illuminance range described in paragraph "0086" of the above publication is also applied to the vacuum ultraviolet illumination on the coating surface received by the polysilazane-containing layer (coating film). be able to.

The range of the irradiation energy amount described in paragraph “0087” of the above publication can also be applied to the irradiation energy amount of vacuum ultraviolet rays on the coating surface of the polysilazane-containing layer (coating film).

As for the vacuum ultraviolet light source and the like, the known rare gas excimer lamp described in paragraphs “0088” to “0092” of the above publication, the principle of excimer emission when the rare gas is xenon, the characteristics of the excimer lamp, and the like can be applied.

The publicly known methods described in paragraphs “0093” to “0110” of the above publication can also be applied to a method for obtaining excimer light emission and a method for obtaining excimer light emission efficiently.

[4] Each functional layer In the gas barrier film according to the present invention, in addition to the above-described constituent layers (first and second gas barrier layers), each functional layer can be provided as necessary.

<4.1> Overcoat layer An overcoat layer may be formed on the second gas barrier layer according to the present invention for the purpose of further improving flexibility. As the organic material used for the formation of the overcoat layer, organic resins such as organic monomers, oligomers and polymers, and organic / inorganic composite resins using siloxane and silsesquioxane monomers, oligomers and polymers having organic groups are preferably used. be able to. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed from the organic resin composition coating solution to be cured.

<4.2> Anchor layer In the gas barrier film according to the present invention, for the purpose of improving the adhesion between the resin substrate and the first gas barrier layer between the resin substrate and the first gas barrier layer, if necessary. And an anchor layer (also referred to as a clear hard coat layer (CHC layer)).

When the resin base material is heated, the anchor layer can also suppress a phenomenon (bleed out) that unreacted oligomers move from the resin base material to the surface and contaminate the contact surface. . The anchor layer is preferably smooth because the first gas barrier layer is disposed thereon, and the surface roughness Ra value is preferably in the range of 0.3 to 3 nm, more preferably 0. Within the range of 5 to 1.5 nm. When the surface roughness Ra value is 0.3 nm or more, the surface has an appropriate smoothness, and the smoothness can be maintained in the roller transportability and the formation of the first gas barrier layer by the plasma CVD method. On the other hand, when the thickness is 3 nm or less, it is possible to prevent the formation of minute defects in the first gas barrier layer when the first gas barrier layer is formed, and it is possible to obtain a high level of gas barrier properties and adhesion.

As the composition of the anchor layer, a thermosetting resin or a photocurable resin is preferable because smoothness is required.

The thickness of the anchor layer is preferably in the range of 0.3 to 10 μm, more preferably in the range of 0.5 to 5 μm, from the viewpoint of adjusting the flatness.

《Electronic device》
The gas barrier film of the present invention as described above has excellent low curling properties, flex resistance, gas barrier properties, and transparency. For this reason, the gas barrier film of the present invention is used for various applications such as electronic devices such as packages for electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. can do.

Examples of the electronic device include an organic electroluminescence panel, an organic electroluminescence element, an organic photoelectric conversion element, and a liquid crystal display element.

[1] Organic EL Panel as Electronic Device The gas barrier film according to the present invention (for example, the gas barrier film F having the configuration shown in FIG. 1) seals, for example, a solar cell, a liquid crystal display element, an organic EL element, and the like. It can be used as a sealing film.

An example of an organic EL panel P that is an electronic device using the gas barrier film F as a sealing film is shown in FIG.

As shown in FIG. 5, the organic EL panel P is formed on the gas barrier film F through the gas barrier film F, the transparent electrode 4 such as ITO formed on the gas barrier film F, and the transparent electrode 4. The organic EL element 5 that is the main body of the electronic device, and a counter film 7 disposed via an adhesive layer 6 so as to cover the organic EL element 5 are provided. The transparent electrode 4 may form part of the organic EL element 5.

