JPWO2015053189A1 - Gas barrier film and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a gas barrier film having high gas barrier properties and bending resistance even when a gas barrier layer in which the composition of carbon atoms and oxygen atoms is continuously inclined is formed under conditions with high productivity. Is to provide. The gas barrier film of the present invention is a gas barrier film having a gas barrier layer containing at least silicon, oxygen, and carbon as constituent elements on a flexible substrate, and plots the ratio between the carbon amount and the oxygen amount. In the carbon / oxygen distribution curve, at least one pair of adjacent extreme values is in the range of 1 to 10 nm, and the carbon atomic ratio is within a distance of 30 nm from the base material interface of the gas barrier layer. A region distributed within a range of 10 to 30 at% exists.

Description

  The present invention relates to a gas barrier film and a method for producing the same. More specifically, the present invention relates to a gas barrier film having high gas barrier properties and bending resistance and a method for producing the same.

  In recent years, in the electronic device field, in addition to demands for weight reduction and size increase, long-term reliability and a high degree of freedom in shape, and the ability to display curved surfaces have been added, resulting in a large area that is heavy and easy to break. Instead of glass substrates that are difficult to handle, film substrates such as transparent plastics have begun to be adopted.

  However, film base materials such as transparent plastics are inferior to glass base materials in terms of gas barrier properties, and if base materials with poor gas barrier properties are used, water vapor and oxygen will permeate, deteriorating the functions in electronic devices. There is a problem of end.

  On the other hand, a gas barrier film is known in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide or silicon oxide is formed on the surface of a plastic substrate or a film substrate. Gas barrier films that prevent the transmission of water vapor, oxygen, etc. are required to be developed into electronic devices such as organic electroluminescence (EL) elements and liquid crystal display (LCD) elements, and have gas barrier properties comparable to glass substrates Gas barrier films have been studied.

  A film having high gas barrier performance can be obtained by forming the gas barrier layer by chemical vapor deposition (hereinafter, also simply referred to as CVD method). The CVD method has a high film formation rate and high productivity. However, in recent years, higher productivity is required while maintaining high gas barrier properties.

  In the film forming apparatus by the CVD method described in Patent Document 1, the gas barrier film can be formed in a roll-to-roll manner, and the composition of carbon atoms and oxygen atoms is contained in a continuously inclined manner only by transporting the substrate. A gas barrier film having high gas barrier properties and bending resistance can be continuously produced.

  However, if the gas barrier layer is formed by increasing the conveyance speed of the substrate in the apparatus or increasing the temperature of the electrode of the film forming roller in order to further increase the productivity, the moisture from the substrate is reduced. Due to vaporization or desorption, the discharge is not stable, the moisture is taken into the gas barrier layer, the continuous composition gradient of carbon atoms and oxygen atoms collapses, especially the carbon atom component is greatly reduced, The remarkable problem that gas barrier property and bending resistance deteriorated occurred.

  In forming a gas barrier layer by a CVD method, a method for removing moisture brought in from a base material is disclosed (for example, see Patent Document 2). The method of Patent Document 2 is to evacuate the substrate in advance for 12 hours or more, but it is possible to remove moisture to some extent, but vaporization is caused by heat generated when the substrate is exposed to plasma. Moisture that desorbs and vaporizes when the substrate transport speed is increased, and moisture that is desorbed cannot be exhausted, and moisture is brought into the plasma, resulting in plasma destabilization and reduced productivity. In addition, deterioration of gas barrier properties and bending resistance due to a decrease in the carbon atom component in the gas barrier layer was observed.

JP 2011-73430 A JP 2013-28163 A

  The present invention has been made in view of the above-described problems and situations, and the solution is to form a gas barrier layer in which the composition of carbon atoms and oxygen atoms is continuously inclined under conditions of high productivity. Another object is to stably provide a gas barrier film having high gas barrier properties and bending resistance. Moreover, it is providing the manufacturing method of the gas barrier film which can form the said gas barrier layer at high speed.

  In order to solve the above problems, the present inventor, in the process of examining the cause of the above problems, a gas in which a gas barrier layer containing at least silicon, oxygen, and carbon as constituent elements is formed on a flexible substrate. In the carbon / oxygen distribution curve in which the ratio between the carbon amount and the oxygen amount is plotted, at least one pair of adjacent extreme values is within a specific range, and the gas barrier layer group is a barrier film. A gas barrier film having a region in which a carbon atom ratio is distributed at a ratio within a specific range within a specific distance range from the material interface is used to form the gas barrier layer on the substrate under conditions with high productivity. In addition, the present inventors have found that a gas barrier film having high gas barrier properties and bending resistance can be obtained, and have reached the present invention.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A gas barrier film having a gas barrier layer containing at least silicon, oxygen, and carbon as constituent elements on a flexible substrate,
In the carbon / oxygen distribution curve in which the ratio between the carbon amount and the oxygen amount is plotted, the interval between at least one pair of adjacent extreme values is in the range of 1 to 10 nm,
And the area | region where a carbon atom ratio distributes within the range of 10-30 at% exists in the distance range of 30 nm from the base-material interface of the said gas barrier layer, The gas barrier film characterized by the above-mentioned.

  2. 2. The gas barrier film according to claim 1, wherein an organic layer containing an organic compound is provided on at least one surface of the flexible substrate.

  3. 3. The gas barrier film according to item 2, wherein the organic layer further contains inorganic particles.

4). A method for producing a gas barrier film according to any one of items 1 to 3, wherein the gas barrier film is produced.
A step of feeding the belt-shaped flexible base material from the feed roller and transporting it with the transport roller;
Heat-treating the flexible substrate;
The flexible substrate subjected to the heat treatment is conveyed while being brought into contact with each of a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. Forming a gas barrier layer on the conductive substrate;
A step of winding the gas barrier film having the gas barrier layer formed on the flexible substrate with a winding roller while transporting the gas barrier film with a transport roller, and
The method for producing a gas barrier film, wherein the conveyance speed of the flexible substrate is 3 m / min or more.

  5. The method for producing a gas barrier film according to claim 4, wherein the heat treatment is performed under a pressure condition equal to or lower than a pressure at the time of forming the gas barrier layer.

  Even if the gas barrier layer in which the composition of carbon atoms and oxygen atoms is continuously inclined by the above-described means of the present invention is formed under conditions with high productivity, the gas barrier film has high gas barrier properties and bending resistance. Can be provided. Moreover, the manufacturing method of the gas barrier film which can form the said gas barrier layer at high speed can be provided.

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

  According to the study by the present inventors, when manufacturing a gas barrier film using a CVD film forming apparatus described in Patent Document 1, in order to further increase the productivity, a substrate is formed with the film forming apparatus. When the gas barrier layer was formed by increasing the conveying speed or increasing the temperature of the electrode of the film forming roller, the gas barrier property and bending resistance were particularly deteriorated.

  In the process of analyzing the cause, the element distribution measurement in the thickness direction of the gas barrier layer was performed by X-ray photoelectron spectroscopy. As a result, the carbon / oxygen distribution curve in which the ratio of the carbon amount to the oxygen amount was plotted was at least 1 The distance between adjacent extreme values in the set is in the range of 1 to 10 nm, and the carbon atom ratio is distributed in the range of 10 to 30 at% within the range of 30 nm from the base material interface of the gas barrier layer. Found that the region does not exist.

  The cause is that a very small amount of water held by the substrate itself is released into the plasma discharge space, and promotes oxidation of the film by a reaction represented by the following reaction formula. As a result, the gas barrier property is deteriorated by impairing the gradient of the continuous composition of the carbon content and the oxygen content, and particularly when the carbon content is lowered, it becomes impossible to disperse the stress at the time of bending. It is considered that the bending resistance of the layer deteriorates.

Reaction formula H ₂ O + e ⁻ → H ^* + OH ^*
SiOC + OH ^* → SiO ₂ + CH _x
In particular, if the gas barrier layer is to be formed under conditions with high productivity, and if the film is formed under conditions where the temperature of the substrate during film formation is high, such as increasing the temperature of the film formation roller or increasing the power, the plasma heat In addition, since the base material is warmed by heat transfer from the film forming roller and the amount of moisture released from the base material is increased, the above deterioration becomes more noticeable when performed under such film forming conditions.

  Furthermore, when the amount of water released increases, particularly in the CVD apparatus described in Patent Document 1, a decrease in adhesion force and a change in color distribution and gas barrier performance in the width are observed.

  When the ionized precursor is accelerated in accordance with the magnetic force and injected into the base material, the local pressure increases due to the gas released from the base material in the vicinity of the base material. Is decelerated, and it is estimated that the precursor injection depth is reduced.

  In addition, since the change in the color and gas barrier performance distribution in the width is usually stored in a wound state, the outer width of the winding is easy to escape from the gas, or from the outside, As a result, when the base material is put into a vacuum, a water content gradient is generated in the width direction. It is presumed that the composition distribution variation of the gas barrier film is caused, and the color and gas barrier performance are unevenly distributed.

In addition, when an organic layer containing an organic binder such as a stress relaxation layer and a smooth layer is provided on the base material in advance, the moisture content increases, so that the influence of the released moisture becomes greater. In addition, in order to adjust the hardness and elastic modulus and to adjust the adhesion with the gas barrier layer, inorganic particles may be contained in the stress relaxation layer and the smoothing layer, but OH groups are present on the surface of the inorganic particles. For this reason, the OH group and H ₂ O are adsorbed in a hydrogen bond state, and the amount of water that can be held by the base material itself increases, so that the deterioration becomes more remarkable. H ₂ O adsorbed by hydrogen bonds cannot be removed simply by evacuation, but is vaporized and desorbed by heating. The desorbed material is released into the plasma space, and the composition of the film is greatly destroyed. As a result, the gas barrier property and the bending resistance are greatly deteriorated.

  In addition, it is considered that the use of a film substrate such as polyethylene terephthalate (PET) having a high water content as the flexible substrate increases the influence of the moisture.

  In the present invention, when forming a gas barrier layer in which the composition of carbon atoms and oxygen atoms is continuously inclined, a substrate or a substrate provided with an organic layer such as the stress relaxation layer or the smooth layer in advance is provided. By heat-treating before film formation, moisture contained in the substrate is efficiently vaporized and desorbed, greatly reducing moisture release from the substrate in the film formation region, and increasing the substrate transport speed. Even when film formation is performed under conditions of high productivity such as speeding up and increasing the temperature of the film forming roller, film formation without the influence of moisture is possible.

