JP2010260347A - Gas barrier laminated film - Google Patents

Abstract

The present invention provides a gas barrier laminate film that has a sufficient gas barrier property and can sufficiently suppress a decrease in gas barrier property even when the film is bent.
A gas barrier laminate film comprising a base material and at least one thin film layer formed on at least one surface of the base material, wherein at least one of the thin film layers includes: A gas barrier laminate film, wherein an electron beam transmittance curve showing a relationship between a distance from the surface of the layer in the film thickness direction of the layer and an electron beam transmittance has at least one extreme value.
[Selection figure] None

Description

  The present invention relates to a gas barrier laminate film that can be suitably used for flexible lighting using organic electroluminescence elements (organic EL elements), organic thin-film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

  The gas barrier film can be suitably used as a packaging container suitable for filling and packaging articles such as foods and drinks, cosmetics, and detergents. In recent years, a gas barrier film in which a thin film of an inorganic oxide such as silicon oxide, silicon nitride, silicon oxynitride, or aluminum oxide is formed on one surface of a base film such as a plastic film has been proposed.

As a method for forming an inorganic oxide thin film on the surface of a plastic substrate, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, etc., low pressure chemical vapor deposition A chemical vapor deposition method (CVD) such as a plasma chemical vapor deposition method is known.
Further, as a gas barrier film using such a film forming method, for example, in Japanese Patent Laid-Open No. 4-89236 (Patent Document 1), two silicon oxide vapor-deposited films are formed on the surface of a plastic substrate. A gas barrier film provided with a laminated vapor deposition film layer laminated as described above is disclosed.

JP-A-4-89236

  However, the gas barrier film as described in Patent Document 1 can be used as a gas barrier film for articles that are satisfactory even if the gas barrier property is relatively low, such as foods and drinks, cosmetics, and detergents. As a gas barrier film for an electronic device such as an EL element or an organic thin film solar cell, the gas barrier property is not always sufficient. Further, the gas barrier film as described in Patent Document 1 has a problem that the gas barrier property against oxygen gas or water vapor is lowered when the film is bent, and the film has a bending resistance like a flexible liquid crystal display. The required gas barrier film is not always sufficient in terms of gas barrier properties when the film is bent.

  The present invention has been made in view of the above-described problems of the prior art, has a sufficient gas barrier property, and can sufficiently suppress a decrease in gas barrier property even when the film is bent. An object of the present invention is to provide a gas barrier laminate film.

  As a result of intensive studies to achieve the above object, the inventors of the present invention provide a gas barrier laminate film including a base material and at least one thin film layer formed on at least one side of the base material. Surprisingly, it has sufficient gas barrier properties because the electron beam transmission curve showing the relationship between the distance from the surface of the thin film layer in the film thickness direction of the layer and the electron beam transmission has an extreme value. In addition, the present inventors have found that a gas barrier laminate film capable of sufficiently suppressing a decrease in gas barrier property even when the film is bent is obtained, and the present invention has been completed.

  That is, the gas barrier laminate film of the present invention is a gas barrier laminate film comprising a base material and at least one thin film layer formed on at least one surface of the base material. In at least one of the layers, an electron beam transmission curve showing a relationship between the distance from the surface of the layer in the film thickness direction of the layer and the electron beam transmission has at least one extreme value. is there.

  In the gas barrier laminate film of the present invention, it is preferable that the electron beam transmittance curve is substantially continuous.

  Furthermore, in the gas barrier laminate film of the present invention, it is preferable that the electron beam transmittance curve has at least three extreme values. In such a case, the absolute value of the difference in distance from the surface of the thin film layer in the film thickness direction of the thin film layer at one extreme value of the electron beam transmission curve and the extreme value adjacent to the extreme value. Are preferably 200 nm or less.

  In the gas barrier laminate film of the present invention, the thickness of the thin film layer is preferably 5 to 3000 nm.

  Furthermore, in the gas barrier laminate film of the present invention, the thin film layer may contain silicon oxide as a main component. In such a case, it is preferable that the thin film layer does not substantially contain nitrogen. In the gas barrier laminate film of the present invention, the thin film layer may contain silicon nitride as a main component. Furthermore, in the gas barrier laminate film of the present invention, the thin film layer preferably contains carbon.

  In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a plasma chemical vapor deposition method. Further, as such a thin film layer, a layer formed by a plasma chemical vapor deposition method in which the base material is disposed on a pair of film forming rolls, and plasma is generated by discharging between the pair of film forming rolls. It is more preferable that Furthermore, when discharging between the pair of film forming rolls, it is preferable to reverse the polarity of the pair of film forming rolls alternately. Further, as a film forming gas used in such a plasma chemical vapor deposition method, a gas containing an organosilicon compound and oxygen is preferable, and the content of oxygen in the film forming gas is the organic gas in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the silicon compound. In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a continuous film forming process. The plasma chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.

  Furthermore, in the gas barrier laminate film of the present invention, the substrate is preferably made of at least one resin selected from the group consisting of polyester resins and polyolefin resins, and is preferably made of polyethylene terephthalate and polyethylene naphthalate. More preferably, it comprises at least one resin selected from the group consisting of:

  Moreover, the organic electroluminescent element of this invention, an organic thin-film solar cell, and a liquid crystal display are each provided with the gas barrier property laminated | multilayer film of the said invention. Thus, the gas barrier laminate film of the present invention can be suitably used for organic electroluminescent elements, organic thin film solar cells, and liquid crystal displays.

  According to the present invention, it is possible to provide a gas barrier laminated film that has a sufficient gas barrier property and can sufficiently suppress a decrease in gas barrier property even when the film is bent. .

It is a schematic diagram which shows one Embodiment of the manufacturing apparatus which can be used suitably for manufacturing the gas-barrier laminated | multilayer film of this invention. (A) shows the transmission electron microscope (TEM) photograph of the cross section of the thin film layer in the gas barrier laminated film obtained in Example 1, and (b) shows the thin film layer of the gas barrier laminated film obtained in Example 1. It is a graph which shows the relationship between the distance from the reference plane in the film thickness direction, and electron beam transmittance. 3 is a transmission electron microscope (TEM) photograph showing a cross section of a thin film layer in a gas barrier laminate film (B) obtained in Example 2. FIG. It is a graph which shows the relationship between the distance from the reference plane in the film thickness direction of the thin film layer in the gas-barrier laminated film (B) obtained in Example 2, and electron beam transmittance. 2 is a transmission electron micrograph showing a cross section of a thin film layer in a gas barrier laminate film obtained in Comparative Example 1. FIG. It is a graph which shows the relationship between the distance from the reference plane in the film thickness direction of the thin film layer in the gas-barrier laminated film obtained in Comparative Example 1, and electron beam transmittance. 4 is a transmission electron micrograph showing a cross section of a thin film layer in a gas barrier laminate film obtained in Comparative Example 2. FIG. It is a graph which shows the relationship between the distance from the reference plane in the film thickness direction of the thin film layer in the gas-barrier laminated film obtained by the comparative example 2, and electron beam transmittance. 4 is a transmission electron micrograph showing a cross section of a thin film layer in a gas barrier laminate film obtained in Comparative Example 3. FIG. It is a graph which shows the relationship between the distance from the reference plane in the film thickness direction of the thin film layer in the gas-barrier laminated film obtained in Comparative Example 3, and electron beam transmittance.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

  The gas barrier laminate film of the present invention is a gas barrier laminate film comprising a substrate and at least one thin film layer formed on at least one surface of the substrate, wherein at least one of the thin film layers. In one layer, an electron beam transmittance curve showing the relationship between the distance from the surface of the layer in the film thickness direction of the layer and the electron beam transmittance has at least one extreme value.