In the electronic device (organic EL panel P) having the above-described configuration, by providing the gas barrier film according to the present invention, excellent gas barrier properties and flexibility (essential effects of the gas barrier film) ( (Bending resistance) and low curl properties, and also exhibits excellent flatness as a gas barrier film when stored over a long period of time in a high temperature and high humidity environment, thereby improving the flatness of the entire organic EL panel. The high-quality electronic device can be obtained.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

[Production of Gas Barrier Film Sample 1: Examples]
(Preparation of resin base material)
A biaxially stretched polyethylene naphthalate film (abbreviation: PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, trade name “Teonex Q65FA”) was used as a resin base material.

(Formation of anchor layer)
After applying the UV curable organic / inorganic hybrid hard coat material OPSTARZ7501 manufactured by JSR Corporation on the easy adhesion surface side of the resin substrate with a wire bar so that the layer thickness after drying is 4 μm, drying conditions As a result, drying was performed at 80 ° C. for 3 minutes. Next, curing was carried out under an air atmosphere using a high-pressure mercury lamp under curing conditions; 1.0 J / cm ² to form an anchor layer.

(Formation of first gas barrier layer: roller CVD method)
Using the inter-roller discharge plasma CVD apparatus to which the magnetic field shown in FIG. 2 is applied (hereinafter, this method is referred to as “roller CVD method”), the surface opposite to the surface on which the anchor layer of the resin substrate is formed (back surface) The resin base material is mounted on the apparatus so as to be in contact with the film formation roller, and the first gas barrier layer (gradient SiOCN barrier film) is formed on the anchor layer with the thickness according to the following film formation conditions (plasma CVD conditions). The film was formed under the condition of 300 nm to prepare a gas barrier film sample 1.

<Plasma CVD conditions>
Supply amount of source gas (hexamethyldisilazane which is a nitrogen-containing organosilicon compound): 100 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Transport speed of resin substrate: 2 m / min.

<Measurement of element distribution profile>
For the first gas barrier layer formed under the above film formation conditions, XPS depth profile measurement was performed under the following conditions, and the silicon element distribution curve, oxygen element with respect to the distance from the surface of the thin film layer (first gas barrier layer) in the layer thickness direction Distribution curves, carbon element distribution curves and nitrogen distribution curves were obtained.

Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

From the silicon element distribution curve, the oxygen element distribution curve, the carbon element distribution curve and the nitrogen distribution curve in the whole layer region of the first gas barrier layer measured as described above, the presence or absence of continuous change regions and the presence or absence of extreme values in each element composition The average atomic ratio of silicon atoms, oxygen atoms, carbon atoms, and nitrogen atoms was determined in the difference between the maximum value and the minimum value of the atomic ratio of carbon and in the region of 90% or more of the total layer thickness.

As a result, as shown in FIG. 3, there is a continuous change region and an extreme value in the composition, the absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio is 8 at%, and the maximum value of the nitrogen atomic ratio is 4 at%. %, The relationship defined by the formula (A) in the region where the average atomic ratio of silicon atoms, oxygen atoms, carbon atoms and nitrogen atoms is 90% or more of the total layer thickness, that is, (carbon average atomic ratio)> (silicon It was confirmed that the relationship of (average atomic ratio)> (oxygen average atomic ratio)> (nitrogen average atomic ratio) was satisfied.

[Production of Gas Barrier Film Sample 2: Example]
In the production of the gas barrier film sample 1, a gas barrier film sample 2 was produced in the same manner except that the plasma CVD conditions were changed as follows.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisilazane): 100 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Supply amount of nitrogen gas (N ₂ ): 50 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Transport speed of resin substrate: 2 m / min.

[Production of Gas Barrier Film Sample 3: Examples]
In the same manner as the production of the gas barrier film sample 1, the anchor layer and the first gas barrier layer (gradient SiOCN barrier film) were formed in this order on the easy adhesion surface side of the resin base material. Further, a second gas barrier layer (polysilazane modified film) having a thickness of 300 nm was formed on the first gas barrier layer by the following procedure, and a gas barrier film sample 3 was produced.

<Preparation of coating solution for forming polysilazane layer>
A 10 mass% dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution for forming a polysilazane layer.

<Formation of polysilazane layer>
The prepared polysilazane layer-forming coating solution is applied with a wireless bar so that the (average) layer thickness after drying is 300 nm, and treated for 1 minute in an atmosphere at a temperature of 85 ° C. and a relative humidity of 55%. It was dried, and further kept in an atmosphere of a temperature of 25 ° C. and a relative humidity of 10% (dew point temperature −8 ° C.) for 10 minutes to perform dehumidification, thereby forming a polysilazane layer.

