WO2018101027A1

WO2018101027A1 - Gas barrier film, and gas barrier film molding method

Info

Publication number: WO2018101027A1
Application number: PCT/JP2017/040900
Authority: WO
Inventors: 森　孝博
Original assignee: コニカミノルタ株式会社
Priority date: 2016-11-30
Filing date: 2017-11-14
Publication date: 2018-06-07
Also published as: JPWO2018101027A1

Abstract

When the composition of a gas barrier layer is represented by SiOxCy, the total of the region with a y<0.20 composition and the region with a y>1.40 composition of a gas barrier film is less than 20 nm in the thickness direction. Moreover, the gas barrier film has a region that is substantially flat and a region with a three-dimensionally curved surface surrounded by the flat region, and a 0.5 mm or greater average gap is formed between the region with the three-dimensionally curved surface and a flat plate.

Description

Gas barrier film and method for molding gas barrier film

The present invention relates to a gas barrier film having a gas barrier layer and a method for forming the gas barrier film.

As a sealing member of an organic electroluminescence (EL) element using a glass substrate, a metal sealing can having a curved surface having a flange shape formed on the outer four sides in a box shape with the side facing the substrate open. It is known (see Patent Document 1). Such a sealing can can be filled with a desiccant in the gap and can be easily designed to improve the durability of the element. On the other hand, since it is a metal, it has drawbacks such as being heavy, poor in flexibility, and being damaged when the metal surface comes into contact with the element when bent.

Further, a gas barrier layer that can suppress the occurrence of cracks on a curved surface having a large curvature has been proposed (see Patent Document 2). In the gas barrier layer, a plasma-deposited amorphous glass layer containing silicon, carbon, and hydrogen is formed on the film by a vapor deposition method.

JP 2003-272826 A Special table 2013-512257 gazette

However, in the method of forming a plasma-deposited amorphous glass layer as a gas barrier layer, since the organic component is contained in the gas barrier layer, the WVTR is as large as several g. For this reason, even if it can be molded into a shape having a curved surface, the barrier property is insufficient for application to sealing of electronic devices that require high barrier properties.
Thus, a gas barrier film having a high barrier property and a curved surface is desired.

In order to solve the above problems, the present invention provides a gas barrier film having a high barrier property and a curved surface.

The gas barrier film of the present invention includes a base material and a gas barrier layer formed on the base material. The gas barrier layer contains silicon, oxygen, and carbon, and when the composition of the gas barrier layer is expressed by SiOxCy, a region having a composition of y <0.20 and a region having a composition of y> 1.40. Is less than 20 nm in the thickness direction. Further, the gas barrier film has a substantially flat region and a region having a cubic curved surface surrounded by the flat region, and a region having a cubic curved surface when the flat region is in contact with the flat plate. Are not in contact with the flat plate, and an average gap of 0.5 mm or more is formed between the region having the cubic curved surface and the flat plate.

According to the present invention, a gas barrier film having a high barrier property and a curved surface can be provided.

It is a top view which shows the structure of a gas barrier film. FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film shown in FIG. It is sectional drawing which shows the structure of a gas barrier film. It is a graph which shows the distribution curve of the silicon of a gas barrier layer, carbon, and oxygen. It is a graph which shows the distribution curve of C / Si ratio of a gas barrier layer, and O / Si ratio. It is a graph which shows the distribution curve of the silicon of a gas barrier layer, carbon, and oxygen. It is a graph which shows the distribution curve of C / Si ratio of a gas barrier layer, and O / Si ratio. It is an orthogonal coordinate showing the composition of SiOxCy which comprises a gas barrier layer. It is an orthogonal coordinate showing the composition of SiOxCy which comprises a gas barrier layer. It is an orthogonal coordinate showing the composition of SiOxCy which comprises a gas barrier layer. It is an orthogonal coordinate showing the composition of SiOxCy which comprises a gas barrier layer. It is the image which displayed the height of the three-dimensional surface roughness conversion data of a gas barrier layer. It is the image which displayed the height of the three-dimensional surface roughness conversion data of a gas barrier layer. It is the image which displayed the height of the three-dimensional surface roughness conversion data of a gas barrier layer. It is a top view which shows the structure of a gas barrier film. FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film shown in FIG. It is a schematic diagram which shows an example of the discharge plasma CVD apparatus between rollers. It is a figure which shows the structure of the board | substrate used for the shaping | molding process of a gas barrier film. It is a figure which shows the structure of the sample for evaluating water vapor permeability (WVTR) in an Example. It is a figure which shows the structure of the board | substrate used for the shaping | molding process of a gas barrier film. It is a figure which shows the shape of the curved surface area | region in an Example.

Hereinafter, although the example of the form for implementing this invention is demonstrated, this invention is not limited to the following examples.
The description will be given in the following order.
1. 1. First embodiment of gas barrier film 2. Second embodiment of gas barrier film 3. Components of gas barrier film Method for forming gas barrier film

<1. First Embodiment of Gas Barrier Film>
Hereinafter, specific embodiments of the gas barrier film will be described.

[Configuration of gas barrier film]
1 and 2 show the structure of the gas barrier film. FIG. 1 is a plan view of a gas barrier film. FIG. 2 is a cross-sectional view taken along line AA of the gas barrier film 10 shown in FIG.

1 and 2, the gas barrier film 10 includes a base material 11 and a gas barrier layer 12 formed on one surface of the base material 11. In addition, if the gas-barrier film 10 provided with the base material 11 and the gas barrier layer 12 satisfy | fills each structure and conditions mentioned later, it will not specifically limit about another structure.

As shown in FIGS. 1 and 2, the gas barrier film 10 includes a substantially flat region (flat region) 13 and a region (curved region) 14 having a cubic curved surface surrounded by the flat region 13. Is provided. In the curved region, a concave portion is formed on one surface of the gas barrier film 10, and a convex portion is formed on the other surface. In the curved region 14 of the gas barrier film 10 shown in FIG. 2, the gas barrier layer 12 side is a surface having a concave portion, and the base material 11 side is a surface having a convex portion.

In FIG. 2, the position of the surface of the flat plate in contact with the gas barrier film 10 on the gas barrier layer 12 side (the surface side having the recesses) of the gas barrier film 10 is indicated by a broken line 20. This flat plate is illustrated for explaining the shape of the gas barrier film 10 and is not included in the configuration of the gas barrier film 10.

The flat region 13 is provided on the peripheral side of the gas barrier film 10. In the flat region 13 of the gas barrier film 10, “substantially flat” means that, as shown in FIG. 2, the gas barrier film 10 is flat when the gas barrier layer 12 side (surface side having a recess) is in contact with a flat plate. It shows that the gap 15 between the region 13 and the surface of the flat plate (broken line 20) is 0.1 mm or less. In addition, the flat area | region 13 corresponds to the area | region in which the part which takes out an electrode from a device area | region is formed when the gas barrier film 10 is applied to an electronic device etc. For this reason, the configuration in which slight unevenness of 0.1 mm or less due to wiring or the like is formed also in the “substantially flat region”.

The curved surface region 14 is provided on the center side in the gas barrier film 10. In the curved region 14 of the gas barrier film 10, the gap 16 between the recess formed on one surface side and the surface of the flat plate (broken line 20) in contact with the gas barrier film 10 is 0.5 mm or more on average.

The gas barrier film 10 is defined by the shape of the surface side (gas barrier layer 12 side) where the concave portion is formed in the curved region 14. For this reason, it does not specifically limit about the shape by the side of the surface (base material 11 side) in which a convex part is formed. In general, the shape of the gas barrier layer 12 is also deformed following the deformation of the base material 11, so that the shape on the surface side (gas barrier layer 12 side) where the concave portion is formed in the curved region 14 and the convex portion are formed. The shape on the surface side (base material 11 side) to be applied substantially matches except for the deviation due to the thickness.

As a method of forming a shape having the curved region 14 like the gas barrier film 10, a method of directly forming the gas barrier layer 12 on the substrate 11 having the curved region 14, or after forming the flat gas barrier film 10. A method of forming into a shape having the curved region 14 can be considered. However, in the method in which the gas barrier layer 12 is directly formed on the base material 11 having the curved region 14, there is a problem in the coverage of the gas barrier layer 12 on the cubic surface in the curved region 14, and therefore the gas barrier is in the region having the cubic surface. Deposition failure tends to occur in the layer 12. For this reason, it is difficult to improve the gas barrier property of the gas barrier film 10 by the method of directly forming the gas barrier layer 12 on the base material 11 having the curved region 14.

On the other hand, in the method of forming a flat gas barrier film 10 and then forming it into a shape having a curved region 14, a gas barrier layer 12 is first formed on a flat substrate 11 to form a flat gas barrier film. 10 is produced. And the heat | fever more than the softening temperature of the base material 11, for example, 80 degreeC or more, is applied in the state which pressed the gas barrier film 10 of the flat shape on the board | substrate (metal mold | die) which has a predetermined surface shape. Thereby, the gas barrier film 10 is formed into a predetermined shape (plastic processing). In such a method of forming the gas barrier film 10, film formation defects of the gas barrier layer 12 are unlikely to occur due to the decrease in film formability in the region having the above-mentioned cubic curved surface. For this reason, even in a shape in which a gap of 0.5 mm or more is formed on the curved surface area 14 on average, the gas barrier film 10 capable of suppressing the deterioration of the gas barrier property of the tertiary curved surface portion can be produced.

In particular, in the gas barrier film 10, the gas barrier layer 12 contains silicon, oxygen, and carbon. For this reason, it is possible to suppress the occurrence of defects in the gas barrier layer 12 even when the curved region 14 is molded into a shape having a cubic curved surface in which gaps of 0.5 mm or more are formed on average. For this reason, the gas barrier film 10 has a water vapor permeability (WVTR) of 0.1 (g / m ² / day) measured under the conditions of 60 ° C., 90% RH and 2 hours even after the above-described molding process. The following can be achieved: Further, in the gas barrier film 10 after the molding process, a preferable water vapor permeability (WVTR) can be 1 × 10 ⁻² (g / m ² / day) or less.

Further, in the gas barrier film 10, the substrate 11 may be a laminate of a plurality of substrates. For example, as shown in FIG. 3, the base material 11 may have a configuration in which the first base material 17 and the second base material 18 are bonded with an adhesive layer 19. In the gas barrier film 10 shown in FIG. 3, the gas barrier layer 12 is provided on one surface of the first base material 17, and the second base material 18 is provided on the other surface through the adhesive layer 19. In addition, the structure of those other than this is the structure similar to the gas barrier film 10 of the above-mentioned FIG.1 and FIG.2.

Furthermore, in the base material 11, the first base material 17 and the second base material 18 are preferably bonded so as to be peelable in the pressure-sensitive adhesive layer 19. For example, it is preferable that the adhesive layer 19 and the second substrate 18 are bonded so as to be peelable from the first substrate 17.

When the pressure-sensitive adhesive layer 19 and the second base material 18 are bonded so as to be peelable from the first base material 17, the second base material 18 functions as a protective film for the first base material 17. In the manufacturing process of the gas barrier film 10 or the manufacturing process of the electronic device to which the gas barrier film 10 is applied, if the substrate disposed on the outermost surface is damaged such as scratches, the appearance of the electronic device is defective. Will occur. For this reason, it is preferable to provide a peelable protective film on the surface of the base material 11 in order to prevent the base material from being damaged during each manufacturing process.

In the gas barrier film 10 shown in FIG. 3, the adhesive layer 19 and the second base material 18 are peeled from the first base material 17, thereby having the same configuration as the gas barrier film 10 shown in FIG. 1. At this time, the first base material 17 shown in FIG. 3 corresponds to the base material 11 shown in FIG.

When the base material 11 as shown in FIG. 3 is a laminate of the first base material 17 and the second base material 18, the thickness [X] of the first base material 17 and the second base material It is preferable that the sum total with the thickness [Y] of 18 is 50 μm or more and 150 μm or less. Furthermore, [X] / [Y] is preferably 0.15 or more and 0.90 or less.

If the sum of the thickness [X] of the first base material 17 and the thickness [Y] of the second base material 18 is 50 μm or more, the thickness becomes easy to handle in the formation of the gas barrier layer 12. Moreover, if the sum total of the thickness [X] of the 1st base material 17 and the thickness [Y] of the 2nd base material 18 is 150 micrometers or less, the base material 11 has sufficient softness | flexibility, and a shaping | molding process The plastic working can be easily performed.

Further, it is preferable that the thickness of the second base material 18 serving as the protective film is larger than the first base material 17 on which the gas barrier layer 12 is formed. In general, when the first base material 17 is applied to an electronic device or the like, the first base material 17 remains as the gas barrier film 10, so that the degree of freedom in design is limited by the requirements of the electronic device or the like. On the other hand, when the second substrate 18 is used as a protective film, the second substrate 18 is peeled off when the gas barrier film 10 is applied to an electronic device or the like. For this reason, the second base material 18 has a higher degree of design freedom than the first base material 17. Therefore, it is preferable that the mechanical strength required for the base material 11 when the gas barrier layer 12 is produced is secured on the second base material 18 side. Therefore, it is preferable that the thickness [Y] of the second base material 18 is larger than the thickness [Y] of the first base material 17 and the thickness [Y] of the second base material 18. / [Y] is preferably 0.15 or more and 0.90 or less.

[Composition of gas barrier layer and carbon distribution curve]
In the gas barrier film 10 described above, the gas barrier layer 12 contains silicon, oxygen, and carbon. That is, the gas barrier layer 12 is represented by a composition of SiOxCy. The value of x in SiOxCy is expressed as the oxygen content (O / Si) with respect to silicon, and the value of y is expressed as the carbon content (C / Si) with respect to silicon.

