WO2015163358A1 - Gas barrier film and manufacturing method thereof - Google Patents

Abstract

The purpose of the present invention is to provide a gas barrier film with excellent and highly uniform gas barrier properties. This gas barrier film (1) is characterized in that, of the distribution curves of the constituent elements of the gas barrier film (3) based on the element distribution in the depth direction measured by X-ray photoelectron spectroscopy, the carbon distribution curve shows the relation between the distance from the surface of the gas barrier layer (3) in the layer thickness direction of the gas barrier layer (3) and the ratio (the carbon atomic ratio) of the number of carbon atoms to the total number (100at%) of carbon atoms, silicon atoms and oxygen atoms, and there is a region of the carbon distribution curve that satisfies a specific carbon atomic ratio between a start point (0%) in the position in the layer thickness direction corresponding to the first extreme value nearest to the substrate (2), and the topmost surface (100%) of the gas barrier layer (3).

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. More specifically, the present invention relates to a highly uniform gas barrier film having excellent gas barrier properties and a method for producing the same.

Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used to wrap articles in the fields of food, medicine, etc. Used for applications. By using the gas barrier film, it is possible to prevent deterioration of the article due to gas such as water vapor or oxygen.

In recent years, gas barrier films that prevent permeation of water vapor, oxygen, and the like have been demanded to be applied to electronic devices such as organic electroluminescence (EL) elements and liquid crystal display (LCD) elements. Is being studied. In these electronic devices, a high gas barrier property, for example, a gas barrier property comparable to a glass substrate is required.

For example, a CVD method (Chemical Vapor Deposition) is used as a method for producing a gas barrier film that is more flexible than a glass substrate.

For example, in Patent Document 1, a silicon oxide carbide (SiOC) film formed by a plasma chemical vapor deposition method improves gas barrier properties, flexibility, and impact resistance.
However, the gas barrier film described in Patent Document 1 does not have sufficient gas barrier properties. In particular, when a defect exists in the gas barrier film, a crack is generated by an external force such as bending, and the crack is formed on the entire film. It was difficult to maintain the bending resistance because the gas barrier property easily deteriorated due to the propagation.

Similarly, as a method for producing a gas barrier film that is more flexible than a glass substrate, for example, in Patent Document 2, a gas barrier film whose composition continuously changes in the thickness direction by plasma chemical vapor deposition is used. Manufacturing methods are mentioned.
In this case, the resistance to bending is improved by repeatedly changing the composition, but since the density of the gas barrier performance is extreme, if the dense part in the layer is destroyed at the defect starting point, the gas barrier property of the non-dense part is low. Therefore, the gas permeation points are concentrated at the end.
As a result, local (dot-like) gas permeation cannot be suppressed, and when a device is sealed, a defect called a dark spot that is easily visible is detected in a short period of time.

JP 2011-73430 A Patent 4690041

The present invention has been made in view of the above-mentioned problems and situations, and a problem to be solved is to provide a gas barrier film having high uniformity and excellent gas barrier properties and a method for producing the same.

Particularly, it is to provide a gas barrier film excellent in gas barrier properties and a method for producing the same, which significantly reduces the occurrence of local defects when various electronic devices are sealed.

In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, among the distribution curves of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the gas barrier layer The relationship between the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer and the ratio of the number of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) The carbon distribution curve shown is a specific carbon atom between the position in the layer thickness direction corresponding to the first extreme value on the nearest side of the substrate and the gas barrier layer outermost surface (100%) starting from the position (0%) The present inventors have found that a gas barrier film having a region satisfying the ratio can provide a highly uniform gas barrier film having excellent gas barrier properties and a method for producing the same, and have led to 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 containing a silicon oxide carbide on a substrate and having a gas barrier layer whose composition changes in the layer thickness direction,
Among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer, and carbon The carbon distribution curve showing the relationship with the ratio of the number of carbon atoms to the total number of atoms (100 at%) of atoms, silicon atoms and oxygen atoms (carbon atom ratio) corresponds to the first extreme value on the nearest side of the substrate The region satisfying the requirements defined in the following (1) to (3) exists between the position in the layer thickness direction to be started (0%) and the outermost surface (100%) of the gas barrier layer. Gas barrier film.

(1) The average carbon atom ratio a (at%) in the region of 0% to 20% is
30 (at%) ≦ a ≦ 40 (at%)
Meet.
(2) The average carbon atom ratio c (at%) in the region of 80% or more and 100% or less is
0.1 × a (at%) ≦ c ≦ 0.5 × a (at%)
Meet.
(3) The average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is
0.5 × a (at%) <b <a (at%)
And satisfy
When the extreme value that has at least one extreme value in the same region and the maximum extreme value among the extreme values is the second extreme value, the carbon atom ratio d (at%) of the second extreme value is:
a (at%) ≦ d ≦ 45 (at%)
Meet.

2. The average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is
0.6 × a (at%) ≦ b ≦ 0.8 × a (at%)
The gas barrier film according to item 1, which satisfies the following conditions.

3. A method for producing a gas barrier film according to item 1 or 2, wherein the gas barrier film is produced.
A method for producing a gas barrier film, comprising transporting a substrate a plurality of times between opposing roller electrodes and forming a gas barrier layer having a different carbon atom ratio in the layer thickness direction by plasma CVD.

By the above means of the present invention, it is possible to provide a gas barrier film excellent in gas barrier properties with high uniformity and a method for producing the same.

The expression mechanism / action mechanism of the effect of the present invention is not clear, but is presumed as follows.

In the gas barrier film described in Patent Document 1, the composition of carbon atoms, silicon atoms, and oxygen atoms changes monotonously and continuously in the layer thickness direction. Such a gas barrier film has a problem that the gas barrier property, particularly the gas barrier property for maintaining the performance of the electronic device in a high temperature and high humidity environment, is not sufficient. This is presumably because the atomic composition of carbon atoms, silicon atoms and oxygen atoms changes continuously in the depth direction, and there is little separation between a composition region having a high gas barrier property and a composition region advantageous for flexibility. For this reason, in the gas barrier film described in Patent Document 1, it is necessary to increase the thickness in order to improve the gas barrier property. As a result, the curl becomes large or the gas barrier property is deteriorated with respect to the bending operation. Another adverse effect arises, such as an increase in.