<Formation of second gas barrier layer: Excimer modification treatment of polysilazane layer by vacuum ultraviolet light (excimer light)>
Next, the polysilazane layer formed above is subjected to excimer modification treatment by installing the following vacuum ultraviolet irradiation device in a vacuum chamber to form a second gas barrier layer (SiON barrier film) which is a polysilazane modified film. As a result, a gas barrier film sample 3 was obtained.

<Vacuum ultraviolet irradiation device>
Apparatus: Excimer irradiation apparatus MODEL manufactured by M.D. Co., Ltd .: MECL-M-1-200 (Excimer lamp)
Irradiation wavelength: 172 nm
Lamp filled gas: Xe (xenon gas).

<Excimer reforming treatment conditions>
Excimer modification treatment was performed on the resin base material on which the polysilazane layer fixed on the operation stage was formed on the first gas barrier layer under the following conditions to form the second gas barrier layer.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0% (volume ratio)
Excimer lamp irradiation time: 5 seconds.

[Production of Gas Barrier Film Sample 4: Example]
In the same manner as the production of the gas barrier film sample 2, a resin base material was prepared, and an anchor layer and a first gas barrier layer (gradient SiOCN barrier film) were formed on the resin base material in this order. Further, a second gas barrier layer (polysilazane modified film) was formed on the first gas barrier layer in the same procedure as the gas barrier film sample 3 to produce a gas barrier film sample 4.

[Production of Gas Barrier Film Sample 5: Comparative Example]
In the production of the gas barrier film sample 1, a gas barrier film sample 5 was produced in the same manner except that the plasma CVD conditions were changed as follows.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisilazane): 100 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 50 sccm
Supply amount of nitrogen gas (N ₂ ): 200 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Transport speed of resin substrate: 2 m / min.

[Production of Gas Barrier Film Sample 6: Comparative Example]
In the production of the gas barrier film sample 1, a gas barrier film sample 6 was produced in the same manner except that the plasma CVD conditions were changed as follows.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisiloxane which is an organosilicon compound not containing nitrogen): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 500 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Transport speed of resin substrate: 2 m / min.

[Production of Gas Barrier Film Sample 7: Example]
A gas barrier film sample 7 was prepared in the same manner as in the preparation of the gas barrier film sample 4 except that the second gas barrier layer (formation method thereof) was changed as follows.

(Formation of second gas barrier layer)
On the first gas barrier layer (gradient SiOCN barrier film), a glassca HPC7003 manufactured by JSR Co., Ltd. was applied under the condition that the layer thickness after drying was 300 nm, and then dried at 120 ° C. for 3 minutes. An ultraviolet irradiation device was installed in the vacuum chamber and the excimer modification treatment was performed to form a second gas barrier layer (polysiloxane modified film), whereby a gas barrier film sample 7 was obtained.

<Excimer reforming treatment conditions>
Excimer modification treatment is performed on the resin base material on which the polysiloxane layer fixed on the operation stage is formed on the first gas barrier layer under the following conditions, so that the second gas barrier layer (SiO ₂₎ that is a polysiloxane modified film is obtained. Barrier film) was formed.

[Production of Gas Barrier Film Sample 8: Comparative Example]
(Plate electrode type CVD equipment)
Similarly to the production of the gas barrier film sample 1, a resin base material was prepared, and an anchor layer was formed on the resin base material. Next, using a commercially available flat plate type plasma CVD apparatus, the first gas barrier layer (non-gradient SiOCN barrier film) is formed on the anchor layer under the following film formation conditions (plasma CVD conditions). A film was formed under the condition of 300 nm, and a gas barrier film sample 8 was produced.

<Plasma CVD conditions>
Source gas (hexamethyldisilazane) supply amount: 20 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 50 sccm
Supply amount of nitrogen gas (N ₂ ): 50 sccm
Degree of vacuum in the vacuum chamber: 10Pa
Applied power from the power source for plasma generation: 0.5 kW
Frequency of power source for plasma generation: 13.56 MHz
Transport speed of resin substrate: 1 m / min.