  At the same time, in the carbon / oxygen distribution curve in which the ratio of carbon amount to oxygen amount (C / O) in the gas barrier layer is plotted with respect to the thickness direction of the gas barrier layer, the interval between adjacent extreme values is 1 By forming the film by adjusting the transport speed of the substrate so as to be within the range of 10 nm, the flexibility of the gas barrier layer due to the distribution of carbon atoms can be maintained and improved, and high gas barrier properties and bending It is presumed that a gas barrier film having resistance is obtained.

Example of configuration of gas barrier film of the present invention An example of another constitution of the gas barrier film of the present invention Schematic showing an example of gas barrier film manufacturing equipment Enlarged view of film formation space of gas barrier film manufacturing equipment The graph which shows each element profile of the thickness direction of the layer by the XPS depth profile of the gas barrier layer which concerns on this invention An example of the carbon / oxygen distribution curve in the thickness direction of the layer according to the XPS depth profile of the gas barrier layer according to the present invention The graph which shows each element profile of the thickness direction of the layer by the XPS depth profile of another gas barrier layer which concerns on this invention An example of the carbon / oxygen distribution curve in the thickness direction of another layer by XPS depth profile of another gas barrier layer according to the present invention The graph which shows each element profile of the thickness direction of the layer by the XPS depth profile of the gas barrier layer of a comparative example Example of carbon / oxygen distribution curve in the layer thickness direction by XPS depth profile of gas barrier layer of comparative example

  The gas barrier film of the present invention is a gas barrier film having a gas barrier layer containing at least silicon, oxygen and carbon as constituent elements on a flexible substrate (hereinafter also simply referred to as “substrate”). In the carbon / oxygen distribution curve in which the ratio between the carbon amount and the oxygen amount is plotted, at least one pair of adjacent extreme values is within a specific range and 30 nm from the base material interface of the gas barrier layer. Within the distance range, there is a region in which the carbon atom ratio is distributed at a ratio within a specific range. This feature is a technical feature common to the inventions according to claims 1 to 5.

  As an embodiment of the present invention, it is preferable that an organic layer containing an organic compound is provided in advance on at least one surface of the flexible substrate from the viewpoint of manifesting the effects of the present invention. The organic layer is preferably a functional layer containing an organic compound such as a stress relaxation layer or a smooth layer, and smoothes the substrate interface to promote the formation of a dense gas barrier layer to enhance gas barrier properties, The adhesion between the barrier layer and the substrate can be improved, and the bending resistance can be further increased. Moreover, since the said organic layer can further improve the said adhesiveness, it is preferable to contain an inorganic particle further.

  In the method for producing a gas barrier film of the present invention, before forming the gas barrier layer by the plasma discharge, the flexible substrate is preheated to vaporize and desorb moisture contained in the substrate. It is preferable to reduce the influence of moisture during the formation of the gas barrier layer. Furthermore, it is preferable from the viewpoint of producing a gas barrier film having high gas barrier properties and bending resistance with good productivity that the flexible substrate is transported at a speed of 3 m / min or more to form a gas barrier layer. Furthermore, it is a more preferable manufacturing method from the viewpoint of promoting the vaporization and desorption of the water, that the heat treatment is performed under atmospheric pressure conditions equal to or lower than the atmospheric pressure when forming the gas barrier layer.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Gas Barrier Film of the Present Invention >>
The gas barrier film of the present invention is a gas barrier film in which a gas barrier layer containing at least silicon, oxygen, and carbon as constituent elements is formed on a flexible substrate, and the ratio of the amount of carbon to the amount of oxygen is determined. In the plotted carbon / oxygen distribution curve, at least one pair of adjacent extreme values is within a range of 1 to 10 nm, and within a distance range of 30 nm from the base material interface of the gas barrier layer, the carbon atom ratio Is characterized in that there is a region in which the distribution is within a range of 10 to 30 at%.

  Here, the ratio of the carbon amount to the total amount of silicon, oxygen and carbon, measured by the XPS depth profile described later, is expressed as “carbon atomic ratio (at%)”, the oxygen amount relative to the total amount of silicon, oxygen and carbon. The ratio is referred to as “oxygen atomic ratio (at%)”, and the ratio of the amount of silicon to the total amount of silicon, oxygen and carbon is referred to as “silicon atomic ratio (at%)”. In any case, the total amount of silicon, oxygen and carbon is 100 at%.

<Configuration of gas barrier film of the present invention>
Although the structure of the gas barrier film of this invention is not specifically limited, FIG. 1A shows an example. The gas barrier film 10 a is a gas barrier film in which the gas barrier layer 3 is laminated on the substrate 1. In that case, providing the smooth layer 2 as the organic layer according to the present invention between the base material 1 and the gas barrier layer 3 improves the adhesion between the base material and the gas barrier layer, and the unevenness of the base material interface. Is a preferable mode in order to make it difficult to affect the gas barrier layer which is a thin layer.

  Moreover, the gas barrier film 10b of this invention which is another aspect is equipped with the smooth layer 2 on the resin base material 1, as shown to FIG. 1B, for example, and the gas barrier layer 3 is laminated | stacked on the smooth layer 2 Furthermore, it is also preferable to provide a bleed-out preventing layer 4 that is an organic layer according to the present invention on the surface of the resin substrate 1 opposite to the surface having the gas barrier layer 3. Furthermore, a second gas barrier layer 5 containing a metal oxide may be laminated on the gas barrier layer 3. An overcoat layer 6 may be laminated on the second gas barrier layer 5.

<Gas barrier layer>
Although the thickness of the gas barrier layer according to the present invention is not particularly limited, it is usually in the range of 20 to 1000 nm in order to improve the gas barrier ability while making it difficult to cause defects. From the viewpoint of increasing the transport speed of the base material in order to improve the properties, the layer thickness per gas barrier layer is preferably in the range of 20 to 100 nm, and is bent in the range of 30 to 80 nm. From the viewpoint of improving resistance, it is more preferable.

  Here, as a method for measuring the thickness of the gas barrier layer according to the present invention, a film thickness measuring method by observation with a transmission microscope (TEM) described later is employed. The gas barrier layer according to the present invention may have a laminated structure including a plurality of sublayers. In this case, the number of sublayers is preferably 2 to 30. Moreover, each sublayer may have the same composition or a different composition.

  The gas barrier layer according to the present invention contains at least silicon, oxygen, and carbon. Moreover, you may contain nitrogen as another element.

  The gas barrier layer according to the present invention contains carbon in addition to silicon and oxygen. Among these, the presence of silicon and oxygen can impart gas barrier properties, and the presence of carbon can impart flexibility to the gas barrier layer.

  Therefore, since the carbon distribution state affects the flexibility, a region in which a certain amount of carbon is distributed in the layer thickness direction is required in the gas barrier layer. When forming the gas barrier layer by increasing the transport speed of the substrate or by increasing the productivity such as increasing the temperature of the deposition roller, the substrate interface is affected by the aforementioned moisture. A region with a reduced carbon distribution is easily formed in a specific range on the side in contact with. For this reason, it is presumed that bending resistance deteriorates due to lack of flexibility due to the presence of carbon. In the present invention, within the distance range of 30 nm from the substrate interface, the presence of a region in which the carbon amount is distributed within the range of 10 to 30 at% as the carbon atom ratio can provide flexibility and improve the bending resistance. It is necessary from.

  By the way, when the gas barrier layer is once formed on the gas barrier layer, there is no influence of moisture from the base material, and the gas barrier has a region where a certain amount of carbon is distributed in the layer thickness direction. It is possible to form the entire region in the layer thickness direction of the layer.

The “gas barrier property” as used in the present invention is a water vapor permeability (temperature: 60 ± 0.5 ° C., relative humidity (RH): 90 ± 2%) measured by a method according to JIS K 7129-1992. ) Is 3 × 10 ⁻³ g / m ² · 24 h or less, and the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ ml / m ² · 24 h · atm or less. Means that.

  The gas barrier layer according to the present invention comprises a silicon atom having a relationship between the condition (i) the distance (L) from the surface of the gas barrier layer according to the present invention in the layer thickness direction of the gas barrier layer according to the present invention and the silicon atomic ratio. In the distribution curve, the oxygen distribution curve showing the relationship between L and the oxygen atom ratio, and the carbon distribution curve showing the relationship between L and the carbon atom ratio, 80% or more of the thickness of the gas barrier layer according to the present invention (upper limit: In the region of 100%, it is preferable to have an order of magnitude relationship represented by the following formula (A) or the following formula (B).

Formula (A) (carbon atom ratio) <(silicon atom ratio) <(oxygen atom ratio)
Formula (B) (oxygen atom ratio) <(silicon atom ratio) <(carbon atom ratio)
Here, at least 80% or more of the layer thickness of the gas barrier layer according to the present invention does not have to be continuous in the gas barrier layer, and only needs to satisfy the above-described relationship at a portion of 80% or more. .

  In the above distribution curve, the relationship between the oxygen atom ratio, the silicon atom ratio, and the carbon atom ratio is more preferably satisfied in a region of at least 90% or more (upper limit: 100%) of the thickness of the gas barrier layer, and at least 93 More preferably, it is satisfied in an area of at least% (upper limit: 100%). Further, in the region of 80% or more (upper limit: 100%) of the thickness of the gas barrier layer according to the present invention, the atomic ratio satisfies C <Si <O, and the order magnitude relationship represented by the formula (A) is satisfied. Is preferred. By satisfying such conditions, the gas barrier property and bending resistance of the obtained gas barrier film are sufficient.

  In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, in the region where the silicon atom ratio, oxygen atom ratio, and carbon atom ratio are 80% or more of the thickness of the gas barrier layer according to the present invention, the formula ( When the condition A) is satisfied, the silicon atom ratio in the layer is preferably 25 to 45 at%, more preferably 30 to 40 at%. The oxygen atomic ratio in the gas barrier layer according to the present invention is preferably 33 to 67 at%, more preferably 45 to 67 at%. Furthermore, the carbon atom ratio in the layer is preferably 3 to 33 at%, and more preferably 3 to 25 at%.