  As a base material used for this invention, the film or sheet | seat which consists of colorless and transparent resin is mentioned. Examples of the resin used for such a substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefin; polyamide Polycarbonate resin; Polystyrene resin; Polyvinyl alcohol resin; Saponified ethylene-vinyl acetate copolymer; Polyacrylonitrile resin; Acetal resin; Polyimide resin. Among these resins, polyester resins and polyolefin resins are preferred, and PET and PEN are particularly preferred from the viewpoints of high heat resistance and linear expansion coefficient and low production cost. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the base material can be appropriately set in consideration of the stability when producing the gas barrier laminate film of the present invention. The thickness of the substrate is preferably in the range of 5 to 500 μm from the viewpoint that the film can be conveyed even in a vacuum. Furthermore, when forming the thin film layer concerning this invention by plasma CVD method, since the thin film layer concerning this invention is formed, discharging through the said base material, the thickness of the said base material is in the range of 50-200 micrometers. More preferably, it is particularly preferably in the range of 50 to 100 μm.

  Moreover, it is preferable to perform the surface activation process for cleaning the surface of a base material to the said base material from an adhesive viewpoint with the thin film layer mentioned later. Examples of such surface activation treatment include corona treatment, plasma treatment, and flame treatment.

  The thin film layer concerning this invention is a layer formed in the at least single side | surface of the said base material. In the gas barrier laminate film of the present invention, at least one of the thin film layers has electron beam transmission indicating the relationship between the distance from the surface of the layer in the film thickness direction and the electron beam transmittance. It is necessary that the degree curve has at least one extreme value. Thus, when the electron beam transmission curve has at least one extreme value, it is possible to achieve a sufficiently high gas barrier property by the thin film layer, and even if the film is bent, the gas barrier property can be achieved. The decrease can be sufficiently suppressed. As such a thin film layer, since a higher effect is obtained, it is more preferable that the electron beam transmission curve has at least two extreme values, and it is particularly preferable that the electron beam transmission curve has at least three extreme values. Further, in the case of having at least three extreme values in this way, one extreme value of the electron beam transmittance curve and an extreme value adjacent to the extreme value of the thin film layer in the thickness direction of the thin film layer. The absolute value of the difference in distance from the surface is preferably 200 nm or less, and more preferably 100 nm or less. In the present invention, the extreme value is the maximum value or the minimum value of a curve (electron beam transmission curve) in which the magnitude of electron beam transmittance is plotted against the distance from the surface of the thin film layer in the film thickness direction of the thin film layer. It means the value. Further, in the present invention, the presence / absence of an extreme value (maximum value or minimum value) of the electron beam transmittance curve can be determined based on a method for determining the presence / absence of an extreme value described later.

  Further, in the present invention, the electron beam transmittance represents the degree of transmission of an electron beam through a material for forming a thin film layer at a predetermined position in the thin film layer. Various known methods can be employed as the method for measuring the electron beam transmittance. For example, (i) a method for measuring electron beam transmittance using a transmission electron microscope, (ii) a scanning electron microscope It is possible to employ a method of measuring electron beam transmittance by measuring secondary electrons and reflected electrons using Hereinafter, taking a case where a transmission electron microscope is used as an example, a method for measuring an electron beam transmittance and a method for measuring an electron beam transmittance curve will be described.

  In the method of measuring the electron beam transmittance when such a transmission electron microscope is used, first, a flaky sample is prepared by cutting a base material having a thin film layer in a direction perpendicular to the surface of the thin film layer. Next, a transmission electron microscope image of the surface of the sample (a surface perpendicular to the surface of the thin film layer) is obtained using a transmission electron microscope. Then, by measuring the image of the transmission electron microscope in this way, the electron beam transmittance at each position of the thin film can be obtained based on the contrast at each position on the image. Here, in the case of observing with a transmission electron microscope a flaky sample obtained by cutting a substrate having a thin film layer in a direction perpendicular to the surface of the thin film layer, the contrast at each position of the image of the transmission electron microscope Represents a change in electron beam transmittance of the material at each position. In order to make such contrast correspond to the electron beam transmittance, it is preferable to ensure an appropriate contrast in the image of the transmission electron microscope, and the thickness of the sample (the thickness in the direction parallel to the surface of the thin film layer) It is preferable to appropriately select observation conditions such as the acceleration voltage and the diameter of the objective aperture. The thickness of the sample is usually 10 to 300 nm, preferably 20 to 200 nm, more preferably 50 to 200 nm, and particularly preferably 100 nm. The acceleration voltage is usually 50 to 500 kV, preferably 100 to 300 kV, more preferably 150 to 250 kV, and particularly preferably 200 kV. The diameter of the objective diaphragm is preferably 5 to 800 μm, more preferably 10 to 200 μm, and particularly preferably 160 μm. Moreover, as such a transmission electron microscope, it is preferable to use what has sufficient resolution about the image of a transmission electron microscope. Such resolution is preferably at least 10 nm or less, more preferably 5 nm or less, and particularly preferably 3 nm or less.

  In addition, in such an electron beam transmittance measurement method, an image (transparency image) of a transmission electron microscope is used to obtain the electron beam transmittance at each position of the thin film based on the contrast at each position on the image. The unit area is divided into repetitions, and a cross-sectional density variable (C) corresponding to the degree of density of the unit area is assigned to each unit area. Such image processing can be easily performed by electronic image processing using a normal computer. In such image processing, it is preferable to first cut out an arbitrary region suitable for analysis from the obtained grayscale image. The gray image cut out in this way must include at least a portion from one surface of the thin film layer to the other surface facing the thin film layer. Moreover, the layer adjacent to a thin film layer may be included. Thus, as a layer adjacent to a thin film layer, a protective layer required in order to implement the observation which obtains a base material and a light and shade image, for example is mentioned. Further, the end face (reference plane) of the grayscale image cut out in this way must be a plane parallel to the surface of the thin film layer. In addition, the grayscale image cut out in this way is a trapezoid or parallelogram surrounded by two sides that are perpendicular to each other and perpendicular to the direction perpendicular to the surface of the thin film layer (film thickness direction). It is preferable that the shape is a quadrangle having two sides and two sides perpendicular to them (parallel to the film thickness direction).

  The gray-scale image cut out in this way is divided into repetitions of a certain unit area. As the division method, for example, a method of dividing by a grid-like section can be adopted. In such a case, each unit area divided by the grid-like sections constitutes one pixel. Such a gray-scale image pixel is preferably as fine as possible in order to reduce the error, but as the pixel becomes finer, the time required for analysis tends to increase. Therefore, the length of one side of such a gray image pixel is preferably 10 nm or less, more preferably 5 nm or less, and particularly preferably 3 nm or less, in terms of the actual size of the sample.

  The cross-sectional density variable (C) given in this way is a value obtained by converting the degree of density in each area into numerical information. The method of conversion into such a cross-sectional density variable (C) is not particularly limited. For example, the darkest unit area is set to 0, the thinnest unit area is set to 255, and 0 to 0 depending on the level of density of each unit area. It is possible to set (256 gradation settings) by giving an integer between 255. However, it is preferable that such a numerical value is determined so that the numerical value of the portion with high electron beam transmittance is large.