As a result of measuring the element distribution profile of the formed first gas barrier layer by the same method, as shown in FIG. 4, the continuous change region and the extreme value in the film composition (particularly, the carbon distribution curve, the silicon distribution curve, and the oxygen distribution curve). The difference between the maximum value and the minimum value of the carbon atom ratio was 0 at%, and the maximum value of the nitrogen atom ratio was 5 at%. Note that the average atomic ratio of silicon atoms, oxygen atoms, carbon atoms, and nitrogen satisfies the relationship defined by the formula (A) in a region of 90% or more of the total layer thickness.

[Production of Gas Barrier Film Sample 9: Comparative Example]
In the same manner as the production of the gas barrier film sample 8, a resin base material was prepared, and an anchor layer and a first gas barrier layer (non-tilted SiOCN barrier film) were formed on the resin base material in this order. Further, a second gas barrier layer (polysilazane modified film) was formed on the first gas barrier layer in the same manner as the gas barrier film sample 3, and a gas barrier film sample 9 was produced.

[Production of Gas Barrier Film Sample 10: Comparative Example]
In the same manner as in the production of the gas barrier film sample 6, a resin base material was prepared, and an anchor layer and a first gas barrier layer (gradient SiOCN barrier film) were formed on the resin base material in this order. Further, a second gas barrier layer (polysilazane modified film) was formed on the first gas barrier layer in the same manner as the gas barrier film sample 3 to prepare a gas barrier film sample 10.

<< Evaluation of gas barrier film sample >>
The gas barrier film samples 1 to 10 produced above were evaluated for water vapor barrier property, bending resistance (flexibility), flatness and film curl according to the amount of permeated water according to the following methods.

[Evaluation of water vapor barrier properties (WVTR)]
According to the following measurement method, the permeated water amount of each gas barrier film sample was measured, and the water vapor barrier property was evaluated according to the following criteria.

(apparatus)
Vapor deposition device: JEOL Ltd., vacuum vapor deposition device JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor impervious metal: Aluminum (diameter (φ) 3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
The part of each gas barrier film sample to be vapor-deposited on the barrier layer surface (outermost surface) of the gas barrier film sample before applying the transparent conductive film using a vacuum vapor deposition device (vacuum vapor deposition device JEE-400 manufactured by JEOL Ltd.) Other than (12 mm × 12 mm at 9 locations) was masked, and metallic calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the entire surface of one side of the sheet (surface on which calcium was deposited). After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays. Further, in order to confirm the change in the gas barrier property before and after bending, the following bending treatment (for the gas barrier film samples 1 to 10 is performed in advance with a curvature having a radius of 10 mm in order to confirm the change in the gas barrier property before and after the bending. Thus, the water vapor barrier property evaluation cell was similarly produced also about the gas barrier property film sample which did not perform bending 100 times at an angle of 180 degree | times.

The obtained sample with both sides sealed (evaluation cell) was stored under high temperature and high humidity of 60 ° C. and 90% RH, and from the amount of corrosion of metallic calcium based on the method described in JP-A-2005-283561. The amount of moisture permeated into the cell was calculated.

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

The permeated water amount (g / m ² · day; “WVTR” in the table) of each gas barrier film sample measured as described above was evaluated by the Ca method.

(Evaluation criteria)
A: Less than 1 × 10 ⁻⁵ g / m ² / day ○: 1 × 10 ⁻⁵ g / m ² / day or more, less than 5 × 10 ⁻⁵ g / m ² / day ○ Δ: 5 × 10 ⁻⁵ g / M ² / day or more, less than 1 × 10 ⁻⁴ g / m ² / day Δ: 1 × 10 ⁻⁴ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day ×: 1 × 10 ⁻² g / m ² / day or more [Evaluation of bending resistance (flexibility)]
Regarding the gas barrier film samples 1 to 10, in order to confirm the change in the gas barrier property before and after the bending, the gas barrier film sample that has been repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm in advance. The water vapor transmission rate (WVTR) was measured and evaluated based on the same evaluation criteria.

