JPWO2018168671A1 - Gas barrier film, gas barrier film, method of manufacturing gas barrier film, and method of manufacturing gas barrier film - Google Patents

Abstract

When the composition is represented by SiOxCy, A (x = 0.8, y = 0.8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E (x = 0.8, y = 0.55) High gas barrier property and transparency having a composition existing in a region surrounded by five points in a thickness direction in a range of 20 nm or more and 1000 nm or less and an arithmetic average roughness (Ra) of 2.0 nm or less. Is produced.

Description

  The present invention relates to a gas barrier film, a gas barrier film provided with a gas barrier film, a method for manufacturing a gas barrier film, and a method for manufacturing a gas barrier film provided with a gas barrier film.

  BACKGROUND ART Light and highly flexible gas barrier films are used for sealing electronic devices such as organic EL (Electro Luminescence) elements, liquid crystal display elements, and solar cells. The gas barrier film generally has a gas barrier film on a resin base film, and the gas barrier film can prevent gas such as water and oxygen in the air from entering.

  As a gas barrier film, in order to enhance gas barrier properties, a silicon (Si) atom, an oxygen (O) atom, and a carbon (C) atom are formed by a plasma chemical vapor deposition method using hexamethyldisiloxane (HMDSO) or the like as a raw material. There has been proposed formation of a gas barrier film in which the atomic composition ratio of atoms is adjusted to a specific range (for example, see Patent Documents 1 and 2).

  In addition, in order to enhance the utility to electronic devices, it is required to enhance the transparency of the gas barrier film. For example, it has been proposed to increase the transparency of a gas barrier film by forming a silicon oxide (SiOx) film as a gas barrier film and adjusting the ratio x of O atoms to Si atoms to around 2.0 (for example, And Patent Document 3).

Japanese Patent No. 4464155 JP 2013-67607 A JP 2009-101548 A

  However, in a configuration in which the transparency x is adjusted by adjusting the ratio x of O atoms, the gas barrier property is reduced. For this reason, in the configuration of the gas barrier film described above, both high gas barrier properties and high transparency cannot be achieved.

  In order to solve the above-described problems, the present invention provides a gas barrier film, a gas barrier film, a method for manufacturing a gas barrier film, and a method for manufacturing a gas barrier film, which can realize high gas barrier properties and high transparency.

The gas barrier film of the present invention is a chemical vapor deposition film containing silicon, oxygen, and carbon. When the composition is expressed by SiOxCy, A (x = 0.8, y = 0.8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0) and E (x = 0.8, y = 0.55) in a region surrounded by five points in the thickness direction in a range of 20 nm or more and 1000 nm or less, The arithmetic average roughness (Ra) is 2.0 nm or less.
Further, the gas barrier film of the present invention includes the above gas barrier film formed on a substrate.
It is characterized by doing.

Further, the method of manufacturing a gas barrier film of the present invention forms a gas barrier film containing silicon, oxygen, and carbon using a chemical vapor deposition method, and in forming the gas barrier film, when the composition of the gas barrier film is represented by SiOxCy, A (x = 0.8, y = 0.8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E (x = 0.8, y = 0.55) The composition present is controlled so as to have a thickness in the range of 20 nm or more and 1000 nm or less, and the arithmetic average roughness (Ra) of the gas barrier film surface is formed to 2.0 nm or less.
In the method for producing a gas barrier film of the present invention, a gas barrier film is formed on a substrate by the above method.

  According to the present invention, it is possible to provide a gas barrier film, a gas barrier film, a method for producing a gas barrier film, and a method for producing a gas barrier film, which can realize high gas barrier properties and high transparency.

It is the figure which represented the structure of SiOxCy composition on the plane. It is a diagram representing a crystal structure of SiO _2. It is a figure showing the crystal structure of SiC. FIG. 3 is a diagram showing orthogonal coordinates in which the horizontal axis is x and the vertical axis is y in a SiOxCy composition. It is a figure which shows the range of five points of ABCDE of (x, y) in a SiOxCy composition. SiOxCy in the composition (x, y) is a diagram showing the range of 5 points _{A 1 B} 1 CDE 1 of. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 8 is a diagram showing (x, y) coordinates of each thickness of the SiOxCy composition in the graph shown in FIG. 7. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 10 is a diagram showing (x, y) coordinates of each thickness of the SiOxCy composition in the graph shown in FIG. 9. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 12 is a diagram showing (x, y) coordinates for each thickness of the SiOxCy composition in the graph shown in FIG. 11. 5 is an image in which three-dimensional surface roughness conversion data of a gas barrier film is displayed as a histogram. 5 is an image in which three-dimensional surface roughness conversion data of a gas barrier film is displayed as a histogram. 5 is an image in which three-dimensional surface roughness conversion data of a gas barrier film is displayed as a histogram. It is a schematic diagram which shows an example of a discharge plasma CVD apparatus between rollers. It is a figure showing the schematic structure of a gas barrier film. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 19 is a diagram showing (x, y) coordinates for each thickness of the SiOxCy composition in the graph shown in FIG. 18. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 21 is a diagram showing (x, y) coordinates for each thickness of the SiOxCy composition in the graph shown in FIG. 20. It is a figure which shows an example of the graph of the measurement of the XPS depth profile in a SiOxCy composition. FIG. 23 is a diagram showing (x, y) coordinates of each thickness of the SiOxCy composition in the graph shown in FIG. 22.

Hereinafter, examples of embodiments for carrying out the present invention will be described, but the present invention is not limited to the following examples.
The description will be made in the following order.
1. 1. Outline of gas barrier film 2. Gas barrier film 3. Manufacturing method of gas barrier film Gas barrier film and method for producing gas barrier film

<1. Overview of gas barrier film>
Prior to description of a specific embodiment of the gas barrier film, an outline of the gas barrier film will be described.

  The gas barrier film contains at least a silicon (Si) atom, an oxygen (O) atom and a carbon (C) atom, and can have a composition represented by SiOxCy. In the gas barrier film of the SiOxCy composition, the value of x is expressed as the content of oxygen to silicon (O / Si: oxygen ratio), and the value of y is expressed as the content of carbon to silicon (C / Si: carbon ratio). You.

  Such a gas barrier film having a SiOxCy composition is prepared by reacting an organic silicon compound having a Si—C skeleton with oxygen using a chemical vapor deposition (CVD) film, or adding an oxygen to an organic silicon compound having a Si—O skeleton. , Carbon dioxide, carbon monoxide, nitrogen dioxide, etc., to form a silicon oxycarbide (SiOC) film. Note that a gas barrier film further containing nitrogen (N) atoms may be formed by supplying a gas such as nitrogen or ammonia during the film formation and nitriding.

The gas barrier property of a gas barrier film having a SiOxCy composition formed by CVD film has a water vapor permeability of 0.1 [g measured at a temperature of 38 ° C. and a humidity of 100% RH by a MOCON water vapor permeability measuring device Aquatran (manufactured by MOCON). / (M ² · 24h)] or less, and preferably 1 × 10 ⁻³ (g / m ² / day) or less.

The thickness of the gas barrier film is not particularly limited, but is preferably in the range of 5 to 1000 nm, more preferably in the range of 20 to 500 nm, and particularly preferably in the range of 40 to 300 nm. When the thickness of the gas barrier film is within the range, a gas barrier film having excellent gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties and having little influence on optical characteristics can be obtained. Also, good gas barrier properties can be obtained even when the gas barrier film is bent. The thickness of the gas barrier film, in XPS analysis to be described later, it is determined by the SiO ₂ equivalent.

The light absorption of the gas barrier film formed by CVD is preferably 10% or less for light having a wavelength of 450 nm. When the absorptance of light having a wavelength of 450 nm is 10% or less, a gas barrier film with low absorption in the visible light region and high transparency can be realized. The light absorptance of the gas barrier film is calculated from, for example, the transmittance A (%) and the reflectance B (%) of light having a wavelength of 450 nm measured using a spectrophotometer CM-3600d manufactured by Konica Minolta. It can be obtained using the following equation.
[Absorptance at 450 nm = 100- (transmittance A (%) of 450 nm light + reflectance B (%) of 450 nm light]]

A gas barrier film having a SiOxCy composition formed by a conventional chemical vapor deposition (CVD) film is made of a material having less than 1 oxygen atom and more than 2 carbon atoms per 1 silicon atom, such as hexamethyldisiloxane (HMDSO). Have been made. The CVD film SiOxCy composition in is as shown in Figure 1 to represent the structure on a plane, a part of the O from the structure of SiO ₂ is considered to have a structure obtained by replacing the CH _2. Furthermore, CVD film SiOxCy composition was HMDSO as a raw material, and Si-CH _3, considered to be a structure of Si-OH.

On the other hand, the original SiO ₂ has a crystal structure as shown in FIG. 2, and the SiC has a crystal structure as shown in FIG. Compared to the structure of SiO ₂ or SiC shown in FIGS. 2 and 3, the CVD film of the SiOxCy composition shown in FIG. 1 using HMDSO as a raw material has a dense structure due to the interposition of CH ₂ between Si—O. It is thought that there is no.

  In addition, a CVD film having a SiOxCy composition using HMDSO as a raw material has a good water vapor barrier property when the carbon ratio y is in the range of 0.8 or more. In the range where the carbon ratio y is less than 0.8, that is, in the composition range where the carbon ratio y is low and the oxygen ratio x is high, the abundance of Si—OH increases, and the gap containing the hydrophilic group due to (—OH) is included. Are easily formed. Therefore, when the carbon ratio y is less than 0.8, a water vapor path is easily formed by the hydrophilic group, and the barrier property of the CVD film having the SiOxCy composition is considered to be reduced. Therefore, in order to enhance the barrier property in the CVD film of the SiOxCy composition, the carbon ratio y is set to a range of 0.8 or more, that is, a composition range in which the carbon ratio y is high and the oxygen ratio x is low, Needs to be reduced.

  On the other hand, a CVD film having a SiOxCy composition using HMDSO as a raw material has a problem that as the carbon ratio y increases, the absorption in the visible light region increases and the film becomes yellowish. As described above, it has been difficult to achieve both good barrier properties and good optical characteristics in a conventional CVD film having a SiOxCy composition using HMDSO as a raw material.

  On the other hand, in the present embodiment, in order to achieve both good water vapor barrier properties and good optical characteristics, a raw material having a composition different from that of HMDSO and oxygen are used, and further, CVD film forming conditions (oxygen ratio, By appropriately adjusting the power and the like, a gas barrier film having a SiOxCy composition is formed by CVD film formation. Thereby, in the SiOxCy composition of the CVD film, the oxygen ratio x and the carbon ratio y are set in a predetermined range, and both good barrier properties and good optical characteristics can be realized.

  Specifically, an organosilicon compound in which O atoms are 1 with respect to 1 Si atom is used as a CVD raw material. Further, as a CVD raw material, it is preferable to use an organosilicon compound having less than 2 C atoms per 1 Si atom, and more preferably an organosilicon compound having 1 or less C atoms. Further, it is preferable to use an organosilicon compound having a Si—H bond as a CVD raw material.

  Examples of the organosilicon compound in which the number of O atoms is 1 and the number of C atoms is less than 2 with respect to the above Si atom 1 include, for example, cyclic siloxane. As the cyclic siloxane which is preferable as the CVD raw material, the number of Si is preferably 3 or more and 8 or less, more preferably 4 or more and 6 or less. Specific examples of such a cyclic siloxane include tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane (Hepta-MCTS), pentamethylcyclopentasiloxane (PMCPS), and hexamethyl Cyclohexasiloxane (HMCHS).