FIG. 4 shows a curve showing the distribution of the silicon atom content in the thickness direction of the gas barrier layer 12 (hereinafter referred to as a silicon distribution curve) and a curve showing the distribution of the carbon atom content in the thickness direction of the gas barrier layer 12 Hereinafter, a graph of a carbon distribution curve) and a curve showing the distribution of the content of oxygen atoms in the thickness direction of the gas barrier layer 12 (hereinafter, oxygen distribution curve) are shown.

FIG. 5 shows a curve (hereinafter referred to as a C / Si ratio distribution curve) showing the distribution of the composition ratio (C / Si) of carbon to silicon in the thickness direction of the gas barrier layer 12, and the thickness direction of the gas barrier layer 12. The graph of the curve (henceforth O / Si ratio distribution curve) which shows distribution of the composition ratio (O / Si) of oxygen with respect to silicon is shown. In the graph shown in FIG. 5, the ratio of silicon is defined as 1 based on the composition formula of SiOxCy.

Note that the content of each element in the thickness direction of the gas barrier layer 12 shown in FIG. 4 and the curve and maximum value indicating this content can be obtained by measurement of an XPS depth profile described later. Further, the composition ratio (C / Si) of carbon atoms to silicon atoms in the thickness direction of the gas barrier layer 12 shown in FIG. 5, the composition ratio of oxygen atoms (O / Si), and a curve or maximum representing this composition ratio The value can be calculated from the measured value of the XPS depth profile in FIG.

As shown in FIG. 4, in the gas barrier layer 12, the contents of silicon atoms, carbon atoms, and oxygen atoms continuously change in the depth direction. That is, as shown in FIG. 4, in the gas barrier layer 12, each distribution curve indicating the relationship between the distance (L) from the layer surface in the film thickness direction and the content of silicon atoms, carbon atoms, and oxygen atoms is , Continuously changing.

Further, as shown in FIG. 5, in the gas barrier layer 12, the C / Si ratio distribution curve showing the distance (L) from the layer surface in the film thickness direction and the ratio of carbon atoms to silicon atoms continuously changes. To do. Similarly, the O / Si ratio distribution curve indicating the ratio of oxygen atoms to silicon atoms changes continuously.

The gas barrier film 10 has a maximum of four or more carbon distribution curves (requirement (1)). Furthermore, [film thickness / maximum value number] of the gas barrier layer 12 is 25 nm or less (requirement (2)). In the graph shown in FIG. 4, in the gas barrier layer having a thickness of about 55 nm, the carbon distribution curve has six maximum values indicated by arrows in the drawing. Therefore, [film thickness / maximum value number] is about 9 nm.

The number of maximum values and [film thickness / maximum number of values] can be arbitrarily adjusted by changing the film formation conditions of the gas-phase film-forming gas barrier layer using the vacuum plasma CVD method described later. For example, the distance between the adjacent maximum values can be reduced by increasing the conveyance speed of the base material in the vapor deposition gas barrier layer deposition. In addition, by increasing the deposition rate of the vapor deposition gas barrier layer, the number of maximum values tends to increase in the gas barrier layer 12 having the same thickness.

In the carbon distribution curve of the gas barrier layer 12, it can be considered as one region where the composition continuously changes between adjacent maximum values. For this reason, the gas barrier layer 12 has a region where the composition continuously changes in the thickness direction by the number of maximum values. Therefore, the configuration in which the carbon distribution curve has six or more maximum values has a plurality of regions with different composition ratios of silicon, oxygen, and carbon in the film thickness direction, and the plurality of regions are stacked in the film thickness direction. Indicates that Furthermore, in the carbon distribution curve of the gas barrier layer 12, as the number of local maximum values increases, there are more regions in the gas barrier layer 12 where the composition changes continuously.

Further, in the gas barrier layer 12, a configuration in which the [film thickness / maximum value number] of the carbon distribution curve is 25 nm or less indicates the occurrence probability of the maximum value in the carbon distribution curve. For example, if [film thickness / number of local maximum values] is 25 nm, it indicates that there is one local maximum per 25 nm average in the thickness direction. By reducing the rate at which the maximum value occurs to 25 nm or less, the thickness of one region where the composition continuously changes can be reduced. That is, the gas barrier layer 12 can have the same configuration as a state in which thinner layers are stacked.

In the gas barrier layer 12, the average distance between adjacent maximum values is 25 nm or less, and there are six or more regions where the composition continuously changes in the thickness direction. In the molding process for forming the cubic curved surface, even if the gas barrier layer is stretched, the deterioration of the water vapor permeability (WVTR) of the gas barrier film 10 can be suppressed.

By having the gas barrier layer 12 having a plurality of regions in which the composition continuously changes, it is possible to suppress the deterioration of the water vapor permeability (WVTR) of the gas barrier film 10 even after a molding process involving the formation of a cubic curved surface. The reason why it can be considered is as follows. In addition, the following description is one of the guesses with respect to the mechanism for suppressing the deterioration of water vapor permeability (WVTR), which is derived from the configuration and effect of the gas barrier layer 12, and the mechanism for suppressing the deterioration of water vapor permeability (WVTR). Etc. are not limited to the following description.

For example, when the gas barrier layer has a single layer structure, when a crack occurs in one place in the gas barrier layer in the molding process of the gas barrier film, the crack propagates in the thickness direction, and the crack is in the thickness direction of the gas barrier layer. Easy to penetrate. Thus, when the crack penetrates the thickness direction of the gas barrier layer, moisture and the like can easily pass through the crack, so that the water vapor permeability (WVTR) of the gas barrier film is deteriorated.

However, since the gas barrier layer 12 has a plurality of regions where the composition changes continuously, a crack occurs in one place (one region) in the gas barrier layer 12, and the crack occurs in the thickness direction in the generated region. Even when the crack penetrates, the crack terminates in the other area, and the crack hardly propagates to the other area. Furthermore, since the gas barrier layer 12 has a plurality of regions laminated, the region where the crack has occurred is covered with another region. For this reason, the micro crack which generate | occur | produced in the gas barrier layer 12, and the area | region where this crack generate | occur | produced are shielded by another area | region. That is, even if a minute crack that cannot be detected by observation with an optical microscope is generated in the gas barrier layer 12, the minute crack does not grow so as to penetrate the entire gas barrier layer 12, and the crack may be caused by another region. Contained within layer 12. Therefore, the gas barrier layer 12 has a plurality of regions in which the composition continuously changes in the thickness direction, thereby suppressing the deterioration of the water vapor permeability (WVTR) of the gas barrier film after forming processing accompanied by the formation of a cubic curved surface. can do.

The gas barrier layer 12 has a maximum value of four or more carbon distribution curves. In general, the number of layers in the region where the composition continuously changes is the number of maximum values of the carbon distribution curve plus one layer. Therefore, if the carbon distribution curve has four or more maximum values, the composition is continuous. 5 or more layers are provided. By providing five or more regions where the composition continuously changes, the effect of covering other regions with the region where the microcracks have occurred is easily exhibited, and the effect of preventing the penetration of cracks in the entire gas barrier layer 12 is achieved. It is easy to express.

Also, as the number of maximum values in the carbon distribution curve increases, the number of layers in the region where the composition continuously changes increases. When the gas barrier layer 12 is in a state where a large number of regions are laminated, the effect of covering the region where the crack has occurred with other regions is more likely to appear. For this reason, the number of maximum values in the carbon distribution curve is preferably as large as possible, and the number of maximum values in the carbon distribution curve is preferably 6 or more, more preferably 8 or more, and particularly preferably 12 or more.

6 and 7 show the distribution curves in the gas barrier layer when the maximum value of the carbon distribution curve is twelve. The graphs shown in FIGS. 6 and 7 correspond to FIGS. 4 and 5 described above, and the details of the graphs are the same as those in FIGS. 4 and 5.

FIG. 6 is a graph showing a silicon distribution curve, a carbon distribution curve, and an oxygen distribution curve of the gas barrier layer 12. FIG. 7 is a graph showing a C / Si ratio distribution curve and an O / Si ratio distribution curve of the gas barrier layer 12. In the graph shown in FIG. 7, the silicon ratio is defined as 1 based on the composition formula of SiOxCy.

The gas barrier film 10 of the example shown in FIGS. 6 and 7 has a carbon distribution curve having 12 maximum values indicated by arrows in the drawings in a gas barrier layer having a thickness of about 105 nm. For this reason, in the graph shown in FIG. 4, [film thickness / maximum value number] is about 9 nm. Accordingly, in the example shown in FIGS. 6 and 7 as well, the [film thickness / maximum value] of the gas barrier layer 12 required for the gas barrier film 10 is 25 nm or less, as in the examples shown in FIGS. Meet the provisions of

Furthermore, under the condition that the thickness of the gas barrier layer 12 is constant, the smaller the thickness of the region where the composition changes continuously, the more regions are laminated. That is, the smaller the value [film thickness / maximum value] obtained by dividing the total thickness of the gas barrier layer 12 by the number of maximum values of the carbon distribution curve, the smaller the thickness of each region where the composition changes continuously. . Therefore, under the condition that the thickness of the gas barrier layer 12 is constant, the smaller the [film thickness / maximum value], the more regions can be stacked, and the region where the microcracks have occurred is replaced with other regions. It becomes easy to express the effect | action to coat | cover. For this reason, the [film thickness / maximum value number] of the gas barrier layer 12 is more preferably 15 nm or less.

[Compositional formula of gas barrier layer SiOxCy]
As described above, the gas barrier layer 12 contains silicon, oxygen, and carbon, and is represented by a composition of SiOxCy. The value of x in SiOxCy is expressed as the oxygen content (O / Si) with respect to silicon, and the value of y is expressed as the carbon content (C / Si) with respect to silicon.

In the gas barrier film 10, the gas barrier layer 12 has a thickness of a region having a composition of y <0.20 and a thickness of a region having a composition of y> 1.40 when the composition of the gas barrier layer 12 is expressed by SiOxCy. Is less than 20 nm.

The composition of y <0.20 is a region with a low carbon ratio and a high oxygen ratio. That is, the gas barrier layer 12 has a composition close to SiO ₂ . A region having a composition close to SiO ₂ is easily cracked by elongation treatment. If a region having a composition of y <0.20 exceeds 20 nm in the thickness direction, the crack generated in this region causes a crack. Difficult to propagate to other regions of different composition. For this reason, the barrier property of the gas barrier layer 12 tends to deteriorate.

Moreover, the composition of y> 1.40 is a region where the oxygen ratio is small and the carbon ratio is large. That is, the gas barrier layer 12 becomes a composition close to SiC _2. Also in this composition, as in the region having a composition close to the above-mentioned SiO ₂ , cracks are easily generated by the elongation treatment, and cracks are easily propagated to regions having different compositions, so that the barrier property of the gas barrier layer 12 is deteriorated. It's easy to do.

8 to 11 show orthogonal coordinates in which the horizontal axis is x and the vertical axis is y in the composition of SiOxCy constituting the gas barrier layer 12. 8 and 9 show (x, y) of the composition represented by SiOxCy for each thickness in the gas barrier layer 12 having the C / Si ratio distribution curve and the O / Si ratio distribution curve shown in FIG. ). 10 and 11 show the composition (x) of SiOxCy for each thickness in the gas barrier layer 12 having the C / Si ratio distribution curve and the O / Si ratio distribution curve shown in FIG. , Y). Each of (x, y) shown in FIGS. 8 to 11 is a thickness at a point indicated by a white triangle in the C / Si ratio distribution curve and the O / Si ratio distribution curve of FIGS. Represents the composition.

As shown in FIG. 8 and FIG. 10, the gas barrier film 10 has a composition that falls within the range of 4 points of the following ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy. It is preferable to have 40 to 200 nm in the 12 thickness direction.
A (x = 0.70, y = 1.10)
B (x = 0.9, y = 1.40)
C (x = 2.0, y = 0.20)
D (x = 1.8, y = 0.20)

Further, as shown in FIGS. 9 and 11, the gas barrier film 10 has a composition that falls within the range of 4 points of the following ABEF in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, More preferably, the gas barrier layer 12 has a thickness of 40 nm or more and 200 nm or less in the thickness direction.
A (x = 0.70, y = 1.10)
B (x = 0.9, y = 1.40)
E (x = 1.8, y = 0.40)
F (x = 1.6, y = 0.40)

Furthermore, the gas barrier layer 12 preferably has a composition that falls within the range of 4 points of the ABCD, and particularly preferably has a composition that falls within the range of 4 points of the ABEF. The composition of SiOxCy constituting the gas barrier layer 12, shown in FIGS. _8-11, in the distribution prone along SiC 2 -SiO ₂ theoretical line. Further, the composition of SiOxCy tends to be distributed in a region having a larger carbon atomic ratio than the SiC ₂ —SiO ₂ theoretical line as a whole. A narrow range surrounded by the four points ABCD in the vicinity of the SiC ₂ —SiO ₂ theoretical line is a preferable composition for the gas barrier layer 12 in terms of gas barrier properties, physical characteristics, and optical characteristics. Further, a narrower range surrounded by four points of ABEF is a particularly preferable composition for the gas barrier layer 12 in terms of gas barrier properties, physical characteristics, and optical characteristics.

The gas barrier layer 12 preferably has both a region where the C / Si has a composition of 0.95 or more and a region where the C / Si has a composition of 0.7 or less. Furthermore, the gas barrier layer 12 has both a region where the composition of C / Si is 0.95 or more and a region where the composition of C / Si is 0.7 or less, and 70% or more of the gas barrier layer 12. Is preferably included in any region where C / Si is 0.95 or more or C / Si is 0.7 or less, and all regions of the gas barrier layer 12 have a C / Si of 0. It is preferably included in any region of 95 or more or C / Si of 0.7 or less.