[Measurement of film curl]
Gas barrier film samples 1 to 10 were treated at 80 ° C. for 100 hours, then placed on a flat plate, and the amount of curling was measured using calipers (when the barrier surface was facing up, the concave was negatively curled. The convexity is defined as plus curl.In Table 1 below, the absolute value of the amount of curling is shown.)

As is apparent from the results shown in Table 1, the gas barrier film samples 1 to 4 and 7 having the constitution defined in the present invention are film curls compared to the gas barrier film samples 5 to 6 and 8 to 10 of the comparative example. There are few, and it turns out that it is excellent in bending tolerance (flexibility), and has high gas barrier property (water vapor barrier property).

Further, in the gas barrier film samples 1 to 4 having the configuration defined in the present invention, the gas barrier film sample 1 is provided with a second gas barrier layer that is a polysilazane modified film, as compared with the gas barrier film sample 1. It can be seen that the functional film sample 3 has higher gas barrier properties (water vapor barrier properties). Similarly, as compared with the gas barrier film sample 2, the gas barrier film sample 4 in which the gas barrier film sample 2 is provided with the second gas barrier layer which is a polysilazane modified film has a higher gas barrier property (water vapor barrier property). It can be seen that

In addition, in the gas barrier film samples 3 to 4 and 7 having the configuration defined in the present invention, a SiOCN barrier film containing nitrogen is used for the first gas barrier layer as in the gas barrier film samples 3 and 4, and the second gas barrier layer is used. In addition, by using the polysilazane modified film containing nitrogen, not only the low curling property and the bending resistance are compatible, but also both the first gas barrier layer as the SiOCN barrier film and the second gas barrier layer as the SiON barrier film. It was confirmed that the nitrogen contained in the film is formed by the interaction between the layers, so that structural defects between the layers are reduced, and a gas barrier film having a large effect of improving the barrier performance at the time of lamination can be obtained.

<< Electronic device: Preparation of organic EL panel >>
[Production of organic EL panel 1]
(Formation of first electrode layer)
On the first gas barrier layer of the gas barrier film sample 1 produced above, an ITO film (indium tin oxide) having a thickness of 150 nm is formed by sputtering, patterned using a photolithography method, and the first electrode layer Formed. The electrode pattern was formed as a pattern having a light emitting area of 50 mm square.

(Formation of hole transport layer)
On the first electrode layer of the gas barrier film sample 1 on which the first electrode layer is formed, the following coating liquid for forming a hole transport layer is used and an extrusion coater in an environment of 25 ° C. and 50% relative humidity. And a hole transport layer was formed by drying and heat treatment under the following conditions. The hole transport layer forming coating solution was applied under the condition that the layer thickness of the hole transport layer after drying was 50 nm.

Before applying the coating liquid for forming the hole transport layer, a low-pressure mercury lamp having a wavelength of 184.9 nm is used as a cleaning surface modification treatment on both surfaces of the gas barrier film sample 1, and an irradiation intensity of 15 mW / cm. ² , carried out at a distance of 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.

<Preparation of coating solution for hole transport layer formation>
A solution obtained by diluting polyethylene dioxythiophene / polystyrene sulfonate (abbreviation: PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with 65% by mass of pure water and 5% by mass of methanol is used as a coating solution for forming a hole transport layer. Using.

<Drying and heat treatment conditions>
After the hole transport layer forming coating solution is applied on the first electrode layer, the height of the hole transport layer forming surface is 100 mm, the discharge wind speed is 1 m / s, the width wind speed distribution is 5%, and the temperature is 100 ° C. After the drying air was blown to remove the solvent, a back surface heat transfer system heat treatment was performed at a temperature of 150 ° C. using a heat treatment apparatus to form a hole transport layer.

(Formation of light emitting layer)
On the hole transport layer thus formed, the following white light emitting layer forming coating solution was applied using an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form a light emitting layer. Formed. The white light-emitting layer forming coating solution was applied under the condition that the thickness of the light-emitting layer after drying was 40 nm.

<Preparation of white light emitting layer forming coating solution>
As a host material, 1.0 g of the compound HA shown below, 100 mg of the following compound DA as the first dopant material, 0.2 mg of the following compound DB as the second dopant material, As a dopant material 3, 0.2 mg of the following compound DC was dissolved in 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating conditions were as follows: in an atmosphere having a nitrogen gas concentration of 99% by volume or more, the coating temperature was 25 ° C. and the coating speed was 1 m / min.