In the gas barrier film described in Patent Document 2, the composition of carbon atoms, silicon atoms, and oxygen atoms repeatedly and continuously changes in the layer thickness direction. By taking this structure, it is easy to improve the durability against the bending operation. However, such a gas barrier film has a plurality of highly organic regions in a partial region in the layer thickness direction, so that the gas barrier property in this region is low, and in particular, the organic EL element is sealed. When the durability performance under high temperature and high humidity environment is seen, gas diffusion from the local defect point of the gas barrier layer becomes remarkable, and as a result, it is called a so-called dark spot, which is a point-like non-light emitting region There was a problem that defects were easily visible.

In the gas barrier film of the present invention, the gas barrier layer has a high carbon content SiOC film region having a low degree of oxidation near the substrate surface, and a low carbon content SiOC film region having a high degree of oxidation on the gas barrier layer surface side. And a high carbon content SiOC film region in a specific intermediate region of the gas barrier layer. By adopting such a configuration, it becomes possible to balance the stress in the film, and to exhibit a highly uniform gas barrier property. Furthermore, even in a high-temperature and high-humidity environment, a high gas barrier can be obtained. It is considered that gas barrier property deterioration after bending and gas diffusion from local defects do not occur.

Sectional drawing which shows an example of the gas barrier film of this invention The graph which shows an example of the carbon distribution curve of the gas barrier layer which concerns on this invention The schematic diagram which shows an example of the manufacturing apparatus used for formation of the gas barrier layer which concerns on this invention Sectional drawing which shows an example of the organic EL element which is an electronic device which used the gas barrier film of this invention as a sealing film

The gas barrier film of the present invention is a distribution curve of each constituent element based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the gas barrier layer, from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer. The carbon distribution curve showing the relationship between the distance between the carbon atoms, the ratio of the number of carbon atoms to the total number of carbon atoms, silicon atoms, and oxygen atoms (100 at%) (carbon atom ratio) A region satisfying a specific carbon atom ratio exists between the position in the layer thickness direction corresponding to the extreme value as a starting point (0%) and the outermost surface (100%) of the gas barrier layer. This feature is a technical feature common to the inventions according to claims 1 to 3.

In the present invention, the average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is 0.5 × a (at%) <b <a (at%). From the point of view
0.6 × a (at%) ≦ b ≦ 0.8 × a (at%)
It is preferable to satisfy.

Moreover, as a manufacturing method of the gas barrier film of this invention, the aspect which forms a gas barrier layer from which a carbon atom ratio differs in a layer thickness direction is conveyed by plasma CVD method by conveying a base material several times between the roller electrodes which oppose. The production method is preferably as a method for producing the gas barrier film of the present invention.

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, “˜” representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.

≪Composition of gas barrier film≫
As shown in FIG. 1, the gas barrier film 1 of the present invention is configured by laminating a gas barrier layer 3 on a substrate 2.
The gas barrier layer 2 contains silicon oxide carbide (SiOC), and its composition changes in the layer thickness direction.

≪Gas barrier layer (3) ≫
The gas barrier layer according to the present invention includes the distance from the surface of the gas barrier layer in the layer thickness direction of the 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. The carbon distribution curve showing the relationship with the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) has at least two extreme values. Furthermore, there is a region that satisfies the requirements defined in the following (1) to (3) in the layer thickness direction.
Hereinafter, it will be described in detail with reference to FIG.

In the present invention, the extreme value means the maximum value of the atomic ratio of the element to the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer.
Here, the maximum value means that the value of the atomic ratio of the element (carbon, silicon or oxygen) changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed.

First, in the gas barrier layer, the position in the layer thickness direction corresponding to the extreme value M1 on the nearest side of the substrate is set as the starting point (0%), and the space between the starting point and the outermost surface of the gas barrier layer is equally divided into 100 ( That is, the outermost surface of the gas barrier layer is defined as 100%.) Region A is in the range of 0% to 20%, region B is in the range of more than 20% and less than 80%, and is in the range of 80% to 100%. Is region C.

(1) In the region A, the average carbon atom ratio a (at%) in the region A is
30 (at%) ≦ a ≦ 40 (at%)
It is characterized by satisfying.
The region A has a high average carbon atom ratio, and thereby the gas barrier property of the gas barrier film can be ensured. When the average carbon atomic ratio a (at%) is lower than 30 at%, good gas barrier properties cannot be expressed. On the other hand, when the average carbon atomic ratio a (at%) is higher than 40 at%, bending or storage at high temperature and high humidity It is difficult to maintain sufficient durability.

(2) In the region C, the average carbon atom ratio c (at%) in the region C is
0.1 × a (at%) ≦ c ≦ 0.5 × a (at%)
It is characterized by satisfying.
Similar to the average carbon atom ratio a (at%) in the region A, when the average carbon atom ratio c (at%) is lower than 0.1 × a (at%), good gas barrier properties are exhibited. On the other hand, if it is higher than 0.5 × a (at%), it is difficult to bend or maintain sufficient durability under high temperature and high humidity storage.

(3) In the region B, the average carbon atom ratio b (at%) in the region B is
0.5 × a (at%) <b <a (at%)
And the carbon atom ratio d (at%) of the extreme value that has at least one extreme value in the same region B and is the maximum of the extreme values is
a (at%) ≦ d ≦ 45 (at%)
It is characterized by satisfying.
In the example shown in FIG. 2, the region B has two extreme values M2 and M3, and of these, the extreme value M2 is an extreme value that is the maximum of the extreme values.
When the average carbon atom ratio b (at%) in the region B is lower than 0.5 × a (at%), or conversely higher than a (at%), the gas barrier property after bending is deteriorated. In addition, the transparency and flatness (curl) of the gas barrier film are liable to occur.
In addition, when the extreme value M2 is lower than a (at%), it is difficult to suppress the occurrence of local defects before and after the bending test, and when it is higher than 45 at%, defects before the bending test are present. Although it can be suppressed, deterioration due to bending increases.
The average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is
0.6 × a (at%) ≦ b ≦ 0.8 × a (at%)
It is preferable to satisfy.