Then, from such a cross-sectional density variable (C), a thickness direction density variable (C _Z ) at a distance (z) from the reference plane in the thickness direction of the thin film layer can be calculated by the following method. That is, the average value of the cross-sectional density variable (C) of the unit region where the distance (z) from the reference plane in the film thickness direction of the thin film layer has a predetermined value is calculated, and the thickness direction density variable (C _Z ) is calculated. Ask. Note that the average value of the cross-sectional density variable (C) here is the cross-sectional density variable (C) of any unit region of 100 points or more where the distance (z) from the reference plane is a predetermined value (the same value). An average value is preferred. Further, when obtaining the thickness direction density variable (C _Z ) in this way, it is preferable to appropriately perform a noise removal process for noise removal. As the noise removal process, a moving average method, an interpolation method, or the like can be employed. Examples of the moving average method include a simple moving average method, a weighted moving average method, and an exponential smoothing moving average method, but it is more preferable to employ the simple moving average method. In the case of using the simple moving average method, the averaged range is appropriately smaller than the typical size of the structure in the thickness direction of the thin film layer, and the obtained data is appropriately smoothed. It is preferable to select. Examples of the interpolation method include a spline interpolation method, a Lagrangian interpolation method, and a linear interpolation method, but it is more preferable to employ a spline interpolation method and a Lagrange interpolation method.

As a result of the noise removal operation, an area where the change in the film thickness direction gradation variable (C _Z ) with respect to the position in the film thickness direction is moderate is generated near both interfaces of the thin film layer (this is called a transition area). It is desirable to remove this transition region from the extreme value determination region of the electron beam transmittance curve of the thin film layer from the viewpoint of clarifying the criterion for determining the presence or absence of the extreme value of the electron beam transmittance curve described later. In addition, as a factor which such a transition region generate | occur | produces, the non-planarity of a thin film interface, the above-mentioned noise removal work, etc. can be considered. Therefore, the transition region can be removed from the determination region of the electron beam transmittance curve by adopting the following method. That is, first, the position of the distance (z) from the reference plane in the film thickness direction of the thin film layer where the absolute value | dC _Z / dz | of the thin film layer becomes the largest in the vicinity of both interfaces of the thin film layer obtained based on the grayscale image. Is set as the temporary interface position. Next, the absolute value of the inclination (dC _Z / dz) is sequentially checked from the outside of the temporary interface position toward the inside (thin film layer side), and the absolute value is 0.1 nm ⁻¹ (256 gradation setting). The distance (z) from the reference plane in the film thickness direction of the thin film layer at the position (in this case) (the vertical axis is the absolute value of dC _Z / dz and the horizontal axis is the distance (z) from the machine gun surface) When a graph is considered, the graph is traced from the distance (z) outside the temporary interface position toward the inside (thin film layer side), and the absolute value of the dC _Z / dz is 0.1 nm ⁻¹ for the first time. The position of the distance (z) in the lower part is set as the interface of the thin film. Then, the transition region can be removed from the determination region by removing the region outside the interface from the determination region of the electron beam transmittance curve of the thin film layer. Further, when obtaining the thickness direction density variable (C _Z ) in this way, normalization is performed so that the average value of the thickness direction density variable (C _Z ) in the range corresponding to the thin film layer is 1. Is preferred.

The thickness direction density variable (C _Z ) calculated in this way is proportional to the electron beam transmittance (T). Therefore, an electron beam transmittance curve can be created by showing the thickness direction density variable (C _Z ) with respect to the distance (z) from the reference plane in the thickness direction of the thin film layer. That is, the electron beam transmittance curve can be obtained by plotting the thickness direction density variable (C _Z ) with respect to the distance (z) from the reference plane in the thickness direction of the thin film layer. Further, by calculating a gradient (dC _Z / dz) obtained by differentiating the thickness direction density variable (C _Z ) by the distance (z) from the reference plane in the film thickness direction of the thin film layer, the electron beam transmittance (T) It is also possible to know a change in the slope (dT / dz).

In addition, in the electron beam transmittance curve thus obtained, the presence or absence of an extreme value can be determined as follows. That is, when the electron beam transmittance curve has an extreme value (maximum value or minimum value), the maximum value of the gradient (dC _Z / dz) of the density coefficient in the film thickness direction is a positive value and the minimum value thereof. Becomes a negative value and the absolute value of the difference between the two becomes large. On the other hand, if there is no extreme value, the maximum and minimum values of the slope (dC _Z / dz) are both positive or negative. The absolute value of the difference between the two becomes small. Therefore, when determining whether or not there is an extreme value, determine whether the maximum value and the minimum value of the slope (dC _Z / dz) are both positive values or both negative values. It can be determined whether or not it has an extreme value, and the magnitude of the absolute value of the difference between the maximum value (dC _Z / dz) _MAX and the minimum value (dC _Z / dz) _MIN of the slope (dC _Z / dz) Based on the above, it can also be determined whether the electron beam transmission curve has an extreme value. The film thickness direction gradation variable (C _Z ) should always show a standardized average value of 1 when there is no extreme value, but the signal actually contains a little noise and is normalized. The value close to the average value of 1 causes fluctuations in the electron beam transmittance curve due to noise. Therefore, when determining whether or not there is an extreme value in the electron beam transmission curve, whether the maximum value and the minimum value of the slope of the electron beam transmission curve are not positive or negative values and the electron beam When the extreme value is determined based only on the absolute value of the difference between the maximum value and the minimum value of the slope of the transmission curve, it is determined that the electron beam transmission curve has an extreme value due to noise There is. Therefore, when determining the presence or absence of the extreme value, the fluctuation due to noise and the extreme value are distinguished according to the following criteria. That is, when the point where the slope (dC _Z / dz) of the film thickness direction gradation variable (C _Z ) is reversed with the sign reversed across zero is set as the temporary extreme value point, the film thickness direction gray variable at the temporary extreme value point and (C _Z), towards absolute value of the absolute value (tentative extremum point adjacent there are two differences in the difference between the film thickness direction gray variables in temporary extreme point adjacent (C _Z) is greater If (select) is 0.03 or more, it can be determined that the temporary extreme point is a point having an extreme value. In other words, the absolute value (adjacent tentative extremum points of the difference between the film thickness direction gray-scale variable (C _Z) between the thickness direction shading variables of the temporary extreme points adjacent (C _Z) in tentative extreme points When there are two, the one with the larger absolute value of the difference is selected) is less than 0.03, it can be determined that the temporary extreme point is noise. Note that when there is only one temporary extreme point, the noise in the case where the absolute value of the difference from the normalized average value 1 is 0.03 or more is greater in the film thickness direction gradation variable (C _Z ). Instead, it is possible to adopt a method for determining that the value is an extreme value. The numerical value “0.03” is a numerical value of the film thickness direction gradation variable (C _Z ) where the average value of the film thickness direction gradation variable (C _Z ) obtained by the above-described 256 gradation setting is 1. This is a numerical value obtained when the size is normalized (note that the numerical value “0” of the film thickness direction gradation variable obtained by the 256 gradation setting at the time of normalization is set to “0” as it is).