The total of the oxygen ratio x and the carbon ratio y is in the range of [x + y ≦ 2] by forming the CVD film of the SiOxCy composition using the cyclic siloxane as a raw material under a specific condition. This is not only a structure in which O is replaced by CH ₂ from the structure of SiO ₂ shown in FIG. 1, that is, a structure in which two Sis are bonded to C, but also a structure in which three or four Sis are bonded to C. It is considered to have a structure. Note that, from the characteristics of CVD film formation, it can be assumed that Si-H having high reactivity does not remain. Therefore, CVD film SiOxCy composition has a cyclic siloxane as a raw material, since the Si-C mediated with CH ₂ between Si-O, CH ₂ interposed between Si-O is reduced. As a result, it is considered that the CVD film having the SiOxCy composition using the cyclic siloxane as a raw material has a more dense structure than the CVD film having the SiOxCy composition using the HMDSO as the raw material.

FIG. 4 shows orthogonal coordinates in the SiOxCy composition, where the abscissa is the oxygen ratio x and the ordinate is the carbon ratio y. In the orthogonal coordinates shown in FIG. 4, a straight line connecting a point of the SiC composition, which has a dense structure and a composition with a high barrier property, and a point of the SiO ₂ composition is [x / 2 + y = 1]. Therefore, it is considered that the closer the SiOxCy composition of the barrier layer is to the straight line of [x / 2 + y = 1], the denser the structure becomes and the higher the barrier property becomes.

On the other hand, a conventional general gas barrier film, a CVD film having a SiOxCy composition using HMDSO as a raw material, has a basic structure in which the sum of the oxygen ratio x and the carbon ratio y is [ x + y ≧ 2]. That is, in the rectangular coordinates shown in FIG. 4, the x and y of the SiOxCy composition are set within the range of [x + y ≧ 2] on the upper right of [x + y = 2] which is a straight line connecting the point of the SiC ₂ composition and the point of the SiO ₂ composition. Are distributed. Therefore, SiOxCy composition is a straight line between SiC composition and SiO ₂ composition away from [x / 2 + y = 1 ], the gas barrier film tends to become coarse grain structure, the barrier property tends to decrease.

On the other hand, the CVD film of the SiOxCy composition using the above-mentioned cyclic siloxane as a raw material is formed under specific conditions, so that the distribution of the oxygen ratio x and the carbon ratio y is in the range of [x + y ≦ 2]. That is, in the orthogonal coordinates shown in FIG. 4, a straight line connecting the points of the points and SiO ₂ composition of SiC ₂ composition in the lower left of the range than [x + y = 2], distributed and the x and y SiOxCy composition. Therefore, CVD film SiOxCy composition a cyclic siloxane described above as a raw material, the composition is distributed in the vicinity of a straight line between SiC composition and SiO ₂ composition [x / 2 + y = 1 ], and is easy to become a dense structure , Barrier properties are likely to be high.

Further, in a CVD film having a SiOxCy composition using a cyclic siloxane as a raw material, in the range of [x / 2 + y> 1] in which the oxygen ratio x and the carbon ratio y are in the upper right range than [x / 2 + y = 1], [x / 2 + y = about distributed approaches the straight line 1], it causes a reduction in the barrier properties Si-CH ₃ and Si-OH is reduced. For this reason, it is considered that the SiOxCy composition closer to the straight line of [x / 2 + y = 1] has a denser structure and tends to have higher barrier properties.

  Accordingly, while a conventional CVD film having a SiOxCy composition using HMDSO as a raw material requires a carbon ratio y of 0.8 or more, a CVD film having a SiOxCy composition using a cyclic siloxane as a raw material has a carbon ratio y of 0. Even in a range of less than 8, particularly a range in which the carbon ratio y of 0.4 or less is very small, a sufficiently good water vapor barrier property can be obtained. Furthermore, when the carbon ratio y is 0.4 or less, sufficiently good optical characteristics can be obtained because the C content is small.

  As described above, from the knowledge of the composition range obtained at the xy orthogonal coordinates 1 of the SiOxCy composition, the preferred composition range of the oxygen ratio x and the carbon ratio y in the CVD film of the SiOxCy composition using the above-mentioned cyclic siloxane as a raw material is determined. You can ask.

<2. Gas barrier film>
[Composition formula of gas barrier film: SiOxCy]
Next, an embodiment of the gas barrier film will be described. As described above, the gas barrier film is a chemical vapor deposition film containing silicon, oxygen, and carbon, and is represented by a composition of SiOxCy. The value of x in SiOxCy is expressed as the content of oxygen relative to silicon (O / Si), and the value of y is expressed as the content of carbon relative to silicon (C / Si).

In the gas barrier film, the composition in which the distribution of (x, y) for each thickness in the SiOxCy composition falls within the range of the following five ABCDEs of the orthogonal coordinates shown in FIG. 5 is changed from 20 nm to 1000 nm in the thickness direction of the gas barrier film. It is preferable to have the following.
A (x = 0.8, y = 0.8)
B (x = 1.2, y = 0.8)
C (x = 1.9, y = 0.1)
D (x = 1.9, y = 0.0)
E (x = 0.8, y = 0.55)

Further, the composition of the gas barrier film is such that the distribution of (x, y) for each thickness in the SiOxCy composition falls within the range of the following five points of A ₁ B ₁ CDE _{1 in} the orthogonal coordinates shown in FIG. More preferably, the thickness is 20 nm or more and 1000 nm or less in the thickness direction.
A ₁ (x = 1.3, y = 0.4)
B ₁ (x = 1.6, y = 0.4)
C (x = 1.9, y = 0.1)
D (x = 1.9, y = 0.0)
E ₁ (x = 1.3, y = 0.3)

5 and 6, a straight line connecting BC and B ₁ -C is a straight line [x + y = 2] connecting a point of the SiC ₂ composition and a point of the SiO ₂ composition. When the SiOxCy composition of the gas barrier film is in the composition range below and to the left of the straight line of [x + y = 2], the gas barrier film has a denser composition than the conventional SiOxCy CVD film using HMDSO as a raw material.

The straight line connecting E-D and E ₁ -D is a straight line along the straight line [x / 2 + y = 1] connecting the point of the SiC composition and the point of the SiO ₂ composition, and [x / 2 + y = 0.95]. Is a straight line. SiOxCy composition of the gas barrier film, by approaching the linear [x / 2 + y = 1 ], as well as SiC and SiO _2, tends to increase the barrier properties of the gas barrier layer.

When the carbon ratio is 0.8 or less, as in the straight line [y = 0.8] connecting AB, when the carbon ratio is 0.8 or less, absorption in the visible light region is suppressed, and deterioration in optical characteristics is suppressed. Is done. Further, as in a straight line [x = 0.4] connecting A ₁ -B ₁ , the optical characteristics of the gas barrier film having the SiOxCy composition are further improved when the carbon ratio is 0.4 or less.

The straight line connecting AE and CD is the upper and lower limits of the oxygen ratio in the SiOxCy composition that actually functions as a gas barrier film. In addition, a straight line connecting A ₁ -E ₁ is a line of [x / 2 + y = 0.95] and a straight line A ₁ -B ₁ having good barrier properties in a region where the carbon ratio is 0.4 or less. It is a connecting line.

[Composition of gas barrier film and carbon distribution curve]
The distribution of (x, y) for each thickness in the SiOxCy composition of the gas barrier film can be obtained by measuring an XPS depth profile described later. By measuring the XPS depth profile, the content of each element in the thickness direction (depth direction) of the gas barrier film can be obtained. From the measured values of the XPS depth profile, the composition ratio of oxygen atoms to silicon atoms in the thickness direction of the gas barrier film (O / Si: oxygen ratio x), the composition ratio of carbon atoms (C / Si: carbon ratio y), In addition, a curve indicating the composition ratio and a maximum value can be calculated.

  The content of oxygen with respect to silicon (O / Si: oxygen ratio x), the content of carbon with respect to silicon (C / Si: carbon ratio y), and the oxygen ratio x determined by measuring the XPS depth profile FIG. 7 shows an example of a graph showing the distribution in the thickness direction of the sum (x + y) with the carbon ratio y. Then, the (x, y) coordinates of each thickness of the SiOxCy composition represented by this graph are shown by the orthogonal coordinates in FIG. 8 where x is the horizontal axis and y is the vertical axis.

  FIG. 9 is a graph showing the distribution of each element in the thickness direction of the gas barrier film having the SiOxCy composition different from the examples shown in FIGS. 7 and 8 measured by the XPS depth profile. Then, the coordinates of (x, y) for each thickness of the SiOxCy composition represented by this graph are shown as orthogonal coordinates in FIG. 10 where x is the horizontal axis and y is the vertical axis.

  As shown in FIGS. 7 and 9, in the SiOxCy composition of the gas barrier film, the oxygen ratio x (O / Si) and the carbon ratio y (C / Si) continuously change in the depth direction (thickness direction). I do. That is, as shown in FIGS. 7 and 9, the SiOxCy composition of the gas barrier film includes a distance (L) from the layer surface in the thickness direction, an oxygen ratio x (O / Si), and a carbon ratio y (C / C Each distribution curve (oxygen ratio distribution curve, carbon ratio distribution curve) indicating the relationship with Si) changes continuously.

  As shown in FIG. 8, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 7 has a composition falling within the above five ranges of ABCDE in the thickness direction of the gas barrier film in the range of 20 nm to 1000 nm. Specifically, in the SiOxCy composition of the gas barrier film shown in the graph of FIG. 7, the oxygen ratio x (O / Si) is in the range of 0.8 to 1.2, and the carbon ratio y (C / Si) is 0.1. 8 and a range of [x / 2 + y ≧ 0.95] and [x + y ≦ 2] in a thickness direction of 20 nm or more and 1000 nm or less.

As shown in FIG. 10, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 9 is such that the composition falling within the above five ranges of A ₁ B ₁ CDE ₁ is changed by 20 nm or more in the thickness direction of the gas barrier film. It has a thickness of 1000 nm or less. Specifically, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 9 has an oxygen ratio x (O / Si) in a range of 1.3 to 1.8 and a carbon ratio y (C / Si) of 0.1%. 4 and a range of [x / 2 + y ≧ 0.95] and [x + y ≦ 2] in the thickness direction from 20 nm to 1000 nm.

Therefore, the gas barrier films shown in FIGS. 7 to 10 fall within the range of 5 points of the above-mentioned ABCDE or 5 points of the above-mentioned A ₁ B ₁ CDE ₁ in a region of 20 nm or more and 1000 nm or less in the thickness direction. It has a SiOxCy composition. Therefore, a gas barrier film having excellent gas barrier properties and optical characteristics can be realized.

On the other hand, the oxygen ratio distribution curve of SiOxCy composition of the gas barrier film, and, the carbon ratio distribution curve, five points above ABCDE, and, SiOxCy composition of examples not within the scope of five points _{A 1 B} 1 CDE 1 above FIG. 11 shows a graph of the XPS depth profile measurement for the gas barrier film of FIG. The (x, y) coordinates of the SiOxCy composition for each thickness represented by this graph are shown by the orthogonal coordinates in FIG. 12 where x is the horizontal axis and y is the vertical axis.

  As shown in FIG. 12, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 11 does not have a composition falling within the above five ranges of ABCDE. Specifically, the SiOxCy composition of the gas barrier film shown in the graph of FIG. 11 is such that the carbon ratio y (C / Si) is in a range exceeding 0.8 or distributed in a range of [x + y> 2]. I have. For this reason, since this gas barrier film has low gas barrier properties and low optical characteristics, a gas barrier film having excellent gas barrier characteristics and optical characteristics cannot be realized.

Note that, in the oxygen ratio distribution curve and the carbon ratio distribution curve of the SiOxCy composition of the gas barrier film shown in the graphs of FIGS. 7 and 9, the above-described five points of ABCDE and the five points of A ₁ B ₁ CDE ₁ described above. Some parts do not fall within the range. For example, at the outermost surface of the gas barrier film or near the interface on the bottom surface side, there are portions that do not fall within the range of the above-mentioned five points of ABCDE and the above-mentioned five points of A ₁ B ₁ CDE ₁ . However, even if the entire region in the thickness direction does not fall within the range of the five points, the gas barrier film has a region within the range of the five points having a thickness of 20 nm or more that is sufficient to exhibit gas barrier properties. If so, sufficient gas barrier properties can be obtained.

[Measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy]
The content ratio of each element in the gas barrier film can be determined by the following XPS depth profile measurement.

  The silicon distribution curve, oxygen distribution curve, silicon distribution curve, etc. in the thickness direction of the gas barrier film are obtained by using both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Thus, it can be created by the so-called XPS depth profile measurement in which the surface composition analysis is sequentially performed while exposing the inside of the sample. The distribution curve obtained by such XPS depth profile measurement can be created, for example, by setting the vertical axis to the atomic ratio of each element (unit: at%) and the horizontal axis to the etching time (sputtering time). In the distribution curve of the elements having the etching time on the horizontal axis, the etching time generally correlates with the distance from the surface of the gas barrier film in the thickness direction of the gas barrier film. For this reason, the distance from the surface of the gas barrier film, which is calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement, is defined as “distance from the surface of the gas barrier film in the thickness direction of the gas barrier film”. Can be adopted. In addition, as a sputtering method employed in measuring the XPS depth profile, the following measurement conditions are preferably used.

(Measurement condition)
Etching ion species: argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film converted value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 3 nm or less X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name “VG Theta Probe”
Irradiated X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm ellipse

  Preferably, the carbon distribution curve is substantially continuous. Here, the term “constantly continuous carbon distribution curve” specifically means a distance from the surface of the gas barrier film in the thickness direction of at least one of the gas barrier films calculated from the etching rate and the etching time. In the relationship between (x, unit: nm) and the atomic ratio of carbon (C, unit: at%), this means that the condition represented by [(dC / dx) ≦ 0.5] is satisfied.

(Profile of each element in gas barrier film)
The gas barrier film contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements. The composition of the gas barrier film changes continuously in the thickness direction in the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy. Further, the gas barrier film has a composition in which the oxygen ratio x (O / Si) and the carbon ratio y (C / Si) are within the above five ranges of ABCDE or the above five points of A ₁ B ₁ CDE _1. With a thickness of 20 nm or more and 1000 nm or less.

  Other configurations of the gas barrier film described above include configurations described in paragraphs [0025] to [0047] of WO2012 / 046767 and paragraphs [0029] to [0040] of JP-A-2014-000782. Can be appropriately referenced and adopted.

[Projection]
The gas barrier film of the SiOxCy composition formed by the above-described CVD film has an arithmetic mean roughness (Ra) of 2.0 nm or less on the surface. Further, the number of protrusions having a height of 10 nm or more on the surface of the gas barrier film is preferably 200 / mm ² or less.

  As for the gas barrier film formed by CVD, the smaller the Ra, the higher the barrier property. In CVD film formation, when abnormal growth occurs in the gas barrier film, projections or defects are generated in portions where the abnormal growth has occurred, and defects (paths) through which gas such as water vapor passes tend to occur. Therefore, it is preferable to reduce abnormal growth in the CVD film formation of the gas barrier film. Further, when a projection or a defect occurs due to abnormal growth of the gas barrier film, the surface roughness of this portion increases, and Ra of the surface of the gas barrier film increases. For this reason, by defining Ra on the surface of the gas barrier film to be 2 nm or less, there is little abnormal growth during CVD film formation, few defects (paths) through which gas such as water vapor passes, and excellent gas barrier properties. Easy to realize gas barrier film.

  In the case where a foreign substance, for example, a particle or the like mixed during film formation exists in the gas barrier film, a portion where the foreign substance such as the particle exists tends to become a defect (path) through which a gas such as water vapor passes. In addition, there is a possibility that a defect (path) through which a gas such as water vapor passes through the film due to foreign matter such as mixed particles. For this reason, it is preferable that the gas barrier film has less foreign matter such as particles mixed therein.

  However, it is very difficult to directly observe and measure foreign substances such as particles inside the gas barrier film. However, when foreign matter such as particles is taken in during the formation of the gas barrier film, even if the foreign matter is smaller than the film thickness of the gas barrier film, the film formation rate in that part is increased, so that the foreign matter mixed part of the gas barrier film It is detected as a minute projection on the surface. That is, in a portion of the gas barrier film in which a foreign substance such as a particle is sealed, a projection is generated due to the foreign substance. Therefore, by observing the protrusions on the surface of the gas barrier film, it is possible to observe the state of foreign matter such as particles inside the gas barrier film. Therefore, a gas barrier film having a smaller number of protrusions due to foreign matter per unit area of the gas barrier film is more likely to realize high barrier properties.

In the gas barrier film, the number of protrusions having a height of 10 nm or more and observed on the surface is preferably 200 / mm ² or less. Further, the number of protrusions having a height of 10 nm or more is preferably less than 100 / mm ² , more preferably 50 / mm ² or less, and particularly preferably less than 10 / mm ² . If the number of protrusions is small, a decrease in the barrier property due to the mixed particles is unlikely to occur, and it is easy to realize a gas barrier film having excellent gas barrier properties.

  In the gas barrier film, minute projections of about 10 nm are difficult to separate and detect due to the influence of the undulation component of the surface roughness (unevenness with a long wavelength). For this reason, the number of minute protrusions of 10 nm or more in the gas barrier film is defined by a value detected and counted by the following method.

  First, the surface of the gas barrier film is measured using an optical interference type three-dimensional surface roughness measuring device (WYKO NT9300 manufactured by Veeco). Then, by this measurement, three-dimensional surface roughness data of the gas barrier film is obtained.

Next, the obtained three-dimensional surface roughness data is subjected to a process of applying a high-pass filter having a wavelength of 10 μm to remove roughness and undulation components. In the three-dimensional surface roughness converted data from which the waviness component is removed obtained by this processing, when the maximum peak position when the data is displayed as a histogram is set to 0, protrusions having a height of 10 nm or more are counted. Then, the counted number of protrusions is calculated as the number per mm ² . More specifically, six fields of view (area 0.114 mm ² ) of 159.2 μm × 119.3 μm are measured and counted under the condition of a measurement resolution of about 250 nm, and the number per 1 mm ² is calculated.

  FIGS. 13 to 15 show images (159.2 μm × 119.3 μm) in which the height of the three-dimensional surface roughness conversion data obtained by processing according to the above method is displayed in gray scale with respect to the surface state of the gas barrier film. . In FIGS. 13 to 15, the color is displayed whiter as the height increases from a reference position on the surface of the gas barrier film.

FIG. 13 is an image of the surface obtained by the above-described processing for the gas barrier film having the number of protrusions of less than 10 / mm ² . FIG. 14 is an image of the surface obtained by the above-described process for a gas barrier film having a number of protrusions of 50 / mm ² or more and less than 100 / mm ² . FIG. 15 is an image of the surface obtained by the above-described processing for a gas barrier film having 200 or more protrusions / mm ² .

As shown in FIG. 13, in the gas barrier film in which the number of protrusions is less than 10 / mm ² , there are few protrusions exceeding 10 nm in height, which are indicated by white dots in the image. Then, as shown in FIGS. 14 and 15, less than the number of projections 50 / mm ² or more 100 / mm ^2, and a number of protrusions 200 / mm ² or more, the number of projections is increased more than the height of 10nm As the number of white points displayed in the image increases, the number of white points increases. Therefore, by detecting and counting by the above method, the number of minute projections of about 10 nm on the surface of the gas barrier film can be defined.

[Gas barrier films of other configurations]
Note that the gas barrier film may have a barrier film of another configuration together with the gas barrier film of the SiOxCy composition formed by the chemical vapor deposition (CVD) within the above-described predetermined composition range. For example, together with the gas barrier film of the above-described embodiment, a gas barrier film formed by a wet coating method using a coating solution containing a silicon compound, or a gas barrier film containing a transition metal can be used. Further, a gas barrier film having these other configurations can be used as an overcoat layer of the gas barrier film having the above-described SiOxCy composition. As a gas barrier film formed by a wet coating method or a gas barrier film containing a transition metal, a conventionally known gas barrier film can be applied.

<3. Manufacturing method of gas barrier film>
Next, a method for manufacturing a gas barrier film having a SiOxCy composition by chemical vapor deposition (CVD) within the above-described predetermined composition range will be described. The gas barrier film is preferably formed by vapor-phase film formation by a chemical vapor deposition method, to which a roll-to-roll method described later can be applied.

[Gas barrier film; vapor phase deposition]
A gas barrier film having a SiOxCy composition formed by vapor deposition by a chemical vapor deposition method (hereinafter also referred to as a vapor deposition gas barrier film) contains silicon, oxygen, and carbon, and is represented by a SiOxCy composition. Note that the gas-phase film-formed gas barrier film represented by the SiOxCy composition may contain the above-mentioned elements other than silicon, oxygen, and carbon as secondary components.

  The chemical vapor deposition method for forming the vapor-phase film-formed gas barrier film is not particularly limited, and a thin film deposition technique using an existing chemical vapor deposition method can be used. For example, a conventionally known vapor deposition method, a plasma enhanced chemical vapor deposition (PECVD), a metal organic (MO) CVD method, or the like can be used. Gas barrier films formed by these vapor deposition methods can be manufactured by applying known conditions.

  For example, in a chemical vapor deposition (CVD) method, a raw material gas containing a component of a target thin film is supplied onto a substrate, and a film is deposited on the surface of the substrate or by a chemical reaction in a gas phase. Is the way. Further, there is a method of generating plasma for the purpose of activating a chemical reaction, such as a thermal CVD method, a catalytic chemical vapor deposition method, an optical CVD method, and a plasma CVD method (PECVD method) using plasma as an excitation source. Known CVD methods, such as a vacuum plasma CVD method and an atmospheric pressure plasma CVD method, are mentioned.

  From the viewpoint of facilitating the adjustment of the atomic composition ratio of the gas barrier film, the PECVD method is preferable. In particular, since the atomic composition in the depth direction can be continuously changed, a plasma is generated between two opposing rollers, and a gas barrier film is formed on a substrate conveyed by each roller. Is preferred. Hereinafter, a vacuum plasma CVD method will be described in detail as a preferable technique of the chemical vapor deposition method.

[Vacuum plasma CVD method]
In the vacuum plasma CVD method, a deposition gas flows into a vacuum vessel equipped with a plasma source, and a power source supplies power to the plasma source to generate discharge plasma in the vacuum vessel. Is decomposed and the generated reactive species are deposited on the substrate. The desired compound can be produced from the vapor-phase film-formed gas barrier film obtained by the vacuum plasma CVD method by selecting conditions such as a film-forming gas as a raw material, a decomposition temperature, and an input power.

(Deposition gas)
As a film-forming gas used for the plasma-enhanced chemical vapor deposition, a source gas containing an organosilicon compound and a reaction gas containing an oxygen gas are used. The content of the oxygen gas in the film-forming gas is Is preferably not more than the theoretical amount of oxygen necessary to completely oxidize the entire amount of the organosilicon compound. In addition, as a deposition gas, an inert gas such as an argon gas or a helium gas may be used as a carrier gas.

(Source gas)
It is preferable to use an organosilicon compound in which the number of O atoms is 1 with respect to the number of Si atoms described above, as a raw material gas constituting a film formation gas used for manufacturing a gas-phase film formation gas barrier film. Further, as a CVD raw material, it is preferable to use an organosilicon compound having less than 2 C atoms per 1 Si atom, and more preferably an organosilicon compound having 1 or less C atoms. Further, it is preferable to use an organosilicon compound having a Si—H bond as a CVD raw material.

  Such organosilicon compounds include, for example, octamethylcyclotetrasiloxane (OMCTS), heptamethylcyclotetrasiloxane (Hepta-MCTS), tetramethylcyclotetrasiloxane (TMCTS), hexamethylcyclohexasiloxane (HMCHS), penta A cyclic siloxane such as methylcyclopentasiloxane (PMCPS) can be given. Among these, tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane, which is a cyclic siloxane having 1 O atom and less than 2 C atoms per 1 Si atom, as shown in the above [Chemical Formula 1] It is preferable to include a cyclic siloxane such as (Hepta-MCTS), pentamethylcyclopentasiloxane (PMCPS), and hexamethylcyclohexasiloxane (HMCHS). These organosilicon compounds can be used alone or in combination of two or more.