The carbon atom ratio and the average carbon atom ratio in each region can be adjusted by adjusting the supply amount and the ratio of the source gas containing the organosilicon compound and the oxygen gas to be introduced into the discharge space in the plasma chemical vapor deposition method. It can be controlled by adjusting the temperature of the electrode and the amount of electric power applied to generate plasma discharge.
In general, the average carbon atom ratio is increased by reducing the supply ratio of oxygen gas to the raw material gas containing the organosilicon compound, and the average carbon atom ratio is decreased by increasing the electrode temperature and the applied electric energy.

≪X-ray photoelectron spectroscopy≫
Carbon distribution curve (distance (L) from the gas barrier layer surface in the thickness direction of the gas barrier layer and the ratio of carbon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (carbon atom ratio) ), A silicon distribution curve (curve showing the relationship between the distance L and the ratio of silicon atoms to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%) (silicon atom ratio) ) And oxygen distribution curve (curve showing the relationship between the distance L and the ratio of the number of oxygen atoms (oxygen atom ratio) to the total number of carbon atoms, silicon atoms and oxygen atoms (100 at%)) is X-ray photoelectron spectroscopy. By using the X-ray Photoelectron Spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination, Issued sequentially performing surface composition analysis while, it can be produced by so-called XPS depth profile measurement.
A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (at%) of each element and the horizontal axis as the etching time (sputtering time).

In the present invention, the average carbon atom ratio (at%) in each region is a value obtained by averaging values measured at 5 nm intervals by etching in the depth direction by XPS depth profile measurement.

≪Measurement method of gas barrier layer thickness≫
The layer thickness was arbitrarily measured at 10 locations by cross-sectional observation with a transmission electron microscope (TEM), and the average value was taken as the layer thickness of the gas barrier layer.

(TEM image of cross section in the layer thickness direction)
As a cross-sectional TEM observation, the observation sample was subjected to TEM observation after a thin piece was prepared by the following focused ion beam (FIB) processing apparatus.
(FIB processing)
Device: SII SMI2050
Processed ion: Ga (30 kV)
Sample thickness: 100-200 nm
(TEM observation)
Apparatus: JEOL JEM2000FX (acceleration voltage: 200 kV)

≪Gas barrier layer thickness≫
The layer thickness of the gas barrier layer according to the present invention is preferably in the range of 50 to 500 nm, and more preferably in the range of 50 to 300 nm, from the viewpoint of achieving both thinning and gas barrier properties.

≪Water vapor permeability of gas barrier layer≫
The gas barrier layer preferably has gas barrier properties. Here, having a gas barrier property means that only a gas barrier layer is laminated on a substrate, and a water vapor permeability (38 ° C., relative humidity 90) measured using a MOCON water vapor permeability measuring apparatus Aquatran manufactured by MOCON. % RH) is 0.1 g / (m ² · day) or less, preferably 0.01 g / (m ² · day) or less.

≪Method of forming gas barrier layer≫
The gas barrier layer according to the present invention can be formed by a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD), hereinafter also simply referred to as “plasma CVD method”).

Although it does not specifically limit as a plasma CVD method, The plasma CVD method using the plasma CVD method in the atmospheric pressure or the atmospheric pressure described in the international publication 2006/033233, and the plasma CVD apparatus with a counter roller electrode is mentioned. . The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

In particular, using a source gas containing an organic silicon compound and oxygen gas, a discharge plasma chemical vapor deposition method (with a roll-to-roll method) having a discharge space between rollers to which a magnetic field is applied is formed. It is preferable. As described above, by using the discharge plasma chemical vapor deposition method, it becomes possible to easily produce a gas barrier layer having an extreme value and in which the carbon atom ratio in each region is controlled within a certain range. A gas barrier film having an appropriate stress balance can be produced. Furthermore, by using the discharge plasma chemical vapor deposition method, the gas barrier layer can be densified and the gas barrier property can be improved.

Hereinafter, a method for forming a gas barrier layer according to the present invention by a discharge plasma chemical vapor deposition method having a discharge space between rollers applied with a magnetic field using a source gas containing an organosilicon compound and oxygen gas will be described. To do.

When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers. (It is more preferable that the base material here includes a form in which the base material is treated.) And discharge between a pair of film forming rollers to generate plasma.
In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible to form a film on the surface part of the base material existing on the other film, and simultaneously form the film on the surface part of the base material present on the other film forming roller, so that a thin film can be produced efficiently. In addition, the film formation rate can be doubled compared to a normal plasma CVD method that does not use a roller.

Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the oxygen content in the film forming gas is the total amount of the organic silicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount required for complete oxidation.

In addition, the gas barrier film of the present invention preferably has a gas barrier layer formed on the surface of the substrate by a roll-to-roll method from the viewpoint of productivity. An apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and a pair of film forming processes. It is preferable that the apparatus has a configuration capable of discharging between the rollers. For example, when the manufacturing apparatus shown in FIG. 3 is used, the apparatus is manufactured by a roll-to-roll method using the plasma CVD method. It is also possible.