<Drying and heat treatment conditions>
A white light emitting layer forming coating solution is applied onto the hole transport layer, and then directed toward the film forming surface, with a height of 100 mm, a discharge wind speed of 1 m / s, a width of 5% of a wide wind speed, and a dry wind at a temperature of 60 ° C. After removing the solvent by spraying, heat treatment was subsequently performed at a temperature of 130 ° C. to form a light emitting layer.

(Formation of electron transport layer)
On the formed light emitting layer, the following electron transport layer forming coating solution was applied by an extrusion coater under the following conditions, and then dried and heat-treated under the following conditions to form an electron transport layer. The coating liquid for forming an electron transport layer was applied under the condition that the thickness of the electron transport layer after drying was 30 nm.

<Preparation of electron transport layer forming coating solution>
The coating solution for forming an electron transport layer was prepared by dissolving the following compound EA in 2,2,3,3-tetrafluoro-1-propanol at 0.5% by mass.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% by volume or more, using a coating solution for forming an electron transport layer, a coating temperature of 25 ° C., and a coating speed of 1 m / min.

<Drying and heat treatment conditions>
After the electron transport layer forming coating solution is applied on the light emitting layer, it is directed toward the film formation surface, and the drying air is blown under the conditions of a height of 100 mm, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5% and a temperature of 60 ° C. The solvent was removed by spraying. Next, in the heat treatment section, heat treatment was performed at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer was formed on the formed electron transport layer according to the following method.

The gas barrier film 1 formed up to the electron transport layer was set in a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. The cesium fluoride previously loaded in the tantalum vapor deposition boat in the vacuum chamber was heated to form an electron injection layer having a thickness of 3 nm on the electron transport layer.

(Formation of second electrode)
On the electron injection layer formed as described above, aluminum is used as the second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa, except for the portion that becomes the extraction electrode of the first electrode, and the extraction electrode is provided. As described above, a mask pattern was formed by vapor deposition so that the light emission area was 50 mm square, and a second electrode having a thickness of 100 nm was laminated.

(Cutting)
As described above, the laminated body formed up to the second electrode was again transferred to a nitrogen atmosphere, and cut into a prescribed size using an ultraviolet laser to produce an organic EL element 1.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element 1, and a flexible printed circuit board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12. 5 μm, surface-treated NiAu plating) was connected.

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

(Sealing)
As a sealing member, a 30 μm thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) is laminated with a polyethylene terephthalate (PET) film (12 μm thickness) using a dry lamination adhesive (two-component reaction type urethane adhesive). (Adhesive layer thickness: 1.5 μm) was prepared.

A thermosetting adhesive was uniformly applied to the aluminum surface of the prepared sealing member with a thickness of 20 μm along the adhesive surface (glossy surface) of the aluminum foil using a dispenser to form an adhesive layer.

At this time, as the thermosetting adhesive, an epoxy adhesive mixed with the following constituent materials (A) to (C) was used.

(A) Bisphenol A diglycidyl ether (DGEBA)
(B) Dicyandiamide (DICY)
(C) Epoxy adduct-based curing accelerator A sealing member is closely attached and arranged so as to cover the joint between the take-out electrode and the electrode lead, and as a pressure bonding condition using a pressure roller, a pressure roller temperature is 120 ° C. and a pressure is 0. The organic EL panel 1 having the configuration shown in FIG. 5 was prepared by closely sealing at 5 MPa and a conveyance speed of 0.3 m / min.

The organic EL panel 1 was subjected to an accelerated deterioration process for 400 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90%, and then the flatness was measured using a CNC image measuring device Quick Vision QVH404 (manufactured by Mitutoyo Corporation). The flatness measurement method was performed at 9 points (3 × 3 points in length and width) on the organic EL panel (opposite film surface). As a result, it was determined that the flatness was less than 0.1 mm at any of the nine measurement points, which was a practically preferable characteristic. That is, it was confirmed that the thick gas barrier film used in the organic EL panel was held without causing film curl even after the accelerated deterioration treatment.