  In particular, within the distance range of 30 nm from the substrate interface, it is necessary from the viewpoint of improving the bending resistance that there is a region in which the carbon amount is distributed within the range of 10 to 30 at% as the carbon atom ratio. That is, the carbon distribution curve showing the distribution of the carbon atom ratio in the layer thickness direction of the gas barrier layer has a horizontal axis a: a distance range of 30 nm from the substrate interface, and a vertical axis b: a range of carbon atom ratio 10-30 at%. It is plotted in the area surrounded by. It is necessary that at least one “region” formed by plotting is continuously present in the region surrounded by the horizontal axis “a” and the vertical axis “b”. Good.

  From the viewpoint of improving the bending resistance of the gas barrier film of the present invention, when the distance range of 30 nm from the substrate interface is 100%, there is a region where the carbon amount is in the range of 10 to 30 at% as the carbon atom ratio. , Preferably within a range of 30% or more of the distance range, more preferably within a range of 50% or more, still more preferably within a range of 60% or more, and a range of 70% or more It is particularly preferred that When there are a plurality of discontinuous locations, it is preferable that the sum of the distance ranges of the existing regions satisfy the ratios of the distance ranges where the carbon exists.

  This will be described with reference to the drawings. FIG. 4 is a graph showing each element profile in the layer thickness direction according to the XPS depth profile of the gas barrier layer according to the present invention.

<About XPS depth profile>
A silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a carbon / oxygen distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement in combination with rare gas ion sputtering such as argon. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (at%) of each element and the horizontal axis as the etching time (sputtering time). In this way, in the element distribution curve with the horizontal axis as the etching time, the etching time is from the surface of the gas barrier layer according to the present invention in the layer thickness direction of the gas barrier layer according to the present invention in the layer thickness direction. The etching rate and the etching time employed in the XPS depth profile measurement as “the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer according to the present invention” are roughly correlated with the distance (L) of The distance from the surface of the gas barrier layer according to the present invention calculated from the relationship between (i.e., layer thickness in terms of SiO ₂ (nm) = (etching time (sec) × etching rate (nm / sec)) is employed. In the present invention, the SiO ₂ equivalent layer thickness (nm) is also referred to as the sputter depth (nm).

  In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve and carbon / oxygen distribution curve were prepared under the following measurement conditions.

[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): SiO ₂ equivalent layer thickness of the gas barrier layer ÷ 20 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopic AlKα X-ray spot and size: 800 × 400 μm ellipse.

  Moreover, when plotting the gas barrier layer produced with the plasma CVD apparatus which has a counter roller electrode, a plot position is defined by the number of a pair of counter rollers which pass (the following etching space | interval).

[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) (data plot interval): SiO ₂ equivalent layer thickness of gas barrier layer ÷ 10 ÷ TR number (number of opposed rollers) (nm)
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval shape “Substrate interface” as used in the present invention refers to the silicon atom ratio (at%) profile and the carbon atom ratio (at%) profile from the surface of the gas barrier layer. When plotting XPS depth profile data in the depth direction, the point P where the silicon atomic ratio changes by −0.5 at% / nm or more and the carbon atomic ratio changes by +1.0 at% or more is defined as “base material interface”. It is defined as

  This is an interface between the gas barrier layer according to the present invention and an organic layer such as a hard coat layer formed on the base material or the base material due to the nature of the measurement when performing composition analysis with the XPS depth profile. This is because there is always a transition region in which both compositions are mixed.

  XPS can obtain information on the elemental composition and chemical state of the surface by irradiating the sample surface with X-rays under vacuum and observing the kinetic energy of photoelectrons emitted from the surface into the vacuum by the photoelectric effect. Although it is possible, near the interface at the time of the X-ray irradiation, X-rays reach not only the film but also the base material, and there is a transition region that is mixed in composition due to the influence thereof, It is difficult to specify a clear position as an interface. Therefore, the “base material interface” as used in the present invention is a transition region in which both the gas barrier layer component and the base material component are detected, and the point P which is the above change point is the “base material interface”. Defined.

  For example, according to FIG. 4, the point P where the silicon atomic ratio changes by −0.5 at% / nm or more and the carbon atomic ratio changes by +1.0 at% or more by the XPS depth profile is at a sputter depth of 50.9 nm. Therefore, the distance range S of 30 nm from the substrate interface corresponds to the sputter depth range of 20.9 to 50.9 nm, in which the carbon amount is distributed in the range of 10 to 30 at% as the carbon atom ratio. The distance range (20.9 to 44.0 nm) of the existing region is within 65% of the distance range of 30 nm from the substrate interface (the thickness in the depth direction of the layer is 23). .1 nm distance range).

  Similarly, according to FIG. 6 showing the XPS depth profile of another gas barrier layer according to the present invention, since the point P has a sputter depth of 57.0 nm, a distance range S of 30 nm from the substrate interface is a sputter depth. This range corresponds to a depth range of 27.0 to 57.0 nm. In this range, there is a region in which the carbon content is distributed in the range of 10 to 30 at% as a carbon atom ratio, and the distance range (27. 0 to 52.5 nm) is present within 74% of the distance range of 30 nm from the substrate interface (a distance range of 22.1 nm as the thickness in the depth direction of the layer).

  On the other hand, according to FIG. 8, which is a graph showing each element profile of the comparative example, the point P has a sputter depth of 53.0 nm, and a distance range S of 30 nm from the substrate interface has a sputter depth of 23. The range of .0 to 53.0 nm is applicable, and in this range, the proportion of the region in which the carbon amount is distributed in the range of 10 to 30 at% as the carbon atom ratio is 0%, and the carbon amount is within the distance range. It can be seen that the content is extremely low.

  The gas barrier layer according to the present invention is a carbon / oxygen distribution curve showing a relationship between a distance (L) from the surface of the gas barrier layer and a ratio of carbon amount to oxygen amount (C / O). Has at least two extreme values. The existence of such an extreme value indicates that the abundance ratio of carbon and oxygen in the layer is not uniform, and the entire layer is flexible due to the presence of a part with a large amount of carbon. And the bending resistance is improved.

  In the gas barrier layer according to the present invention, the carbon / oxygen distribution curve preferably has at least three extreme values, and more preferably has at least five extreme values.

  Here, the extreme value means the maximum value or the 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. In the present invention, the maximum value is a point in the element distribution curve where the value of the atomic ratio of the element changes from increasing to decreasing with a continuous change in the distance from the surface of the gas barrier layer. The atomic ratio value of the element at a position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer from the point to the surface of the gas barrier layer is further changed by 5 nm is reduced by 1 at% or more. It means a point. The minimum value is a point in the element distribution curve where the atomic ratio of the element changes from decreasing to increasing with a continuous change in the distance from the surface of the gas barrier layer, and the atomic ratio of the element at that point. Is a point where the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer from this point is further changed by 5 nm is increased by 1 at% or more. .

  The number of such extreme values is theoretically determined when the number of opposed rollers (TR number, number of two roller sets opposite to each other) is n (n is an integer of 1 or more) in the apparatus shown in FIG. The number of extreme values is about (5 + 4 × (n−1)). However, the actual number of extreme values is not always the theoretical number of extreme values depending on the conveyance speed of the substrate, and may increase or decrease. When the extreme value of the carbon / oxygen distribution curve is 1 or less, the gas barrier property when the obtained gas barrier film is bent is insufficient. The upper limit of the extreme value of the carbon / oxygen distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. Since the number of extreme values is also caused by the thickness of the gas barrier layer, it cannot be specified unconditionally.

  In addition, in the carbon / oxygen distribution curve in the layer thickness direction of the gas barrier layer, the interval between at least one pair of adjacent extreme values is in the range of 1 to 10 nm from the viewpoint of improving the bending resistance of the present invention. is necessary. Preferably, the interval between two or more adjacent extreme values is in the range of 1 to 10 nm.

  The effect is more remarkable when the distance between at least one set of adjacent extreme values is in the range of 1 to 7 nm, and even better is in the range of 1 to 5 nm. A film having a gas barrier layer according to the present invention having a small interval between adjacent extreme values, that is, a rapid change in the composition of the film, exhibits an excellent effect in terms of flexibility of the gas barrier layer and at the same time has a gas barrier property. Also excellent.

  The interval between at least one pair of adjacent extreme values is a value proportional to the conveyance speed of the base material when the apparatus shown in FIG. Specifically, when the conveyance speed of the base material is increased, the interval between adjacent extreme values tends to be shortened. In consideration of a realistic conveyance speed, the interval between at least one set of adjacent extreme values is 1 nm or more. Here, in the carbon / oxygen distribution curve, the gas barrier layer according to the present invention in which the distance between at least one pair of adjacent extreme values is 10 nm or less, particularly the substrate transport speed of 3 m / min in the apparatus of FIG. In this case, it can be easily formed. Furthermore, if it is 5 m / min or more, it becomes easier. That is, in a preferred embodiment of the present invention, the gas barrier layer according to the present invention is a layer formed by a plasma CVD method using a plasma CVD apparatus having a counter roller electrode, and has a carbon / oxygen distribution. In the curve, the distance between at least one pair of adjacent extreme values is in the range of 1 to 10 nm (more preferably 1 to 7 nm, still more preferably 1 to 5 nm).

The interval between the extreme values in the carbon / oxygen distribution curve is determined from the carbon / oxygen distribution curve, and the SiO ₂ equivalent layer thickness (sputter depth (nm)) from the surface of the gas barrier layer according to the present invention at each extreme value. Is calculated from In addition, the space | interval between adjacent extreme values is the gas which concerns on this invention in the layer thickness direction of the gas barrier layer which concerns on one extreme value which a carbon / oxygen distribution curve has, and the extreme value adjacent to this extreme value. The absolute value of the difference in distance (L) from the surface of the barrier layer (hereinafter, also simply referred to as “distance between extreme values”). Further, the “extreme value” in the carbon / oxygen distribution curve refers to the maximum value or the minimum value of C / O (carbon content / oxygen content) in the carbon / oxygen distribution curve. As described above, the maximum value in the carbon / oxygen distribution curve means that the value of the atomic ratio (C / O) of the carbon amount to the oxygen amount increases when the distance from the surface of the gas barrier layer according to the present invention is changed. This is the point that changes from a decrease to a decrease. Furthermore, the minimum value in the carbon / oxygen distribution curve means that when the distance from the surface of the gas barrier layer according to the present invention is changed, the value of the atomic ratio (C / O) of the carbon amount to the oxygen amount decreases. The point that changes to increase.