Hereinafter, the method for forming a gas barrier layer according to the present invention will be described in more detail with reference to FIG. FIG. 3 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for manufacturing the gas barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

3 includes a feed roller 12, transport rollers 13 to 18, film forming rollers 19 and 20, a gas supply pipe 21, a plasma generating power source 22, and film forming rollers 19 and 20. Magnetic field generators 23 and 24 and winding rollers 25 installed inside are provided. Further, in such a manufacturing apparatus 10, at least the film forming rollers 19 and 20, the gas supply pipe 21, the plasma generating power source 22, and the magnetic field generating apparatuses 23 and 24 are provided in the film forming (vacuum) chamber 28. Has been placed. Further, in such a manufacturing apparatus 10, the film forming chamber 28 is connected to a vacuum pump (not shown), and the pressure in the film forming chamber 28 can be appropriately adjusted by such a vacuum pump.
The feed roller 12 and the transport roller 13 are disposed in the transport system chamber 27, and the winding roller 25 and the transport roller 18 are disposed in the transport system chamber 29. The transfer system chambers 27 and 29 and the film forming chamber 28 are connected via connecting portions 30 and 31, respectively. For example, the film forming chamber 28 and the transfer system chambers 27 and 29 may be physically separated by providing a vacuum gate valve in the connecting portions 30 and 31. By using the vacuum gate valve, for example, only the film forming chamber 28 can be a vacuum system, and the transfer system chambers 27 and 29 can be in the atmosphere. Further, by physically separating the film forming chamber 28 and the transfer system chambers 27 and 29, it is possible to suppress the transfer system chambers 27 and 29 from being contaminated by particles generated in the film forming chamber 28. .

In such a manufacturing apparatus, each film-forming roller 19 and 20 is a power source for plasma generation so that the pair of film-forming rollers (film-forming rollers 19 and 20) can function as a pair of counter electrodes. 22 is connected. Therefore, in such a manufacturing apparatus 10, it is possible to discharge to the space between the film forming roller 19 and the film forming roller 20 by supplying power from the plasma generating power source 22. Plasma can be generated in the space between the film roller 19 and the film formation roller 20. In addition, when using the film-forming roller 19 and the film-forming roller 20 as electrodes as described above, the material and design may be changed as appropriate so that the film-forming roller 19 and the film-forming roller 20 can also be used as electrodes.
Moreover, in such a manufacturing apparatus 10, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 19 and 20) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 19 and 20), the film forming rate can be doubled as compared with a normal plasma CVD method that does not use a roller.

According to such a manufacturing apparatus 10, the gas barrier layer 3 can be formed on the surface of the base material 2 (here, the base material includes a form in which the base material is treated) by a CVD method. It is possible to deposit a gas barrier layer component on the surface of the substrate 2 on the film forming roller 19 and further deposit a gas barrier layer component on the surface of the substrate 2 also on the film forming roller 20. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate 2.

In the film forming rollers 19 and 20, magnetic field generators 23 and 24 fixed so as not to rotate even when the film forming rollers 19 and 20 rotate are provided, respectively.

The magnetic field generators 23 and 24 provided in the film forming rollers 19 and 20 are respectively a magnetic field generator 23 provided in one film forming roller 19 and a magnetic field generator 24 provided in the other film forming roller 20. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between each other and the magnetic field generators 23 and 24 form a substantially closed magnetic circuit. By providing such magnetic field generators 23 and 24, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surfaces of the film forming rollers 19 and 20, 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 23 and 24 provided on the film forming rollers 19 and 20 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 23 and the other magnetic field generator 24 are It is preferable to arrange the magnetic poles so that the opposing magnetic poles have the same polarity. By providing such magnetic field generators 23 and 24, each of the magnetic field generators 23 and 24 is opposed to the space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force oppose each other. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 2 is excellent in that the gas barrier layer 3 that is a vapor deposition film can be efficiently formed.

The tension on the substrate 2 in each of the film forming rollers 19 and 20 may all be the same, but only the tension in the film forming roller 19 or the film forming roller 20 may be increased. By increasing the tension of the film forming rollers 19 and 20 to the base material 2, the adhesion between the base material 2 and the film forming rollers 19 and 20 is improved, heat exchange is efficiently performed, and film uniformity is improved. There is an advantage that heat wrinkles are also suppressed.

As the film forming rollers 19 and 20, known rollers can be used as appropriate. As such film forming rollers 19 and 20, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rollers 19 and 20 is preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate 2 in a short time. It is preferable because damage to the material 2 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space. Each film-forming roller 19 and 20 may be provided with a nip roll, and by providing the nip roll, the adhesion of the base material 2 to the film-forming rollers 19 and 20 is improved. Thereby, heat exchange is efficiently performed between the base material 2 and the film forming rollers 19 and 20, and there is an advantage that film uniformity is improved and heat wrinkles are suppressed.

In such a manufacturing apparatus 10, the base material 2 is disposed on a pair of film forming rollers (film forming rollers 19 and 20) so that the surfaces of the base material 2 face each other. By disposing the base material 2 in this manner, a pair of film-forming rollers (film-forming rollers 19) is formed when plasma is generated by performing discharge in the facing space between the film-forming roller 19 and the film-forming roller 20. And 20) it is possible to simultaneously form the respective surfaces of the substrate 2 existing between them. That is, according to such a manufacturing apparatus 10, the gas barrier layer component is deposited on the surface of the substrate 2 on the film forming roller 19 by the plasma CVD method, and further the gas barrier layer is formed on the film forming roller 20. Since components can be deposited, a gas barrier layer can be efficiently formed on the surface of the substrate 2.

The substrate width of the substrate 2 may be wider, narrower, or the same as the film forming roller width. By making the substrate width wider than the film forming roller width, the film forming rollers 19 and 20 are not exposed, so that the film forming rollers 19 and 20 can be prevented from being contaminated by particles, the maintainability is improved, and performance is improved. There is an advantage of stabilization. Further, since the base material width is narrower than the film forming roller width, there is an advantage that the effective width of the film to be formed is widened. Similarly, in consideration of the effective width of film formation, the positions of the discharge width (film formation space) on the film forming rollers 19 and 20 and the end of the base material are appropriately adjusted by appropriately selecting the base material width. Can do.

Further, the substrate 2 may be heated before being transported to the film forming chamber 28. The heating temperature is preferably equal to or higher than the glass transition temperature of the substrate. The substrate shrinkage during film formation can be suppressed by heating the substrate and shrinking the substrate in advance.

The substrate temperature during film formation of the substrate 2 is not particularly limited, but is preferably in the range of 30 to 150 ° C. Such a substrate temperature depends on the temperature of the discharge space and the temperature of the film forming rollers 19 and 20. The temperature of the film forming rollers 19 and 20 is preferably within a range of −30 to 100 ° C. In order to adjust to such a roller temperature, the film forming rollers 19 and 20 may be appropriately heated and cooled. .