  In addition, other organosilicon compounds can be used together with the cyclic siloxane in which the number of O atoms is 1 and the number of C atoms is less than 2 with respect to the above Si atom 1. Examples of the organosilicon compound applicable to the production of the gas barrier film together with the cyclic siloxane include, for example, hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane , Dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. Is mentioned. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling in film formation and gas barrier properties of the obtained gas-phase gas barrier film. These organosilicon compounds can be used alone or in combination of two or more.

(Reactive gas / carrier gas)
The deposition gas preferably contains oxygen gas as a reaction gas in addition to the source gas. Oxygen gas is a gas that reacts with a source gas to become an inorganic compound such as an oxide. As the film forming gas, a carrier gas may be used as needed to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary to generate plasma discharge. As the carrier gas and the discharge gas, known gases can be used as appropriate. For example, a rare gas such as helium, argon, neon, or xenon, or a hydrogen gas can be used.

  When such a film forming gas contains a raw material gas containing an organic silicon compound containing silicon and oxygen gas, the ratio of the raw material gas to the oxygen gas is such that the raw material gas and the oxygen gas are completely reacted. It is preferable that the ratio of the oxygen gas is not excessively larger than the ratio of the amount of the oxygen gas theoretically necessary for the formation. Regarding this, for example, the description in WO2012 / 046767 can be referred to.

(Vacuum plasma CVD equipment)
Hereinafter, a preferred embodiment of the vacuum plasma CVD method will be specifically described. FIG. 16 shows an example of a schematic diagram of a roll-to-roll type inter-roller discharge plasma CVD apparatus applied to a vacuum plasma CVD method.

  There is no particular limitation on a film forming apparatus that manufactures a gas-phase film-formed gas barrier film using the above-described plasma CVD method. As a film forming apparatus, for example, a manufacturing apparatus shown in FIG. The manufacturing apparatus shown in FIG. 16 can manufacture a gas-phase film-formed gas barrier film by a roll-to-roll method while utilizing a plasma CVD method. Hereinafter, with reference to FIG. 16, a method for manufacturing a gas-phase deposited gas barrier film will be described in detail. FIG. 16 is a schematic diagram showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field is applied, which can be suitably used in the production of a gas-phase deposited gas barrier film.

  The inter-roller discharge plasma CVD apparatus (hereinafter, also simply referred to as a plasma CVD apparatus) 50 to which a magnetic field is applied shown in FIG. 16 mainly includes a feeding roller 51, a transport roller 52, a transport roller 54, a transport roller 55, and a transport. Roller 57, film forming roller 53 and film forming roller 56, film forming gas supply pipe 59, power supply 63 for plasma generation, magnetic field generator 61 installed inside film forming roller 53, film forming roller 56 And a take-up roller 58 provided inside the device. Further, in such a plasma CVD manufacturing apparatus, at least the film forming rollers 53 and 56, the film forming gas supply pipe 59, the power supply 63 for plasma generation, and the magnetic field generators 61 and 62 are formed by a vacuum not shown. It is located inside the chamber. In FIG. 16, an electrode drum connected to a power source 63 for plasma generation is provided on the film forming rollers 53 and 56. Further, in such a plasma CVD 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 the vacuum pump. I have.

  In such a plasma CVD manufacturing apparatus, each of the film-forming rollers (the film-forming roller 53 and the film-forming roller 56) is formed by a plasma so that the film-forming roller can function as a pair of counter electrodes. It is connected to a power supply 63 for generation. By supplying power from the power supply 63 for plasma generation to the film forming roller 53 and the film forming roller 56, plasma can be generated by discharging to a space between the film forming roller 53 and the film forming roller 56. In such a plasma CVD manufacturing apparatus, it is preferable to arrange the pair of film forming rollers 53 and 56 such that the central axes thereof are substantially parallel on the same plane. Thus, by disposing the pair of film forming rollers 53 and 56, the film forming rate can be doubled and a film having the same configuration can be formed.

  Further, inside the film forming roller 53 and the film forming roller 56, there are provided a magnetic field generator 61 and a magnetic field generator 62 fixed so as not to rotate even when the film forming roller rotates.

  As the film forming roller 53 and the film forming roller 56, known rollers can be appropriately used. It is preferable to use rollers having the same diameter as the film forming roller 53 and the film forming roller 56 from the viewpoint of efficiently forming a thin film. The diameter of the film-forming roller 53 and the film-forming roller 56 is preferably in the range of 100 to 1000 mm, preferably 100 to 700 mm, from the viewpoint of optimizing the discharge conditions and reducing the space in the vacuum chamber. More preferably, it is within the range. When the diameter φ is 100 mm or more, a sufficiently large discharge space can be formed, and a decrease in productivity can be prevented. Further, a sufficient film thickness can be obtained by a short-time discharge, and the amount of heat applied to the base material 60 at the time of the discharge can be suppressed, so that the residual stress can be suppressed. Further, when the diameter φ is 1000 mm or less, uniformity of the discharge space can be maintained, which is practical in designing the apparatus. As the feeding roller 51 and the transport rollers 52, 54, 55, and 57 used in such a plasma CVD manufacturing apparatus, known rollers can be appropriately selected and used. The winding roller 58 may be any roller that can wind the substrate 60 on which the vapor-phase film-formed gas barrier film is formed, and is not particularly limited, and a known roller can be used as appropriate.

  As the film forming gas supply pipe 59, a pipe capable of supplying or discharging a source gas and an oxygen gas at a predetermined rate can be used as appropriate. Further, as the power source 63 for plasma generation, a power source of a conventionally known plasma generator can be used. As such a plasma generation power supply 63, a power supply (such as an AC power supply) capable of alternately reversing the polarities of a pair of film forming rollers can be used because the plasma CVD method can be efficiently performed. It is preferable to use it. In addition, as the amount of power supplied from the plasma generation power supply 63, when the effective film formation width is 200 mm to 1000 mm, the applied power can be in the range of 0.1 to 10.0 kW. When the effective film forming width is set to about 300 mm, it is preferable that the supplied electric energy is in the range of 0.6 to 3.0 kW from the viewpoint of improving gas barrier properties. If it is 0.1 kW or more, generation of foreign substances called particles can be suppressed. If it is 10.0 kW or less, the amount of generated heat can be suppressed, and the occurrence of wrinkles of the base material 60 due to a rise in temperature can be suppressed. When an AC power supply is used, the AC frequency is preferably in the range of 50 Hz to 500 kHz. Further, as the magnetic field generators 61 and 62, known magnetic field generators can be appropriately used.

  Using the plasma CVD apparatus 50 shown in FIG. 16, 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 degree of pressure reduction), the diameter of the film forming roller, A desired gas barrier film can be manufactured by appropriately adjusting the transfer speed of the substrate and the like.

  In the plasma CVD apparatus 50 shown in FIG. 16, a film forming gas (a raw material gas or the like) is supplied into a vacuum chamber, and a plasma discharge is performed between a pair of film forming rollers 53 and 56 while generating a magnetic field. The film gas (raw material gas or the like) is decomposed by the plasma, and the vapor-phase film-forming gas barrier film is formed on the surface of the substrate 60 held by the film forming roller 53 and on the surface of the substrate 60 held by the film forming roller 56. Is formed. In such film formation, the base material 60 is conveyed by the feeding roller 51, the conveyance rollers 52, 54, 55, 57, the winding roller 58, the film formation rollers 53, 56, etc. The vapor deposition gas barrier film can be formed by the continuous film formation process described above.

  In the plasma CVD apparatus 50 shown in FIG. 16, the film forming gas supply pipe 59 is provided on the center line between the film forming rollers 53 and 56. The rollers 53 and 56 may be arranged so as to be offset toward one of them. Accordingly, the supply amounts of the source gases to the film forming roller 53 and the film forming roller 56 can be made different, and a film having an atomic composition different from that on the film forming roller 53 and the film forming roller 56 can be formed. .

  In the plasma CVD apparatus 50 shown in FIG. 16, when film forming conditions such as a supply amount of a source gas change during film formation, films having different atomic compositions are stacked on the substrate 60. Specifically, when the substrate 60 passes through the point where the film forming roller 53 and the film forming roller 56 are closest, the ratio of C atoms in the depth direction in the formed film changes from decreasing to increasing, The ratio of O atoms changes from increasing to decreasing. On the other hand, when the base material 60 passes through a point shifted in the transport direction of the base material 60 from the point where the film forming roller 53 and the film forming roller 56 are closest to each other, the depth direction in the formed film is changed. The ratio of C atoms changes from increasing to decreasing, and the ratio of O atoms changes from decreasing to increasing. For this reason, in the gas barrier film formed by the above method, the atomic composition in the depth direction changes continuously. Further, in the gas barrier film, the existence of an extreme value in which the ratio of C atoms and the ratio of O atoms are turned from decreasing to increasing or from increasing to decreasing is not uniform in the abundance ratio of C atoms and O atoms in the formed film. Indicates that Thereby, for example, a portion having high density and a portion having low density can be formed in the thickness direction of the gas barrier film.

(Degree of vacuum)
The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the source gas and the like, but is preferably in the range of 0.5 to 100 Pa. For example, when the effective film formation width is about 300 mm, it is preferable that the degree of vacuum be in the range of 0.5 to 3.0 Pa.

(Roller film formation)
In the plasma CVD method using the plasma CVD apparatus 50 shown in FIG. 16, the electric power applied to the electrode drum connected to the plasma generating power supply 63 for discharging between the film forming rollers 53 and 56 depends on the type of the source gas. And the pressure in the vacuum chamber can be adjusted as appropriate. The electric power applied to the electrode drum is preferably, for example, in the range of 0.1 to 10 kW. With the applied power in such a range, generation of particles (illegal particles) can be suppressed, and the amount of heat generated during film formation is within the control range. In addition, thermal deformation of the base material, performance degradation due to heat, and generation of wrinkles during film formation can be suppressed.

  In the plasma CVD apparatus 50, the transfer speed (line speed) of the base material 60 can be appropriately adjusted according to the type of the source gas, the pressure in the vacuum chamber, and the like, but is in the range of 0.25 to 100 m / min. And more preferably in the range of 0.5 to 40.0 m / min. When the line speed is within the range, wrinkles due to the heat of the base material hardly occur, and the thickness of the formed gas-phase gas barrier film can be sufficiently controlled.

(Method of forming gas barrier film)
The chemical vapor deposition method for forming the gas barrier film is not particularly limited, and a known method can be used. From the viewpoint of forming a gas barrier film in which the element distribution is controlled densely, the method shown in FIG. It is preferable to use an inter-roller discharge plasma CVD apparatus to form a film by a discharge plasma chemical vapor deposition method having a discharge space between rollers to which a magnetic field is applied. In addition, as a chemical vapor deposition method for forming a gas barrier film, for example, the methods described in paragraphs [0049] to [0069] of WO2012 / 046767 can be referred to.

  More specifically, in the inter-roller discharge plasma CVD apparatus shown in FIG. 16, a base material is wound around a pair of film forming rollers by using an inter-roller discharge plasma processing apparatus to which a magnetic field is applied, and formed between the pair of film forming rollers. It is preferable to form a gas barrier film by a plasma chemical vapor deposition method in which plasma discharge is performed while supplying a film gas. Further, when discharging while applying a magnetic field between the pair of film forming rollers, it is preferable that the polarity between the pair of film forming rollers is alternately reversed. As described above, by using a pair of film forming rollers, winding the substrate on the pair of film forming rollers, and performing a plasma discharge between the pair of film forming rollers, the distance between the substrate and the discharge space is reduced. As a result, the plasma intensity on the substrate surface changes continuously, so that a gas barrier film in which each atomic ratio changes continuously in the layer can be formed.