  This will be described with reference to FIG. 5. In FIG. 5, the distance Z between a pair of adjacent local maximum values X and local minimum values Y obtained from the carbon / oxygen distribution curve in a distance range of 30 nm from the substrate interface is 5 nm. In FIG. 7, the interval Z is 4 nm, and in FIG. 9, the interval Z is 11 nm.

  Further, in the gas barrier layer according to the present invention, the value obtained by dividing the layer thickness (nm) measured by the film thickness measurement method by observation with a transmission electron microscope (TEM) by the number of extreme values of the carbon / oxygen distribution curve (hereinafter, It is preferable that “layer thickness by TEM (nm) / number of extreme values” is 20 (nm / number) or less. This value indicates the relationship between the layer thickness and the extreme value. For example, when the layer thickness is the same and one of the extreme values is large, the gas barrier layer according to the present invention having a large number of extreme values. In this case, the extreme value interval is smaller than that of the other gas barrier layer according to the present invention. Therefore, it can be said that the composition in the layer thickness direction changes as the TEM layer thickness (nm) / extremum number decreases. In this invention, even if it is a film which has the gas barrier layer which concerns on this invention which has such a rapid in-film composition change, the fall of the gas barrier property at the time of high temperature and high humidity is suppressed. The lower limit of the layer thickness (nm) / number of extreme values by TEM is not particularly limited, but is usually 3.5 (nm / number) or more. The case where the layer thickness (nm) / extremum number by TEM is 15 (nm / number) or less is more preferable because the effect is particularly great. Here, the gas barrier layer according to the present invention having a layer thickness (nm) / number of extreme values by TEM of 20 (nm / number) or less is the base material in the apparatus of FIG. 2 (that is, in the case of TR number = 1). Can be formed when the transport speed is increased, particularly when the transport speed is 3 m / min or more. Further, in the oxygen / carbon distribution curve, when at least one set of adjacent extreme value intervals is 1 to 10 nm, and further two or more sets, the effect is great. That is, in a preferred embodiment of the present invention, the gas barrier layer according to the present invention is a layer formed by a plasma CVD method using a plasma CVD apparatus having a counter roller electrode, and a transmission electron microscope The value obtained by dividing the layer thickness (nm) measured by the film thickness measurement method by (TEM) observation by the number of extreme values of the carbon / oxygen distribution curve (hereinafter referred to as “the layer thickness (nm) by TEM / number of extreme values”). ) Is preferably 20 (nm / number) or less.

  Also, the carbon distribution curve preferably has at least two extreme values, preferably at least three extreme values, and more preferably at least five extreme values. When the carbon distribution curve has at least two extreme values, the carbon atom ratio continuously changes with a concentration gradient, and the gas barrier property at the time of bending increases. Here, the “extreme value” in the carbon distribution curve means the carbon distribution indicating the distance (L) from the surface of the gas barrier layer according to the present invention and the carbon atom ratio in the layer thickness direction of the gas barrier layer according to the present invention. The maximum or minimum value of carbon atoms in the curve. The maximum value in the carbon distribution curve means that the value of the carbon atom ratio changes from increasing to decreasing when the distance from the surface of the gas barrier layer according to the present invention is changed. Furthermore, the minimum value in the carbon distribution curve refers to a point where the value of the carbon atom ratio changes from decrease to increase when the distance from the surface of the gas barrier layer according to the present invention is changed.

  The oxygen distribution curve of the gas barrier layer according to the present invention preferably has at least one extreme value, more preferably has at least two extreme values, still more preferably has at least three extreme values, and at least 5 It is particularly preferred to have two extreme values. When the oxygen distribution curve has at least one extreme value, the gas barrier property when the obtained gas barrier film is bent is further improved. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a portion caused by the thickness of the gas barrier layer, and it cannot be defined unconditionally. Here, the “extreme value” in the oxygen distribution curve means the oxygen distribution indicating the distance (L) from the surface of the gas barrier layer according to the present invention and the oxygen atomic ratio in the layer thickness direction of the gas barrier layer according to the present invention. The maximum or minimum value of the oxygen atom in the curve. Further, the maximum value in the oxygen distribution curve means that the value of the oxygen atomic ratio changes from increase to decrease when the distance from the surface of the gas barrier layer according to the present invention is changed. Furthermore, the minimum value in the oxygen distribution curve means that the value of the oxygen atomic ratio changes from decrease to increase when the distance from the surface of the gas barrier layer according to the present invention is changed.

In the present invention, the total amount of carbon and oxygen atoms in the thickness direction of the gas barrier layer according to the present invention is preferably substantially constant. Thereby, the gas barrier layer according to the present invention exhibits appropriate bending resistance, and the generation of cracks when the gas barrier film is bent can be more effectively suppressed / prevented. More specifically, the relationship between the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer according to the present invention and the ratio of the total amount of oxygen and carbon (oxygen and carbon atom ratio). The absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the distribution curve (hereinafter, also simply referred to as “OC _max −OC _min difference”) is less than 5 at%. Is preferably less than 4 at%, more preferably less than 3 at%. When the absolute value is less than 5 at%, the gas barrier property of the obtained gas barrier film is further improved. _The lower limit of the OC max _{-OC min difference,} since preferably as OC max _{-OC min} difference is small, but is 0 atomic%, it is sufficient if more than 0.1 at%.

  From the viewpoint of forming a gas barrier layer according to the present invention that is uniform over the entire film surface and has excellent gas barrier properties, the gas barrier layer according to the present invention is in the direction of the film surface (on the surface of the gas barrier layer according to the present invention). It is preferably substantially uniform in the (parallel direction). Here, the gas barrier layer according to the present invention is substantially uniform in the film surface direction means that the oxygen distribution at any two measurement points on the film surface of the gas barrier layer according to the present invention by XPS depth profile measurement. When the curve, the carbon distribution curve, and the oxygen / carbon distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the respective carbon distribution curves The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is the same as each other or within 5 at%.

  Furthermore, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, “substantially continuous carbon distribution curve” means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, the carbon distribution curve is calculated from the etching rate and the etching time. Satisfying the condition represented by the following formula (1) in the relationship between the distance from the surface in the layer thickness direction (x, unit: nm) and the atomic ratio of carbon (C, unit: at%). Say.

Formula 1 (dC / dx) ≦ 0.5
The gas barrier layer forming method according to the present invention is a chemical vapor deposition method (CVD), in particular, a plasma chemical vapor deposition method (plasma CVD, plasma-enhanced chemical vapor deposition (PECVD)), hereinafter simply referred to as “plasma CVD method”. ").

  Hereinafter, a manufacturing method for forming the gas barrier layer according to the present invention using the plasma CVD method according to the present invention will be described.

  The plasma CVD method according to the present invention is a plasma CVD method using a plasma CVD apparatus having a counter roller electrode because of its high productivity. The gas barrier layer according to the present invention is formed by the plasma CVD apparatus. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

<Method for Producing Gas Barrier Layer According to the Present Invention>
When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a substrate is provided for each of the pair of film forming rollers. (Here, the base material includes a form in which the base material has been processed or has an organic layer on the base material.) And discharge between a pair of film forming rollers to generate plasma. It is more preferable. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible to form a film on the surface part of the base material existing on the other film, and simultaneously form the film on the surface part of the base material present on the other film forming roller, so that a thin film can be produced efficiently. In addition, the film formation rate can be doubled compared to the normal plasma CVD method that does not use a roller, and a film with substantially the same structure can be formed, so it is possible to at least double the extreme value in the carbon distribution curve. Thus, it is possible to efficiently form a layer that satisfies the condition (i).

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, the film forming gas used in such a plasma CVD method preferably includes an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is determined by the organosilicon compound in the film forming gas. It is preferable that the amount of oxygen be less than the theoretical oxygen amount necessary for complete oxidation. In the gas barrier film of the present invention, the gas barrier layer according to the present invention is preferably a layer formed by a continuous film forming process.

  Moreover, it is preferable that the gas barrier film which concerns on this invention forms the gas barrier layer which concerns on this invention on the surface of a base material by a roll to roll system from a viewpoint of productivity. Further, an apparatus that can be used when producing a gas barrier layer by such a plasma CVD method is not particularly limited, and includes at least a pair of film forming rollers and a plasma power source, and the pair of components. It is preferable that the apparatus has a configuration capable of discharging between film rollers. For example, when the manufacturing apparatus shown in FIG. 2 is used, the apparatus is manufactured by a roll-to-roll method using a plasma CVD method. It is also possible to do.

  Hereinafter, the gas barrier layer forming method according to the present invention will be described in more detail with reference to FIG. FIG. 2 is a schematic view showing an example of a production apparatus that can be suitably used for producing the gas barrier layer according to the present invention. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

The method for producing a gas barrier film for producing the gas barrier film of the present invention is as follows.
A step of feeding the belt-shaped flexible base material from the feed roller and transporting it with the transport roller;
Heat-treating the flexible substrate;
The flexible substrate subjected to the heat treatment is conveyed while being brought into contact with each of a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers. Forming a gas barrier layer on the conductive substrate;
Winding the gas barrier film having the gas barrier layer formed on the flexible base material with a take-up roller while transporting it with a transport roller, and the transport speed of the flexible base material is 3 m / It is preferable that it is a manufacturing method of the gas barrier film characterized by being more than minutes.

  The plasma CVD manufacturing apparatus 30 shown in FIG. 2 includes a feed roller 31 that feeds out the substrate 1, transport rollers 32, 35, and 36, heating rollers 33 and 34, and a temperature adjusting device 48 that adjusts the temperature of the heating roller. A chamber (also referred to as a heat treatment chamber) having a feeding / conveying step and a heat treatment step, film forming rollers 40 and 41, a gas supply pipe 44, a plasma generating power source 52, and film forming rollers 40 and 41. Chamber B having a film forming process (also referred to as a film forming chamber), transport rollers 45 and 46, and a take-up roller, including magnetic field generators 42 and 43 and transport rollers 37, 38, and 39 installed therein. 47 is a plasma CVD apparatus comprising three chambers of a C chamber (also referred to as a winding chamber) having a winding process. Each room is independent, and it is preferable to have a device (not shown) that can individually control the pressure and temperature. The temperature of each chamber is measured by a commercially available temperature monitor 49-51.