As the feed roller 12 and the transport rollers 13 to 18 used in the manufacturing apparatus 10, known rollers can be appropriately used. Further, the take-up roller 25 is not particularly limited as long as it can take up the gas barrier film 1 in which the gas barrier layer 3 is formed on the substrate 2, and a known roller is appropriately used. Can do. As the transport rollers 13 to 18, stepped rollers may be used. The stepped roller is a transport roller in which only both ends of the roller are in contact with the base material 2, and for example, a stepped roller described in FIG. 2 of JP-A-2009-256709 can be used. By using a stepped roller, it can be conveyed to the surface of the gas barrier layer in a non-contact manner, and deterioration of the film due to contact can be suppressed. Further, the feed roller 12 and the take-up roller 25 may be a turret type. The turret may be multiaxial with two or more axes, and may have a structure in which only some of the axes can be opened to the atmosphere.

Further, as the gas supply pipe 21 and the vacuum pump, those capable of supplying or discharging the raw material gas at a predetermined speed can be appropriately used.

The gas supply pipe 21 serving as a gas supply means is preferably provided in one of the facing spaces (discharge region, film formation zone) between the film formation roller 19 and the film formation roller 20, and is a vacuum serving as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. In this way, by providing the gas supply pipe 21 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 19 and the film formation roller 20. It is excellent in that the film formation efficiency can be improved.

In FIG. 3, the gas supply pipe 21 is provided on the center line between the film formation roller 19 and the film formation roller 20. However, the present invention is not limited to this. You may shift | deviate to either one side from the centerline between the rollers 20, and you may shift | deviate from the centerline in the left-right direction. By shifting the gas supply pipe 21 from the center line between the film formation roller 19 and the film formation roller 20, the gas supply pipe 21 is closer to one film formation roller and farther from the other film formation roller. The film composition formed on the film forming roller 19 and the film composition formed on the film forming roller 20 become different, and the position of the gas supply pipe 21 may be appropriately shifted when it is desired to change the film quality. Further, the gas supply pipe 21 may be appropriately separated from or closer to the film forming roller on the center line (the arrangement position may be moved on the center line in the vertical direction). There is an advantage that particles can be prevented from adhering to the gas supply pipe 21 by moving the gas supply pipe 21 away from the center axis of the film forming roller and separating the gas supply pipe 21 from the discharge space. There is an advantage that the film forming rate can be improved by bringing the film closer to the discharge space on the central axis of the film forming roller.
In FIG. 3, there is one gas supply pipe 21, but there may be a plurality of gas supply pipes 21, and different supply gases may be discharged from each nozzle.

Further, as the plasma generating power source 22, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 22 for generating plasma supplies power to the film forming roller 19 and the film forming roller 20 connected thereto, and makes it possible to use them as a counter electrode for discharging. As such a plasma generation power source 22, since it is possible to perform plasma CVD more efficiently, a power source (AC power source or the like) that can alternately reverse the polarity of a pair of film forming rollers is used. It is preferable to use it.
Further, such a plasma generating power source 22 is preferably capable of performing plasma CVD more efficiently, so that the applied power is preferably in the range of 100 W to 20 kW, and in the range of 100 W to 10 kW. And the AC frequency is preferably in the range of 50 Hz to 13.56 MHz, and more preferably in the range of 50 Hz to 500 kHz.
Further, from the viewpoint of stabilizing the plasma process, a high frequency power source in which both the high frequency current wave and the voltage wave are sine waves may be used.

In FIG. 3, power is supplied to both the film forming rollers 19 and 20 by one plasma generating power source 22 (both film forming roller power supply), but is not limited to such a form. The film roller may be supplied with power (one-side film formation roller power supply) and the other film formation roller may be grounded.
Moreover, as a power feeding method to the film forming roller, roller one-end power feeding from only one of the roller ends may be used, or roller both-end power feeding from both ends of the roller may be used. In the case of supplying a high frequency band, it is possible to supply both ends of the roller because uniform supply is possible.
Further, as a feeding method, two-frequency feeding may be performed in which different frequencies are applied, and one film-forming roller and the other film-forming roller may be applied even when two different frequencies are applied to one film-forming roller. A different frequency may be applied. By such two-frequency power feeding, the plasma density can be increased and the film formation rate can be improved.

Although not shown in FIG. 3, the plasma emission intensity in the discharge space is monitored from the outside. If the desired emission intensity is not obtained, the distance between the magnetic fields (distance between the opposing rollers), the magnetic field intensity, and the applied power of the power source In addition, a feedback circuit that adjusts the power supply frequency, the amount of supplied gas, and the like to obtain a desired plasma emission intensity may be provided. By having such a feedback circuit, film formation / production can be stabilized.

Also, as the magnetic field generators 23 and 24, known magnetic field generators can be used as appropriate. Furthermore, as the base material 2, in addition to the base material used in the present invention, a material in which the gas barrier layer 3 is previously formed can be used. As described above, the thickness of the gas barrier layer 3 can be increased by using the substrate 2 in which the gas barrier layer 3 is previously formed.

For example, a gas barrier layer containing carbon atoms, silicon atoms, and oxygen atoms can be formed using the manufacturing apparatus 10 shown in FIG. At this time, the method for controlling the atomic ratio of the carbon atom content of the gas barrier layer is not particularly limited, but the ratio of raw materials used (supply ratio of oxygen and HMDSO described later), power, pressure, etc. By controlling, the atomic ratio of the carbon atom content can be controlled.

The pressure in the vacuum chamber (degree of vacuum) can be appropriately adjusted according to the type of the raw material gas, and is preferably about 0.5 to 50 Pa, and preferably within the range of 0.5 to 10 Pa. More preferred.

Further, in such a plasma CVD method, an electrode drum (in this embodiment, the film forming roller 19) connected to the plasma generating power source 22 for discharging between the film forming roller 19 and the film forming roller 20. The electric power to be applied can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but is 0.1 to 10 kW. It is preferable to be within the range. If the applied power is 0.1 kW (100 W) or more, the generation of particles can be sufficiently suppressed. It can suppress that the temperature of the base-material surface at the time rises. Therefore, it is excellent in that wrinkles can be prevented from occurring during film formation without causing the substrate to lose heat.