  Further, at the time of film formation, a gas barrier film is formed on the surface of the substrate present on one of the film forming rollers, and the gas barrier film is simultaneously formed on the surface of the substrate present on the other film forming roller. It becomes possible. That is, since the film formation efficiency can be doubled and a film having the same configuration can be formed, the extreme value of the carbon distribution curve can be doubled, and the gas barrier film can be formed efficiently.

[Other gas barrier films]
As the gas barrier film, a gas barrier film formed by a wet coating method using a coating solution containing a silicon compound together with a gas barrier film having a SiOxCy composition formed by chemical vapor deposition (CVD) within the above-described predetermined composition range, or a transition metal May be used. Hereinafter, an example of a method of forming a gas barrier film formed by a wet coating method will be described.

[Gas barrier film; wet coating]
As a gas barrier film formed by a wet coating method using a coating solution containing a silicon compound, a polysilazane coating formed by applying a coating solution containing a polysilazane compound by a known wet coating method, and then performing a modification treatment on the coating film. Quality layer.

(Polysilazane compound)
The polysilazane compound used for forming the gas barrier film is a polymer that is a precursor of silicon oxynitride having a silicon-nitrogen bond in the structure. As the polysilazane compound, a compound having a structure represented by the following general formula (1) is preferably used.

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

From the viewpoint of the denseness of the gas barrier film, it is preferable to use perhydropolysilazane in which all of R ¹ , R ² and R ³ are hydrogen atoms. In addition, for details of polysilazane, see paragraphs [0024] to [0040] of JP2013-255910A, paragraphs [0037] to [0043] of JP2013-188942A, and JP2013-151123A. Paragraphs [0014] to [0021], Paragraphs [0033] to [0045] of JP-A-2013-052569, Paragraphs [0062] to [0075] of JP-A-2013-129557, and JP-A-2013-226758. Paragraphs [0037] to [0064] can be referred to.

  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 coating solution. Commercially available polysilazane solutions include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials.

(Method of forming gas barrier film using polysilazane compound)
A coating film using a solution containing a polysilazane compound can be formed by applying a solution containing a polysilazane compound, an additive, and the like onto a substrate. Any appropriate method can be adopted as a method of applying the solution. For example, a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, a gravure printing method and the like can be mentioned. After applying the solution, the coating is preferably dried. By drying the coating film, the organic solvent contained in the coating film can be removed. For the method of forming a coating film, paragraphs [0058] to [0064] of JP-A-2014-151571 and paragraphs [0052] to [0056] of JP-A-2011-183773 can be referred to.

(Reforming treatment)
The reforming treatment is a treatment for performing a conversion reaction of the polysilazane compound into silicon oxide or silicon oxynitride. For the modification treatment, a known method for the conversion reaction of the polysilazane compound can be used. As the reforming treatment, a conversion reaction using plasma, ozone, or ultraviolet light, which can perform a conversion reaction at a low temperature, is preferable. For the conversion reaction using plasma, ozone, or ultraviolet light, a conventionally known method can be used. The modification treatment is preferably performed by irradiating the coating film of the liquid containing the polysilazane compound with vacuum ultraviolet rays (VUV) having a wavelength of 200 nm or less.

  The thickness of the gas barrier film formed by the wet coating method is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. The gas barrier film may be entirely a modified layer, and the thickness of the modified layer subjected to the modification treatment may be 1 to 50 nm, preferably 1 to 10 nm.

(Vacuum UV treatment)
In the step of irradiating the coating film containing the polysilazane compound with VUV, it is preferable that at least a part of the polysilazane be modified into silicon oxynitride. In VUV irradiation step, it is preferable that the illuminance of VUV in the coating film surface for receiving the coating film containing a polysilazane compound ranges from 30~200mW / cm ^2, and more preferably in the range of 50~160mW / cm ² . The illuminance of the VUV With 30 mW / cm ² or more, it is possible to obtain a reforming efficiency sufficiently, the 200 mW / cm ² or less, extremely reducing the damage occurrence rate of the coating film, even damage to the substrate reduced Can be done.

Irradiation energy amount of VUV in the surface of the coating film containing a polysilazane compound is preferably in the range of 200~10000mJ / cm ^2, and more preferably in the range of 500~5000mJ / cm ^2. By setting the irradiation energy amount of VUV to 200 mJ / cm ² or more, the polysilazane is sufficiently modified. Further, when the content is not more than 10,000 mJ / cm ² , excessive reforming can be suppressed, and the occurrence of cracks in the gas barrier film and thermal deformation of the substrate can be suppressed as much as possible.

As a vacuum ultraviolet light source, a rare gas excimer lamp is preferably used.
Since the vacuum ultraviolet ray is absorbed by oxygen, the efficiency in the ultraviolet ray irradiation step is likely to decrease. Therefore, it is preferable that the VUV irradiation be performed in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration at the time of VUV irradiation is preferably in the range of 10 to 10000 ppm, more preferably in the range of 50 to 5000 ppm, further preferably in the range of 80 to 4500 ppm, and most preferably in the range of 100 to 1000 ppm.

  Further, as a gas that satisfies the irradiation atmosphere used at the time of VUV irradiation, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of the oxygen gas and the inert gas introduced into the irradiation chamber, and changing the flow rate ratio.

  These modification treatments are described, for example, in paragraphs [0055] to [0091] of JP-A-2012-086394, paragraphs [0049] to [0085] of JP-A-2012-006154, and JP-A-2011-251460. The contents described in paragraphs [0046] to [0074] can be referred to.

(Middle layer)
When gas barrier films are stacked, an intermediate layer may be provided between the gas barrier films. It is preferable to apply a polysiloxane modified layer as the intermediate layer. The polysiloxane-modified layer can be formed by applying a coating solution containing polysiloxane on a gas barrier film using a wet coating method, drying the coating film, and irradiating the dried coating film with vacuum ultraviolet rays. it can.

  Examples of the method of applying the coating solution for forming the intermediate layer include spin coating, dipping, roller blade, and spraying. As the vacuum ultraviolet ray, it is preferable to use VUV irradiation similar to the above-described modification treatment of the polysilazane compound.

  The coating liquid used for forming the intermediate layer mainly contains a polysiloxane and an organic solvent. The polysiloxane applicable to the formation of the intermediate layer is not particularly limited, but an organopolysiloxane represented by the following general formula (2) is particularly preferable.

In the general formula (2), R ^{4 to} R ⁹ each represent the same or different organic groups having 1 to 8 carbon atoms. Here, at least one group of R ^{4 to} R ⁹ includes any of an alkoxy group and a hydroxyl group. m is an integer of 1 or more.

  In the organopolysiloxane represented by the general formula (2), it is particularly preferable that m is 1 or more and the weight average molecular weight in terms of polystyrene is 1,000 to 20,000. When the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1,000 or more, cracks are less likely to be formed in the formed intermediate layer, and gas barrier properties can be maintained. Is sufficient, and sufficient hardness is obtained as the intermediate layer.

  The dry thickness of the intermediate layer is preferably in the range of 100 nm to 10 μm, more preferably 50 nm to 1 μm. When the thickness of the intermediate layer is 100 nm or more, sufficient gas barrier properties can be secured. When the thickness of the intermediate layer is 10 μm or less, stable coating properties can be obtained during the formation of the intermediate layer.

  In addition, for details of polysiloxane, see paragraphs [0028] to [0032] of JP-A-2013-151123, paragraphs [0050] to [0064] of JP-A-2013-086501, and JP-A-2013-059927. Paragraphs [0063] to [0081], paragraphs [0119] to [0139] of JP-A-2013-226673, and the like can be referred to.

<4. Gas barrier film, and method for producing gas barrier film>
Next, a gas barrier film having the above-described gas barrier film will be described. FIG. 17 shows a schematic configuration of the gas barrier film.

  The gas barrier film 10 shown in FIG. 17 has a substrate 11 and a gas barrier film 13 provided on the substrate 11. Further, the gas barrier film 10 has a plasma polymerization layer 12 provided between a base material 11 and a gas barrier film 13. Note that the gas barrier film 10 only needs to have the base material 11 and the gas barrier film 13, and other configurations are not particularly limited. For this reason, the gas barrier film 10 may have a configuration in which another layer is interposed between the substrate 11 and the gas barrier film 13 as shown in FIG. May further have another layer.

  Further, the method for producing the gas barrier film 10 includes a step of preparing the substrate 11, a step of forming the plasma polymerized layer 12 on the substrate 11, and a step of forming the gas barrier film 13 on the plasma polymerized layer 12. Have. Among these, the above-mentioned method can be applied to the step of forming the gas barrier film 13. In addition, the method of manufacturing the gas barrier film 10 may include a step of preparing the base material 11 and a step of forming the gas barrier film 13, and the steps of forming other components are not particularly limited. . For this reason, the manufacturing method of the gas barrier film 10 may include a step of forming another layer between the base material 11 and the gas barrier film 13, on the back surface of the base material 11, on the gas barrier film 13, or the like. .

[Gas barrier film]
In the gas barrier film 10, the gas barrier film 13 has at least one chemical vapor deposition (CVD) film having a SiOxCy composition within the above-described predetermined composition range in a thickness direction of 20 nm or more and 1000 nm or less. I have. The gas barrier film 13 may be provided in a plurality of layers on the substrate 11, and may be provided not only on one side but also on both sides of the substrate 11.

[Plasma polymerization layer]
The plasma polymerization layer 12 is interposed between the base material 11 and the gas barrier film 13 and functions as a base layer of the gas barrier film 13.

  The plasma polymerization layer 12 is a gas-phase formed resin layer that can be formed by the same apparatus as the gas barrier film 13 formed by the above-described CVD film formation. The plasma polymerization layer 12 is preferably manufactured using the above-described roller discharge plasma CVD apparatus shown in FIG. In addition, the plasma polymerization layer 12 and the gas barrier film 13 may be manufactured by the same device, or may be manufactured by different devices.

  By forming the plasma polymerized layer 12 on the substrate 11, the surface on which the gas barrier film 13 is formed is covered with irregularities on the surface of the substrate 11 and foreign substances adhering to the surface of the substrate 11, so that the surface is smooth. be able to. For this reason, by forming the gas barrier film 13 by the CVD film formation while maintaining the vacuum of the CVD apparatus following the formation of the plasma polymerization layer 12, the surface smoothness of the gas barrier film 13 is improved. Further, since the occurrence of defects in the gas barrier film 13 can be reduced, the water vapor barrier property of the gas barrier film 13 also improves.

The plasma polymerization layer 12 has a different water vapor transmission rate from the gas barrier film 13. Specifically, a sample is prepared by forming a gas barrier film 13 or a plasma polymerized layer 12 on a resin film substrate by a plasma CVD method, and the sample is formed at 38 ° C. and 100% RH using MOCON AQUATRAN. When the water vapor transmission rate is measured, when the water vapor transmission rate is 0.1 g / m ² / d or less, the gas barrier film 13 is obtained. When the water vapor transmission rate exceeds 0.1 g / m ² / d, This is the plasma polymerization layer 12.

  The thickness of the plasma polymerization layer 12 is preferably 10 nm to 10 μm, more preferably 100 nm to 5 μm, and further preferably 200 nm to 2 μm. The thickness of the plasma polymerization layer 12 can be measured by cross-sectional SEM observation. If the interface of the plasma polymerization layer 12 is unclear, the cross-sectional composition is analyzed using an EDX (energy dispersive X-ray analysis) device attached to the SEM device. You can ask.