  For example, in such a manufacturing apparatus, the film forming rollers 40 and 41, the gas supply pipe 44, the plasma generating power source 52, and the magnetic field generating apparatuses 42 and 43 are arranged in a vacuum chamber (not shown). Yes. Further, in such a manufacturing apparatus 30, the vacuum chamber is connected to a vacuum pump (not shown), and the atmospheric pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  Initially, the heat processing which is the characteristic of the manufacturing method of the gas barrier film of this invention is demonstrated.

  As described above, the inventors of the present invention have a trace amount retained by a base material (herein, the base material includes a form in which the base material is processed or has an organic layer on the base material). Moisture is released into the plasma discharge space of the B chamber to promote the oxidation of the film, impair the continuous compositional gradient of the carbon content and the oxygen content, and cause deterioration of the bending resistance accompanying the decrease in the carbon content. I found out.

  In the formation of the gas barrier layer according to the present invention, the removal of the moisture from the base material is not effective only by removing the water by conventional vacuuming. It is characterized by promoting the vaporization or desorption of water. In particular, a base material having a high moisture content such as PET, a base material provided with an organic layer such as a stress relaxation layer or a smooth layer in advance, is heat-treated before the formation of the gas barrier layer, so that the base material or organic The moisture contained in the layer is vaporized and desorbed, and the moisture release from the base material in the film forming region is greatly reduced, thereby enabling film formation without the influence of moisture.

  The heat treatment is preferably performed at a temperature of 10 ° C. or higher than the temperature of the film forming roller, preferably 70 ° C. or higher, and 80 ° C. or higher, in order to obtain the desired effect of the treatment. It is more preferable to heat. Further, from the viewpoint of preventing deformation of the base material and the like, it is preferable to carry out at a temperature below the glass transition temperature of the base material.

  Here, the glass transition temperature (Tg) refers to a temperature measured at a rate of temperature increase of 10 ° C./min by differential scanning calorimetry based on JIS K7121, such as a thermomechanical analyzer (TMA). It can detect by measuring in the range of 30-290 degreeC with an apparatus.

  In addition, even when heated below the glass transition temperature of the substrate, if an organic layer is formed on the substrate, the organic layer can be heated at a temperature higher than the lowest glass transition temperature of the substance constituting the organic layer. Therefore, it is preferable to heat the base material or the organic layer at a temperature lower than the lowest glass transition temperature.

  The conditions for the heat treatment can be appropriately changed. For example, the heating temperature is preferably 70 ° C. to (the lowest glass transition temperature of the material constituting the base material or the organic layer) for 1 second. The intended purpose can be achieved if it is carried out within a range of about 10 minutes. The heat treatment time may be a long time if the heating temperature is low, or a short time if the temperature is high.

  Examples of the heat treatment method include a hot plate, hot air treatment, an infrared irradiation method, a radiant heat method, and the like. Although not particularly limited, it is convenient and preferable to use the heating roller shown in FIG. Although a pair of heating rollers is illustrated as the heating rollers 33 and 34 in FIG. 2, a plurality of pairs of heating rollers may be used.

  As shown in FIG. 2, the heating rollers 33 and 34 are hollow rollers supported by bearings, and hot water or steam supplied from a temperature adjusting device 48 that is a heat source along the axial direction is heated. It is a circulating structure. Further, gears are formed on the peripheral edges of the heating rollers 33 and 34, and these gears mesh with gears attached to a drive motor (not shown) for driving the heating rollers 33 and 34. Thereby, the driving force of the drive motor is transmitted to the gears and gears, and the heating rollers 33 and 34 are rotationally driven in a predetermined direction.

  The heating rollers 33 and 34 are preferably formed of a material having high thermal conductivity so that the base material 1 can be heated efficiently by heat supplied from the temperature adjusting device 48, and a metal roller is preferable. Used. The surface is preferably coated with a fluororesin to prevent contamination when the substrate 1 is heated and pressurized. In addition, a silicon rubber roller coated with heat-resistant silicon rubber can also be used.

  The diameter of the heating roller is not particularly limited, but the effect of the heat treatment changes depending on the conveyance speed and contact time of the substrate, so it is appropriately designed depending on the degree of vaporization and desorption of moisture contained in the substrate. do it.

  Further, the heating rollers 33 and 34 are controlled by the temperature adjusting device 48 so as to keep the temperature within a predetermined temperature range. The temperature adjusting device 48 is preferably a device capable of controlling the temperature in the range of 50 ° C to 200 ° C.

  As another heating roller, the heating roller preferably has a hollow cylindrical shape formed of nonmagnetic stainless steel and has a structure including a roller heating source inside (hollow portion). As the roller heating source, a halogen heater is used to heat the cored bar disposed around. The halogen heater is a high-efficiency heat source having a low loss characteristic that heat loss with respect to input electric power is extremely small. The roller heating source does not necessarily need to be a halogen heater, and may be one in which a planar heating element is disposed so as to contact the inner peripheral surface of the cored bar. The planar heating element is a thin and flexible sheet-like heating element using, for example, a polyester film or a polyimide film as an insulating material.

The atmospheric pressure in the heat treatment chamber A is appropriately adjusted. However, since the effect of promoting the volatilization or desorption of moisture from the base material by reducing the pressure is achieved, the heat treatment is performed on the gas barrier layer. It is preferable to carry out under atmospheric pressure conditions below the atmospheric pressure for forming. Since the atmospheric pressure (degree of vacuum) at the time of forming the gas barrier layer is preferably adjusted to a range of 0.5 to 50 Pa as described later, it is preferably performed at a pressure of less than 0.5 Pa. It is preferable to carry out at the atmospheric | air pressure of 1/3 or less of the range, for example, it is preferable to heat-process with the vacuum degree in the range of 1 * 10 < ^-1 > ^-1 * 10 < ^-3 > Pa, for example.

  The water vaporized or desorbed from the substrate is exhausted by a vacuum pump. At this time, it is preferable to maintain the pressure in the chamber at a predetermined value while adjusting the exhaust amount.

  Next, the B chamber in which the gas barrier layer according to the present invention is formed will be described.

  In the manufacturing apparatus shown in FIG. 2, each film forming roller is for plasma generation so that the pair of film forming rollers (film forming roller 40 and film forming roller 41) can function as a pair of counter electrodes. A power source 52 is connected. Therefore, in such a manufacturing apparatus 30, it is possible to discharge to the space between the film formation roller 40 and the film formation roller 41 by supplying electric power from the plasma generation power source 52. Plasma can be generated in the space between the film roller 40 and the film formation roller 41. In this way, when the film forming roller 40 and the film forming roller 41 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 to arrange | position a pair of film-forming rollers (film-forming rollers 40 and 41) so that the central axis may become substantially parallel on the same plane. In this way, by arranging a pair of film forming rollers (film forming rollers 40 and 41), the film forming rate can be doubled compared with a normal plasma CVD method that does not use a roller, and the structure is the same. Since the film can be formed, the extreme value in the carbon distribution curve can be at least doubled. And according to such a manufacturing apparatus, the surface of the base material 1 (here, the base material includes a form in which the base material is processed or has an organic layer on the base material) by a CVD method. It is possible to form the gas barrier layer 3 according to the present invention on the film forming roller 41 while depositing the gas barrier layer component according to the present invention on the surface of the substrate 1 on the film forming roller 40. Since the gas barrier layer component according to the present invention can also be deposited on the surface of the substrate 1, the gas barrier layer can be efficiently formed on the surface of the substrate 1.

  Inside the film forming roller 40 and the film forming roller 41, magnetic field generators 42 and 43 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 42 and 43 provided on the film forming roller 40 and the film forming roller 41, respectively, are a magnetic field generating device 42 provided on one film forming roller 40 and a magnetic field generating device provided on the other film forming roller 41. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between 43 and the magnetic field generators 42 and 43 form a substantially closed magnetic circuit. By providing such magnetic field generators 42 and 43, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell in the vicinity of the opposing surface of each of the film forming rollers 40 and 41, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 42 and 43 provided on the film forming roller 40 and the film forming roller 41 respectively have racetrack-like magnetic poles that are long in the roller axis direction, and one magnetic field generating device 42 and the other magnetic field generating device. It is preferable to arrange the magnetic poles so that the magnetic poles facing 43 have the same polarity. By providing such magnetic field generators 42 and 43, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 42 and 43 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. The material 1 is excellent in that the gas barrier layer 3 according to the present invention, which is a vapor deposition film, can be efficiently formed.

  As the film forming roller 40 and the film forming roller 41, known rollers can be appropriately used. As such film forming rollers 40 and 41, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 40 and 41 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity is not deteriorated, and it is possible to avoid applying the total amount of plasma discharge to the substrate 1 in a short time. It is preferable because damage to the material 1 can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  The temperature of the film forming roller affects the formation rate of the gas barrier layer, but is preferably in the range of 40 to 60 ° C. from the viewpoint of preventing heat loss of the substrate and generation of wrinkles.

  As the feed roller 31 and the transport rollers 32, 35, 36, 37, 38, 39, 45, and 46 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the winding roller 47 is not particularly limited as long as it can wind the gas barrier film 10 in which the gas barrier layer 3 according to the present invention is formed on the substrate 1, and is appropriately known. A roller can be used.

  Further, as the gas supply pipe 44 and the vacuum pump, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 44 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 40 and the film formation roller 41, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, the gas supply pipe 44 as the gas supply means and the vacuum pump as the vacuum exhaust means are arranged to efficiently supply the film formation gas to the facing space between the film formation roller 40 and the film formation roller 41. It is excellent in that the film formation efficiency can be improved.