In the gas barrier laminate film of the present invention, at least one thin film layer has at least one extreme value in the electron beam transmittance curve. It can be said that a thin film layer having at least one extreme value in such an electron beam transmission curve is a layer whose composition varies in the film thickness direction. A gas barrier laminate film having such a thin film layer can achieve a sufficiently high gas barrier property, and even if the film is bent, a decrease in gas barrier property can be sufficiently suppressed. Become. Moreover, it is preferable that the electron beam transmittance curve is substantially continuous. In this specification, that the electron beam transmission curve is substantially continuous means that the electron beam transmission curve in the electron beam transmission curve does not include a portion where the electron beam transmission changes discontinuously. It means that the absolute value of the slope (dC _Z / dz) of the thickness direction density variable (C _Z ) is not more than a predetermined value, preferably not more than 5.0 × 10 ⁻² / nm.

  In the present invention, the thin film layer is substantially in the film surface direction (direction parallel to the surface of the thin film layer) from the viewpoint of forming a thin film layer having a uniform and excellent gas barrier property over the entire film surface. Preferably it is uniform. In this specification, the fact that the thin film layer is substantially uniform in the film surface direction is obtained even when the electron beam transmittance curve is created by measuring the electron beam transmittance at any location on the film surface of the thin film layer. It means that the number of extreme values of the electron beam transmission curve is the same. In addition, when the sample for measurement at two arbitrary points was cut out from the film surface of the thin film layer and the electron beam transmission curve of each sample was created, the extreme values of the electron beam transmission curve in all the samples If the numbers are the same, the thin film layer can be assumed to be substantially uniform.

  The thin film layer according to the present invention can be formed by appropriately using a known material known to have gas barrier properties. Examples of the material of the thin film layer include metals such as aluminum, silver, chromium, and titanium; oxides such as silicon oxide, aluminum oxide, titanium oxide, and silicon oxynitride; nitrides such as silicon nitride; sulfides; Fluorides; including carbides. These materials can be used singly or in combination of two or more.

  In addition, the gas barrier laminate film of the present invention needs to include at least one such thin film layer, but may include two or more layers. Further, when two or more such thin film layers are provided, the materials of the plurality of thin film layers may be the same or different. When two or more such thin film layers are provided, such a thin film layer may be formed on one surface of the base material, and is formed on both surfaces of the base material. May be. Moreover, as such a some thin film layer, the thin film layer which does not necessarily have gas barrier property may be included.

Among these thin film layer materials, it is preferable to use silicon oxide as a main component from the viewpoint of the balance between transparency and gas barrier properties of the obtained gas barrier laminate film, and the general formula: SiO _X (the above general formula In which X represents a number of 1 to 2 is more preferably used as a main component, and a general formula: SiO _X (wherein X is a number of 1.5 to 2.0) It is particularly preferable to use silicon oxide represented by In this specification, the term “used as a main component” means that the content of the component is 50% by mass or more (preferably 70% by mass or more) with respect to the mass of all the components of the material.

Moreover, the thin film layer which has these silicon oxides as a main component may contain elements other than silicon and oxygen. An example of such an element is carbon. The thin film layer containing silicon, oxygen, and carbon has a general formula: SiO _X C _Y (wherein X represents a number from 0 to 2 and Y represents a number from 0 to 2). It is preferable to use an oxygen-carbon compound as a main component. Moreover, these thin film layers may contain hydrogen as elements other than silicon, oxygen, and carbon.

The thin film layer containing silicon, oxygen, carbon, and hydrogen has a general formula: SiO _X C _Y H _Z (wherein X is a number from 0 to 2, Y is a number from 0 to 2, Z is 0 to 0) It is preferable to use as a main component a silicon-oxygen-carbon-hydrogen compound represented by the following formula:

  These thin film layers may contain elements other than silicon, oxygen, carbon, and hydrogen. Examples of such elements include nitrogen, and further boron, aluminum, phosphorus, sulfur, fluorine, Examples include chlorine.

  In the case where the material of the thin film layer is silicon oxide, the ratio X of oxygen to silicon in the general formula may be a constant value in the thin film layer. The ratio X may be changed.

  When the material of the thin film layer is a silicon oxygen carbon compound, the ratio X of oxygen to silicon and the ratio Y of carbon to silicon in the general formula may be constant values in the thin film layer. The ratio X and the ratio Y may change with respect to the film thickness direction of the thin film layer.

  When the material of the thin film layer is a silicon oxygen carbon hydrogen compound, the ratio X of oxygen to silicon, the ratio Y of carbon to silicon, and the ratio Z of hydrogen to silicon in the general formula are constant in the thin film layer. The ratio X, the ratio Y, and the ratio Z may be changed with respect to the film thickness direction of the thin film layer.

  The film structure of such a thin film layer is, for example, a surface analysis device such as an X-ray photoelectron spectrometer (XPS: Xray Photoelectron Spectroscopy) or a secondary ion mass spectrometer (SIMS: Secondary Ion Mass Spectroscopy). This can be confirmed by analyzing the thin film layer using a method of analysis while performing ion etching in the film thickness direction.

  The thickness of the thin film layer is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and particularly preferably in the range of 100 to 1000 nm. If the thickness of the thin film layer is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the thickness exceeds the upper limit, the gas barrier properties tend to decrease due to bending.

  When the gas barrier laminate film of the present invention includes a plurality of thin film layers, the total thickness of the thin film layers is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 5000 nm. , More preferably in the range of 100 to 3000 nm, particularly preferably in the range of 200 to 2000 nm. If the total thickness of the thin film layer is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the upper limit is exceeded, the gas barrier properties tend to decrease due to bending. .

  The gas barrier laminate film of the present invention includes the base material and the thin film layer, and may further include a primer coat layer, a heat sealable resin layer, an adhesive layer, and the like as necessary. Such a primer coat layer can be formed using a known primer coat agent capable of improving the adhesion between the substrate and the thin film layer. Moreover, such a heat-sealable resin layer can be suitably formed using a well-known heat-sealable resin. Furthermore, such an adhesive layer can be appropriately formed using a known adhesive, and a plurality of gas barrier laminate films may be adhered to each other by such an adhesive layer.

  In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a plasma chemical vapor deposition method. As a thin film layer formed by such a plasma chemical vapor deposition method, plasma chemistry in which the base material is disposed on the pair of film forming rolls and plasma is generated by discharging between the pair of film forming rolls. A layer formed by a vapor deposition method is more preferable. Further, when discharging between the pair of film forming rolls in this way, it is preferable to reverse the polarities of the pair of film forming rolls alternately. Further, the film forming gas used in such a plasma chemical vapor deposition method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film forming gas is the organic gas in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the silicon compound. In the gas barrier laminate film of the present invention, the thin film layer is preferably a layer formed by a continuous film forming process. In addition, the method of forming a thin film layer using such a plasma chemical vapor deposition method is demonstrated in the method of manufacturing the gas-barrier laminated film of this invention mentioned later.

  Next, a method for producing the gas barrier laminate film of the present invention will be described. The gas barrier laminate film of the present invention can be produced by forming the thin film layer on the surface of the substrate. As a method of forming such a thin film layer according to the present invention on the surface of the substrate, it is preferable to employ plasma chemical vapor deposition (plasma CVD) from the viewpoint of gas barrier properties. The plasma chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.