The conveyance speed (line speed) of the substrate 2 can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. A range of 0.5 to 100 m / min is more preferable.

As the film forming gas (raw material gas or the like) supplied from the gas supply pipe 21 to the facing space, a raw material gas, a reactive gas, a carrier gas, or a discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the gas barrier layer 3 can be appropriately selected and used according to the material of the gas barrier layer 3 to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the resulting gas barrier layer. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. Especially, since it can adjust to the film | membrane composition of this embodiment easily, it is preferable that an organosilicon compound is included as source gas.

Further, as the film forming gas, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide can be appropriately selected and used. Since the gas barrier layer 3 of the present embodiment contains oxygen, for example, oxygen and ozone can be used as the reactive gas, and oxygen is preferably used from the viewpoint of simplicity. In addition, a reactive gas for forming a nitride may be used. For example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the film forming chamber 28. Further, as a 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, rare gases such as helium, argon, neon, xenon, hydrogen, and nitrogen can be used.

When such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is the amount of the reactive gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessively higher than the ratio. It is excellent in that excellent gas barrier properties and bending resistance can be obtained by the formed gas barrier layer 3 by not excessively increasing the ratio of the reaction gas. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

Hereinafter, a film containing hexamethyldisiloxane (organic polysilazane, HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is used as a film forming gas, and silicon -Taking the case of forming an oxygen-based thin film as an example, the preferred ratio of the source gas to the reaction gas in the film-forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reactive gas is reacted by plasma CVD to form a silicon-oxygen-based system When the thin film is produced, a reaction represented by the following reaction formula (1) occurs by the film forming gas, and silicon dioxide is generated.

In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, a uniform silicon dioxide film is formed when oxygen is contained in the film forming gas in an amount of 12 moles or more per mole of hexamethyldisiloxane and a uniform silicon dioxide film is formed (a carbon distribution curve exists). Therefore, it becomes impossible to form the gas barrier layer 3 containing carbon. Therefore, when forming the gas barrier layer according to the present invention, the stoichiometric amount of oxygen is set to 1 mole of hexamethyldisiloxane so that the reaction of the reaction formula (1) does not proceed completely. The ratio is preferably less than 12 moles.
In the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas Even if the (flow rate) is 12 times the molar amount (flow rate) of the raw material hexamethyldisiloxane (flow rate), the reaction cannot actually proceed completely, and the oxygen content is reduced. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane.)
Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane as a raw material is preferably a stoichiometric ratio of 12 times or less, more preferably 10 times or less.

By containing hexamethyldisiloxane and oxygen at such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer. From the viewpoint of use as a flexible substrate for electronic devices that require transparency such as organic EL elements and solar cells, the mole of oxygen relative to the mole amount (flow rate) of hexamethyldisiloxane in the deposition gas. The lower limit of the amount (flow rate) is preferably more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane, more preferably more than 0.5 times.

In the present embodiment, the maximum atomic ratio of the oxygen atom content to the total number of carbon atoms, silicon atoms, and oxygen atoms in the region near the base material of the gas barrier layer is relatively within a range of 30 to 45 at%. By controlling to a low value, the composition ratio of carbon atoms is relatively increased to form a dense region.
For this reason, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas when forming the film forming gas is preferably in the range of 1 to 10 times. More preferably, it is in the range of 1 to 6 times, and more preferably in the range of 1 to 3 times.

Using the manufacturing apparatus 10 shown in FIG. 3, discharge is generated between a pair of film forming rollers (film forming rollers 19 and 20) while supplying a film forming gas (such as a source gas) into the film forming chamber 28. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the first film-forming layer is formed on the surface of the base material 2 on the film-forming roller 19 and on the surface of the base material 2 on the film-forming roller 20. Is formed by plasma CVD. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 19 and 20, and the plasma is converged on the magnetic field. By repeating this process with the second film-forming layer and the third film-forming layer in which one or more of the aforementioned conditions are changed, the composition of each constituent atom changes continuously in the layer thickness direction. It will be.

Specifically, in the carbon distribution curve, the silicon distribution curve, and the oxygen distribution curve, when the substrate 2 passes through the point A of the film forming roller 19 and the point B of the film forming roller 20, the maximum value of the carbon distribution curve The minimum value of the oxygen distribution curve is formed. On the other hand, when the substrate 2 passes through the points C1 and C2 of the film forming roller 19 and the points C3 and C4 of the film forming roller 20, the minimum value of the carbon distribution curve and the maximum value of the oxygen distribution curve are obtained. It is formed.

The existence of such an extreme value indicates that the abundance ratio of carbon atoms and oxygen atoms in the film is a non-uniform layer, and that there is a part with a low density with few carbon atoms. Thus, the entire layer has a flexible structure, and durability against bending is improved.

Also, the distance between the extreme values of the gas barrier layer (the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon / oxygen distribution curve and the extreme value adjacent to the extreme value ( The absolute value of the difference of L) can be adjusted by the rotation speed of the film forming rollers 19 and 20 (conveying speed of the substrate 2). In such film formation, the base material 2 is transported by the feed roller 12 and the film formation roller 19, respectively, so that the film is formed on the surface of the base material 2 by a roll-to-roll continuous film formation process. Then, the gas barrier layer 3 is formed.

As described above, as a more preferable aspect of the present embodiment, the gas barrier layer according to the present invention is formed by a plasma CVD method using a plasma CVD apparatus (roll-to-roll method) having a counter roller electrode shown in FIG. Preferably, the film is formed a plurality of times while changing the conditions. This is excellent in flexibility (flexibility), high gas barrier property under high temperature and high humidity, and mechanical strength when mass-produced using a plasma CVD apparatus (roll to roll method) having a counter roller electrode. This is because, in particular, a gas barrier layer with few defects that reduce durability and gas barrier properties during conveyance from roll to roll can be efficiently produced. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film that is required for durability against temperature changes used in solar cells, electronic parts, and the like.