Further, as shown in the carbon distribution curves shown in FIGS. 4 to 7, a region where the C / Si has a composition of 0.95 or more and a region where the C / Si has a composition of 0.7 or less are formed in the thickness direction. It is preferable that they are laminated. In particular, it is preferable that four or more regions each having a composition having a C / Si composition of 0.95 or more and a region having a composition having a C / Si composition of 0.7 or less are alternately stacked. As shown in the carbon distribution curve shown in FIG. 7, it is more preferable that six or more regions are alternately stacked.

In the composition of SiOxCy that constitutes the gas barrier layer 12, the physical characteristics are different in regions having different compositions, and the conditions under which cracks are likely to occur in the regions are also different. For example, in the composition of SiOxCy constituting the gas barrier layer 12, small atomic ratio of carbon, the atomic ratio of oxygen is increased, the composition of the gas barrier layer 12 approaches the composition of SiO _2, the physical properties of the gas barrier layer 12 Is brittle like glass and easily breaks. For this reason, when the gas barrier layer 12 includes a composition having a large carbon atomic ratio and a C / Si ratio of 0.95 or more, it is possible to make it difficult for the gas barrier layer 12 to crack.

In addition, a region having a composition with a C / Si of 0.95 or more, a region with a composition with a small C / Si, and a region with a composition with a C / Si of 0.70 or less have different crack resistance. In a condition in which a region is laminated, a crack is likely to occur in either one of a region having a composition in which C / Si is 0.95 or more and a region having a composition in which C / Si is 0.70 or less. However, cracks hardly occur in the other region. For this reason, when there are two or more regions having greatly different compositions in the gas barrier layer 12, regions having different crack resistances are stacked, and large cracks that penetrate the thickness direction of the gas barrier layer 12 at a time are formed. Generation can be suppressed. Therefore, in the gas barrier layer 12, since all the regions are not damaged at once, the region where the crack is generated is covered with the other region, and the crack is shielded by the other region and enclosed in the gas barrier layer 12. It is easier to obtain the effect.

[Protrusions]
The gas barrier layer 12 is preferably less contaminated with foreign matters such as particles. When foreign substances such as particles mixed during film formation are present inside the gas barrier layer 12, when the gas barrier film 10 is molded to form a cubic curved surface and the gas barrier layer is stretched, stress is applied around the foreign substances. It is thought that this becomes the starting point for cracks to concentrate. Therefore, it is considered that the smaller the number of foreign matters per unit area of the gas barrier layer 12, the generation of cracks after the molding process accompanied by the formation of the cubic curved surface in the gas barrier film 10 is suppressed.

However, it is very difficult to directly observe and measure foreign matters such as particles inside the gas barrier layer 12. However, when foreign substances such as particles are taken in when forming the gas barrier layer 12, even if the foreign substance is smaller than the film thickness of the gas barrier layer 12, the film forming rate of the portion is increased. Are detected as minute protrusions. That is, in the gas barrier layer 12, protrusions due to the foreign matter are generated at a place where foreign matters such as particles are contained inside. For this reason, by observing the protrusions on the surface of the gas barrier layer 12, it is possible to observe the mixing of foreign matters such as particles inside the gas barrier layer 12. Therefore, it is considered that the generation of cracks when the gas barrier film 10 is stretched is more easily suppressed when the number of protrusions due to foreign matters per unit area of the gas barrier layer 12 is smaller.

In the gas barrier layer 12, the number of protrusions with a height of 10 nm or more observed on the surface is preferably 100 pieces / mm ² or less. If the number of protrusions is 100 / mm ² or less, the crack resistance of the gas barrier layer 12 is not lowered, and the gas barrier property of the gas barrier film 10 is hardly lowered.

In the gas barrier layer 12, minute protrusions of about 10 nm are difficult to separate and detect due to the influence of the undulation component of the surface roughness (unevenness having a long wavelength). For this reason, the number of minute protrusions of 10 nm or more in the gas barrier layer 12 is defined by a value detected and counted by the following method.

First, the surface of the gas barrier layer 12 is measured using an optical interference type three-dimensional surface roughness measuring device (Veeco WYKO NT9300). And by this measurement, the three-dimensional surface roughness data of the gas barrier layer 12 are acquired.

Next, the acquired three-dimensional surface roughness data is subjected to a process of removing a roughness waviness component by applying a high-pass filter having a wavelength of 10 μm. In the three-dimensional surface roughness conversion data from which the waviness component obtained by this process is removed, protrusions having a height of 10 nm or more are counted when the maximum peak position when the data is displayed as a histogram is set to zero. Then, the counted number of protrusions is calculated as the number per mm ² . More specifically, under the conditions of a measurement resolution of about 250 nm, it was measured and counted (0.114 mm ² as the area) range 6 field of 159.2μm × 119.3μm, calculated as the number per 1 mm ^2.

Regarding the surface state of the gas barrier layer 12, images (159.2 μm × 119.3 μm) in which the three-dimensional surface roughness conversion data obtained by processing by the above method are displayed as histograms are shown in FIGS. 12 to 14, the color is displayed in white as the height increases from the reference position on the surface of the gas barrier layer 12.

FIG. 12 is an image of the surface obtained by the above processing for the gas barrier layer 12 having a number of protrusions of less than 10 / mm ² . FIG. 13 is an image of the surface obtained by the above-described treatment with respect to the gas barrier layer 12 having the number of protrusions of 50 pieces / mm ² or more and less than 100 pieces / mm ² . FIG. 14 is an image of the surface obtained by the above processing for the gas barrier layer 12 having a number of protrusions of 200 pieces / mm ² or more.

As shown in FIG. 12, in the gas barrier layer 12 having the number of protrusions of less than 10 / mm ² , there are few protrusions exceeding a height of 10 nm displayed as white dots in the image. As shown in FIGS. 13 and 14, the number of protrusions is 50 / mm ² or more and less than 100 / mm ² and the number of protrusions is 200 / mm ² or more, and the number of protrusions exceeding 10 nm in height increases. Every time, the number of white spots displayed in the image increases. Therefore, by detecting and counting with the above method, the number of minute protrusions of about 10 nm on the surface of the gas barrier layer 12 can be defined.

<2. Second Embodiment of Gas Barrier Film>
Hereinafter, a second embodiment of the gas barrier film will be described. In addition, the gas barrier film of 2nd Embodiment is the structure similar to the gas barrier film of the above-mentioned 1st Embodiment except that the processing shape of a cubic curved surface differs. For this reason, in the following description, description is abbreviate | omitted about the structure similar to the gas barrier film of the above-mentioned 1st Embodiment.

[Configuration of gas barrier film]
15 and 16 show the configuration of the gas barrier film. FIG. 15 is a plan view of the gas barrier film. FIG. 16 is a cross-sectional view taken along line AA of the gas barrier film 70 shown in FIG.

15 and 16, the gas barrier film 70 includes a base material 11 and a gas barrier layer 12 formed on one surface of the base material 11 of the base material 11. In addition, if the gas barrier film 70 which consists of the base material 11 and the gas barrier layer 12 satisfy | fills each structure and conditions mentioned later, it will not specifically limit about another structure.

Further, as shown in FIGS. 15 and 16, the gas barrier film 70 includes a tertiary curved surface portion 76 on which a three-dimensional curved surface is formed, and a substantially flat surface disposed outside the tertiary curved surface portion 76. And a flat region 74 composed of a large region. The gas barrier film 70 includes a flat region 74 disposed in the cubic curved surface portion 76, and the curved region is formed from the flat region 74 disposed in the cubic curved surface portion 76 and the cubic curved surface portion 76. 14 is formed. In the gas barrier film 70, the flat region 74 formed of a substantially flat region is a region that is in contact with the flat plate as a surface with substantially no gap. On the other hand, in the gas barrier film 70, the cubic curved surface portion 76 having a three-dimensional curved surface is a region in contact with the flat plate by a line or a point. In this embodiment, the gas barrier film 70 has a concave surface on one surface and a convex surface on the other surface. In the curved region 14 of the gas barrier film 70 shown in FIG. 16, the gas barrier layer 12 side is a surface having a concave portion, and the base material 11 side is a surface having a convex portion.

In FIG. 16, the position of the surface of the flat plate in contact with the gas barrier film 70 on the gas barrier layer 12 side (the surface side having the recesses) of the gas barrier film 70 is indicated by a broken line 20. Further, in FIG. 16, the position of the surface of the flat plate in contact with the gas barrier film 70 on the base material 11 side (surface side having the convex portion) of the gas barrier film 70 is indicated by a broken line 21. This flat plate is illustrated for explaining the shape of the gas barrier film 70 and is not included in the configuration of the gas barrier film 70.

The flat region 74 is provided in the gas barrier film 70 at the peripheral side and the central portion. In the gas barrier film 70 shown in FIGS. 15 and 16, the flat portion around the frustoconical convex portion provided at the center of the gas barrier film 70 is a flat region 74 on the peripheral side. In addition, in the truncated cone-shaped convex portion, the flat portion of the portion serving as the upper base of the truncated cone is a flat region 74 at the center of the gas barrier film 70. In the flat region 74 of the gas barrier film 70, substantially flat and substantially in contact with no gap means that, as shown in FIG. 16, the gas barrier layer 70 side (surface side having a recess) of the gas barrier film 70 is used. When contacting the flat plate, the gap 15 between the flat plate surface (broken line 20) is 0.1 mm or less, and the base material 11 side (surface side having the convex portion) of the gas barrier film 70 is in contact with the flat plate. In this case, the gap 22 between the surface of the flat plate (broken line 21) is 0.1 mm or less.

The flat region 74 on the peripheral side of the gas barrier film 70 corresponds to a region where a portion for taking out an electrode from the device region is formed when the gas barrier film 70 is applied to an electronic device or the like. For this reason, the configuration in which slight unevenness of 0.1 mm or less due to wiring or the like is formed also in the “substantially flat region”.

Further, in the gas barrier film 70, the flat region 74 provided on the center side of the cubic curved surface portion 76 is a recess formed on one surface side of the gas barrier film 70 and a flat plate in contact with the gas barrier film 70. The gap 16 with the surface (broken line 20) is 0.5 mm or more on average.

In the gas barrier film 70, the tertiary curved surface portion 76 is provided between the peripheral flat region 74 and the central flat region 74. In the gas barrier film 70 shown in FIG. 15 and FIG. 16, in the truncated cone-shaped convex portion, the part that becomes the hypotenuse of the side surface of the truncated cone is the tertiary curved surface portion 76 of the gas barrier film 70. The tertiary curved surface portion 76 of the gas barrier film 70 is provided at 9% or more and 11% or less of the projected area of the entire region including the flat region 74 on the peripheral side, the tertiary curved surface portion 76, and the flat region 74 at the center. ing.

In the above definition, the projection area of the flat region 74 and the cubic curved surface portion 76 is not a projection area of the entire gas barrier film 70 but a specific area for measuring the gas barrier property in the gas barrier film 70. This is a measurement area 73. The measurement area 73 is an area in a range that can be measured by the measurement apparatus, and is defined in accordance with the area obtained from the area ratio between the flat area 74 and the cubic curved surface portion 76. That is, the area of the measurement region 73 is defined so that the projected area of the cubic curved surface portion 76 is 9% or more and 11% or less of the projection area of the measurement region 73.

Further, the gas barrier film 70 has a three-dimensional curved surface molded so that the measured area of the cubic curved surface portion 76 is 5% or more larger than the projected area of the cubic curved surface portion 76 described above. The actual measurement area is an area assumed to be a state in which a processed surface having a curved surface is extended on a plane.

In the gas barrier film 70, the flat region 74 and the tertiary curved surface portion 76 are either on the surface side where the concave portion is formed (gas barrier layer 12 side) or on the surface side where the convex portion is formed (base material 11 side). It is defined by the shape of In general, since the shape of the gas barrier layer 12 is also deformed following the deformation of the base material 11, the shape of the flat region 74 and the tertiary curved surface portion 76 is a surface on which a recess is formed except for deviation due to thickness. The shape on the side (gas barrier layer 12 side) and the shape on the surface side (base material 11 side) on which the convex portions are formed substantially coincide. For this reason, by defining the shape of one surface, the shape of the other surface is also defined.

[Water vapor permeability before and after molding]
As a method of forming a shape having the third curved surface portion 76 such as the gas barrier film 70, a flat gas barrier film 70 is formed in order to suppress a decrease in gas barrier property, as in the first embodiment. After that, it is molded into a shape having a tertiary curved surface portion 76. In this method, film formation failure of the gas barrier layer 12 of the cubic curved surface portion 76 is unlikely to occur, so that even when the measured area of the cubic curved surface portion 76 is processed to a shape that is 5% or more larger than the projected area, The gas barrier film 70 in which the deterioration of the property is suppressed can be produced.

In particular, in the gas barrier film 70, the gas barrier layer 12 contains silicon, oxygen, and carbon. For this reason, it is possible to suppress the occurrence of defects in the gas barrier layer 12 even when forming into a shape having a curved surface in which the measured area is 5% or more larger than the projected area.

The gas barrier film 70 includes both a flat gas barrier film [A] in a state before the curved surface processing is formed and a gas barrier film [B] in which the flat region 74 and the tertiary curved surface portion 76 are formed by molding. In the measurement region 73, the water vapor transmission rate (WVTR) measured under the conditions of 38 ° C. and 100% RH for 2 hours is 0.1 (g / m ² / day) or less.
Furthermore, the water vapor transmission rate (WVTR) in the measurement region 73 of the flat gas barrier film [A] in the state before forming the curved surface processing under the above conditions, and the gas barrier film [B after forming the cubic curved surface portion 76 into processing [B] ] In relation to the water vapor transmission rate (WVTR) in the measurement area 73 satisfies “(B water vapor transmission rate (WVTR) / [A] water vapor transmission rate (WVTR)) <5”.