This application is based on Japanese Patent Application No. 2013-249444 filed on December 2, 2013, the disclosure content of which is incorporated by reference as a whole.

1 resin base material,
2 first gas barrier layer,
3 second gas barrier layer,
4 Anode (transparent electrode),
5 Organic EL elements (electronic device body),
6 Adhesive layer,
7 Opposite film,
F gas barrier film,
P Organic EL panel (electronic device),
11 Feeding roller,
21, 22, 23, 24 transport rollers,
31, 32 Deposition rollers
41 gas supply pipe,
51 Power source for plasma generation,
61, 62 Magnetic field generator,
71 take-up roller,
A carbon distribution curve,
B silicon distribution curve,
C oxygen distribution curve,
D Nitrogen distribution curve.

Claims

A gas barrier film comprising a resin substrate and a first gas barrier layer formed on at least one surface side of the resin substrate,
The first gas barrier layer contains carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms, the composition continuously changes in the layer thickness direction, and satisfies the following requirements (1) and (2): Gas barrier film;
(1) Of the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer, the first gas barrier layer in the layer thickness direction of the first gas barrier layer Carbon showing the relationship between the distance from the surface and the ratio of the amount of carbon atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”). The distribution curve has at least one extreme value, and an absolute value of a difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more, and the first The distance from the surface of the first gas barrier layer in the layer thickness direction of the gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (“nitrogen atom ratio That at%) ".) In a nitrogen distribution curve showing the relationship between the maximum value of the nitrogen atomic ratio is in the range of 0.5 ~ 10at%,
(2) In the region of 90% or more of the total thickness of the first gas barrier layer, the average atomic ratio of each atom to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms is expressed by the following formula ( It has an order of magnitude relationship represented by A) or (B).
The gas barrier film according to claim 1, further comprising a second gas barrier layer containing a polysilazane modified product on the first gas barrier layer.
The gas barrier film according to claim 2, wherein the second gas barrier layer is obtained by applying an excimer modification treatment to a coating film formed by applying and drying a liquid containing polysilazane.
A method for producing a gas barrier film comprising at least a first gas barrier layer on at least one surface side of a resin substrate,
A step of forming a first gas barrier layer containing a carbon atom, a silicon atom, an oxygen atom, and a nitrogen atom, the composition continuously changing in the layer thickness direction, and satisfying the following requirements (1) and (2): A method for producing a gas barrier film,
(1) The first gas barrier layer in the layer thickness direction of the first gas barrier layer among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy for the first gas barrier layer And the ratio of the amount of carbon atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (referred to as “carbon atom ratio (at%)”). The carbon distribution curve has at least one extreme value, and an absolute value of a difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio is 5 at% or more, The distance from the surface of the first gas barrier layer in the thickness direction of one gas barrier layer and the ratio of the amount of nitrogen atoms to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms (“nitrogen atom ratio In nitrogen distribution curve showing the relationship between the called.) And (at%) ", is in the range maximum value of the nitrogen atom ratio of 0.5 ~ 10at%,
(2) In the region of 90% or more of the total thickness of the first gas barrier layer, the average atomic ratio of each atom to the total amount (100 at%) of carbon atoms, silicon atoms, oxygen atoms and nitrogen atoms is expressed by the following formula ( It has an order of magnitude relationship represented by A) or (B).
The first gas barrier layer is formed by a discharge plasma chemical vapor deposition method using a source gas containing a nitrogen-containing organosilicon compound and an oxygen gas and having a discharge space between rollers to which a magnetic field is applied. The manufacturing method of the gas-barrier film of Claim 4.
The first gas barrier layer is formed by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied, using a source gas containing an organic silicon compound, oxygen gas, and nitrogen gas. The method for producing a gas barrier film according to claim 4.
The method further includes forming a second gas barrier layer by applying a liquid containing polysilazane on the first gas barrier layer, drying to form a coating film, and applying an excimer modification treatment to the coating film. The method for producing a gas barrier film according to any one of claims 4 to 6, wherein:
The method for producing a gas barrier film according to claim 7, wherein the modifying means used for forming the second gas barrier layer is a method of irradiating vacuum ultraviolet light having a wavelength of 200 nm or less.