  Further, as the plasma generating power source 52, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 52 supplies power to the film forming roller 40 and the film forming roller 41 connected thereto, and makes it possible to use them as a counter electrode for discharging. Such a plasma generating power source 52 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, since it becomes possible to implement plasma CVD more efficiently as such a power source 52 for plasma generation, 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 to do this. As the magnetic field generators 42 and 43, known magnetic field generators can be used as appropriate. Furthermore, as the base material 1, in addition to the base material used in the present invention, a material in which the gas barrier layer 3 according to the present invention is formed in advance can be used. As described above, by using the substrate 1 in which the gas barrier layer 3 according to the present invention is formed in advance, the thickness of the gas barrier layer 3 according to the present invention can be increased.

  Using such a manufacturing apparatus 30 shown in FIG. 2, 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 roller, and the transport of the film (base material) The gas barrier layer according to the present invention can be produced by appropriately adjusting the speed.

  FIG. 3 is an enlarged view of a film formation space for performing plasma CVD. That is, using the manufacturing apparatus 30 shown in FIG. 3, a discharge is generated between the pair of film forming rollers (film forming rollers 40 and 41) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. Thus, the film-forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier according to the present invention is formed on the surface of the substrate 1 on the film-forming roller 40 and on the surface of the substrate 1 on the film-forming roller 41. Layer 3 is formed by plasma CVD. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axis of the film forming rollers 40 and 41, and the plasma is converged on the magnetic field. For this reason, when the base material 1 passes through the point A of the film forming roller 40 and the point B of the film forming roller 41 in FIG. 3, the maximum value of the carbon / oxygen distribution curve is obtained in the gas barrier layer according to the present invention. It is formed. On the other hand, when the substrate 1 passes through the points C1 and C2 of the film forming roller 40 and the points C3 and C4 of the film forming roller 41 in FIG. 3, the gas barrier layer shows a carbon / oxygen distribution curve. A local minimum is formed. For this reason, five extreme values are usually generated for two film forming rollers.

  Further, the distance between the extreme values of the gas barrier layer according to the present invention (the gas in the thickness direction of the gas barrier layer according to the present invention at one extreme value of the carbon / oxygen distribution curve and the extreme value adjacent to the extreme value) The absolute value of the difference in the distance (L) from the surface of the barrier layer can be adjusted by the rotation speed of the film forming rollers 40 and 41 (base material conveyance speed). In such film formation, the substrate 1 is transported by the delivery roller 31 and the film formation roller 40, respectively, so that the surface of the substrate 1 is formed by a roll-to-roll continuous film formation process. Then, the gas barrier layer 3 according to the present invention is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 44 to the facing space, source gas, reaction gas, carrier gas, and discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the gas barrier layer 3 according to the present invention can be appropriately selected and used depending on the material of the gas barrier layer 3 according to the present invention to be formed. As such a source gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyldisilane. , Methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltriethoxy Examples include silane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferred from the viewpoints of the handleability of the compound and the characteristics of the resulting barrier layer such as gas barrier. These organosilicon compounds can be used alone or in combination of two or more. Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer 3 according to the present invention.

  In addition to the source gas, a reactive gas may be used as the film forming 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, a reaction gas for forming an oxide and a nitride are formed. It can be used in combination with a reaction gas.

  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 carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon and xenon; hydrogen; nitrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. The gas barrier layer 3 according to the present invention to be formed is excellent in that excellent gas barrier properties and bending resistance can be obtained by not excessively increasing the ratio of the reaction gas. 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.

  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 0.5-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 40 and the film forming roller 41, an electrode drum connected to the plasma generating power source 52 (in this embodiment, the film forming roller 40). The power to be applied to the power source can be adjusted as appropriate according to the type of the source gas, the pressure in the vacuum chamber, and the like. It is preferable to be in the range. If such an applied power is 100 W or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated at the time of film formation can be suppressed. An increase in the interface temperature can be suppressed. Therefore, it is excellent in that wrinkles can be prevented during film formation without causing the substrate to lose heat.

  In the present invention, in the plasma CVD apparatus having the counter roller electrode as shown in FIG. 2, high gas barrier properties and bending resistance are maintained even if the substrate transport speed is increased for the purpose of increasing productivity. For this reason, when the conveyance speed of a base material is quick, the effect of this invention becomes more remarkable. That is, the preferred production method of the present invention forms a gas barrier layer according to the present invention containing silicon, oxygen and carbon by conveying a substrate to a plasma CVD apparatus having a counter roller electrode at a conveyance speed of 3 m / min or more. It is preferable to do. In a more preferred embodiment, the substrate is transported to a plasma CVD apparatus having a counter roller electrode at a transport speed of 5 m / min or more (more preferably 10 m / min or more), and the gas barrier according to the present invention contains silicon, oxygen and carbon. Forming a layer. The upper limit of the line speed is not particularly limited, and is preferably faster from the viewpoint of productivity. However, if it is 100 m / min or less, it is excellent in that a sufficient thickness can be secured as a gas barrier layer. Yes.

  As described above, as a more preferable aspect of the present embodiment, the gas barrier layer according to the present invention is formed by the plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roller electrode shown in FIG. It is characterized by forming a film. This is excellent in flexibility (flexibility) and mechanical strength, especially durability when transported by roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll system) having a counter roller electrode. This is because it is possible to efficiently produce a gas barrier layer that achieves both gas barrier properties. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce a gas barrier film that is required for durability against temperature changes used in solar cells, electronic parts, and the like.

<Flexible substrate>
The gas barrier film of the present invention usually uses a plastic film as a flexible substrate. The term “flexibility” as used herein refers to a base material that is wound around a φ (diameter) 50 mm roll and is not cracked before and after winding with a constant tension, and more preferably a base that can be wound around a φ30 mm roll. Say the material.

  The plastic film to be used is not particularly limited in material, thickness and the like as long as it is a film capable of holding the gas barrier laminate, and can be appropriately selected according to the purpose of use. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  When using the gas barrier film of this invention as a board | substrate of devices, such as an organic EL element, it is preferable that a base material consists of a raw material which has heat resistance.

  The Tg and the linear expansion coefficient of the substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and alicyclic. Polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C, manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C), polyethersulfone (PES: 220 ° C), polysulfone (PSF: 190 ° C), cycloolefin copolymer (COC: Compound described in JP-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP In 2000-227603 Listed compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: 300 ° C.) And the like) (Tg is shown in parentheses). In particular, when transparency is required, it is preferable to use an alicyclic polyolefin or the like.

  Since the gas barrier film of the present invention can be used as a device such as an organic EL element, the plastic film is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

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

  The substrate preferably has a high surface smoothness. As the surface smoothness, those having an average surface roughness (Ra) of 2 nm or less are preferable. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both surfaces of the substrate, at least the side on which the gas barrier layer is provided, may be polished to improve smoothness.

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

  Various known treatments for improving adhesion, corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, lamination of smooth layers, etc. on both sides of the substrate, at least on the side where the gas barrier layer according to the present invention is provided Can be performed in combination as necessary.

<Organic layer>
The base material and gas barrier layer according to the present invention may be separately provided with an organic layer containing an organic compound as long as the effects of the present invention are not impaired. For example, before forming the gas barrier layer, it is preferable that an organic layer is provided in advance on at least one surface of the base material, and that the organic layer further contains inorganic particles, It is preferable from the viewpoint of improving the adhesion to the substrate.

  Even if the gas barrier layer of the present invention is formed on a substrate on which the organic layer is formed in advance, the gas barrier layer is formed after the moisture contained in the organic layer is vaporized and desorbed by heat treatment. By adopting a manufacturing method for forming a film, it is possible to form a gas barrier layer without the influence of moisture.

  The organic layer referred to in the present invention is synonymous with a functional layer containing an organic compound, and is preferably each functional layer listed below.

<Curable resin layer>
The gas barrier film of the present invention may have a curable resin layer (generally also referred to as a hard coat layer) formed by curing a curable resin on a substrate. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. These curable resins may be used alone or in combination of two or more.

  Such a curable resin layer is at least one of (1) smoothing the interface of the substrate, (2) relaxing the stress of the upper layer to be laminated, and (3) improving the adhesion between the substrate and the upper layer. Has one function. For this reason, the curable resin layer may also be used as a smooth layer and an anchor coat layer (easy adhesion layer) described later.

  Examples of the active energy ray-curable material include a composition containing an acrylate compound, a composition containing an acrylate compound and a mercapto compound containing a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene Examples thereof include compositions containing polyfunctional acrylate monomers such as glycol acrylate and glycerol methacrylate. Specifically, it is possible to use a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series (compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles) manufactured by JSR Corporation. it can. It is also possible to use any mixture of the above-mentioned compositions, and an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in the molecule. If there is no restriction in particular.

  It is preferable that the composition containing an active energy ray-curable material contains a photopolymerization initiator.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Coat, Nanohybrid Silicone manufactured by Adeka, Unicom manufactured by DIC, Inc. Dick (registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), silicon resin X-12-2400 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., Nitto Boseki Co., Ltd. Inorganic / organic nanocomposite material SSG coating, thermosetting urethane resin consisting of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicon resin, polyamidoamine-epichlorohydrin resin And the like.

  The method for forming the curable resin layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a gravure printing method or other wet coating method, or a vapor deposition method. After applying the dry coating method to form a coating film, irradiation with active energy rays such as visible rays, infrared rays, ultraviolet rays, X-rays, α rays, β rays, γ rays, electron rays and / or heating are performed. A method of forming the film by curing is preferred. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm. Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

  The curable resin layer can contain additives such as a thermoplastic resin, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary, in addition to the above-described materials. In addition, an appropriate resin or additive may be used for improving the film formability and preventing the film from generating pinholes.

It is also preferable that the curable resin layer contains inorganic particles that are matting agents. By containing the matting agent, the adhesion between the gas barrier layer and the substrate can be improved. As described above, since there are OH groups on the surface of the inorganic particles, the OH groups and H ₂ O are adsorbed in a hydrogen bond state, and the amount of water that can be held by the substrate itself is increased. By performing the treatment, the vaporization and desorption of moisture due to heating is promoted, so that the influence of moisture can be reduced in the film forming process.

  As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable. As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. .

  Here, the matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 100 parts by mass of the solid content of the hard coating agent. It is preferable that they are mixed in a proportion of 18 parts by mass or less, more preferably 16 parts by mass or less.