When both the gas barrier film [A] before molding and the gas barrier film [B] after molding satisfy the water vapor transmission rate (WVTR) of 0.1 (g / m ² / day) or less, the curved surface Both of the gas barrier films 70 have sufficient gas barrier properties before and after the forming process. For this reason, the gas barrier film 70 satisfying this condition has a sufficient gas barrier property.

In addition, the gas barrier film [B] after the molding process slightly deteriorates in water vapor permeability (WVTR) due to the elongation treatment of the gas barrier layer 12 accompanying the curved surface processing of the cubic curved surface portion 76. However, if the water vapor permeability (WVTR) of the gas barrier film [B] after molding is 5 times or less than the water vapor permeability (WVTR) of the gas barrier film [A] before molding, sufficient gas barrier properties are obtained. have. For this reason, even after the gas barrier film 70 is subjected to curved surface processing by satisfying “([B] water vapor permeability (WVTR) / [A] water vapor permeability (WVTR)) <5”]. Therefore, it has a sufficient gas barrier property.

<3. Components of Gas Barrier Film>
Hereinafter, each configuration of the gas barrier film 10 shown in FIGS. 1 to 3 and the gas barrier film 70 shown in FIGS. 15 to 16 will be described. In addition, the following description is an example of a gas barrier film, and the structure of a gas barrier film is not limited to these. Moreover, the gas barrier film may have a configuration other than these.

[Gas barrier film]
The

gas barrier films

10 and 70 have a base material 11 and a gas barrier layer 12, and the gas barrier layer contains silicon, oxygen, and carbon, and is surrounded by a substantially flat region and the flat region. Other configurations are not limited as long as they have a region (curved surface region) having a cubic curved surface portion on which a three-dimensional curved surface is formed.

[Base material]
Examples of the base material 11 used for the

gas barrier films

10 and 70 include a resin film. As long as the resin film is a film that can hold the gas barrier layer, the material, the thickness, and the like are not particularly limited, and can be appropriately selected according to the purpose of use. As the resin film, a conventionally known resin film can be used. The base material 11 may be formed from a plurality of materials. Examples of the resin film include resin films described in paragraphs [0124] to [0136] of JP2013-226758A, paragraphs [0044] to [0047] of WO2013 / 002026, and the like. .

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).

It is preferable that the base material 11 has little light absorption and small haze. For this reason, the base material 11 can be appropriately selected from resin films that are generally applied to optical films.

In addition, the base material 11 may be a resin film or a plurality of layers may be used alone or may be formed of a plurality of layers. For example, as shown in FIG. 3, the first base material 17 and the second base material 18 may be bonded by an adhesive layer 19. As the first base material 17 and the second base material 18, the resin film can be used. Moreover, as the adhesive layer 19, the structure similar to the adhesive layer of the protective film mentioned later is applicable.

The substrate 11 is not limited to a single wafer shape and a roll shape, but a roll shape that can be handled by a roll-to-roll method is preferable 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]
Moreover, the structure by which the hard-coat layer was provided in both surfaces may be sufficient as the base material 11. FIG.
When the base material 11 has a hard coat layer on the surface, durability and smoothness of the

gas barrier films

10 and 70 are improved. The hard coat layer is preferably formed from a curable resin. Examples of the curable resin include epoxy resins, cyanate ester resins, phenol resins, bismaleimide-triazine resins, polyimide resins, acrylic resins, vinyl benzyl resins and other thermosetting resins, ultraviolet curable urethane acrylate resins, and ultraviolet curable polyesters. Examples thereof include active energy ray curable resins such as acrylate resins, ultraviolet curable epoxy acrylate resins, ultraviolet curable polyol acrylate resins, and ultraviolet curable epoxy resins.

Also, the hard coat layer has fine particles of inorganic compounds such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, magnesium oxide, or polymethyl methacrylate to adjust the 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, Ultraviolet curable resin compositions such as polyamide resin powder, polyimide resin powder, and polyfluorinated ethylene resin powder can be added. Further, 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.), alcohols (eg, methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.). , Ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, methyl acetate, ethyl acetate, methyl lactate, etc.), glycol ethers, other organic solvents, or these Can be used as a mixture. The content of the curable resin contained in the coating solution is, for example, 5 to 80% by mass.

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

The coating film formed by applying the coating solution is irradiated with active energy rays such as ultraviolet rays to cure the resin. 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 ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp. The irradiation conditions are preferably in the range of 50 to 2000 mJ / cm ² , for example.

[Gas barrier layer]
The gas barrier layer 12 constituting the

gas barrier films

10 and 70 is a layer having a barrier property and contains silicon, oxygen, and carbon, and four curves indicating the carbon content in the thickness direction of the gas barrier layer. It has the above maximum value, and satisfies the above-mentioned composition of the gas barrier layer and the carbon distribution curve. The gas barrier layer 12 is preferably formed by vapor-phase film formation of an inorganic compound that can be applied by a roll-to-roll method, which will be described later.

[Gas barrier layer; vapor deposition]
The gas barrier layer 12 formed by vapor deposition of an inorganic compound (hereinafter also referred to as a vapor deposition gas barrier layer) includes an inorganic compound containing silicon, oxygen, and carbon. The gas-phase film-forming gas barrier layer containing an inorganic compound may contain an element other than the inorganic compound as a secondary component.

The gas barrier property of the gas-phase film-forming gas barrier layer is preferably a water vapor transmission rate (WVTR) of 1 × 10 ⁻¹ (g / m ² / day) or less, preferably 1 × 10 ⁻² (g / m ² / day). day) or less. In addition, the gas barrier film after the molding process preferably has a water vapor transmission rate (WVTR) of 1 × 10 ⁻² (g / m ² / day) or less. The film thickness of the gas-phase film-forming gas barrier layer is not particularly limited, but is preferably 5 to 1000 nm. If it is such a range, it will be excellent in high gas barrier performance, bending tolerance, and cutting workability. Further, the vapor deposition gas barrier layer may be composed of two or more layers.

The vapor phase film forming method for forming the vapor phase film forming gas barrier layer is not particularly limited. An existing thin film deposition technique can be used to form the vapor deposition gas barrier layer. For example, a conventionally known vapor deposition method such as a vapor deposition method, a reactive vapor deposition method, a sputtering method, a reactive sputtering method, or a chemical vapor deposition method can be used. The gas barrier layer formed by these vapor deposition methods can be manufactured by applying known conditions.

For example, in the chemical vapor deposition (Chemical Vapor Deposition: CVD), a raw material gas containing a target thin film component is supplied onto a base material, and the film is deposited by a chemical reaction on the surface of the base material or in the gas phase. Is the method. In addition, 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, a photo CVD method, or 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 may be mentioned. In particular, the PECVD method is a preferable method. Hereinafter, the vacuum plasma CVD method will be described in detail as a preferred method of the chemical vapor deposition method.

[Vacuum plasma CVD method]
In the vacuum plasma CVD method, material gas flows into a vacuum vessel equipped with a plasma source, power is supplied from the power source to the plasma source, discharge plasma is generated in the vacuum vessel, and the material gas is decomposed and reacted with the plasma. The reactive species deposited on the substrate. A gas-phase film-forming gas barrier layer obtained by a vacuum plasma CVD method can produce a target compound by selecting conditions such as a raw material metal compound, decomposition gas, decomposition temperature, input power, and the like.

As the raw material compound, it is preferable to use a compound containing silicon and a compound containing metal, such as a silicon compound, a titanium compound, and an aluminum compound. These raw material compounds may be used alone or in combination of two or more.

Conventionally known compounds can be used as these silicon compounds, titanium compounds, and aluminum compounds. For example, known compounds include those described in paragraphs [0028] to [0031] of JP2013-063658A, paragraphs [0078] to [0081] of JP2013-047002A, and the like. it can. Preferably, silane, tetramethoxysilane, tetraethoxysilane, hexamethyldisiloxane, etc. are mentioned.

In addition, as a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide Examples thereof include gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, and water vapor. Further, the decomposition gas may be used by mixing with an inert gas such as argon gas or helium gas. A desired vapor deposition gas barrier layer can be obtained by appropriately selecting a source gas containing a raw material compound and a decomposition gas.

(Vacuum plasma CVD equipment)
Hereinafter, the vacuum plasma CVD method which is a preferable embodiment will be specifically described. FIG. 17 shows an example of a schematic diagram of an inter-roller discharge plasma CVD apparatus using a roll-to-roll method, which is applied to the vacuum plasma CVD method.

When the manufacturing apparatus shown in FIG. 17 is used as the film forming apparatus used when manufacturing the vapor-phase film forming gas barrier layer by the plasma CVD method, the roll-to-roll method is used while using the plasma CVD method. A phase-forming gas barrier layer can be produced. Hereinafter, with reference to FIG. 17, a method for producing a vapor deposition gas barrier layer will be described in more detail. FIG. 17 is a schematic diagram showing an example of an inter-roller discharge plasma CVD apparatus to which a magnetic field that can be suitably used in the production of a gas phase deposition gas barrier layer is applied.

An inter-roller discharge plasma CVD apparatus (hereinafter also simply referred to as a plasma CVD apparatus) 50 to which a magnetic field shown in FIG. 17 is applied includes a feeding roller 51, a transport roller 52, a transport roller 54, a transport roller 55, and a transport roller 57. Film roller 53 and film formation roller 56, film formation gas supply pipe 59, plasma generation power source 63, magnetic field generation device 61 and magnetic field generation device 62 installed inside

film formation rollers

53 and 56, winding And a roller 58. In such a plasma CVD manufacturing apparatus, at least the

film forming rollers

53 and 56, the film forming gas supply pipe 59, the plasma generating power source 63, and the magnetic

field generating apparatuses

61 and 62 are not shown in the vacuum. Located in the chamber. In FIG. 17, electrode drums connected to the plasma generating power source 63 are installed on the

film forming rollers

53 and 56. Further, in such a plasma CVD manufacturing apparatus, a vacuum chamber (not shown) is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by this vacuum pump. Yes.

In such a plasma CVD manufacturing apparatus, each film forming roller generates plasma so that a pair of film forming rollers (film forming roller 53 and film forming roller 56) can function as a pair of counter electrodes. The power supply 63 is connected. By supplying electric power to the pair of film forming rollers from the plasma generating power source 63, it is possible to discharge into the space between the film forming roller 53 and the film forming roller 56 and generate plasma. In such a plasma CVD manufacturing apparatus, the pair of

film forming rollers

53 and 56 are preferably arranged so that their central axes are substantially parallel on the same plane. By arranging the pair of

film forming rollers

53 and 56 in this manner, the film forming rate can be doubled and a film having the same structure can be formed.

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

Furthermore, as the film forming roller 53 and the film forming roller 56, known rollers can be used as appropriate, and those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, as the feed roller 51 and the

transport rollers

52, 54, 55, 57 used in such a plasma CVD manufacturing apparatus, known rollers can be appropriately selected and used. Further, the winding roller 58 is not particularly limited as long as it can wind the substrate 60 on which the vapor-phase film-forming gas barrier layer is formed, and a known roller can be appropriately used.

As the film forming gas supply pipe 59, one capable of supplying or discharging the source gas and the oxygen gas at a predetermined rate can be appropriately used. Further, as the plasma generating power source 63, a conventionally known power source of a plasma generating apparatus can be used. As such a plasma generation power source 63, since it is possible to efficiently perform the plasma CVD method, a power source (AC power source or the like) capable of alternately reversing the polarity of the pair of film forming rollers is used. It is preferable to use it. Further, it is more preferable that such a plasma generating power source 63 is one that can apply electric power in a range of 100 W to 10 kW and an AC frequency in a range of 50 Hz to 500 kHz. . As the

magnetic field generators

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

Using the plasma CVD apparatus 50 shown in FIG. 17, 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 (decompression degree), the diameter of the film forming roller, A desired gas barrier layer can be produced by appropriately adjusting the conveying speed of the resin substrate.

In the plasma CVD apparatus 50 shown in FIG. 17, a film forming gas (raw material gas or the like) is supplied into the vacuum chamber, and plasma discharge is performed while a magnetic field is generated between the pair of

film forming rollers

53 and 56. A gas-phase film-forming gas barrier layer is formed on the surface of the base material 60 held by the film-forming roller 53 and on the surface of the base material 60 held by the film-forming roller 56 when the film gas (source gas or the like) is decomposed by plasma. Is formed. In such film formation, the substrate 60 is conveyed by the feed roller 51, the

conveyance rollers

52, 54, 55, 57, the take-up roller 58, the

film formation rollers

53, 56, etc. The gas-phase film-forming gas barrier layer can be formed by a continuous roll-type film forming process.

(Deposition gas)
As a film forming gas used in the plasma chemical vapor deposition method, a source gas containing an organosilicon compound and an oxygen gas are used, and the content of the oxygen gas in the film forming gas is the same as that of the organosilicon compound in the film forming gas. It is preferable that the amount is less than the theoretical oxygen amount necessary for complete oxidation of the whole amount.

It is preferable to use an organosilicon compound containing at least silicon as the source gas constituting the film forming gas used for the production of the vapor phase film forming gas barrier layer. Examples of the organosilicon compound applicable to the production of the gas-phase film-forming gas barrier layer include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane Etc. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of handling in film formation and gas barrier properties of the obtained gas-phase film formation gas barrier layer. preferable. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

Further, the film forming gas can contain oxygen gas as a reaction gas in addition to the source gas. Oxygen gas is a gas that reacts with a raw material gas to become an inorganic compound such as an oxide. As the film forming gas, a carrier gas may be used as necessary in order to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, xenon, or hydrogen gas can be used.