  Further, when generating plasma in the plasma enhanced chemical vapor deposition method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rolls, and a pair of film forming rolls is used, and the pair of film forming films is used. More preferably, the substrate is disposed on each of the rolls, and plasma is generated by discharging between the pair of film forming rolls. In this way, a pair of film forming rolls are used, a base material is disposed on the pair of film forming rolls, and discharge is performed between the pair of film forming rolls. In addition to forming the surface portion of the base material present on the other film, the surface portion of the base material existing on the other film forming roll can be formed at the same time. Since the film rate can be doubled, and a film having the same structure can be formed, the extreme value can be at least doubled, and the formed thin film layer can be efficiently added to the electron beam transmittance curve with at least one extreme value. It becomes possible to set it as the layer which has. Moreover, it is preferable that the gas-barrier laminated film of this invention forms the said thin film layer on the surface of the said base material by a roll-to-roll system from a viewpoint of productivity. An apparatus that can be used when producing a gas barrier laminate film by such a plasma chemical vapor deposition method is not particularly limited, and includes at least a pair of film forming rolls and a plasma power source, and It is preferable that the apparatus has a configuration capable of discharging between a pair of film forming rolls. For example, when a manufacturing apparatus as shown in FIG. 1 is used, a plasma chemical vapor deposition method is used. However, it is also possible to manufacture by a roll-to-roll method.

  Hereinafter, the method for producing the gas barrier laminate film of the present invention will be described in more detail with reference to FIG. FIG. 1 is a schematic view showing an example of a production apparatus that can be suitably used for producing the gas barrier laminate film of the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

  1 includes a feed roll 11, transport rolls 21, 22, 23, 24, film forming rolls 31, 32, a gas supply pipe 41, a plasma generating power supply 51, a film forming roll 31, and 32 includes magnetic field generators 61 and 62 installed inside 32, and a winding roll 71. In such a manufacturing apparatus, at least the film forming rolls 31, 32, the gas supply pipe 41, the plasma generating power source 51, and the magnetic field generating apparatuses 61, 62 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roll has a plasma generation power source so that the pair of film-forming rolls (film-forming roll 31 and film-forming roll 32) can function as a pair of counter electrodes. 51 is connected. Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roll 31 and the film forming roll 32 by supplying power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roll 31 and the film forming roll 32. In this way, when the film forming roll 31 and the film forming roll 32 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable that the pair of film forming rolls (film forming rolls 31 and 32) are arranged so that their central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rolls (film forming rolls 31 and 32), the film forming rate can be doubled, and a film having the same structure can be formed, so that the extreme value is at least doubled. Is possible. And according to such a manufacturing apparatus, it is possible to form a thin film layer on the surface of the film 100 by the CVD method, while depositing a film component on the surface of the film 100 on the film forming roll 31, Furthermore, since the film component can be deposited on the surface of the film 100 also on the film forming roll 32, the thin film layer can be efficiently formed on the surface of the film 100.

  Further, inside the film forming roll 31 and the film forming roll 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roll rotates are provided, respectively.

  Further, as the film forming roll 31 and the film forming roll 32, known rolls can be appropriately used. As such film forming rolls 31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rolls 31 and 32 is preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in such a manufacturing apparatus, the film 100 is arrange | positioned on a pair of film-forming roll (The film-forming roll 31 and the film-forming roll 32) so that the surface of the film 100 may oppose, respectively. By disposing the film 100 in this manner, each of the films 100 existing between the pair of film forming rolls is generated when the plasma is generated by performing discharge between the film forming roll 31 and the film forming roll 32. It becomes possible to form a film on the surface simultaneously. That is, according to such a manufacturing apparatus, the film component can be deposited on the surface of the film 100 on the film forming roll 31 and further the film component can be deposited on the film forming roll 32 by the CVD method. Therefore, the thin film layer can be efficiently formed on the surface of the film 100.

  Also, as the feed roll 11 and the transport rolls 21, 22, 23, 24 used in such a manufacturing apparatus, known rolls can be used as appropriate. Further, the winding roll 71 is not particularly limited as long as it can wind the film 100 on which the thin film layer is formed, and a known roll can be appropriately used.

  Further, as the gas supply pipe 41, a pipe capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used. Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roll 31 and the film forming roll 32 connected to the power source 51 and makes it possible to use them as a counter electrode for discharging. As such a plasma generation power source 51, it is possible to more efficiently carry out plasma CVD, so that the polarity of the pair of film forming rolls can be alternately reversed (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 51 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate. Furthermore, as the film 100, in addition to the substrate used in the present invention, a film in which the thin film layer is formed in advance can be used. As described above, by using the film 100 in which the thin film layer is formed in advance, it is possible to increase the thickness of the thin film layer.

  Using the manufacturing apparatus shown in FIG. 1, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roll, and the film transport speed are adjusted as appropriate. By doing so, the gas barrier laminate film of the present invention can be produced. That is, by using the manufacturing apparatus shown in FIG. 1 to generate a discharge between a pair of film forming rolls (film forming rolls 31 and 32) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. The film forming gas (raw material gas or the like) is decomposed by plasma, and the thin film layer is formed on the surface of the film 100 on the film forming roll 31 and on the surface of the film 100 on the film forming roll 32 by the plasma CVD method. Is done. In such film formation, the film 100 is transported by the delivery roll 11 and the film formation roll 31, respectively, so that it is formed on the surface of the film 100 by a roll-to-roll continuous film formation process. The thin film layer is formed.

  The source gas in the film-forming gas used for forming such a thin film layer can be appropriately selected and used according to the material of the thin film layer to be formed. As such a source gas, for example, when the material of the thin film layer contains silicon such as silicon oxide, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane are preferable from the viewpoints of properties such as handling of the compound and gas barrier properties of the obtained thin film layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  Further, as the film forming gas, when the material of the thin film layer is an inorganic compound such as an oxide, a nitride, or a sulfide, a reactive gas may be used in addition to the source gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

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

  When such a film-forming gas contains a raw material gas and a reactive gas, the reaction gas that is theoretically necessary for completely reacting the raw material gas and the reactive gas in the ratio of the raw material gas and the reactive gas. It is preferable that the ratio of the reaction gas is not excessively increased rather than the ratio of the amount. If the reaction gas ratio is excessively increased, the reaction proceeds too much, resulting in a uniform film of a completely reacted product, the composition of the thin film layer is not changed, and the electron beam transmission curve is extremely different. The value can no longer be seen. In this case, excellent barrier properties and bending resistance cannot be obtained depending on the formed thin film layer. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

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

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material. When producing a thin film, the following reaction formula (1) is given by the film-forming gas:
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
Reaction occurs as described in 1 to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen per mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. The thin film layer having at least one extreme value in the degree curve cannot be formed. Therefore, in the present invention, when forming the thin film layer, the oxygen amount is set to the stoichiometric ratio with respect to 1 mol of hexamethyldisiloxane so that the reaction of the above formula (1) does not proceed completely. It must be less than 12 moles. Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is the raw material hexamethyldisiloxane. (It may be about 20 times or more of the molar amount (flow rate).) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By including hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that were not completely oxidized are taken into the thin film layer, so the composition varies in the film thickness direction. It is possible to form a thin layer having at least one extreme value in the electron beam transmission curve, and the resulting gas barrier laminate film has excellent barrier properties and resistance. Flexibility can be exhibited. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, carbon atoms and hydrogen atoms that have not been oxidized are excessively taken into the thin film layer. In this case, the transparency of the barrier film decreases, and the barrier film cannot be used for a flexible substrate for a device that requires transparency such as an organic EL device or an organic thin film solar cell. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming rolls 31 and 32, an electrode drum connected to the plasma generating power source 51 (in this embodiment, the film is installed on the film forming rolls 31 and 32). The electric power to be applied can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but may be in the range of 0.1 to 10 kW. preferable. When the applied power is less than the lower limit, particles tend to be generated. On the other hand, when the applied power exceeds the upper limit, the amount of heat generated during film formation increases, and the temperature of the substrate surface during film formation increases. The substrate loses heat and wrinkles occur during film formation. In severe cases, the film melts due to heat, and a large current discharge occurs between the bare film formation rolls. There is a possibility of hurting itself.