  The plasma polymerization layer 12 can be formed in a state of being in close contact with the substrate 11 by subjecting a material containing carbon atoms to plasma polymerization on the substrate 11. The method for plasma-polymerizing a material containing carbon atoms is not particularly limited. For example, when the plasma polymerized layer 12 having an effective film forming width of about 300 mm is produced using the inter-roller discharge plasma CVD apparatus shown in FIG. From the viewpoint of forming the above, it is preferable that the electric energy is in the range of 0.1 to less than 0.6 kW and the degree of vacuum is in the range of more than 3.0 Pa to 20.0 Pa or less. The film formation conditions of the plasma polymerization layer 12 include, for example, gas pressure of 0.1 to 100 Pa, preferably 1 to 50 Pa, substrate temperature of −20 to 200 ° C., preferably 0 to 100 ° C., and monomer component on the substrate. Glow discharge (usually using high-frequency electric power) while supplying the gas.

  As the plasma polymerized layer 12, amorphous carbon nitride, amorphous carbon, a five-membered heterocyclic organic compound plasma polymer such as furan and pyrrole, a methyl methacrylate plasma polymer, an acrylic organic compound plasma polymer such as an acrylonitrile plasma polymer, Fluorine organic compound plasma polymer such as tetrafluoroethylene plasma polymer, chlorine organic compound polymer such as dichloroethylene plasma polymer, tetraethoxy silicon plasma polymer, hexamethyldisiloxane plasma polymer, tetramethyltetracyclosiloxane plasma It is preferable to employ any layer of a silicon-based organic compound plasma polymer such as a polymer and a hexamethyldisilazane plasma polymer, or a layer containing at least one of these. The plasma polymerization layer 12 is preferably a layer of a silicon-based organic compound plasma polymer or a layer containing a silicon-based organic compound plasma polymer from the viewpoint of excellent heat resistance and hardness.

  Further, in the production of the plasma polymerization layer 12, it is preferable to use the same material as the organosilicon compound used as the source gas in the production of the gas barrier film 13. By sharing the material for forming the plasma polymerization layer 12 with the gas barrier film 13, the production efficiency of the gas barrier film 10 can be improved. Therefore, as a film forming gas used for forming the plasma polymerization layer 12, tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane (Hepta-MCTS), and pentamethylcyclopentasiloxane It is preferable to use cyclic siloxane such as (PMCPS) and hexamethylcyclohexasiloxane (HMCHS).

[Base material]
Examples of the substrate 11 used for the gas barrier film 10 include a resin film. The resin film is not particularly limited in material, thickness and the like as long as it can hold the gas barrier film, and can be appropriately selected according to the purpose of use and the like. As the resin film, a conventionally known resin film can be used. The substrate 11 may be formed from a plurality of materials. Examples of the resin film include resin films described in paragraphs [0124] to [0136] of JP-A-2013-226758 and paragraphs [0044] to [0047] of WO2013 / 002026. .

  More preferable specific examples of the resin film that can be used as the substrate 11 include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and polycycloolefin (COP).

  The substrate 11 preferably has low light absorption and low haze. For this reason, the base material 11 can be appropriately selected and used from resin films generally applied to optical films.

  The base material 11 may be a single resin film or a plurality of resin films, or may be formed of a plurality of layers. For example, a configuration in which a resin film is used as a support, and a hard coat layer and other functional layers are provided on both surfaces of the support may be employed. Examples of other functional layers include a smooth layer (underlayer, primer layer), a bleed-out prevention layer, an anchor coat layer, and a desiccant layer. Conventionally known configurations can be applied to these layers.

  The substrate 11 is not limited to a single-wafer shape or a roll shape, but preferably has a roll shape applicable to a roll-to-roll production method from the viewpoint of productivity. The thickness of the substrate 11 is not particularly limited, but is preferably about 5 to 500 μm.

[Hard coat layer]
Further, it is preferable that the substrate 11 has a configuration in which the above-mentioned resin film or the like is used as a support, and a hard coat layer is provided on both surfaces of the support.
When the substrate 11 has a hard coat layer on the surface, the durability and smoothness of the gas barrier film 10 are improved. The hard coat layer is preferably formed from a curable resin. As the curable resin, epoxy resin, cyanate ester resin, phenol resin, bismaleimide-triazine resin, polyimide resin, acrylic resin, thermosetting resin such as vinylbenzyl resin, ultraviolet curing urethane acrylate resin, ultraviolet curing polyester Active energy ray-curable resins such as acrylate resins, ultraviolet-curable epoxy acrylate resins, ultraviolet-curable polyol acrylate resins, and ultraviolet-curable epoxy resins.

  In addition, the hard coat layer may include fine particles of an inorganic compound such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, and magnesium oxide, or polymethyl methacrylate in order to adjust scratch resistance, slipperiness, and refractive index. Acrylate resin powder, acrylic styrene resin powder, polymethyl methacrylate resin powder, silicone resin powder, polystyrene resin powder, polycarbonate resin powder, benzoguanamine resin powder, melamine resin powder, polyolefin resin powder, polyester resin powder, An ultraviolet curable resin composition such as a polyamide resin powder, a polyimide resin powder, and a polyfluoroethylene resin powder can be added. In order to increase the heat resistance of the hard coat layer, an antioxidant that does not suppress the photocuring reaction can be selected and used. Further, the hard coat layer may contain a silicone-based surfactant, a polyoxyether compound, and a fluorine-siloxane graft polymer.

  Examples of the organic solvent contained in the coating solution for forming the hard coat layer include hydrocarbons (eg, toluene, xylene, etc.) and alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.). , Ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (e.g., methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, and other organic solvents, or a mixture thereof. Can be mixed and used. The content of the curable resin contained in the coating liquid is, for example, 5 to 80% by mass.

  The hard coat layer can be applied by a known wet application method such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an inkjet method using the above-mentioned coating solution. The coating thickness of the coating liquid is, for example, 0.1 to 30 μm. In addition, it is preferable to perform a surface treatment such as vacuum ultraviolet irradiation on the base material 11 before applying the coating liquid to the base material 11.

The resin is cured by irradiating the coating film formed by applying the coating liquid with active energy rays such as ultraviolet rays. Thereby, a hard coat layer is formed. Examples of the light source used for curing include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, and the like. Irradiation conditions are preferably in the range of, for example, 50 to 2000 mJ / cm ² .

  Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto.

<Preparation of base material>
By the following method, clear hard coat layers (CHC) were formed on both sides of the support, and five types of base materials having a width of 350 mm (base materials 1 to 5) were produced.

[Preparation of base material 1]
Substrate 1: PET support with a thickness of 100 μm, front clear hard coat, back antistatic / anti-block hard coat

(Support)
As a support, a 100 μm-thick PET film, Lumirror U403, manufactured by Toray Industries and having an easy-adhesion layer on both surfaces was prepared.

(Preparation of surface hard coat coating solution HC1)
The following materials were mixed to prepare a hard coat coating solution HC1.
Polymerizable binder: 12.0 parts by mass of SR368 manufactured by Sartomer Co., Ltd. Polymerizable binder: 22.0 parts by mass of beam set 575 manufactured by Arakawa Chemical Co., Ltd. Polymerization initiator: 1.0 part by mass of Irgacure 651 manufactured by BASF Solvent: propylene glycol monomethyl ether 65 0.0 parts by mass

(Preparation of backside hard coat coating solution HC2)
According to Example 2 described in JP-A-2017-33891, a conductive polymer organic solvent dispersion was obtained. Next, the following materials were mixed to adjust HC2. Note that HC2 has an antistatic function and an antiblock function.
53.5 parts by mass of conductive polymer organic solvent dispersion (solid content: 0.5% by mass) Polymerizable binder: 1368 parts by mass of SR368 manufactured by Sartomer Polymerizable binder: Beam set 575 22.0 masses by Arakawa Chemical Co. Parts Polymerization initiator: 1.0 part by mass of Irgacure 651 manufactured by BASF Silica dispersion: 2.0 parts by mass of MA-ST-ZL manufactured by Nissan Chemical Co., Ltd. Solvent: 9.5 parts by mass of diacetone alcohol

(Preparation of base material)
Using a roll-to-roll coating device, HC1 was applied to one surface of the support (PET film) so that the dry film thickness was 4 μm, dried, and then irradiated with ultraviolet rays at 500 mJ / cm ^2. Cured and rolled up. Next, a hard coat layer having a thickness of 2 μm was formed on the opposite surface of the support (PET film) in the same manner as in the case of HC1, except that HC2 was used, and wound up. Next, it was slit into a width of 350 mm and wound up to obtain a substrate roll (base material 1) having a width of 350 mm.

[Preparation of base material 2]
Substrate 2: 23 μm thick PET support, UV absorbing hard coat, back PET protective film

(Support)
As a support, a 23 μm-thick PET film, KFL12W # 23, manufactured by Teijin Dupont Film Co., Ltd. having an easy-adhesion layer on both sides was prepared.

(Preparation of hard coat coating solution HC3)
The following materials were mixed to prepare a hard coat coating solution HC3.
Polymerizable binder: 20.0 parts by mass U-6LPA manufactured by Shin-Nakamura Chemical Co., Ltd. Polymerizable binder: 10.0 parts by mass A-9550 manufactured by Shin-Nakamura Chemical Co. Reactive UV absorber: RUVA-93 3.0 manufactured by Otsuka Chemical Co., Ltd. Parts by mass Polymerization initiator: 2.0 parts by mass of Irgacure 184 manufactured by BASF Solvent: 20.0 parts by mass of methyl ethyl ketone Solvent: 45.0 parts by mass of propylene glycol monomethyl ether

(Preparation of base material)
Using a roll-to-roll coating apparatus, HC3 is applied to one side of the support (PET film) so that the dry film thickness becomes 4 μm, and dried, and then irradiated with ultraviolet rays at 500 mJ / cm ^2. Cured and rolled up. Next, a hard coat layer having a thickness of 4 μm was formed on the opposite surface of the support (PET film) using the above-mentioned HC3 in the same manner. Further, a protective film in which a slightly adhesive layer was provided on a 50-μm-thick PET film was laminated in-line on the hard coat layer on the opposite side, and then wound up. Next, it was slit into a width of 350 mm and wound up to obtain a substrate roll (substrate 2) having a width of 350 mm.

[Preparation of base material 3]
Substrate 3: 100 μm thick PEN support, clear hard coat, backside antistatic / anti-block hard coat

(Support)
As a support, a 100 μm-thick polyethylene naphthalate film Q65FWA having an easy-adhesion layer on both sides manufactured by Teijin Dupont Film Co., Ltd. was prepared.
A substrate roll (substrate 3) having a width of 350 mm was obtained in the same manner as in the above-described substrate 1, except that the support was changed to the above.

[Preparation of base material 4]
Substrate 4: 50 μm thick COP (ZF14) support, clear hard coat, back PET protective film

(Support)
As a support, a cycloolefin polymer ZEONOR (registered trademark) ZF14 having a thickness of 50 μm manufactured by Zeon Corporation was prepared.

(Preparation of base material)
Corona discharge treatment was performed on both sides of the support by a roll-to-roll method. Next, using a roll-to-roll coating device, the above-mentioned HC1 was applied to one surface of the support so as to have a dry film thickness of 4 μm, dried, and then irradiated with ultraviolet rays at 500 mJ / cm ^2. Cured and rolled up. Next, a 4 μm-thick hard coat layer was formed on the opposite surface of the support in the same manner as described above, and a 50 μm-thick PET film provided with a slight adhesive layer was further covered with a hard film on the opposite surface. After laminating on the coat layer in-line, it was wound up. Next, it was slit into a width of 350 mm and wound up to obtain a substrate roll (substrate 4) having a width of 350 mm.

[Preparation of base material 5]
Substrate 5: PET support having a thickness of 100 μm, front clear hard coat / thin layer, back antistatic / anti-block hard coat

(Preparation of base material)
A substrate roll (substrate 5) having a width of 350 mm was obtained in the same manner as in the substrate 1, except that the dried film thickness of HC1 was applied to be 0.5 μm.

<Preparation of gas barrier film and plasma polymerization layer>
The film forming conditions of the gas barrier film and the plasma polymerized layer formed on each substrate prepared by the above-described method were set to the following film forming conditions 1 to 11. Then, by selecting film forming conditions from the film forming conditions 1 to 11, a gas barrier film and a plasma polymerized layer were formed on the substrate roll by the following method.