When such a film forming gas contains a source gas containing an organosilicon compound containing silicon and an oxygen gas, the ratio of the source gas to the oxygen gas is such that the source gas and the oxygen gas are completely reacted. It is preferable that the oxygen gas ratio is not excessively larger than the theoretically required oxygen gas ratio. About this, description, such as international publication 2012/046767, can be referred, for example.

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

(Roller film formation)
In the plasma CVD method using the plasma CVD apparatus 50 shown in FIG. 17, the electric power applied to the electrode drum connected to the plasma generating power source 63 to discharge between the

film forming rollers

53 and 56 is the raw material gas. It can be appropriately adjusted according to the type, the pressure in the vacuum chamber, and the like. The power applied to the electrode drum is preferably in the range of 0.1 to 10 kW, for example. If the applied power is in such a range, no particles (illegal particles) are generated, and the amount of heat generated during film formation is within the control range. Thermal deformation of the material, performance deterioration due to heat, and generation of wrinkles during film formation can be suppressed.

In the plasma CVD apparatus 50, the conveyance speed (line speed) of the substrate 60 can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., but is within the range of 0.25 to 100 m / min. Preferably, it is more preferably in the range of 0.5 to 20 m / min. If the line speed is within the range, wrinkles due to the heat of the resin base material are not easily generated, and the thickness of the gas-phase film-forming gas barrier layer to be formed can be sufficiently controlled.

[Measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy]
The average value of the carbon atom content ratio in the gas barrier layer 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 layer use both X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. Thus, it can be created by so-called XPS depth profile measurement in which the composition of the surface is sequentially analyzed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve having the horizontal axis as the etching time, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer. For this reason, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement is referred to as “distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer”. Can be adopted. Moreover, it is preferable to set it as the following measurement conditions as a sputtering method employ | adopted in such XPS depth profile measurement.

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

In the gas barrier layer, the carbon distribution curve is preferably substantially continuous. Here, the carbon distribution curve is substantially continuous, specifically, the distance from the surface of the gas barrier layer in the film thickness direction of at least one of the gas barrier layers calculated from the etching rate and the etching time ( x, unit: nm) and the atomic ratio of carbon (C, unit: at%) satisfy the condition represented by [(dC / dx) ≦ 0.5].

(Carbon element profile in gas barrier layer)
The gas barrier layer contains carbon atoms, silicon atoms, and oxygen atoms as constituent elements of the gas barrier layer. The composition continuously changes in the layer thickness direction, and the carbon distribution curve among the distribution curves of the constituent elements based on the element distribution measurement in the depth direction by X-ray photoelectron spectroscopy satisfies the requirement (1). . From the viewpoint of achieving both gas barrier properties and flexibility, the gas barrier layer preferably has a configuration in which the carbon atom ratio continuously changes with a concentration gradient in a specific region.

In the gas barrier layer having such a carbon atom distribution profile, the carbon distribution curve in the layer has a plurality of extreme values. When the carbon distribution curve has a plurality of extreme values, sufficient gas barrier properties can be obtained even when the gas barrier layer is bent.

The extreme value of the above distribution curve is the maximum or minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer. The maximum value is an inflection point at which the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed, and 2 in the thickness direction from the position of the inflection point. It means that the atomic ratio value of the element at a position changed by ˜20 nm decreases by 1 at% or more. The minimum value is an inflection point at which the atomic ratio value of the element changes from decrease to increase when the distance from the surface of the gas barrier layer is changed, and the thickness direction from the position of the inflection point In other words, the atomic ratio of the element at the position changed by 2 to 20 nm is increased by 1 at% or more. That is, the maximum value and the minimum value are points where the atomic ratio value of the element decreases or increases by 1 at% or more in any range when the position in the thickness direction is changed in the range of 2 to 20 nm.

(Each element profile in the gas barrier layer)
The gas barrier layer is characterized by containing carbon atoms, silicon atoms, and oxygen atoms as constituent elements. Preferred embodiments of the ratio of each atom and the maximum and minimum values will be described below.

(Relationship between maximum and minimum carbon atom ratio)
In the gas barrier layer, the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) of the carbon atom ratio in the carbon distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. . By setting the difference between the maximum value and the minimum value of the carbon atom ratio to 3 at% or more, sufficient gas barrier properties can be obtained when the manufactured gas barrier layer is bent. When the difference between the maximum value and the minimum value is 5 at% or more, sufficient gas barrier properties can be obtained even when the gas barrier layer is bent.

(Relationship between maximum and minimum oxygen atom ratio)
In the gas barrier layer, the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the oxygen distribution curve is preferably 3 at% or more, and more preferably 5 at% or more. .

(Relationship between maximum and minimum silicon atom ratio)
In the gas barrier layer, the absolute value of the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) in the silicon distribution curve is preferably less than 10 at%, and more preferably less than 5 at%. . If the difference between the maximum extreme value (maximum value) and the minimum extreme value (minimum value) is less than 10 at%, the gas barrier properties and mechanical strength of the gas barrier layer can be obtained.

In order to improve the uniformity of the entire film surface and the gas barrier property, it is preferable that the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer). The gas barrier layer is substantially uniform in the film surface direction. The XPS depth profile measurement indicates that the oxygen distribution curve, the carbon distribution curve, and the oxygen-carbon total distribution at any two measurement points on the film surface of the gas barrier layer. When a curve is created, the number of extreme values of the carbon distribution curve obtained at any two measurement points is the same, and the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve Are the same as each other or a difference within 5 at%.

Other configurations of the gas barrier layer described above are described in paragraphs [0025] to [0047] of International Publication No. 2012/046767, paragraphs [0029] to [0040] of JP 2014-000782 A, and the like. Can be referred to and adopted as appropriate.

(Gas barrier layer thickness)
The thickness of the gas barrier layer 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. If the thickness of the gas barrier layer is within the range, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties are excellent, and good gas barrier properties can be obtained even in a bent state. Further, when the total thickness of the gas barrier layers is within the range, desired flatness can be realized in addition to the above effects.

(Method for forming gas barrier layer)
A method for forming a gas barrier layer that simultaneously satisfies the requirements (1) and (2) is not particularly limited, and a known method can be used. From the viewpoint of forming a gas barrier layer whose element distribution is precisely controlled, discharge plasma chemistry having a discharge space between rollers to which a magnetic field is applied using the inter-roller discharge plasma CVD apparatus shown in FIG. It is preferable to use a vapor deposition method. For example, the method described in paragraphs [0049] to [0069] of International Publication No. 2012/046767 can be referred to.

More specifically, in the inter-roller discharge plasma CVD apparatus shown in FIG. 17, an inter-roller discharge plasma processing apparatus to which a magnetic field is applied is used, the substrate is wound around a pair of film forming rollers, and the film is formed between the pair of film forming rollers. It is preferable to form the gas barrier layer 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 to reverse the polarity between the pair of film forming rollers alternately. Thus, by using a pair of film forming rollers, winding the base material on the pair of film forming rollers, and performing plasma discharge between the pair of film forming rollers, the substrate and the film forming roller By changing the distance and the plasma intensity, it becomes possible to form a gas barrier layer in which the carbon atom ratio has a concentration gradient and continuously changes in the layer.

In addition, during film formation, the surface portion of the substrate existing on one film forming roller can be formed, and the surface portion of the substrate existing on the other film forming roller can be formed simultaneously. It becomes possible. That is, since the film formation efficiency can be doubled and a film having the same structure is formed, the extreme value of the carbon distribution curve can be doubled, and the above requirements (1) and (2) can be efficiently performed simultaneously. It is possible to form a gas barrier layer that fills.

<4. Gas barrier film molding method>
Next, a method for forming the above

gas barrier films

10 and 70 will be described. In the following description of the molding method, the configurations and symbols of the

gas barrier films

10 and 70 shown in FIGS. 1 to 3 are used.

[Preparation of gas barrier film]
Next, a method for forming the gas barrier film 10 will be described. In the following description of the molding method, the configurations and symbols of the

gas barrier films

10 and 70 shown in FIGS. 1 to 3 and FIGS. 15 to 16 are used.
In the molding process of the

gas barrier films

10 and 70, first, the flat

gas barrier films

10 and 70 including the flat base material 11 and the gas barrier layer 12 are prepared. Hereinafter, an example of preparing the gas barrier film 10 having a flat shape will be described.

First, the base material 11 for preparing the

gas barrier films

10 and 70 having a flat shape is prepared. As the base material 11, a commercially available resin film capable of satisfying the above regulations is prepared. Or the 2nd base material 18 is bonded together to the 1st base material 17 using the adhesive layer 19, and the base material 11 of a laminated structure is produced. As the base material 11, the first base material 17, the second base material 18, and the pressure-sensitive adhesive layer 19, the above-described materials and conventionally known materials can be applied.

Further, when the base material 11 having a laminated structure including the first base material 17, the pressure-sensitive adhesive layer 19, and the second base material 18 is produced, the second base material 18 is prepared, and then the second base material 18 is prepared. The pressure-sensitive adhesive layer 19 is formed on one surface of the film. Moreover, you may prepare the commercially available protective film with an adhesive layer in which the 2nd base material 18 and the adhesive layer 19 were integrated. And the 2nd base material 18 is bonded to the back surface side of the 1st base material 17 through the adhesive layer 19. As shown in FIG. The bonding method of the 2nd base material 18 to the 1st base material 17 is not specifically limited, A conventionally well-known method is applicable. It is preferable to use an on-line method in which the gas barrier layer 12 described later is formed continuously with the bonding of the second base material 18. Moreover, the 2nd base material 18 is bonded to the 1st base material 17, and the base material 11 of the laminated structure which consists of the 1st base material 17, the adhesive layer 19, and the 2nd base material 18 is wound up with a winding shaft. After that, an off-line method in which the base material 11 having a laminated structure is unwound in a separate process and the gas barrier layer 12 is formed on the surface side of the first base material 17 may be used.

After preparing the base material 11 by the above method, the gas barrier layer 12 is produced on the base material 11. The gas barrier layer 12 may be produced as long as a film satisfying the above-described composition can be formed, and the above-described conventionally known method can be applied as a method for forming the gas barrier layer 12. Preferably, the gas barrier layer 12 is produced using an inter-roller discharge plasma CVD apparatus to which a magnetic field having a configuration shown in FIG. 17 is applied.

[Formation of gas barrier film (1)]
Next, a substrate (mold) having a predetermined surface shape to be used for molding the gas barrier film 10 is prepared. In FIG. 18, the perspective view which shows schematic structure of a board | substrate used for the shaping | molding process of the gas barrier film 10 is shown.

A substrate 30 shown in FIG. 18 includes a substantially flat portion (flat portion) 31 provided on the peripheral side and a convex portion 32 provided on the center side surrounded by the flat portion 31. In the molding process of the gas barrier film 10, the portion where the flat portion 31 of the substrate 30 abuts becomes the flat region 13 of the gas barrier film 10. Further, the portion with which the convex portion 32 abuts becomes the curved region 14 of the gas barrier film 10. For this reason, the board | substrate 30 needs to have the convex part 32 corresponding to the curved-surface area | region 14 of the gas barrier film 10. FIG.

In the substrate 30 shown in FIG. 18, the convex portion 32 has a quadrangular frustum shape provided with a predetermined height from the flat portion 31. In the substrate 30, the height of the convex portion 32 becomes a gap 16 with the flat plate surface (broken line 20) in the curved region 14 of the gas barrier film 10. For this reason, it is preferable that the height of the convex part 32 in the substrate 30 is 0.5 mm or more higher than the flat part 31 on average.

Further, in the substrate 30, the convex portion 32 has an inclined surface forming a side surface of the quadrangular pyramid with an angle of 15 ° to 45 ° with respect to the flat portion 31, and preferably 15 ° to 30 °. It is more preferable. Moreover, it is preferable that the corner | angular part around the upper surface of a quadrangular pyramid is rounded by the curvature radius of about 0.5 mm or more and 2 mm or less. The curved region 14 of the gas barrier film 10 is formed into a shape having a cubic curved surface by the side surfaces of the quadrangular pyramid and the corners around the upper surface. For this reason, even if gaps having an average of 0.5 mm or more are formed in the curved surface region 14 having a cubic curved surface by forming the side surfaces of the quadrangular pyramid and the corners around the upper surface within the above-mentioned definition, the gas barrier It is possible to suppress a decrease in gas barrier properties of the cubic curved surface portion due to the forming process of the conductive film 10.

Next, heat is applied to the gas barrier film 10 with the gas barrier film 10 having a flat shape pressed against the prepared substrate 30. At this time, it is preferable that the gas barrier layer 12 side of the gas barrier film 10 face the substrate 30 and the gas barrier layer 12 side and the substrate 30 are brought into contact with each other.

Further, it is preferable that the gas barrier layer 12 side of the gas barrier film 10 is disposed so as to face the substrate 30, and a buffer layer is interposed between the gas barrier layer 12 and the substrate 30. The buffer layer is preferably a protective film, a pressure-sensitive adhesive layer, an adhesive layer, or the like. By providing the buffer layer, damage to the gas barrier layer 12 during molding, for example, generation of scratches can be suppressed. Thereby, the fall of the gas barrier property resulting from the damage of the gas barrier layer 12 can be suppressed.

Examples of the method for pressing the gas barrier film 10 having a flat shape against the substrate 30 include vacuum forming using a vacuum laminating apparatus and pressure forming using a mold having a recess corresponding to the shape of the substrate 30. It is done. The application of heat to the gas barrier film 10 is preferably not less than the softening temperature of the substrate 11 and preferably less than the melting point of the substrate 11. By setting the heating temperature to be equal to or higher than the softening temperature, the gas barrier film 10 can be molded quickly. The molding processing time of the gas barrier film 10 is not particularly limited, and can be arbitrarily set between several seconds to 60 minutes.