  Moreover, the conveyance speed (line speed) of the film 100 can be appropriately adjusted according to the type of the raw material gas, the pressure in the vacuum chamber, and the like, and is not particularly limited. The range is preferably 100 m / min, and more preferably 0.5 to 20 m / min. If the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film. On the other hand, if the upper limit is exceeded, the thickness of the formed thin film layer tends to be thin.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the water vapor permeability of the gas barrier laminate film and the water vapor permeability after the bending test were measured by the following methods.

(I) Measurement of water vapor permeability Under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side, a water vapor permeability measuring device (model name “GTR Tech− 30XASC ") was used to measure the water vapor permeability of the gas barrier laminate film. In addition, using a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) under conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. The water vapor permeability of the gas barrier laminate film was measured.

(Ii) Measurement of water vapor permeability after bending test A gas barrier laminate film was wound around a metal rod, and then subjected to a bending test that was allowed to stand for 1 minute, and then the gas barrier laminate film was flattened to prepare a sample. The radius of curvature R in the bending test corresponds to ½ of the diameter of the rod. However, when the number of turns of the gas barrier laminate film increases, ½ of the diameter when the film is wound is defined as the radius of curvature R. did. Next, a water vapor permeability measuring machine (manufactured by Lyssy, model name “Lyssy-L80-5000”) is used under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. Then, the water vapor permeability of the sample was measured.

Example 1
A gas barrier laminate film was produced using the production apparatus shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”) is used as a base material (film 100). -It was attached to And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to the film-forming roll 31 and the film-forming roll 32, respectively, Plasma is generated by discharging, and a film forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (also functioning as a discharge gas) as a reaction gas) is supplied to such a discharge region. Then, a thin film was formed by the plasma CVD method under the following conditions to obtain a gas barrier laminate film.

<Film formation conditions>
Deposition gas mixing ratio (hexamethyldisiloxane / oxygen): 50/500 [unit: sccm (Standard Cubic Centimeter per Minute)]
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

The thickness of the thin film layer in the gas barrier laminate film thus obtained was 0.3 μm. Further, in the obtained gas barrier laminate film, the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 0% RH on the low humidity side, and a humidity of 90% RH on the high humidity side is 3.1 × 10 ⁻⁴ g / (m a ² · day), the temperature 40 ° C., humidity 10% RH of low humidity side, the water vapor permeability at a humidity of 100% RH of high humidity side was a value below the detection limit. Furthermore, the water vapor transmission rate under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. In the case where the obtained gas barrier laminate film was bent, it was confirmed that the deterioration of the gas barrier property can be sufficiently suppressed.

  Moreover, about the obtained gas-barrier laminated | multilayer film, the relationship between the distance (z) from the reference plane (predetermined surface parallel to the surface of a thin film layer) in the film thickness direction of a thin film layer, and electron beam transmittance (T) is shown. The electron beam transmission curve shown was created. That is, first, after providing a protective layer on the surface of the thin film layer of the obtained gas barrier laminate film, using a focused ion beam (FIB, Focused Ion Beam), cut in a direction perpendicular to the film surface, A sample having a thickness of 100 nm was produced. Then, the cut surface (surface perpendicular to the membrane surface) of the obtained sample was observed using a transmission electron microscope (TEM, manufactured by Hitachi, Ltd., model number “FE-SEM HF-2000”). An image (magnification: 100,000 times) was obtained. The obtained result is shown in (a) of FIG.

  In the TEM image shown in FIG. 2A thus obtained, the film thickness direction of the thin film layer is the horizontal direction of the image. As measurement conditions, the acceleration voltage was 200 KV, and the objective aperture was 160 μm. A striped pattern was observed in the obtained TEM image.

  Next, the obtained TEM image is read into a personal computer, and image processing software (manufactured by Adobe System, product name “Adobe PhotoShop Elements 7”) is used to display the image in the vertical direction on the screen in the film thickness direction of the thin film layer. A part of the image was cut out and rotated to obtain a grayscale image. The gray image cut out in this way was divided into a lattice pattern and divided into 700 unit regions in the vertical direction (film thickness direction) and 500 in the horizontal direction (film surface direction). In the obtained gray image, 200 nm was a length corresponding to 202 unit regions. Then, in the obtained shade image, the cross-sectional shade variable (C) was given to each unit region according to the shade level. Specifically, 0 is set when the pixel is pure black, and 255 is set when the pixel is pure white, and a cross-sectional density variable (C) from 0 to 255 is assigned to each unit area according to the level of density. did. Such an operation of assigning the section and the cross-sectional density variable was performed using image analysis software (product name “Rigaku R-AXIS Display Software Ver. 1.18” manufactured by Rigaku Corporation).

Next, at each position in the vertical direction (film thickness direction), an average value in the horizontal direction (film surface direction) (an average value for 500 unit regions arranged side by side) is calculated, and a thickness direction density variable (C _Z )
Further, the noise of the film thickness direction gradation variable (C _Z ) is removed using the simple moving average method, and then the average value of the film thickness direction gradation variable (C _Z ) in the range corresponding to the thin film layer becomes 1. Thus, in the gas barrier laminate film, an electron beam transmission curve was prepared by showing the relationship of the thickness direction density variable (C _Z ) to the distance (z) from the reference plane in the thickness direction of the thin film layer. In preparing the electron beam transmittance curve, a plane parallel to the surface of the thin film layer in the vicinity of the interface between the base material and the thin film layer was used as a reference plane in the film thickness direction of the thin film layer. The obtained result is shown in FIG. Since the thickness direction density variable (C _Z ) and the electron beam transmittance (T) are in a proportional relationship, FIG. 3 shows the thickness direction of the thin film layer in the gas barrier laminate film obtained in Example 1. The relationship between the distance (z) from a reference plane and electron beam transmittance (T) is shown.

As is clear from the results shown in FIG. 2B, it was confirmed that the obtained electron beam transmission curve has a plurality of distinct extreme values. Further, in the range corresponding to the thin film layer, that is, in the range where the distance (z) from the reference plane in the film thickness direction of the thin film layer is 210 nm to 520 nm, the thickness direction density variable (C _Z ) is set to the film thickness of the thin film layer. The gradient (dC _Z / dz) differentiated by the distance (z) from the reference plane in the direction was calculated, and the maximum value and the minimum value were obtained. The maximum value was 3.79 × 10 ⁻³ nm ⁻¹ . The minimum value was −4.75 × 10 ⁻³ nm ⁻¹ . The absolute value of the difference between the maximum value and the minimum value was 8.54 × 10 ⁻³ nm ⁻¹ . Further, in the obtained electron beam transmittance curve, there are some parts where the absolute value of the difference between the adjacent maximum value and minimum value in the thickness direction density variable (C _Z ) is 0.03 or more.

(Example 2)
First, the gas barrier laminated film having a thickness of 0.3 μm obtained in Example 1 is used as the film 100 and attached to the delivery roll 11 to form a new thin film layer on the surface of the thin film layer. A gas barrier laminate film (A) was obtained in the same manner as in Example 1 except that. In addition, the thickness of the thin film layer on the base material (PEN film) in the obtained gas-barrier laminated film (A) was 0.6 μm.