[Deposition conditions of gas barrier film and plasma polymerization layer]
The gas barrier film and the plasma polymerized layer are formed by two film forming units (a first film forming unit, a second film forming unit, and a second film forming unit) in the roller-to-roll (roll-to-roll) inter-roller discharge plasma CVD apparatus shown in FIG. It was manufactured using an apparatus (see FIG. 2 of JP-A-2015-131473) in which film-forming units were continuously arranged.

  Source gas type, gas supply amount, degree of vacuum, applied voltage, so that the film forming conditions in the first film forming unit and the second film forming unit are the film forming conditions 1 to 11 shown in Table 1 below. The power supply frequency, the film forming roll temperature, and the transport speed of the substrate roll were set. Then, in each film forming unit, a gas barrier film or a plasma polymerized layer was produced by applying any one of the film forming conditions 1 to 11. In addition, as conditions common to the film forming conditions 1 to 11, the effective film forming width was about 300 mm, the power supply frequency was 80 kHz, and the temperature of the film forming roll was 10 ° C.

<Preparation of gas barrier film>
The above substrates 1 to 5, the above film forming conditions 1 to 11, and the combination for forming a laminated film were selected, and gas barrier films of samples 101 to 117 were produced.

[Production of gas barrier film of sample 101]
A gas barrier film having a thickness of 81 nm was formed on the substrate 1 using the deposition condition 1, and a gas barrier film of the sample 101 was formed.

[Preparation of Gas Barrier Film of Sample 102]
A gas barrier film having a thickness of 325 nm was formed on the substrate 1 using the deposition condition 2, and a gas barrier film of the sample 102 was formed.

[Preparation of gas barrier film of sample 103]
A gas barrier film having a thickness of 73 nm was formed on the base material 1 using the deposition condition 3, and a gas barrier film of the sample 103 was formed.

[Production of gas barrier film of sample 104]
Using the deposition condition 4, a gas barrier film having a thickness of 582 nm was formed on the substrate 1, and a gas barrier film of the sample 104 was formed.

[Preparation of gas barrier film of sample 105]
A gas barrier film having a thickness of 53 nm was formed on the base material 1 under the deposition condition 5, and a gas barrier film of the sample 105 was formed.

[Production of gas barrier film of sample 106]
Using film forming condition 6, a gas barrier film having a thickness of 504 nm was formed on substrate 1, and a gas barrier film of sample 106 was formed.

[Preparation of Gas Barrier Film of Sample 107]
A gas barrier film having a thickness of 350 nm was formed on the substrate 1 using the film forming condition 7, and a gas barrier film of the sample 107 was formed.

[Production of gas barrier film of sample 108]
Using film forming condition 8, a gas barrier film having a thickness of 50 nm was formed on substrate 1, and a gas barrier film of sample 108 was formed.

[Production of gas barrier film of sample 109]
After forming a plasma-polymerized layer having a thickness of 500 nm on the substrate 1 using the film-forming condition 9, the film-forming apparatus was once returned to the atmospheric pressure, and the roll on which the plasma-polymerized layer had been formed was taken out. Then, after confirming that there is no contamination of the raw material supply pipe in place of the raw material under the film forming condition 5, the roll on which the plasma polymerization layer is formed is set again, and the plasma polymerization layer is formed under the film forming condition 5. A gas barrier film having a thickness of 53 nm was formed thereon, and a gas barrier film of Sample 109 was formed.

[Preparation of Gas Barrier Film of Sample 110]
After forming a plasma-polymerized layer having a thickness of 800 nm on the substrate 1 using the film forming condition 10, the same material as the film forming condition 10 is used without returning the film forming apparatus to the atmospheric pressure. In 5, a gas barrier film having a thickness of 53 nm was formed on the plasma polymerization layer, and a gas barrier film of Sample 110 was formed.

[Production of gas barrier film of sample 111]
A sheet was cut out from the gas barrier film manufactured by the above-described method of Sample 109, an overcoat layer having a thickness of 250 nm was formed on the gas barrier film, and a gas barrier film of Sample 111 was manufactured. The overcoat layer was produced by the following method.

(Overcoat layer: polysilazane modified layer)
First, as a polysilazane-containing coating solution, a 10% by mass dibutyl ether solution of perhydropolysilazane (PHPS: Aquamica NN120-10, non-catalyst type, manufactured by AZ Electronic Materials) was prepared. Then, the prepared polysilazane-containing coating solution is applied on a gas barrier film by spin coating so that the average layer thickness after drying is 250 nm, and dried for 1 minute in an atmosphere at a temperature of 85 ° C. and a humidity of 55% RH. Was. Further, the film was kept in an atmosphere at a temperature of 25 ° C. and a humidity of 10% RH (dew point temperature −8 ° C.) for 10 minutes, and subjected to a dehumidification treatment to form a coating film containing polysilazane. Thereafter, an excimer light irradiation treatment was performed under the following conditions to produce an overcoat layer.

(Excimer light irradiation treatment conditions)
Irradiation wavelength: 172 nm
Lamp filling gas: Xe
Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1 mm
Film heating temperature: 70 ° C
Oxygen concentration in irradiation device: 1.0%
Excimer lamp irradiation time: 5 seconds

[Production of gas barrier film of sample 112]
A sheet was cut out from the gas barrier film produced by the method of Sample 110 described above, and an overcoat layer having a thickness of 120 nm was produced on the gas barrier film, whereby a gas barrier film of Sample 112 was produced. The overcoat layer was manufactured by the same method as the above-described method of manufacturing the overcoat layer of Sample 111 except for the thickness of the coating.

[Production of gas barrier film of sample 113]
A gas barrier film of Sample 113 was produced in the same manner as in Sample 112 described above, except that Substrate 2 was used instead of Substrate 1.

[Production of gas barrier film of sample 114]
A gas barrier film of Sample 114 was produced in the same manner as in Sample 112 except that Substrate 3 was used instead of Substrate 1.

[Preparation of Gas Barrier Film of Sample 115]
A gas barrier film of Sample 115 was produced in the same manner as in Sample 112 except that Substrate 4 was used instead of Substrate 1.

[Production of Gas Barrier Film of Sample 116]
A gas barrier film of Sample 116 was produced in the same manner as in Sample 105 described above, except that Substrate 5 was used instead of Substrate 1.

[Production of gas barrier film of sample 117]
A gas barrier film having a thickness of 20 nm was formed on the substrate 1 using the film forming condition 11, and a gas barrier film of the sample 117 was formed.

<Evaluation>
The following evaluation was performed with respect to the produced gas barrier films of Samples 101 to 117.

[Thickness of plasma polymerized layer and overcoat layer]
In the gas barrier film, after preparing a section using the following focused ion beam (FIB) processing apparatus, a cross section of the section is observed with a transmission electron microscope (TEM), and the plasma polymerized layer and the overcoat are observed. The thickness of the coat layer was measured.
(FIB processing)
-Apparatus: SMI2050 manufactured by SII
・ Processing ion: (Ga 30kV)
-Sample thickness: 100 nm to 200 nm
(TEM observation)
-Apparatus: JEM2000FX manufactured by JEOL (acceleration voltage: 200 kV)

[XPS analysis]
The thickness of the gas barrier film of the gas barrier film and the composition distribution in the thickness direction of the gas barrier film were measured using the following photoelectron spectroscopy (XPS) analysis.

(XPS analysis conditions)
・ Apparatus: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: monochromatic Al-Kα
Measurement area: Si2p, C1s, O1s
・ Sputter ion: Ar (2 keV)
-Depth profile: Measurement was repeated after sputtering for a certain period of time. In one measurement, the sputtering time was adjusted so that the thickness became about 2.8 nm in terms of SiO ₂ .
-Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak areas. For data processing, MultiPak manufactured by ULVAC-PHI was used.

XPS analysis was performed at 2.8 nm intervals in the thickness direction. In the determination of the SiOxCy composition constituting the gas barrier film, the measurement points on the surface layer of the gas barrier film were excluded because of the influence of surface adsorbed substances. In the gas barrier film, the thickness within the range of the above-mentioned ABCDE or the above-mentioned A ₁ B ₁ CDE ₁ is the second point from the composition just below the surface layer and the second point from the surface layer because the film is continuously formed. Was determined to be close to the composition at the measurement point, and the thickness was measured assuming that the composition at the second measurement point from the surface layer was continuously formed up to the surface position.

As an example of the XPS analysis, graphs showing the sum (x + y) of the oxygen ratio x and the carbon ratio y in Sample 101, Sample 103, Sample 105, Sample 106, Sample 107, and Sample 108 are shown in FIGS. , FIG. 20, FIG. 22, FIG. 9, and FIG. In addition, in the graphs of these samples, the coordinates of (x, y) of the above-described ABCDE or the SiOxCy composition having a composition within the above-described A ₁ B ₁ CDE ₁ are shown in FIGS. 21, FIG. 23, FIG. 10, and FIG.

[Arithmetic average roughness (Ra) of gas barrier film, number of surface protrusions]
Regarding the gas barrier film of the gas barrier film, the arithmetic average roughness (Ra) of the gas barrier film and the projection on the surface were detected and counted by the following method.

(Arithmetic average roughness (Ra))
First, the surface of the gas barrier film was measured using an optical interference type three-dimensional surface roughness measuring device (WYKO NT9300 manufactured by Veeco) to obtain three-dimensional surface roughness data. Then, the arithmetic average roughness (Ra) of the gas barrier film surface was calculated from the obtained three-dimensional surface roughness data.

(Number of surface protrusions)
First, the surface of the gas barrier film was measured using an optical interference type three-dimensional surface roughness measuring device (WYKO NT9300 manufactured by Veeco) to obtain three-dimensional surface roughness data. Next, in the three-dimensional surface roughness conversion data (removing the roughness waviness component) obtained by applying a high-pass filter having a wavelength of 10 μm to the obtained three-dimensional surface roughness data, the maximum value when the data is displayed in a histogram is shown. Assuming that the height position of the peak was 0, the number of protrusions having a height of 10 nm or more was counted and calculated as the number per 1 mm ² . Specifically, the measurement resolution was about 250 nm, and six visual fields (area 0.114 mm ² ) in a range of 159.2 μm × 119.3 μm were measured and counted, and calculated as the number per 1 mm ² .

The number of protrusions of the obtained gas barrier film was evaluated according to the following criteria (rank).
Less than 5:10 pieces / mm ² 4:10 pieces / mm ² or more, 50 / mm ² less than 3:50 pieces / mm ² or more, 100 / mm ² less than 2: 100 pieces / mm ² or more, 200 / less than mm ² 1: 200 pieces / mm ² or more

[Optical property evaluation]
The absorption at 450 nm of the gas barrier film was determined using a spectrophotometer (CM-3600d, manufactured by Konica Minolta). The absorptance at 450 nm is determined by using the following formula using the transmittance A (%) and the reflectance B (%) at 450 nm measured using a spectrophotometer (CM-3600d, manufactured by Konica Minolta). I asked. [Absorptance at 450 nm = 100- (transmittance A (%) of 450 nm light + reflectance B (%) of 450 nm light]]

[Water vapor transmission rate (WVTR) evaluation]
The gas barrier film was subjected to AQUATRAN evaluation by MOCON, and the water vapor permeability (WVTR) of the gas barrier film was determined. Further, in the AQUATRAN evaluation, a sample below the measurement limit was evaluated by the Ca method described below to determine the water vapor transmission rate (WVTR).

(AQUATRAN evaluation)
The gas barrier film was set in a measurement chamber of a water vapor permeability measuring device (trade name: Aquatran MODEL1 manufactured by Mocon) such that the surface on which the gas barrier film was formed was on the detection side of the device. Then, the water vapor permeability (WVTR) of the gas barrier film was measured in an atmosphere of 38 ° C. and 100% RH.