Through the above steps, the gas barrier film 10 can be molded. In addition, what is necessary is just to select suitably according to the shape etc. which are requested | required of the gas barrier film 10 about the shape of a board | substrate, and it is not limited to said shape. Moreover, the molding process conditions of the gas barrier film 10 can be arbitrarily adjusted according to the configuration of the gas barrier film 10.

[Formation of gas barrier film (2)]
Next, the gas barrier film 70 has a curved surface area 14 composed of a cubic curved surface portion 76 and a flat region 74 disposed in the cubic curved surface portion 76, and a flat surface disposed outside the cubic curved surface portion 76. A molding method for forming the region 74 will be described. First, a substrate (mold) having a predetermined surface shape to be used for molding the gas barrier film 70 is prepared. In FIG. 19, the perspective view which shows schematic structure of a board | substrate used for the shaping | molding process of the gas barrier film 70 is shown.

A substrate 80 shown in FIG. 19 includes a substantially flat portion (flat portion) 81 provided around the frustoconical convex portion disposed in the center of the substrate 80 and on the upper bottom portion of the truncated cone. A curved surface processing part 82 is provided between the peripheral flat part 81 and the central flat part 81, which is provided on the hypotenuse of the truncated cone. In the molding process of the gas barrier film 70, the portion where the flat portion 81 of the substrate 80 abuts becomes the flat region 74 of the gas barrier film 70. Further, the portion with which the curved surface processed portion 82 abuts becomes the tertiary curved surface portion 76 of the gas barrier film 70. For this reason, the curved surface processing portion 82 of the substrate 80 needs to have a shape corresponding to the tertiary curved surface portion 76 of the gas barrier film 70.

In the substrate 80 shown in FIG. 19, the curved surface processing portion 82 is a side surface of a truncated cone provided with a predetermined height from the flat portion 81 on the peripheral side, and the height of the truncated cone (curved surface processing portion 82) is the same. The gap between the convex portion of the gas barrier film 70 and the surface of the flat plate (broken line 20). The height of the frustoconical convex portion on the substrate 80 is preferably 0.5 mm or more higher than the flat portion 81 on the average. The width of the truncated cone (curved surface processing portion 82) is the width of the cubic curved surface portion 76. The width of the oblique side of the truncated cone shape on the substrate 80 is arbitrarily set according to the area of the cubic curved surface portion 76.

Further, in the substrate 80, the curved surface processing portion 82 preferably has an angle of a slope forming the side surface of the truncated cone of 15 ° or more and 45 ° or less with respect to the flat portion 81 around the convex portion of the truncated cone shape. More preferably, the angle is 15 ° or more and 30 ° or less. Moreover, it is preferable that the corner | angular part of the upper base periphery and side face bottom part of a truncated cone is rounded by the curvature radius of about 0.5 mm or more and 2 mm or less. The cubic curved surface portion 76 of the gas barrier film 70 is formed into a shape having a curved surface by the corners of the upper base periphery and the side surface bottom portion of the truncated cone. For this reason, even if the cubic curved surface portion 76 having a curved surface is formed by setting the corners of the upper base periphery and side surface bottom portions of the truncated cone to the shapes within the above definition, the gas barrier film 70 is molded. It is possible to suppress a decrease in gas barrier properties of the tertiary curved surface portion.

Next, heat is applied to the gas barrier film 70 in a state where the gas barrier film 70 having a flat shape is pressed against the prepared substrate 80 by the same method as the molding process (1) of the gas barrier film described above. At this time, it is preferable that the gas barrier layer 12 side of the gas barrier film 70 face the substrate 80 and the gas barrier layer 12 side and the substrate 80 are brought into contact with each other.

Further, it is preferable that the gas barrier layer 12 side of the gas barrier film 70 is disposed so as to face the substrate 80, and a buffer layer is interposed between the gas barrier layer 12 and the substrate 80. The buffer layer is preferably a protective film, a pressure-sensitive adhesive layer, an adhesive layer, or the like. By providing the buffer layer, damage to the gas barrier layer 12 during molding, for example, generation of scratches can be suppressed. Thereby, the fall of the gas barrier property resulting from the damage of the gas barrier layer 12 can be suppressed.

Examples of the method for pressing the gas barrier film 70 having a flat shape against the substrate 80 include vacuum forming using a vacuum laminating apparatus and pressure forming using a mold having a recess corresponding to the shape of the substrate 80. It is done. The application of heat to the gas barrier film 70 is preferably not less than the softening temperature of the substrate 11 and preferably less than the melting point of the substrate 11. By setting the heating temperature to be equal to or higher than the softening temperature, the gas barrier film 70 can be quickly formed. The molding processing time of the gas barrier film 70 is not particularly limited, and can be arbitrarily set between several seconds to 60 minutes.

Through the above steps, the gas barrier film 70 can be molded. In addition, what is necessary is just to select suitably about the shape etc. of a board | substrate according to the shape etc. which are requested | required of the gas barrier film 70, and it is not limited to said shape. Moreover, the molding process conditions of the gas barrier film 70 can be arbitrarily adjusted according to the configuration of the gas barrier film 70.

[Protective film]
The protective film includes a protective substrate and a pressure-sensitive adhesive layer for bonding the protective substrate onto the gas barrier layer 12 of the

gas barrier films

10 and 70. As long as the protective film can be peeled off from the

gas barrier films

10 and 70 in the pressure-sensitive adhesive layer, materials used for the protective substrate and the pressure-sensitive adhesive layer are not particularly limited.

Further, the protective film may be provided not only on the gas barrier layer 12 of the

gas barrier films

10 and 70 but also on the substrate 11 side of the

gas barrier films

10 and 70. The surface of the base material 11 can be protected by providing a protective film on the base material 11 side of the

gas barrier films

10 and 70.

Also, as the protective film, a self-adhesive coextrusion stretched multilayer film can be used. Examples of such self-adhesive coextrusion stretched multilayer films include self-adhesive OPP films FSA-010M, FSA-020M, FSA-050M, FSA-100M, FSA-150M, and FSA-300M manufactured by Futamura Chemical Co., Ltd. FSA-010B or the like can be used.

[Protective substrate]
As the protective base material, the same resin film as the base material 11 of the

gas barrier films

10 and 70 described above can be used. From the viewpoint of heat resistance and optical properties, it is preferable to use polypropylene (PP), polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) as the protective substrate.

The protective substrate may be a single resin film or a plurality of resin films, or may be formed of a plurality of layers. The protective substrate is not limited to a single wafer shape and a roll shape, but a roll shape that can be handled by a roll-to-roll method is preferable from the viewpoint of productivity.

The thickness of the protective substrate is not particularly limited, but is preferably about 5 to 500 μm, and more preferably 25 to 150 μm. If the thickness of the protective substrate is 5 μm or more, the thickness becomes a sufficient thickness that is easy to handle. Moreover, if the thickness of a protective base material is 500 micrometers or less, it has sufficient softness | flexibility and sufficient transportability and adhesiveness to a roll are obtained.

[Adhesive layer]
An adhesive layer is comprised including an adhesive. The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited as long as the pressure-sensitive adhesive force required for the protective film can be obtained, and conventionally known materials can be used. As the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer, a pressure-sensitive pressure-sensitive adhesive is preferable. The pressure sensitive adhesive has cohesive strength and elasticity, and can maintain stable adhesiveness for a long time. Moreover, when forming an adhesive layer, requirements, such as a heat | fever and an organic solvent, are not required, but a protective film can be bonded to the

gas barrier films

10 and 70 only by applying a pressure.

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, a material having excellent transparency is preferable. Examples of the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer include pressure-sensitive adhesives including epoxy resins, acrylic resins, rubber resins, urethane resins, vinyl ether resins, and silicon resins. As the form of the pressure-sensitive adhesive, for example, a solvent type, an emulsion type, and a hot melt type can be used.

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer, an acrylic pressure-sensitive adhesive is preferable from the viewpoints of durability, transparency, and ease of adjustment of pressure-sensitive adhesive properties. The acrylic pressure-sensitive adhesive is obtained by adding an acrylic polymer having an acrylic acid alkyl ester as a main component and copolymerizing a polar monomer component thereto. The alkyl acrylate ester is an alkyl ester of acrylic acid or methacrylic acid and is not particularly limited. For example, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, (meth ) Pentyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. Specifically, Toyo Ink BPS5978 can be used.

As the curing agent for the acrylic pressure-sensitive adhesive, for example, an isocyanate-based, epoxy-based, or alidiline-based curing agent can be used. As the isocyanate curing agent, it is preferable to use an aromatic system such as toluylene diisocyanate (TDI) in order to obtain a stable adhesive force even after long-term storage and to form a harder adhesive layer. Specifically, Toyo Ink BXX5134 can be used.

The addition amount of the curing agent is preferably 3% by mass to 9% by mass and more preferably 5% by mass to 7% by mass with respect to the pressure-sensitive adhesive. Within such a range, the pressure-sensitive adhesive component can be sufficiently cured, sufficient adhesive force can be secured, and after the protective film is peeled off from the

gas barrier film

10, 70, the gas barrier film 10, The pressure-sensitive adhesive layer hardly remains on the 70 side.

The weight average molecular weight of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably 400,000 or more and 1.4 million or less. If the weight average molecular weight is a value within this range, the adhesive force is rarely excessive, and the adhesive force can be obtained within a necessary range. Furthermore, if it is the range of said weight average molecular weight, the residual of the adhesive layer to the

gas barrier films

10 and 70 side after peeling can be prevented.

In addition to the above resins contained in the pressure-sensitive adhesive, various additives can be used from the viewpoint of improving the physical properties of the pressure-sensitive adhesive layer. For example, natural resins such as rosin, modified rosin, rosin and modified rosin derivatives, polyterpene resins, terpene modified products, aliphatic hydrocarbon resins, cyclopentadiene resins, aromatic petroleum resins, phenolic resins, alkyl- Tackifiers such as phenol-acetylene resins, coumarone-indene resins, vinyltoluene-α-methylstyrene copolymers, anti-aging agents, stabilizers, and softeners can be used as necessary. . Two or more of these may be used as necessary. Moreover, in order to improve light resistance, organic ultraviolet absorbers, such as a benzophenone series and a benzotriazole series, can also be added to an adhesive.

The thickness of the pressure-sensitive adhesive layer is preferably 10 μm or more and 50 μm or less for easy handling of the protective film. If it is such a range, sufficient contact | adhesion power can be acquired to a protective film and the gas-

barrier film

10,70. Furthermore, when peeling off the protective film, it is not necessary to apply an excessive force to the

gas barrier films

10 and 70, and damage to the

gas barrier films

10 and 70 can be suppressed.

The method for forming (coating) the pressure-sensitive adhesive layer on the surface of the protective substrate is not particularly limited. For example, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive on a protective substrate using a screen method, a gravure method, a mesh method, a bar coating method, or the like, and drying or curing.

[Adhesive layer]
An adhesive bond layer is a layer for protecting the surface of the gas barrier layer 12 of the

gas barrier films

10 and 70 similarly to the above-mentioned protective film and adhesive layer. The adhesive used as the adhesive layer is preferably one that can be adhesively cured from room temperature to 80 ° C. The adhesive may be applied using a commercially available dispenser or screen printing.

Examples of the adhesive layer include photocurable or thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, moisture curable adhesives such as 2-cyanoacrylates, and epoxy. Thermosetting or chemical curable (two-component mixed) adhesives such as hot-melt adhesives, hot-melt type polyamide-based, polyester-based, polyolefin-based adhesives, cationic-curing type UV-curable epoxy resin adhesives, etc. .

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

[Preparation of Substrate 1]
The base material 1 having a hard coat layer formed on both sides of the support was produced by the following method.

(Support)
A Teijin DuPont Films company-made PET film having a thickness [X] of 50 μm and an easy-adhesion layer on both sides, KFL12W # 50 (first substrate) was prepared.

(Preparation of hard coat coating solution HC1)
A hard coat coating solution HC1 in which the following materials were mixed was prepared.
Polymerizable binder: SR368 manufactured by Sartomer 12.0 parts by mass Polymerized binder: Beam set 575 manufactured by Arakawa Chemical Co., Ltd. 22.0 parts by mass Polymerization initiator: Irgacure 651 manufactured by BASF Co. 1.0 parts by mass Solvent: Propylene glycol monomethyl ether 65 .0 parts by mass

(Preparation of base material)
Using a roll-to-roll type coating apparatus, HC1 was applied to one side of a support (PET film) so that the dry film thickness was 4 μm, dried, and then irradiated with ultraviolet rays under the condition of 500 mJ / cm ^2. Cured and wound up. Next, a hard coat layer having a thickness of 4 μm is formed on the opposite surface of the support (PET film) in the same manner as described above, and further, a PET film (second substrate) having a thickness [Y] of 50 μm is formed. The protective film provided with the slightly adhesive layer was bonded inline on the hard coat layer on the opposite side, and then wound up.

[Preparation of Substrate 2]
As a support, prepared by Teijin DuPont Films Co., Ltd., a 23 μm-thick PET film having an easy-adhesion layer on both sides, KFL12W # 23 was prepared, and HC2 was used as a hard coat coating solution. The base material 2 was produced by the method.

(Preparation of hard coat coating solution HC2)
Polymerizable binder: 2-6 parts by mass of U-6LPA manufactured by Shin-Nakamura Chemical Co., Ltd. Polymerizable binder: A-9550 10.0 parts by mass of Shin-Nakamura Chemical Co., Ltd. Reactive UV absorber: RUVA-93 3.0 manufactured by Otsuka Chemical Co., Ltd. Mass parts Polymerization initiator: BASF Irgacure 184 2.0 parts by mass Solvent: Methyl ethyl ketone 20.0 parts by mass Solvent: Propylene glycol monomethyl ether 45.0 parts by mass

[Preparation of Substrate 3]
A base material 3 was prepared in the same manner as the base material 1 except that a 100 μm-thick PET film having an easy-adhesion layer on both sides and Lumirror U34 were prepared as a support.