≪Base material (2) ≫
A plastic film is used as the base material of the gas barrier film of the present invention. The plastic film used is not particularly limited in material, thickness and the like as long as it can hold the gas barrier layer, and can be appropriately selected according to the purpose of use.
Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide resin. , Cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin, alicyclic modification Examples include films of thermoplastic resins such as polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

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

In addition, the base material using the above-described resins or the like may be an unstretched film or a stretched film.

The base material can be manufactured by a conventionally known general method.

Various treatments known for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, lamination of smooth layers, etc., as required, on both surfaces of the substrate, at least the side where the gas barrier layer is provided Can be combined.

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

≪Smooth layer≫
The gas barrier film of the present invention may have a smooth layer on the surface of the substrate having the gas barrier layer. The smooth layer is used to flatten the rough surface of the substrate where protrusions are present, or to fill the unevenness and pinholes generated in the gas barrier layer with the protrusions present on the resin substrate. Provided. As the constituent material, forming method, surface roughness, layer thickness and the like of the smooth layer, materials, methods and the like disclosed in paragraphs 0233 to 0248 of JP2013-52561A are appropriately employed.

≪Bleed-out prevention layer≫
The gas barrier film of the present invention can further have a bleed-out preventing layer. The bleed-out prevention layer is used for the purpose of suppressing a phenomenon that, when a film having a smooth layer is heated, unreacted oligomers migrate from the resin base material to the surface and contaminate the contact surface. It is provided on the opposite surface of the substrate. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function. As the constituent material, formation method, layer thickness, and the like of the bleed-out prevention layer, the materials, methods, and the like disclosed in paragraphs 0249 to 0262 of JP2013-52561A are appropriately employed.

≪Electronic device≫
The gas barrier film of the present invention as described above has excellent gas barrier properties, transparency, and flexibility. For this reason, the gas barrier film of this invention is a gas barrier film used for electronic devices, such as a photoelectric conversion element (solar cell element), an organic EL element, and a liquid crystal display element, and an electronic device using this, an electronic device, etc. It can be used for various purposes such as packaging.

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

Hereinafter, an organic EL element will be described as an example.

≪Organic EL element≫
An example of the organic EL element which is an electronic device using the gas barrier film 1 of the present invention as a sealing film is shown in FIG.
As shown in FIG. 4, the organic EL element 9 is formed on the gas barrier film 1, the transparent electrode 4 such as ITO formed on the gas barrier film 1, and the transparent electrode 4. The organic EL element main body 5 and an opposing film 7 disposed via an adhesive layer 6 so as to cover the organic EL element main body 5 are provided. It can be said that the transparent electrode 4 forms a part of the organic EL element body 5.
A transparent electrode 4 and an organic EL element body 5 are formed on the surface of the gas barrier film 1 where the gas barrier layer 3 is formed. The counter film 7 may be a gas barrier film of the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used for the counter film 7, the surface on which the gas barrier layer is formed may be attached to the organic EL element body 5 with the adhesive layer 6.

Examples of constituent layers of the organic EL element body 5 (anode, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, cathode, etc.) and methods for producing them are disclosed in, for example, JP-A-2014-045101. Reference can be made to those described in paragraphs [0110] to [0159] of the publication.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

<< Production of gas barrier films 1-20 >>
(Preparation of resin base material)
As a sheet roll-shaped resin base material, a polyethylene terephthalate film having a thickness of 100 μm, which is a thermoplastic resin support and easily bonded on both sides (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET). Was used.

(Formation of anchor coat layer)
Using a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 manufactured by JSR Corporation on one easy-adhesive surface side of the resin base material, a wire bar is formed so that the layer thickness after drying becomes 3 μm. Then, the coating was dried at 80 ° C. for 3 minutes as a drying condition. Next, using a high-pressure mercury lamp in an air atmosphere, curing was performed under curing conditions: 1.0 J / cm ² to form an anchor coat layer.

(Formation of bleed-out prevention layer)
On the other easy-adhesive surface side of the resin base material, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7535 manufactured by JSR Corporation is used so that the layer thickness after drying becomes 3 μm. After coating at 80 ° C. for 3 minutes, the coating was cured at 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere to form a bleed-out prevention layer. After forming this bleed-out prevention layer, it was used as a resin substrate that was conditioned and stored for 96 hours in an environment of 35 ° C. under a reduced pressure of 5 Pa.

(Formation of gas barrier layer: Roller CVD method)
Using the inter-roller discharge plasma CVD apparatus to which the magnetic field shown in FIG. 3 is applied (hereinafter, this method is referred to as “roller CVD method”), the surface of the resin substrate on which the bleed-out prevention layer is formed contacts the film forming roller. In this way, the resin substrate is mounted on the apparatus, and among the following film formation conditions (plasma CVD conditions), the source gas, oxygen gas, the degree of vacuum in the vacuum chamber, and the power applied from the plasma generation power source are described. By changing the carbon atom ratio within a range of 2 and combining them a plurality of times, a film was formed on the anchor coat layer so as to have a final layer thickness of 160 nm, and this was used as a gas barrier layer. In this example, the film formation was repeated four times to form gas barrier layers having different carbon atom ratios in the layer thickness direction.
In order to increase the carbon atom ratio, adjustment is performed mainly by increasing the supply amount of HMDSO in all the supply gases or decreasing the supply amount of oxygen gas, and the degree of vacuum in the vacuum chamber is adjusted to adjust the layer thickness. Increased or decreased.

<Plasma CVD conditions>
Feed rate of raw material gas (hexamethyldisiloxane (HMDSO)): 100 to 400 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ₂ ): 400 to 2500 sccm
Degree of vacuum in the vacuum chamber: 1.5 to 3.0 Pa
Applied power from the power source for plasma generation: 1.0 to 4.0 kW
Frequency of power source for plasma generation: 70 kHz
Resin substrate transport speed: 12 m / min

(Measurement of element distribution profile)
The gas barrier layer thus formed was subjected to XPS depth profile measurement under the following conditions to obtain a carbon distribution curve, a silicon distribution curve, and an oxygen distribution curve with respect to the distance from the surface of the thin film layer in the layer thickness direction.