  Although it does not restrict | limit especially as thickness of a curable resin layer, The range of 0.1-10 micrometers is preferable.

<Smooth layer>
It is preferable that a gas barrier film has a smooth layer in the surface which has a gas barrier layer of a base material. The smooth layer is provided in order to flatten the rough surface of the substrate on which protrusions and the like exist. Such a smooth layer is basically formed by curing an active energy ray curable material or a thermosetting material. The smooth layer may basically have the same material and configuration as the curable resin layer as long as it has the above-described function.

  Examples of the active energy ray-curable material and thermosetting material used in the smooth layer, examples of the matting agent, and the method of forming the smooth layer are the same as those described in the column of the curable resin layer above, so here Then, explanation is omitted.

  Although it does not restrict | limit especially as thickness of a smooth layer, The range of 0.1-10 micrometers is preferable.

  The smooth layer may be used as the following anchor coat layer.

<Anchor coat layer>
An anchor coat layer may be formed on the substrate interface according to the present invention as an easy-adhesion layer for the purpose of improving adhesion (adhesion) with the gas barrier layer. Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. 1 or 2 or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  The anchor coat layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

<Bleed-out prevention layer>
In the gas barrier film of the present invention, a bleed-out prevention layer can be provided. The purpose of the bleed-out prevention layer is to suppress the phenomenon in which unreacted oligomers migrate from the film base material to the surface when the film having the curable resin layer / smooth layer is heated and contaminate the contact surface. Thus, it is provided on the surface opposite to the surface of the substrate having the curable resin layer / smooth layer. The bleed-out prevention layer may basically have the same configuration as the curable resin layer / smooth layer as long as it has this function.

  The hard coat agent that can be included in the bleed-out prevention layer is a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or one polymerizable unsaturated in the molecule. Examples thereof include monounsaturated organic compounds having a group.

  Here, examples of the polyunsaturated organic compound include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.

  Examples of the monounsaturated organic compound include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.

  As other additives, the matting agent described in the cured resin layer may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable, and the slipperiness of the gas barrier film is improved.

  In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.

  The bleed-out prevention layer as described above is prepared as a coating solution by using a hard coat agent and other components as required, and appropriately preparing a coating solution by using a diluent solvent as necessary. After coating by a conventionally known coating method, it can be formed by irradiating with ionizing radiation and curing. In addition, as a method of irradiating with ionizing radiation, ultraviolet rays in a wavelength region of preferably 100 to 400 nm, more preferably 200 to 400 nm, emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp or the like are irradiated. Alternatively, the irradiation can be performed by irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

  The thickness of the bleed-out prevention layer in the present invention is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the smooth film, and the curable resin layer / smooth layer is transparent. When it is provided on one surface of the polymer film, curling of the gas barrier film can be easily suppressed.

<Second gas barrier layer>
In the present invention, a layer having gas barrier properties can be further provided as a second gas barrier layer on the gas barrier layer according to the present invention. The second gas barrier layer may be a layer in which two or more first gas barrier layers are stacked, and is not limited. Among them, it is also preferable to provide a coating film of a polysilazane-containing liquid of a coating method and to provide a second gas barrier layer that is formed by irradiating vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less and performing a modification treatment. . By providing the second gas barrier layer on the gas barrier layer provided by the CVD method, minute defects remaining in the gas barrier layer can be filled with the gas barrier component of polysilazane from above, and further It is preferable because gas barrier properties and flexibility can be improved. Regarding the coating film of the polysilazane-containing liquid of the coating method, a conventionally known configuration can be used. For example, paragraphs [0134] to [0183] of JP2013-180520A, JP2013-123895A The configuration described in paragraphs [0042] to [0065] and the like.

  The thickness of the second gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm.

<Overcoat layer>
An overcoat layer may be formed on the second gas barrier layer used in the present invention in order to further improve the flexibility. As the organic substance used for the overcoat layer, an organic resin such as an organic monomer, oligomer or polymer, or an organic-inorganic composite resin layer using a siloxane or silsesquioxane monomer, oligomer or polymer having an organic group is preferably used. Can do. These organic resins or organic-inorganic composite resins preferably have a polymerizable group or a crosslinkable group, contain these organic resins or organic-inorganic composite resins, and contain a polymerization initiator, a crosslinking agent, etc. as necessary. It is preferable to apply a light irradiation treatment or a heat treatment to the layer formed by coating from the organic resin composition coating solution to be cured.

<Electronic device>
As described above, the gas barrier film of the present invention has excellent gas barrier properties, transparency, and bending resistance. For this reason, the gas barrier film of the present invention is a gas barrier film used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various purposes such as an electronic device using the same.

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

<Example 1: Production of gas barrier film 1>
(Flexible substrate)
As a reversible substrate, a hard coat film G1STB (PET film thickness 125 μm, no matting agent) manufactured by Kimoto Co., Ltd. was used.

(Formation of gas barrier layer according to the present invention)
A gas barrier layer according to the present invention was formed on the flexible substrate under the following film forming conditions using the vacuum plasma CVD apparatus shown in FIG.

[Heat treatment (degassing) conditions]
The base material was set as it was on the delivery roller of the film forming apparatus of FIG. And after the degree of vacuum reached 5 × 10 ⁻³ Pa, the heating rollers 33 and 34 were set to 80 ° C. Then, the base material was conveyed at the conveyance speed of the following film-forming conditions, the base material was conveyed to the film-forming space (B chamber), and film-forming was implemented on the following plasma conditions. The time until the degree of vacuum reached 5 × 10 ⁻³ Pa was 3 hours, and the time until the heating roller reached a predetermined temperature was 0.5 hours.

[Plasma deposition conditions]
<Film formation conditions>
・ Supply amount of source gas (HMDSO): 100 sccm (Standard Cubic Centimeter per Minute)
・ Supply amount of oxygen gas (O ₂ ): 500 sccm
・ Degree of vacuum in the vacuum chamber: 1.5 Pa
・ Applied power from the power source for plasma generation: 2.0 kW
・ Power supply frequency for plasma generation: 80 kHz
-Film transport speed: 10 m / min-Film-forming roller diameter: 300 mmφ
-Number of times TR passes: 2-Heating roller temperature: 80 ° C
・ Film roller temperature: 60 ℃
At this time, each element profile in the layer thickness direction based on the XPS depth profile of the gas barrier layer performed under the conditions described later is as shown in the graph of FIG. 4, and is 65 in a distance range of 30 nm from the substrate interface. %, A region having a carbon atom ratio in the range of 10 to 30 at% was present.

  Further, the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer is as shown in the graph of FIG. 5, and the interval between the adjacent extreme values was 5 nm.

<Example 2: Production of gas barrier film 2>
In the gas barrier film 1, the gas barrier film 2 was produced in the same manner except that the heat treatment (degassing) conditions and the film forming conditions were adjusted as follows.

[Heat treatment (degassing) conditions]
The base material was set to the feed roller of the plasma CVD manufacturing apparatus shown in FIG. Then, after the degree of vacuum reached 3.0 Pa, Ar gas was introduced into the atmosphere and maintained at 3.0 Pa. Thereafter, the heating roller was set to 80 ° C., the film forming roller was set to 60 ° C., the substrate was conveyed at a conveyance speed of 5 m / min, and the heat treatment was performed. At this time, the pressure was maintained at 3.0 Pa by adjusting the displacement of the vacuum pump. Next, in the same manner as in Example 1, a gas barrier layer was formed under the following conditions to produce a gas barrier film 2.

[Plasma deposition conditions]
<Film formation conditions>
・ Supply amount of source gas (HMDSO): 100 sccm (Standard Cubic Centimeter per Minute)
・ Supply amount of oxygen gas (O ₂ ): 500 sccm
・ Degree of vacuum in the vacuum chamber: 1.5 Pa
・ Applied power from the power source for plasma generation: 2.0 kW
・ Power supply frequency for plasma generation: 80 kHz
-Film transport speed: 10 m / min
・ Drawing roller diameter: 300mmφ
-Number of times TR passes: 2-Heating roller temperature: 80 ° C
・ Film roller temperature: 60 ℃
At this time, each element profile in the layer thickness direction according to the XPS depth profile of the gas barrier layer is within a distance range of 59% within a distance range of 30 nm from the substrate interface, and a carbon atom ratio is in a range of 10 to 30 at%. There was an area inside.

  The interval between adjacent extreme values of the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer was 7 nm.

<Example 3: Production of gas barrier film 3>
In the gas barrier film 1, the gas barrier film 3 was produced in the same manner as in the heat treatment (degassing) conditions and the film forming conditions except that the conveyance speed of the base material was 30 m / min and the TR passage number was six.

  At this time, each element profile in the layer thickness direction according to the XPS depth profile of the gas barrier layer is within a distance range of 63% within a distance range of 30 nm from the substrate interface, and a carbon atom ratio is within a range of 10 to 30 at%. There was an area inside.

  The interval between adjacent extreme values of the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer was 1 nm.

<Example 4: Production of gas barrier film 4>
A gas barrier film 4 was produced in the same manner as in the gas barrier film 1 except that the conveyance speed of the substrate was 3 m / min.

  At this time, each element profile in the layer thickness direction according to the XPS depth profile of the gas barrier layer is in the range of 40% within the range of 30 nm from the substrate interface, and the range of the carbon atom ratio of 10 to 30 at%. There was an area inside.

  Further, the interval between adjacent extreme values of the carbon / oxygen distribution curve in the thickness direction of the layer according to the XPS depth profile of the gas barrier layer was 10 nm as a result of slowing the substrate conveyance speed.

<Example 5: Production of gas barrier film 5>
In the gas barrier film 1, the flexible base material is changed as follows, and the gas barrier film 5 is produced by performing heat treatment (degassing) and film formation in the same manner except that the hard coat layer is not formed. did.

(Flexible substrate)
As the flexible substrate, a 125 μm thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET SLA) that is easily bonded to both surfaces, which is a thermoplastic resin, was used.

  At this time, each element profile in the thickness direction of the layer according to the XPS depth profile of the gas barrier layer is a 55% distance range within a distance range of 30 nm from the substrate interface, and a carbon atom ratio is in a range of 10 to 30 at%. There was an area inside.