[Gas barrier layer deposition conditions]
In the gas barrier layer, two film forming units (first film forming unit and second film forming unit) are continuous in the inter-roller discharge plasma CVD apparatus using the roll-to-roll method shown in FIG. (See FIG. 2 of JP-A-2015-131473).

The film forming conditions in the first film forming unit and the second film forming unit were set to any of the conditions C1 to C14 shown in Table 1 below. And in each film-forming part, the gas barrier layer was produced by applying one of the conditions of C1-C14. As common conditions for C1 to C14, the film formation effective width was converted to 1000 mm, the power supply frequency was 80 kHz, and the film formation roll temperature was 10 ° C.

Note that, in forming the gas barrier layer, an apparatus having two film forming units (a first film forming unit and a second film forming unit) is used, so that two layers each time the substrate is passed through the film forming apparatus. The gas barrier layer is formed. In the production of the gas barrier layer, the first film formation transports the substrate from the first film formation unit to the second film formation unit (forward direction), and the second film formation starts from the second film formation unit. The substrate was transported toward the first film forming unit (reverse direction). Similarly, in the odd-numbered film formation, the substrate is transported from the first film-forming unit to the second film-forming unit (forward direction), and in the even-numbered film formation, the first film-forming unit starts from the second film-forming unit. The base material was conveyed toward the film part (reverse direction).

<Preparation of Gas Barrier Films of Samples 101 to 122>
The base materials 1 to 3, the film formation conditions C1 to C14 and the number of film formations are selected from the combinations shown in Table 2 below to produce gas barrier films of samples 101 to 122, and further molded by the following method. processed. In the gas barrier films of Samples 118 to 122, SiO ₂ was produced as a gas barrier layer by a conventional method using a roll-to-roll type sputtering film forming apparatus. In sputtering film formation, a polycrystalline Si target was used as a target, and oxygen was introduced to adjust the composition to SiO ₂ . Moreover, the film thickness was adjusted by adjusting the sputtering rate and the conveyance speed.

[Molding process of gas barrier film]
First, a metal substrate 30 having a flat portion 31 and a quadrangular pyramid-shaped convex portion 32 provided at the center of the flat portion 31 shown in FIG. 18 was prepared. In the substrate 30, the upper surface of the convex portion 32 of the quadrangular pyramid is approximately 24 × 24 mm, and the angle of each hypotenuse of the quadrangular pyramid with respect to the flat portion 31 is 20 degrees. The convex part 32 of the quadrangular pyramid is rounded around the upper surface with a radius of 0.5 mm. Further, as the metal substrate 30, five types of substrates 30 having different heights of the convex portions 32 of 0.2 mm, 0.6 mm, 0.8 mm, 1.0 mm, or 1.2 mm were prepared.

Next, both sides of the gas barrier film were bonded using FSA-020M manufactured by Phutamura Chemical Co., Ltd. as a protective film to prepare a gas barrier film laminate. Then, the gas barrier film laminate is opposed to the substrate so that the gas barrier layer of the gas barrier film is on the substrate 30 side, the substrate 30 is heated to 100 ° C. using a vacuum laminating apparatus, and the molding processing time is 10 minutes. As described above, a gas barrier film was molded.

<Evaluation>
The following evaluations were performed on the gas barrier films of the produced samples 101 to 122.

[Gas barrier layer thickness]
In the prepared gas barrier films of the samples 101 to 122, after the thin piece was prepared using the following focused ion beam (FIB) processing apparatus, the section of the section was observed with a transmission electron microscope (TEM), The thickness of the gas barrier layer was measured.
(FIB processing)
・ Apparatus: SII SMI2050
・ Processed ions: (Ga 30 kV)
Sample thickness: 100 nm to 200 nm
(TEM observation)
・ Device: JEOL JEM2000FX (acceleration voltage: 200kV)

[XPS analysis]
The composition distribution in the thickness direction of the gas barrier layer of the produced gas barrier films of Samples 101 to 117 was measured using the following photoelectron spectroscopy (XPS) analysis.

(XPS analysis conditions)
・ Equipment: ULVAC-PHI QUANTERASXM
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, C1s, O1s
・ Sputtering ion: Ar (2 keV)
Depth profile: repeats measurement after sputtering for a certain time. In one measurement, the sputtering time was adjusted so that the thickness was 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 area. For data processing, MultiPak manufactured by ULVAC-PHI was used.

The XPS analysis was measured at 2.8 nm intervals in the thickness direction. Further, in determining the composition of SiOxCy constituting the gas barrier layer, the measurement points on the surface layer of the gas barrier layer were excluded because of the influence of the surface adsorbate. In addition, in the gas barrier layer, the thickness within the range of ABCD and ABEF described above is such that the composition immediately below the surface layer and the composition at the second measurement point from the surface layer are close because the film is continuously formed. The thickness was measured on the assumption that the composition of the second measurement point from the surface layer was continuously formed up to the surface position.

[Number of surface protrusions of gas barrier layer]
For the gas barrier layers of the gas barrier films of the produced samples 101 to 122, protrusions on the surface of the gas barrier layer were detected and counted by the following method.

First, the surface of the gas barrier layer was measured using an optical interference type three-dimensional surface roughness measuring apparatus (WYKO NT9300 manufactured by Veeco) to obtain three-dimensional surface roughness data. Next, in the three-dimensional surface roughness conversion data obtained by applying a high-pass filter having a wavelength of 10 μm to the acquired three-dimensional surface roughness data (removing the roughness waviness component), the maximum when the data is displayed as a histogram When the peak height position was 0, protrusions having a height of 10 nm or more were counted and calculated as the number per mm ² . Specifically, the measurement resolution of about 250 nm, measured and counted (0.114 mm ² as the area) range 6 field of 159.2μm × 119.3μm, was calculated as the number per 1 mm ^2.

The number of protrusions of the obtained gas barrier layer 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 / mm ² or more

[Evaluation of water vapor permeability (WVTR)]
For the gas barrier films of the produced samples 101 to 122, the water vapor transmission rate (WVTR) was determined using the following Ca method evaluation. In the evaluation of each sample, when Ca was completely corroded at the time of storage for 2 hours, the water vapor transmission rate (WVTR) was set to 1.5 (g / m ² / d) or more.

(Ca method evaluation)
A glass substrate 40 having a quadrangular pyramid-shaped convex portion 42 formed at the center of the flat portion 41, which is shown in FIG. 20, was prepared. The shape of the quadrangular frustum-shaped convex portion 42 is the same as the shape of the substrate used for the molding process of the gas barrier film described above. That is, five types of glass substrates 40 each having a height of the convex portion 42 of 0.2 mm, 0.6 mm, 0.8 mm, 1.0 mm, or 1.2 mm were prepared.

Then, calcium (Ca: corrosive metal) is vapor-deposited in the center of the convex portion 42 of the glass substrate 40 with an area of 20 mm × 20 mm using a vacuum evaporation apparatus JEE-400 manufactured by JEOL Ltd., and the thickness is 80 nm. The Ca layer 43 was prepared.

Next, after peeling off the protective film on the gas barrier layer side from the molded gas barrier film, the surface of the gas barrier layer was cleaned under a condition of 6 J / cm ² using a UV cleaning device. Further, the gas barrier film was dried in a glove box.

Next, a gas barrier film was bonded and sealed on the glass substrate 40 on which the Ca layer 43 was formed using an adhesive (manufactured by ThreeBond 1655) to prepare a Ca method evaluation sample. The gas barrier film to which the adhesive was bonded was left in a glove box (GB) for one day and night in order to remove the moisture of the adhesive and the adsorbed water on the surface of the gas barrier film.

In the glove box, TB3124 (20 μm gap agent included) manufactured by ThreeBond Co., Ltd. as a sealing adhesive was applied to the flat portion 41 of the glass substrate 40 using a dispenser. The sealing adhesive application position and application amount do not run on the Ca deposition part when the flat part around the molded gas barrier film is adhered and pressed to increase the adhesive thickness to 20 μm. And it adjusted so that it might not protrude from the circumference.

Next, after irradiating ultraviolet rays from the gas barrier film side, it was heated on a hot plate at 100 ° C. for 60 minutes to cure the adhesive. After curing, the protective film on the opposite side of the gas barrier layer was peeled off to produce a Ca method evaluation sample. The molded part of the gas barrier film that was molded was not in contact with the Ca vapor deposition surface, and the average gap maintained the gap set during the molding process.

The Ca method evaluation sample was stored in an environment of 40 ° C. and 90% RH, and images of Ca corrosion state were taken under transmission conditions at regular intervals. The amount of Ca corrosion was calculated from the concentration change of the Ca vapor deposition part, and WVTR was calculated under the condition that the evaluation area was 20 mm × 20 mm.

The evaluation results of the gas barrier films of the samples 101 to 122 are shown in Table 3 below.

As shown in Table 3, in the gas barrier films of Samples 101 to 113, the gas barrier layer contains silicon, oxygen, and carbon, and y <0.20 or y> 1.40 when represented by SiOxCy. The sum of the thickness of the region having the composition is less than 20 nm. For this reason, even if it is molded into a shape having a gap of 0.5 mm or more in the bent region, the water vapor transmission rate (WVTR) is sufficiently low.

In particular, in the samples 104 to 108 having the maximum number of carbon distribution curves of 12 or more and the gas barrier film of the sample 113, the water vapor permeability (WVTR) is 1 × 10 ⁻² (g / m ² / day) or less, and the gas barrier property is particularly good. This is because when the number of maximum values in the carbon distribution curve is large, the number of layers in the gas barrier layer where the composition continuously changes increases. This is probably because the fine cracks that were easily covered with other regions became difficult to penetrate the gas barrier layer.

In addition, the gas barrier films of Samples 101 to 113 have a composition that falls within the range of the above four points of ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, in the thickness direction of the gas barrier layer. 40 nm to 200 nm. In the gas barrier films of Samples 101 to 113, the thickness of the composition within the range of the four points of ABEF described above was the same as the thickness of the composition within the range of the four points of ABCD.

Thickness having a composition in which the gas barrier layer is within the range of 4 points of the above-mentioned ABCD as in the gas barrier film of the samples 104 to 108 and the sample 113 having the maximum value of the carbon distribution curve of 12 or more. Is larger than the gas barrier film having a small composition thickness within the range of 4 points of ABCD even if the number of maximum values of the carbon distribution curve is 12, as in Sample 111, (WVTR) is improved.

On the other hand, in the gas barrier film of Samples 114 to 117, the total thickness of regions having a composition of y <0.20 or y> 1.40 in the composition of SiOxCy is more than 20 nm and 110 nm or more. As described above, if the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.

Further, the gas barrier films of Samples 118 to 122 having a gas barrier layer of SiO ₂ composition formed by sputtering film formation have a water vapor transmission rate (WVTR) of 1 × 10 ⁻¹ (g / m ² / day) or more. . In particular, even in the gas barrier film of the sample 118 having a small gap of 0.2 mm in the bent region, the water vapor permeability (WVTR) is 0.15 (g / m ² / day), and the gas barrier properties of the samples 101 to 113 are as follows. Water vapor transmission rate (WVTR) is worse than film.

<Preparation of Gas Barrier Films for Samples 201 to 211>
The base materials 1 to 3, the film formation conditions C1 to C14, and the number of film formation times were selected from combinations shown in Table 4 below, and gas barrier films of Samples 201 to 211 were produced. In the gas barrier films of Samples 209 to 211, SiO ₂ was prepared as a gas barrier layer by a conventional method using a roll-to-roll type sputtering film forming apparatus. In sputtering film formation, a polycrystalline Si target was used as a target, and oxygen was introduced to adjust the composition to SiO ₂ . Moreover, the film thickness was adjusted by adjusting the sputtering rate and the conveyance speed.

<Evaluation>
The gas barrier films of the produced samples 201 to 211 were evaluated in the same manner as in Example 1 above. The evaluation results of the gas barrier films of Samples 201 to 211 are shown in Table 5 below.

As shown in Table 5, in the gas barrier films of Samples 201 to 206, the gas barrier layer contains silicon, oxygen, and carbon, and y <0.20 or y> 1.40 when represented by SiOxCy. The sum of the thickness of the region having the composition is less than 20 nm. In addition, the gas barrier films of Samples 201 to 206 have a composition that falls within the range of the four points of ABCD described above in the distribution of (x, y) for each thickness in the composition expressed by SiOxCy. 40 nm to 200 nm. In the gas barrier films of Samples 201 to 206, the thickness of the composition within the range of 4 points of the above-described ABEF was also the same as the thickness of the composition within the range of 4 points of ABCD. For this reason, even if it is molded into a shape having a gap of 0.5 mm or more in the bent region, the water vapor transmission rate (WVTR) is sufficiently low.

On the other hand, the gas barrier films of the sample 207 and the sample 208 have a SiOxCy composition in which the total thickness of regions having a composition of y <0.20 or y> 1.40 exceeds 20 nm and is 122 nm or more. is there. As described above, if the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.

Further, the gas barrier films of Samples 209 to 211 having a gas barrier layer of SiO ₂ composition formed by sputtering film formation have a water vapor transmission rate (WVTR) of 1 × 10 ⁻¹ (g / m ² / day) or more. . In particular, even in the gas barrier film of the sample 209 having a small gap of 0.2 mm in the bent region, the water vapor permeability (WVTR) is 0.14 (g / m ² / day), and the gas barrier properties of the samples 201 to 206 are as follows. Water vapor transmission rate (WVTR) is worse than film.