  Next, the obtained gas barrier laminate film (A) was used as the film 100 and attached to the delivery roll 11, and the same as in Example 1 except that a thin film layer was newly formed on the surface of the thin film layer. Thus, a gas barrier laminate film (B) was obtained.

The thickness of the thin film layer on the base material (PEN film) in the gas barrier laminate film (B) thus obtained was 0.9 μm. Further, in the obtained gas barrier laminate film (B), the water vapor transmission rate under the conditions of a temperature of 40 ° C., a low humidity side humidity of 0% RH, and a high humidity side humidity of 90% RH was 6.9 × 10 ⁻⁴ g. / (M ² · day), and the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit. Further, the water vapor permeability under the conditions of a temperature of 40 ° C. after bending under a condition of a curvature radius of 8 mm, a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is a value below the detection limit. It was confirmed that even when the obtained gas barrier laminate film (B) was bent, the gas barrier property could be sufficiently suppressed.

Moreover, about the obtained gas-barrier laminated | multilayer film (B), after obtaining a TEM image (magnification: 100,000 times) like Example 1, it is fundamental except the point shown below based on this TEM image. In the same manner as in Example 1, the electron indicating the relationship between the distance (z) from the reference plane (predetermined plane parallel to the surface of the thin film layer) and the electron beam transmittance (T) in the film thickness direction of the thin film layer. A line transmission curve was created. That is, when creating the electron beam transmission curve, the noise in the film thickness direction gradation variable (C _Z ) was removed using the simple moving average method. From the gradation image obtained from the TEM image, After reading the position as 25 nm and 990 nm, the interface position was set to 50 nm and 920 nm from the gradient (dC _Z / dz) of the thickness direction density variable (C _Z ). In preparing the electron beam transmittance curve, the average value of the thickness direction density variable (C _Z ) was normalized to 1 in the range corresponding to the thin film layer inside the interface position. In preparing the electron beam transmittance curve, a plane parallel to the surface of the thin film layer in the vicinity of the interface between the substrate and the thin film layer was used as a reference plane in the film thickness direction of the thin film layer.

As a result thus obtained, a transmission electron microscope of the gas barrier laminate film (B) is shown in FIG. 3, and an electron beam drop degree curve is shown in FIG. Since the thickness direction density variable (C _Z ) and electron beam transmittance (T) are in a proportional relationship, FIG. 4 shows the thickness direction of the thin film layer in the gas barrier laminate film obtained in Example 2. The relationship between the distance (z) from a reference plane and electron beam transmittance (T) is shown.

As is clear from the results shown in FIG. 4, it was confirmed that the obtained electron beam transmission curve has a plurality of distinct extreme values. Further, in the range corresponding to the thin film layer, that is, in the range in which the distance (z) from the reference plane in the film thickness direction of the thin film layer is 50 to 920 nm, the thickness direction density variable (C _Z ) is set to the film thickness of the thin film layer. The inclination (dC _Z / dz) differentiated by the distance (z) from the reference plane in the direction was calculated, and the maximum value and the minimum value of the inclination were obtained. The maximum value of the inclination was 1.59 × 10 ⁻³ nm ^{− 1} and the minimum value of the inclination was −1.82 × 10 ⁻³ nm ⁻¹ . The absolute value of the difference between the maximum value and the minimum value of the slope was 3.41 × 10 ⁻³ nm ⁻¹ . Further, in the obtained electron beam transmittance curve, there are some parts where the absolute value of the difference between the adjacent maximum value and minimum value in the thickness direction density variable (C _Z ) is 0.03 or more.

(Comparative Example 1)
On the surface of a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”), using a silicon target, in an oxygen-containing gas atmosphere, After forming a thin film layer made of silicon oxide by reactive sputtering, a gas barrier laminate film for comparison was obtained.

The thickness of the thin film layer in the gas barrier laminate film thus obtained was 100 nm. Further, in the obtained gas barrier laminate film, the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is 1.3 g / (m ² · day). And the gas barrier property was insufficient.

  About the obtained gas-barrier laminated | multilayer film, after obtaining a TEM image (magnification: 100,000 times) similarly to Example 1, based on this TEM image, fundamentally with Example 1 except the point shown below. Similarly, an electron beam transmission curve showing the relationship between the distance (z) from the reference plane (a predetermined plane parallel to the surface of the thin film layer) and the electron beam transmission (T) in the film thickness direction of the thin film layer. Created. In Comparative Example 1, the surface of the protective layer (the layer produced when the sample was formed) was used as a reference plane in the film thickness direction of the thin film layer when creating the electron beam transmittance curve.

  A transmission electron micrograph of the gas barrier laminate film thus obtained is shown in FIG. 5, and an electron beam transmittance curve is shown in FIG. In the TEM image shown in FIG. 5, the film thickness direction of the thin film layer is the horizontal direction of the image.

As is clear from the results shown in FIG. 6, it was confirmed that the obtained electron beam transmittance curve has no extreme value. Further, in the range corresponding to the thin film layer, that is, in the range where the distance (z) from the reference plane in the film thickness direction of the thin film layer is 640 to 690 nm, the thickness direction density variable (C _Z ) is set to the film thickness of the thin film layer. The inclination (dC _Z / dz) differentiated by the distance (z) from the reference plane in the direction was calculated, and the maximum value and the minimum value of the inclination were obtained. The maximum value of the inclination was 0.477 × 10 ⁻³ nm ^{− 1} and the minimum value of the slope was 0.158 × 10 ⁻³ nm ⁻¹ . Thus, since the maximum value and the minimum value of the slope are both positive values, it can be seen that there is no extreme value. The absolute value of the difference between the maximum value and the minimum value was 0.319 × 10 ⁻³ nm ⁻¹ .

(Comparative Example 2)
A gas barrier laminate film was produced in the same manner as in Example 1 except that the film formation conditions were changed to the following conditions and a thin film was formed by plasma CVD.

<Film formation conditions>
Film-forming gas mixing ratio (hexamethyldisiloxane / oxygen): 25/500 [unit: sccm (Standard Cubic Centimeter per Minute)]
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

The thickness of the thin film layer in the gas barrier laminate film thus obtained was 190 nm. Further, in the obtained gas barrier laminate film, the water vapor permeability under the conditions of a temperature of 40 ° C., a low humidity side humidity of 10% RH, and a high humidity side humidity of 100% RH is 0.0075 g / (m ² · day). And the gas barrier property was insufficient. Further, the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit, but after bending under the condition of a curvature radius of 8 mm. The water vapor permeability was 0.27 g / (m ² · day) under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. Even when bent, the gas barrier property could not be sufficiently suppressed.

  About the obtained gas-barrier laminated film, after obtaining a TEM image (magnification: 100,000 times) in the same manner as in Example 1, the film thickness direction of the thin film layer is obtained in the same manner as in Example 1 based on the TEM image. An electron beam transmission curve showing the relationship between the distance (z) from the reference plane (a predetermined plane parallel to the surface of the thin film layer) and the electron beam transmission (T) was prepared. The obtained transmission electron micrograph is shown in FIG. 7, and the electron beam transmittance curve is shown in FIG. In the TEM image shown in FIG. 7, the film thickness direction of the thin film layer is the horizontal direction of the image.