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 its size: 800 μm × 400 μm oval

From the carbon distribution curve, silicon distribution curve, and oxygen distribution curve in the whole layer region measured as described above, the presence or absence of a continuous change region and the presence or absence of an extreme value in each elemental composition were observed.
As a result, it was confirmed that the carbon atom ratio in the gas barrier layer continuously changed in the depth direction while having a plurality of extreme values.

≪Evaluation of gas barrier film≫
<Evaluation of gas barrier properties>
(1) Measurement of water vapor transmission rate (WVTR) before bending treatment About each produced gas barrier film, the water vapor transmission rate in 38 degreeC and 90% RH is measured using MOCON water vapor transmission rate measuring apparatus Aquatran made from MOCON. The gas barrier properties were evaluated according to the following evaluation rank.
The evaluation results are shown in Table 1.

5: Less than 0.005 g / (m ² · day) 4: 0.005 g / (m ² · day) or more and less than 0.010 g / (m ² · day) 3: 0.010 g / (m ² · day) or more 0.100g ^/ (m 2 · day) under a is ^{2: 0.100g / (m 2 ·} day) or more 0.500g ^/ (m 2 · day) under a is 1: 0.500 g / ( m ² · day) or more

(2) Measurement of water vapor permeability after bending treatment (durability evaluation)
About each produced gas barrier film, after giving the following bending process, the water-vapor permeability in 38 degreeC and 90% RH was measured, and gas barrier property was evaluated according to the same evaluation rank as the above.
The evaluation results are shown in Table 1.

(Bending treatment)
As the bending treatment, each of the produced gas barrier films was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm.

<Detection of defects (corrosion points)>
(1) Detection of defects (corrosion points) before bending treatment (production of water vapor barrier property evaluation cell)
Use a vacuum vapor deposition device (JEOL Ltd., vacuum vapor deposition device JEE-400) on the gas barrier layer surface (outermost surface) of each gas barrier film that was produced. (Except squares) were masked and metal calcium was deposited. Thereafter, the mask was removed in a vacuum state, and aluminum was deposited from another metal deposition source on the calcium deposition surface. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

The obtained sample (evaluation cell) sealed on both sides was stored at 60 ° C. and 90% RH under high temperature and high humidity for 120 hours, and then the corrosion point newly grown from the initial state of the Ca deposited layer was examined using an optical microscope. And observed according to the following evaluation rank.
The evaluation results are shown in Table 1.

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 Ca corrosion point having a diameter exceeding 100 μm was generated even after 1000 hours.

The number of Ca corrosion points grown with a diameter of more than 100 μm per 25 cm ^{2 of the} Ca deposition surface is
5: 0 or 1 location 4: 2 or more and 4 or less locations 3: 5 or more locations but 9 or less locations 2: 10 or more locations but 30 or less locations 1:30 locations Or has developed into a sheet of corrosion where the corrosion points are connected

(2) Detection of defects (corrosion points) after bending treatment (durability evaluation)
About each produced gas barrier film, after giving the following bending process, the cell for evaluation was produced like the above, and it evaluated according to the same evaluation rank as the above.
The evaluation results are shown in Table 1.

(Bending treatment)
As the bending treatment, each of the produced gas barrier films was repeatedly bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm.

From the above results, the gas barrier film of the present invention has a lower water vapor permeability and fewer local defects than the gas barrier film of the comparative example. Further, it can be seen that the gas barrier property after bending is small and the durability is high.

The present invention can be particularly suitably used for providing a gas barrier film having high uniformity and excellent gas barrier properties and a method for producing the same.

DESCRIPTION OF SYMBOLS 1 Gas barrier film 2 Base material 3 Gas barrier layer 4 Transparent electrode 5 Organic EL element main-body part 6 Adhesive layer 7 Opposite film 9 Organic EL element 10 Manufacturing apparatus 12 Delivery roller 13-18 Conveyance roller 19, 20 Film-forming roller 21 Gas supply pipe 22 Plasma generation power source 23, 24 Magnetic field generator 25 Winding roller,
27, 29 Transport system chamber 28 Deposition chamber 30, 31 Connecting part A to C Region M1 to M3 Extreme value

Claims (3)

1. A gas barrier film containing a silicon oxide carbide on a substrate and having a gas barrier layer whose composition changes in the layer thickness direction,
   Among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy of the gas barrier layer, the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer, and carbon The carbon distribution curve showing the relationship with the ratio of the number of carbon atoms to the total number of atoms (100 at%) of atoms, silicon atoms and oxygen atoms (carbon atom ratio) corresponds to the first extreme value on the nearest side of the substrate The region satisfying the requirements defined in the following (1) to (3) exists between the position in the layer thickness direction to be started (0%) and the outermost surface (100%) of the gas barrier layer. Gas barrier film.
   (1) The average carbon atom ratio a (at%) in the region of 0% to 20% is
   30 (at%) ≦ a ≦ 40 (at%)
   Meet.
   (2) The average carbon atom ratio c (at%) in the region of 80% or more and 100% or less is
   0.1 × a (at%) ≦ c ≦ 0.5 × a (at%)
   Meet.
   (3) The average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is
   0.5 × a (at%) <b <a (at%)
   And satisfy
   When the extreme value that has at least one extreme value in the same region and the maximum extreme value among the extreme values is the second extreme value, the carbon atom ratio d (at%) of the second extreme value is:
   a (at%) ≦ d ≦ 45 (at%)
   Meet.
2. The average carbon atom ratio b (at%) in the region of more than 20% and less than 80% is
   0.6 × a (at%) ≦ b ≦ 0.8 × a (at%)
   The gas barrier film according to claim 1, wherein:
3. A method for producing a gas barrier film according to claim 1 or 2, wherein the gas barrier film is produced.
   A method for producing a gas barrier film, comprising transporting a substrate a plurality of times between opposing roller electrodes and forming a gas barrier layer having a different carbon atom ratio in the layer thickness direction by plasma CVD.

Images