The base material 1 and the base material 2 were produced by the same method as in Example 1 described above. Further, in the same manner as in Example 1 described above, in the inter-roller discharge plasma CVD apparatus using the roll-to-roll method shown in FIG. The conditions of C14 were set.

<Preparation of Gas Barrier Film of Samples 301 to 316>
The base materials 1 and 2, the film formation conditions C1 to C14, and the number of film formations are selected from the combinations shown in Table 6 below to produce gas barrier films of samples 301 to 316, and the following method is used. Molded. In the gas barrier films of Samples 314 to 316, SiO ₂ was produced as a gas barrier layer by a conventional method using a roll-to-roll type sputtering film forming apparatus. In sputtering film formation, a polycrystalline Si target was used as a target, and oxygen was introduced to adjust the composition to SiO ₂ . Moreover, the film thickness was adjusted by adjusting the sputtering rate and the conveyance speed.

[Molding process of gas barrier film]
First, as shown in FIG. 19, a metal substrate 80 having a truncated cone-shaped convex portion formed at the center was prepared. In the substrate 80, the convex shape of the truncated cone has a lower bottom radius of 56 mm and an upper bottom radius of 50 mm. Furthermore, as shown in FIG. 21, the height of the truncated cone is 1 mm, and the width of the hypotenuse that becomes the side surface of the truncated cone is 3 mm. Further, the corner between the flat portion 81 and the curved surface processing portion 82 is rounded with a curvature radius of 0.5 mm. The side surface of the truncated cone has a projected area of 499.5 mm ^{2 in a} state where the corners are not rounded. This corresponds to about 10% of 5000 mm ² which is a measurement area of Aquatran MODEL1 (manufactured by Mocon) used for water vapor permeability (WVTR) evaluation described later. Similarly, the side surface of this truncated cone has a ratio of projected area / measured area of 1.054. Even if the corners are rounded, these numbers are almost the same. Accordingly, when molding is performed using the substrate 80, the measured area of the curved surface area becomes 5% or more larger than the projected area.

Next, both sides of the gas barrier film were bonded using FSA-020M manufactured by Phutamura Chemical Co., Ltd. as a protective film to prepare a gas barrier film laminate. Then, the gas barrier film laminate is made to face the substrate so that the gas barrier layer of the gas barrier film is on the substrate 80 side, the substrate 80 is heated to 100 ° C. using a vacuum laminating apparatus, and the molding processing time is 10 minutes. As described above, a gas barrier film was molded.

<Evaluation>
The following evaluations were performed on the gas barrier films of the produced samples 301 to 316.

[Gas barrier layer thickness]
In the produced gas barrier films of Samples 301 to 316, a thin piece was produced in the same manner as in Example 1 described above, and the section of the section was observed with a transmission electron microscope (TEM). The thickness was measured.

[XPS analysis]
The composition distribution in the thickness direction of the gas barrier layer of the gas barrier films of the produced samples 301 to 316 was measured using photoelectron spectroscopy (XPS) analysis in the same manner as in Example 1 described above.

[Number of surface protrusions of gas barrier layer]
With respect to the gas barrier layers of the produced gas barrier films of Samples 301 to 316, protrusions on the surface of the gas barrier layer were detected and counted in the same manner as in Example 1 above, and the number of protrusions was evaluated based on a standard (rank).

[Evaluation of water vapor permeability (WVTR)]
In the produced gas barrier films of Samples 301 to 316, the water vapor permeability of the gas barrier film [B] after the above-described molding process and the sample [A] of the flat gas barrier film before the above-described molding process are obtained. (WVTR) and “[B] water vapor permeability (WVTR) / [A] water vapor permeability (WVTR)” were determined.

(Measurement of water vapor permeability)
The surface protective film and the back surface protective film were peeled off from the gas barrier film. Each gas barrier film was set in a measurement chamber of a water vapor transmission rate measuring device (trade name: Aquatran Model 1 manufactured by Mocon) so that the surface on which the gas barrier layer was formed was on the detection side of the device. In addition, the gas barrier film was set so that the portion subjected to the cubic curved surface processing was approximately the center of the measurement chamber. And the water vapor permeability (WVTR) of the gas barrier film was measured in an atmosphere of 38 ° C. and 100% RH. In addition, when water vapor permeability (WVTR) exceeded 2 (g / m < ² > / day), it evaluated as 2 or more.

The evaluation results of the gas barrier films of the samples 301 to 316 are shown in Table 7 below.

As shown in Table 7, in the gas barrier films of Samples 301 to 309, the gas barrier layer contains silicon, oxygen, and carbon, and the number of protrusions on the surface of the gas barrier layer is 100 pieces / mm ² or less. For this reason, in the region of 10% of the projected area of the gas barrier film, the water vapor transmission rate (WVTR) is sufficient even after the molding process is performed to form a curved region where the measured area is 5% or more larger than the projected area. Very low.

Among them, in the gas barrier films of Sample 304, Sample 305, and Sample 309 in which the thickness of the gas barrier layer is 100 nm or more and the number of maximum values of the carbon distribution curve is 12 or more, [A] and [B] Both have water vapor permeability (WVTR) of 1 × 10 ⁻² (g / m ² / day) or less, and gas barrier properties are particularly good.

In addition, the gas barrier films of Samples 301 to 309 have a composition that falls within the range of the above four points of ABCD in the distribution of (x, y) for each thickness in the composition represented by SiOxCy, in the thickness direction of the gas barrier layer. 40 nm to 200 nm. In the gas barrier films of Samples 301 to 309, the thickness of the composition within the range of the four points of ABEF described above was the same as the thickness of the composition within the range of the four points of ABCD.

On the other hand, in the gas barrier films of Sample 302 and Sample 307, although [A] has a water vapor transmission rate (WVTR) of 1 × 10 ⁻² (g / m ² / day) or less, [B] has a water vapor transmission rate. Since (WVTR) is 0.02 (g / m ² / day), “[B] water vapor permeability / [A] water vapor permeability” is 2.0 or 2.2. Although this satisfies “water vapor permeability of [B] / water vapor permeability of [A] <5”, the film thickness and the thickness of the ABCD composition region are close to each other and 0.1 of the sample 304 having a large number of maximum values. It is worse than.

This is because, as the number of maximum values of the carbon distribution curve increases, the number of layers in the gas barrier layer where the composition continuously changes increases. It is considered that the fine cracks generated in the region are easily covered with other regions, and the fine cracks are less likely to penetrate the gas barrier layer.

Further, the gas barrier film of the sample 308 has a sufficient gas barrier property with a water vapor transmission rate (WVTR) of 0.1 (g / m ² / day) or less, but compared with the sample 301, the sample 302, and the like. The gas barrier property with respect to the thickness is low. This is because the gas barrier film such as the sample 301 or the sample 302 has a C / Si ratio of 0.95 or more or 0.7 or less because the region having a composition of 90% or more is C / Si 0.95 or more or This is presumably because the gas barrier property is easier to improve than the sample 308 in which the region having a composition of 0.7 or less is less than 80%.

On the other hand, the gas barrier films of Samples 310 to 313 having a low evaluation of the number of surface protrusions of the gas barrier layer, and the gas barrier films of Samples 314 to 316 having a gas barrier layer having a SiO ₂ composition formed by sputtering deposition are [B]. Has a water vapor transmission rate (WVTR) of 2 (g / m ² / day) or more. Further, “[B] water vapor permeability / [A] water vapor permeability” is 5 or more. As described above, in a gas barrier layer having a large number of protrusions or a single-layer gas barrier layer having a SiO ₂ composition, cracks penetrating the gas barrier layer are easily generated by an elongation process that occurs during molding processing for forming a curved surface. Therefore, the water vapor permeability of the gas barrier film after the molding process is greatly deteriorated.

Furthermore, the gas barrier films of Samples 301 to 309 have a total thickness of less than 20 nm with a region having a composition of y <0.20 or y> 1.40 when expressed in SiOxCy. On the other hand, in the gas barrier film of samples 310 to 313, the total thickness of regions having a composition of y <0.20 or y> 1.40 exceeds 110 nm and is 110 nm or more in the composition of SiOxCy. . As described above, if the thickness of the region having an extremely large oxygen ratio or carbon ratio is large, cracks are likely to occur, and cracks are likely to propagate to the entire gas barrier layer. it is conceivable that.

Therefore, the gas barrier layer contains silicon, oxygen, and carbon, and the number of protrusions on the surface is small, so that the measured area is 5% or more larger than the projected area in the area of 9 to 11% of the projected area. Even when this is performed, a gas barrier film with little deterioration of water vapor permeability can be realized. Furthermore, when the gas barrier layer is represented by SiOxCy, the total thickness of the regions having a composition of y <0.20 or y> 1.40 is less than 20 nm, so that the gas barrier film is less deteriorated in water vapor permeability. Can be realized.

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

10,70 ... Gas barrier film, 11, 60 ... Base material, 12 ... Gas barrier layer, 13, 74 ... Flat region, 14 ... Curved region, 15, 16, 22 ... Gaps, 17 ... first substrate, 18 ... second substrate, 19 ... adhesive layer, 20, 21 ... broken line, 30,80 ... substrate, 31,41,81. ..Flat part, 32, 42 ... convex part, 40 ... glass substrate, 43 ... Ca layer, 50 ... plasma CVD apparatus, 51 ... feeding roller, 52, 54, 55, 57 ... Transfer rollers, 53, 56 ... Film forming rollers, 58 ... Winding rollers, 59 ... Film forming gas supply pipes, 61, 62 ... Magnetic field generators, 63 ... Plasma generation Power source, 73 ... measurement area, 76 ... cubic curved surface part, 82 ... curved surface processed part

Claims

A gas barrier film comprising a substrate and a gas barrier layer formed on the substrate,
The gas barrier layer contains silicon, oxygen, and carbon;
When the composition of the gas barrier layer is represented by SiOxCy, the total of the region having a composition of y <0.20 and the region having a composition of y> 1.40 is less than 20 nm in the thickness direction,
The gas barrier film has a substantially flat region and a region having a cubic curved surface surrounded by the flat region;
When the flat region is in contact with a flat plate, the region having the cubic curved surface does not contact the flat plate, and an average gap of 0.5 mm or more is formed between the region having the cubic curved surface and the flat plate. Gas barrier film.
The gas barrier film [B] on which the cubic curved surface is formed, and the flat gas barrier film [A] in a state before forming the cubic curved surface on the gas barrier film [B] are the following (1). And (2) (A) The water vapor transmission rate (WVTR) of [A] and the water vapor transmission rate (WVTR) of [B] are 0.1 (g / m 2 / day) or less. The gas barrier film according to claim 1, wherein (2) (water vapor permeability (WVTR) of [B] / water vapor permeability (WVTR) of [A]) <5 is satisfied.
The gas barrier film according to claim 2, wherein the cubic curved surface has a measured area of the cubic curved surface that is 5% or more larger than a projected area.
The base material is a laminate of a first base material and a second base material, and the second base material is peelable on a surface of the first base material opposite to the surface on which the gas barrier layer is formed. The gas barrier film according to claim 1, wherein a base material is bonded.
The sum of the thickness [X] of the first base material and the thickness [Y] of the second base material is 50 μm or more and 150 μm or less, and [X] / [Y] is 0.15 or more and 0.90 or less. The gas barrier film according to claim 4.
The gas barrier film according to claim 1, wherein the gas barrier layer is a vapor deposition layer.
The gas barrier layer contains silicon, oxygen, and carbon, and the curve indicating the carbon content in the thickness direction of the gas barrier layer has a maximum value of 4 or more, and the [film thickness of the gas barrier layer] 2. The gas barrier film according to claim 1, wherein the / maximum value number is 25 nm or less.
When the composition of the gas barrier layer is represented by SiOxCy, A (x = 0.70, y = 1.10), B (x = 0.9) on the coordinates where the horizontal axis is x and the vertical axis is y. , Y = 1.40), C (x = 2.0, y = 0.20), D (x = 1.8, y = 0.20). The gas barrier film according to claim 1, wherein the gas barrier film has a thickness in the range of 40 nm to 200 nm.
The gas barrier layer has both a region where C / Si has a composition of 0.95 or more and a region where C / Si has a composition of 0.7 or less, and 70% or more of the gas barrier layer is The gas barrier film according to claim 8, which is a region where the C / Si has a composition of 0.95 or more, or a region where the C / Si has a composition of 0.7 or less.
The gas barrier film according to claim 8, wherein in the gas barrier layer, the curve indicating the carbon content in the thickness direction has a maximum value, and the number of maximum values is 6 or more.
The gas barrier film according to claim 1, wherein the film thickness / maximum value of the gas barrier layer is 15 nm or less.
2. The gas barrier film according to claim 1, wherein the number of protrusions having a height of 10 nm or more is 100 pieces / mm 2 or less on the surface of the gas barrier layer.
A gas barrier film is pressed against a substrate having a substantially flat region and a region having irregularities or steps,
In a state where the gas barrier film is pressed against the substrate, heat of 80 ° C. or more is applied to the gas barrier film,
The gas barrier film is surrounded by a substantially flat region, and an average gap of 0.5 mm or more is formed between the flat plate when the flat region is in contact with the flat plate. And a region having a cubic curved surface. A method for forming a gas barrier film.
The method for forming a gas barrier film according to claim 13, wherein the gas barrier layer of the gas barrier film faces the substrate and the gas barrier film is pressed against the substrate.
The method for forming a gas barrier film according to claim 13, wherein a buffer layer is interposed between the substrate and the gas barrier film.
The method for molding a gas barrier film according to claim 15, wherein the buffer layer is a pressure-sensitive adhesive layer or an adhesive layer.