As is clear from the results shown in FIG. 8, it was confirmed that the obtained electron beam transmittance curve has no extreme value. Further, in the range corresponding to the thin film layer, that is, in the range where the distance (z) from the reference plane in the film thickness direction of the thin film layer is 400 nm to 520 nm, the thickness direction density variable (C _Z ) is set to the film thickness of the thin film layer. The inclination (dC _Z / dz) differentiated by the distance (z) from the reference plane in the direction was calculated, and the maximum value and the minimum value of the inclination were obtained. The maximum value of the inclination was 0.406 × 10 ⁻³ nm ^{− 1} and the minimum value of the inclination was −0.548 × 10 ⁻³ nm ⁻¹ . The absolute value of the difference between the maximum value and the minimum value was 0.954 × 10 ⁻³ nm ⁻¹ . Further, in the obtained electron beam transmission curve, there is no portion where the absolute value of the difference between the adjacent maximum value and the minimum value in the film thickness direction gradation variable (C _Z ) is 0.03 or more. It was found that positive and negative fluctuations were caused by so-called noise.

(Comparative Example 3)
A gas barrier laminate film was produced in the same manner as in Example 1 except that the film formation conditions were changed to the following conditions and a thin film was formed by plasma CVD.

<Film formation conditions>
Deposition gas mixture ratio (hexamethyldisiloxane / oxygen): 25/1000 [unit: sccm (Standard Cubic Centimeter per Minute)]
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

The thickness of the thin film layer in the gas barrier laminate film thus obtained was 180 nm. Further, in the obtained gas barrier laminate film, the water vapor transmission rate at a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side is 0.022 g / (m ² · day). And the gas barrier property was insufficient. Further, the water vapor transmission rate under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side was a value below the detection limit, but after bending under the condition of a curvature radius of 8 mm. The water vapor permeability was 0.12 g / (m ² · day) under the conditions of a temperature of 40 ° C., a humidity of 10% RH on the low humidity side, and a humidity of 100% RH on the high humidity side. In the case of bending, the gas barrier property could not be sufficiently suppressed.

  About the obtained gas-barrier laminated | multilayer film, after obtaining a TEM image (magnification: 100,000 times) similarly to Example 1, based on this TEM image, fundamentally Example 1 except the point shown below. Similarly, the electron beam transmission curve showing the relationship between the distance (z) from the reference plane (predetermined plane parallel to the surface of the thin film layer) and the electron beam transmission (T) in the film thickness direction of the thin film layer It was created. That is, in creating the electron beam transmittance curve, the surface of the protective layer was used as a reference plane in the film thickness direction of the thin film layer. In preparing the electron beam transmission curve, 200 nm was a length corresponding to 194 unit regions in the obtained grayscale image.

  A transmission electron micrograph of the obtained gas barrier laminate film is shown in FIG. 9, and an electron beam transmission curve is shown in FIG. In the TEM image shown in FIG. 9, the film thickness direction of the thin film layer is the horizontal direction of the image.

As is clear from the results shown in FIG. 10, it was confirmed that the obtained electron beam transmittance curve had no extreme value. Further, in the range corresponding to the thin film layer, that is, in the range in which the distance (z) from the reference plane in the film thickness direction of the thin film layer is 480 nm to 580 nm, the thickness direction density variable (C _Z ) is set to the film thickness of the thin film layer. The inclination (dC _Z / dz) differentiated by the distance (z) from the reference plane in the direction was calculated, and the maximum value and the minimum value of the inclination were obtained. The maximum value of the inclination was 0.342 × 10 ⁻³ nm ^{− 1} and the minimum value of the inclination was −0.887 × 10 ⁻³ nm ⁻¹ . Moreover, the absolute value of the difference between the maximum value and the minimum value of the slope was 1.23 × 10 ⁻³ nm ⁻¹ . Further, in the obtained electron beam transmission curve, there is no portion where the absolute value of the difference between the adjacent maximum value and the minimum value in the film thickness direction gradation variable (C _Z ) is 0.03 or more. It was found that positive and negative fluctuations were caused by so-called noise.

  As described above, according to the present invention, there is provided a gas barrier laminated film that has a sufficient gas barrier property and can sufficiently suppress a decrease in gas barrier property even when the film is bent. It becomes possible to do.

  Therefore, the gas barrier laminate film of the present invention can be suitably used for flexible lighting using organic electroluminescence elements (organic EL elements), organic thin film solar cells, liquid crystal displays, pharmaceutical packaging containers, and the like.

  DESCRIPTION OF SYMBOLS 11 ... Sending roll, 21, 22, 23, 24 ... Conveyance roll, 31, 32 ... Film-forming roll, 41 ... Gas supply pipe, 51 ... Power source for plasma generation, 61, 62 ... Magnetic field generator, 71 ... Winding roll , 100 ... film.

Claims (20)

  A gas barrier laminate film comprising a base material and at least one thin film layer formed on at least one surface of the base material, wherein at least one of the thin film layers has a film thickness of the layer A gas barrier laminate film, wherein an electron beam transmission curve showing a relationship between a distance from the surface of the layer in the direction and electron beam transmission has at least one extreme value.   The gas barrier laminate film according to claim 1, wherein the electron beam transmittance curve is substantially continuous.   The gas barrier laminate film according to claim 1 or 2, wherein the electron beam transmittance curve has at least three extreme values.   The absolute value of the difference between the distance from the surface of the thin film layer in the thickness direction of the thin film layer at one extreme value and the extreme value adjacent to the extreme value of the electron beam transmittance curve is 200 nm or less. The gas barrier laminate film according to any one of claims 1 to 3, wherein   The thickness of the said thin film layer is 5-3000 nm, The gas-barrier laminated film as described in any one of Claims 1-4 characterized by the above-mentioned.   The gas barrier laminate film according to any one of claims 1 to 5, wherein the thin film layer contains silicon oxide as a main component.   The gas barrier laminate film according to claim 6, wherein the thin film layer substantially does not contain nitrogen.   The gas barrier laminate film according to claim 1, wherein the thin film layer contains silicon nitride as a main component.   The said thin film layer contains carbon, The gas barrier property laminated film as described in any one of Claims 1-8 characterized by the above-mentioned.   The gas barrier laminate film according to any one of claims 1 to 9, wherein the thin film layer is a layer formed by a plasma chemical vapor deposition method.   The thin film layer is a layer formed by a plasma chemical vapor deposition method in which the substrate is disposed on a pair of film forming rolls, and plasma is generated by discharging between the pair of film forming rolls. The gas barrier laminate film according to any one of claims 1 to 10.   The gas barrier laminate film according to claim 11, wherein when discharging is performed between the pair of film forming rolls, the polarities of the pair of film forming rolls are alternately reversed.   The gas barrier laminate film according to any one of claims 10 to 12, wherein a film forming gas used in the plasma chemical vapor deposition method contains an organosilicon compound and oxygen.   The content of the oxygen in the film-forming gas is equal to or less than a theoretical oxygen amount required to completely oxidize the entire amount of the organosilicon compound in the film-forming gas. Gas barrier laminate film.   The gas barrier laminate film according to claim 1, wherein the thin film layer is a layer formed by a continuous film forming process.   The gas barrier laminate film according to any one of claims 1 to 15, wherein the substrate is made of at least one resin selected from the group consisting of polyester resins and polyolefin resins.   The gas barrier laminate film according to any one of claims 1 to 16, wherein the substrate is made of at least one resin selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate.   An organic electroluminescent element provided with the gas-barrier laminated film as described in any one of Claims 1-17.   An organic thin-film solar cell provided with the gas-barrier laminated film as described in any one of Claims 1-17. A liquid crystal display provided with the gas barrier laminated film according to any one of claims 1 to 17.