  The interval between adjacent extreme values in the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer was 10 nm.

<Example 6: Production of gas barrier film 6>
In the gas barrier film 1, except that the flexible substrate is changed as follows, a bleed-out prevention layer and a curable resin layer (smooth layer) are provided, and a gas barrier layer is provided on the curable resin layer Produced a gas barrier film 6 in the same manner as the gas barrier film 1.

(Flexible substrate)
A 125 μm-thick polyethylene terephthalate film (manufactured by Teijin DuPont Films Ltd., extremely low heat yield PET SLA), which is a thermoplastic resin and easily bonded to both surfaces, was used as a base material.

(Formation of bleed-out prevention layer: In Table 1, expressed as BO prevention layer)
On one side of the base material, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied, applied with a die coater so that the layer thickness after drying was 4 μm, and then drying conditions: 80 ° C., After drying for 3 minutes, curing was performed in air using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a bleed-out prevention layer.

(Formation of curable resin layer (smooth layer))
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the base material, and after applying with a die coater such that the layer thickness after drying was 4 μm, drying conditions; After drying at 80 ° C. for 3 minutes, curing was performed in an air atmosphere using a high-pressure mercury lamp, curing conditions: 1.0 J / cm ² to form a curable resin layer.

  Each element profile in the layer thickness direction of the obtained gas barrier film 6 according to the XPS depth profile of the gas barrier layer is 74% within a distance range of 30 nm from the substrate interface as shown in FIG. There was a region with a carbon atom ratio in the range of 10 to 30 at%.

  Further, the interval between adjacent extreme values of the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer was 4 nm as shown in FIG.

<Comparative Example 1: Production of gas barrier film 7>
In the gas barrier film 6, a gas barrier film 7 was produced in the same manner except that the heat treatment (degassing) conditions were as follows.

[Heat treatment (degassing) conditions]
The base material was set to the feed roller of the plasma CVD manufacturing apparatus shown in FIG. And after the degree of vacuum reached 5 × 10 ⁻³ Pa, it was held for 12 hours. The degree of vacuum at that time was always less than 5 × 10 ⁻³ Pa. Next, in the same manner as in Example 5, a gas barrier layer was formed under the following conditions to produce a gas barrier film 7.

  At this time, each element profile in the layer thickness direction according to the XPS depth profile of the gas barrier layer is as shown in the graph of FIG. 8. There was no region within the 30 at% range.

  Further, the carbon / oxygen distribution curve in the layer thickness direction according to the XPS depth profile of the gas barrier layer is as shown in the graph of FIG. 9, and the interval between adjacent extreme values was 11 nm.

[Plasma deposition conditions]
<Film formation conditions>
・ Supply amount of source gas (HMDSO): 100 sccm (Standard Cubic Centimeter per Minute)
・ Supply amount of oxygen gas (O ₂ ): 500 sccm
・ Degree of vacuum in the vacuum chamber: 1.5 Pa
・ Applied power from the power source for plasma generation: 2.0 kW
・ Power supply frequency for plasma generation: 80 kHz
-Film transport speed: 10 m / min-Film-forming roller diameter: 300 mmφ
-Number of times TR passes: 2-Heating roll temperature: 30 ° C
・ Film roll: 60 ° C
≪Evaluation method≫
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm ellipse Based on the data evaluated in this way, the distance (nm) linked to the sputter depth from the surface of the gas barrier layer is plotted on the horizontal axis, with silicon atoms, oxygen atoms and The silicon atom ratio, oxygen atom ratio, and carbon atom ratio with respect to the total amount of carbon atoms are plotted on the vertical axis, and the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and carbon / oxygen distribution curve are shown in FIGS. 4 to 9, respectively. .

<Gas barrier property evaluation method>
The permeated water amount of each gas barrier film was measured according to the following measurement method, and the water vapor barrier property was evaluated according to the following criteria.

(apparatus)
Vapor deposition apparatus: manufactured by JEOL Ltd., vacuum vapor deposition apparatus JEE-400
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
(Preparation of water vapor barrier property evaluation cell)
Using a vacuum vapor deposition device (manufactured by JEOL Ltd., vacuum vapor deposition device JEE-400) on the gas barrier layer surface of the sample, the gas barrier film sample is masked except for the portion to be vapor-deposited (12 mm × 12 mm 9 locations), and metal Calcium (granular) was deposited (deposition film thickness 80 nm). Then, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  Based on the gas barrier property evaluation method described in Japanese Patent Application Laid-Open No. 2005-283561, the amount of moisture permeated into the cell was calculated from the corrosion amount of metallic calcium.

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

The permeated water amount (g / m ² · day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated according to the following criteria. Three or more are good as a gas barrier film.

(Rank evaluation)
Less than 5: 5 × 10 ⁻⁴ g / m ² / day 4: 5 × 10 ⁻⁴ g / m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 3: 1 × 10 ⁻³ g / day m ² / day or more, less than 5 × 10 ⁻³ g / m ² / day 2: 5 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g / m ² / day or more [Evaluation of bending resistance (flexibility)]
For the gas barrier film, in order to confirm the change in the gas barrier properties before and after bending, the water vapor transmission rate of the gas barrier film that has been repeatedly bent 100 times at an angle of 180 degrees so as to have a curvature of 10 mm in advance. (WVTR) was measured and the same rank evaluation was performed.

[Evaluation of bending resistance (adhesion)]
The gas barrier film evaluated for flexibility was cut into a 10 cm long and 10 cm wide square sample using a roll cutter, and the appearance was evaluated according to the following criteria. 3 or more is practically acceptable.

5: No crack or film peeling 4: Film peeling less than 1%, no crack 3: Film peeling 1% or more but less than 5%, no crack 2: Film peeling 5% or more but less than 10%, cracks on the entire surface 1: Table 1 shows the structure of the above gas barrier film and the above evaluation results.

[Evaluation of hue distribution]
Using a spectroscopic color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the b value is measured by the transmission method according to JIS-K-7105, and the following R value is used as an index representing the amount of color variation. Using the rank evaluation.

  The b value was measured every 2 cm of the width of the sample, and the difference between the maximum value and the minimum value of the b value was defined as the R value. Δ or more is acceptable in practical use.

A: R is 0.2 or less. Δ: R is 0.2 to 0.5.
X: R is 0.5 or more
[Evaluation of adhesion]
A cross-cut test based on JIS K 5400 was performed. Using a single-edged razor on the surface of the thin film on which the sample was formed, 11 cuts were made vertically and horizontally at intervals of 1 mm at 90 degrees with respect to the surface to make 100 1 mm square grids. A commercially available cellophane tape is affixed to this, and one end of the tape is peeled off vertically by hand, and the ratio of the peeled area of the thin film to the affixed tape area from the score line is measured. Evaluation was performed. ○ The above is acceptable in practice.

A: No occurrence of peeling was observed. B: The peeled area ratio was 0.1% or more and less than 5%. Δ: The peeled area ratio was 5% or more and less than 10%. The peeled area ratio was 10% or more

  From the results of Table 1, the gas barrier films 1 to 6 of the present invention all have a region in which the carbon atom ratio is distributed in the range of 30 nm from the base material interface to 10 to 30%, there is no such distribution, carbon / Adjacent extreme value of oxygen distribution curve is outside of the present invention, and gas barrier property, bending resistance (flexibility, adhesion), color distribution, and thin film adhesion to the gas barrier film 7 of the comparative example It turns out that power is excellent.

  Among them, the gas barrier film 1 formed after providing an organic layer on the substrate in advance and setting the vacuuming pressure during the heat treatment to a low value is compared with the gas barrier film 2 having a slightly high vacuuming pressure. Excellent results for the evaluation items. Further, the gas barrier film 6 in which the matting agent was added to the smooth layer showed further excellent characteristics due to the smoothing effect of the substrate surface.

  The gas barrier film of the present invention is a gas barrier film having high gas barrier properties and bending resistance, and is preferably used as a gas barrier film for electronic devices such as organic electroluminescence elements, solar cells, liquid crystal display devices, etc. Can do.

DESCRIPTION OF SYMBOLS 1 Base material 2 Smooth layer 3 Gas barrier layer 4 Bleed-out prevention layer 5 2nd gas barrier layer 6 Overcoat layer 10a, 10b Gas barrier film 30 Plasma CVD manufacturing apparatus 31 Delivery roller 32, 35, 36, 37, 38, 39, 45, 46 Conveying roller 33, 34 Heating roller 40, 41 Film forming roller 42, 43, Magnetic field generator 44 Gas supply pipe 47 Winding roller 48 Temperature controller 49, 50, 51 Temperature monitor 52 Power source for plasma generation

Claims (5)

A gas barrier film having a gas barrier layer containing at least silicon, oxygen, and carbon as constituent elements on a flexible substrate,
In the carbon / oxygen distribution curve in which the ratio between the amount of carbon and the amount of oxygen is plotted, the interval between at least one pair of adjacent extreme values is in the range of 1 to 10 nm, and 30 nm from the base material interface of the gas barrier layer A gas barrier film characterized in that there is a region in which the carbon atom ratio is distributed within a range of 10 to 30 at% within the distance range.   The gas barrier film according to claim 1, wherein an organic layer containing an organic compound is provided on at least one surface of the flexible substrate.   The gas barrier film according to claim 2, wherein the organic layer further contains inorganic particles. It is a manufacturing method of the gas barrier film which manufactures the gas barrier film according to any one of claims 1 to 3,
A step of feeding the belt-shaped flexible base material from the feed roller and transporting it with the transport roller;
Heat-treating the flexible substrate;
The heat-treated flexible base material is conveyed while being brought into contact with each of a pair of film forming rollers, and plasma discharge is performed while supplying a film forming gas between the pair of film forming rollers, Forming a gas barrier layer thereon;
Winding the gas barrier film having the gas barrier layer formed on the flexible base material with a take-up roller while transporting the gas barrier film with a transport roller, and the transport speed of the flexible base material is 3 m It is more than / min. The manufacturing method of the gas barrier film characterized by the above-mentioned.   The method for producing a gas barrier film according to claim 4, wherein the heat treatment is performed under a pressure condition equal to or lower than a pressure at the time of forming the gas barrier layer.

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