(Ca method evaluation)
First, calcium (Ca: corrosive metal) was vapor-deposited on an area of 20 mm × 20 mm on a glass substrate using a vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd. to form a Ca layer having a thickness of 80 nm. Next, a gas barrier film was bonded and sealed on a glass substrate on which a Ca layer was formed using an adhesive (1655 manufactured by Three Bond) to prepare a Ca method evaluation sample. In addition, the gas barrier film to which the adhesive was bonded was left in a glove box (GB) for 24 hours to remove moisture of the adhesive and adsorbed water on the surface of the gas barrier film.

  Next, the prepared Ca method evaluation sample was stored in an environment of 85 ° C. and 85% RH. Then, light was incident on the Ca method evaluation sample after storage for 20 hours from the normal direction on the glass surface side, and photographed from the opposite surface side using an area-type CCD camera to obtain an evaluation image of the Ca layer.

Next, the average density of the Ca-evaporated portion of the obtained evaluation image was quantified. This evaluation was also performed after storage for 40, 60, 80, and 100 hours, and the average value of the water vapor transmission rate (WVTR) (g / m ² ) was determined from the average value of the slope of the average concentration of the Ca vapor deposition portion over time from 20 to 100 hours. / Day) was calculated. This value was converted to a water vapor permeability (WVTR) in a 40 ° C., 90% RH environment. The conversion factor used at this time is 1/25.

  Table 2 below shows the evaluation results of the gas barrier films of Samples 101 to 117 described above.

As shown in Table 2, the above-mentioned ABCDE or the above-mentioned composition in the range of A ₁ B ₁ CDE ₁ is 20 nm or more, and the arithmetic average roughness (Ra) of the surface of the gas barrier film is 2 Samples 105 to 115 having a wavelength of 0.0 nm or less have an absorptivity of light of 450 nm of less than 10% and a water vapor transmission rate of 1.0 × 10 ⁻³ or less. Therefore, by satisfying the above requirements, a gas barrier film and a gas barrier film having both high gas barrier properties and high transparency can be realized.

  Samples 109 to 115 have a plasma polymerized layer as a base layer of the gas barrier film. The sample 109 and the sample 110 have a lower water vapor transmission rate than the sample 105 in which the gas barrier film is formed directly on the substrate 1 under the same film forming condition 5. From these results, it is possible to realize a higher gas barrier property by forming a plasma polymerization layer as a base layer of the gas barrier film. Further, by forming an overcoat layer on the gas barrier film as in samples 111 to 115, higher gas barrier properties can be realized.

In the samples 101 and 102, the supply amount of oxygen of the reaction gas is small in forming the gas barrier film. Further, in the samples 103 and 104, the supply amount of oxygen of the reaction gas is excessive in forming the gas barrier film. For this reason, the samples 101 to 104 do not have the above-described ABCDE or the region having the composition within the above-described A ₁ B ₁ CDE ₁ . Then, in the samples 101 and 102 in which the supply amount of oxygen is small, the carbon ratio y (C / Si) in the gas barrier film is large, and the absorptance of light at 450 nm is large. Therefore, the optical characteristics of the gas barrier film are not sufficient. Further, in the samples 103 and 104 to which the supply amount of oxygen is excessive, since the oxygen ratio x (O / Si) in the gas barrier film is increased, the water vapor transmission rate is deteriorated. It is considered that this is because the increase in the oxygen ratio x (O / Si) in the gas barrier film increased the existence ratio of Si—OH in the gas barrier film, and formed a water vapor path by the hydrophilic group.

Although the sample 116 has a thickness of 20 nm or more that has a composition within the above-described range of A ₁ B ₁ CDE ₁ , the arithmetic average roughness (Ra) of the surface of the gas barrier film exceeds 2.0 nm. As a result, since the sample 116 has a water vapor transmission rate exceeding 1.0 × 10 ⁻³ , the gas barrier property is not sufficient. This is presumably because abnormal growth occurred during the production of the gas barrier film, and a defect or the like serving as a water vapor path occurred in the gas barrier film.

In addition, when the sample 116 in which the film-forming condition 5 is applied to the substrate 5 is compared with the sample 105 in which the same film-forming condition 5 is applied to the substrate 1, the sample 105 has a defect due to abnormal growth and has a reduced gas barrier property. There is no. Further, Samples 109 to 115 in which the same film formation condition 5 as that of Sample 116 was applied on the plasma polymerized layer also did not generate defects due to abnormal growth or decrease in gas barrier properties. From this result, it is considered that the abnormal growth of the gas barrier film is largely affected by the affinity between the base material or the underlying layer and the gas barrier film. Therefore, in forming the gas barrier film, the affinity between the substrate and the underlayer and the gas barrier film is taken into consideration, and the above-mentioned ABCDE or the above-mentioned A ₁ B ₁ CDE ₁ is within the range, and the arithmetic average roughness It is preferable to apply the condition that (Ra) is 2.0 nm or less.

In addition, the sample 117 has a thickness of 14 nm in the above-described ABCDE or the composition in the above-described A ₁ B ₁ CDE ₁ , and does not have a composition in the range of the above five points of 20 nm or more. . This is because the total thickness of the gas barrier film of the sample 117 is only 20 nm, so that the composition within the range of the above five points cannot be formed with a sufficient thickness. As a result, the sample 117 has a water vapor transmission rate exceeding 1.0 × 10 ⁻³ and does not have sufficient gas barrier properties.

  It should be noted that the present invention is not limited to the configuration described in the above embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

  DESCRIPTION OF SYMBOLS 10 ... Gas barrier film, 11, 60 ... Base material, 12 ... Plasma polymerization layer, 13 ... Gas barrier film, 50 ... Plasma CVD apparatus, 51 ... Feeding roller, 52, 54 , 55, 57: transport roller, 53, 56: film forming roller, 58: winding roller, 59: film forming gas supply pipe, 61, 62: magnetic field generator, 63 ..Power supply for plasma generation

Claims (24)

A chemical vapor deposition film containing silicon, oxygen, and carbon,
When the composition is represented by SiOxCy, A (x = 0.8, y = 0.8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E (x = 0.8, y = 0.55) A composition present in a region surrounded by five points in a thickness direction in a range from 20 nm to 1000 nm,
A gas barrier film having an arithmetic average roughness (Ra) of 2.0 nm or less. When the composition is represented by SiOxCy, A ₁ (x = 1.3, y = 0.4), B ₁ (x = 1.6, y = 0.4), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E ₁ (x = 1.3, y = 0. 3. The gas barrier film according to claim 1, wherein the composition present in the region surrounded by the five points in 3) has a thickness in the range of 20 nm or more and 1000 nm or less in the thickness direction. ^2. The gas barrier film according to claim 1, wherein the number of protrusions having a surface height of 10 nm or more is 200 / mm ² or less. A substrate, a gas barrier film comprising a gas barrier film formed on the substrate,
The gas barrier film is a chemical vapor deposition film containing silicon, oxygen, and carbon,
When the composition is represented by SiOxCy, A (x = 0.8, y = 0.8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E (x = 0.8, y = 0.55) A composition present in a region surrounded by five points in a thickness direction in a range from 20 nm to 1000 nm,
A gas barrier film in which the arithmetic average roughness (Ra) of the gas barrier film is 2.0 nm or less. When the composition of the gas barrier film is represented by SiOxCy, A ₁ (x = 1.3, y = 0.4), B ₁ (x = 1.6, y = 0.4), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E ₁ (x = 1.3) 5. The gas barrier film according to claim 4, wherein the composition present in the region surrounded by the five points (y, 0.3) ranges from 20 nm to 1000 nm in the thickness direction.   The gas barrier film according to claim 4, further comprising a plasma polymerization layer between the substrate and the gas barrier film.   The gas barrier film according to claim 6, wherein the plasma polymerization layer contains silicon, oxygen, and carbon.   The gas barrier film according to claim 4, further comprising an overcoat layer on the gas barrier film.   The gas barrier film according to claim 8, wherein the overcoat layer contains silicon, oxygen, and nitrogen.   The gas barrier film according to claim 9, wherein the overcoat layer is a polysilazane-modified layer. A method for producing a gas barrier film, comprising:
Form a gas barrier film containing silicon, oxygen and carbon using a chemical vapor deposition method,
In the formation of the gas barrier film, when the composition of the gas barrier film is represented by SiOxCy, A (x = 0.8, y = 0.8) on orthogonal coordinates where the horizontal axis is x and the vertical axis is y , B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E (x = 0.8, y = 0.55) is controlled so that the composition present in the region surrounded by the five points is in the range of 20 nm or more and 1000 nm or less in the thickness direction.
A method for manufacturing a gas barrier film, wherein the arithmetic average roughness (Ra) of the surface of the gas barrier film is 2.0 nm or less. When the composition of the gas barrier film is represented by SiOxCy, A ₁ (x = 1.3, y = 0.4), B ₁ (x = 1.6, y = 0.4), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E ₁ (x = 1.3, The method of manufacturing a gas barrier film according to claim 11, wherein the composition present in a region surrounded by five points (y = 0.3) is controlled to have a thickness in a range of 20 nm or more and 1000 nm or less in a thickness direction.   The method for producing a gas barrier film according to claim 11, wherein the formation of the gas barrier film by a chemical vapor deposition method is performed between two opposing electrode rollers.   The gas barrier according to claim 11, wherein the film-forming gas used for forming the gas barrier film includes an organosilicon compound in which 1 O atom is 1 for Si atom and C atom is less than 2 for 1 Si atom. Manufacturing method of membrane.   The method for producing a gas barrier film according to claim 14, wherein the film forming gas contains a cyclic siloxane as the organosilicon compound. A method for producing a gas barrier film for forming a gas barrier film on a substrate,
Forming the gas barrier film containing silicon, oxygen, and carbon using a chemical vapor deposition method,
In the step of forming the gas barrier film, when the composition of the gas barrier film is represented by SiOxCy, A (x = 0.8, y = 0. 8), B (x = 1.2, y = 0.8), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E ( x = 0.8, y = 0.55) is controlled so that the composition present in the region surrounded by the five points is in the range of 20 nm or more and 1000 nm or less in the thickness direction,
A method for producing a gas barrier film, wherein the arithmetic average roughness (Ra) of the gas barrier film surface is 2.0 nm or less. When the composition of the gas barrier film is represented by SiOxCy, A ₁ (x = 1.3, y = 0.4), B ₁ (x = 1.6, y = 0.4), C (x = 1.9, y = 0.1), D (x = 1.9, y = 0.0), E ₁ (x = 1.3, 17. The method for producing a gas barrier film according to claim 16, wherein the composition present in a region surrounded by five points (y = 0.3) is controlled so as to have a thickness in the range of 20 nm or more and 1000 nm or less in the thickness direction. .   The method for producing a gas barrier film according to claim 16, wherein the gas barrier film is formed on the plasma polymerized layer after forming the plasma polymerized layer on the substrate.   The method for producing a gas barrier film according to claim 18, wherein the plasma polymerized layer is formed between two opposing electrode rollers.   17. The gas barrier according to claim 16, wherein a film forming gas used for forming the gas barrier film includes an organosilicon compound in which 1 O atom is 1 for 1 Si atom and C atom is less than 2 for 1 Si atom. Production method of conductive film.   The method for producing a gas barrier film according to claim 20, wherein the film forming gas contains a cyclic siloxane as the organosilicon compound.   19. The method for producing a gas barrier film according to claim 18, wherein a film forming gas containing the same organosilicon compound is used for forming the plasma polymerized layer and forming the gas barrier film.   The method for producing a gas barrier film according to claim 22, wherein the formation of the plasma polymerized layer and the formation of the gas barrier film are performed using the same film forming apparatus.   24. The method for producing a gas barrier film according to claim 23, wherein a step of returning the pressure in the film forming apparatus to the atmospheric pressure is not provided between the formation of the plasma polymerization layer and the formation of the gas barrier film.