JP6983039B2 - Gas barrier film and flexible electronic device - Google Patents

Description

The present invention relates to a gas barrier film and a flexible electronic device having the gas barrier film.

Gas barrier films are widely used in packaging applications such as foods, industrial products and pharmaceuticals. In recent years, in flexible substrates and the like of electronic devices such as solar cells and organic EL displays, films having further improved gas barrier properties as compared with the above-mentioned food applications and the like have been required. In order to improve the gas barrier property of the gas barrier film, various studies have been made on the composition of the gas barrier film and the method for producing the same.

For example, in Patent Document 1, a base material having a specific thickness and a coating liquid containing a specific element are applied to at least one surface of the base material to obtain a coating film layer, and then the coating film layer is modified. A gas barrier film having a first gas barrier layer formed by subjecting a quality treatment and a second gas barrier layer formed by a specific method adjacent to the first gas barrier layer is disclosed.

Patent Document 2 focuses on the possibility that the barrier layer may be cracked when the OLED substrate provided with the barrier layer and the aluminum-deposited PET layer on the surface side of the substrate is cut from the aluminum-deposited PET layer side. The OLED base material cutting device made in the above is disclosed.

Japanese Unexamined Patent Publication No. 2016-22593 International Publication No. 2015/152395

Although various attempts have been made to improve the gas barrier property, there is still a demand for further improvement of the gas barrier property. In particular, the gas barrier film is usually cut into a desired shape and incorporated into an electronic device such as a display for use, but when the device containing the cut gas barrier film is used particularly under high temperature and high humidity conditions, it is cut. Peeling or cracking may occur due to the end face, and the gas barrier property may deteriorate over time.

Therefore, an object of the present invention is to provide a gas barrier film in which a decrease in gas barrier property with time is suppressed, particularly under high temperature and high humidity.

In order to solve the above problems, the present inventors have repeated detailed studies on the composition of the gas barrier film, and have completed the present invention.

That is, the present invention includes the following preferred embodiments.
[1] A gas barrier film having at least a base material layer containing at least a flexible base material and an inorganic thin film layer, and the adhesion between the base material layer and the inorganic thin film layer is measured according to ASTM D3359. The inorganic thin film layer has at least one cut end face and has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, and here. When the inorganic thin film layer has the defect, the region where the inorganic thin film layer is present is within a range of 120 μm or less in the normal direction from the cut end face, which is a gas barrier film.
[2] The gas barrier film according to the above [1], wherein the base material layer further contains an organic layer A.
[3] The gas barrier film according to the above [1] or [2], wherein the base material layer contains an organic layer A on both sides.
[4] The gas barrier film according to any one of [1] to [3] above, wherein the inorganic thin film layer contains at least silicon atoms, oxygen atoms and carbon atoms.
[5] The above-mentioned [4], wherein the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in the film thickness direction of the inorganic thin film layer. Gas barrier film.
[6] The inorganic thin film layer according to the above [4] or [5], wherein the average atomic number ratio of the carbon atom (C) to the silicon atom (Si) in the inorganic thin film layer is in the range of the formula (1). Gas barrier film.
0.10 <C / Si <0.50 (1)
[7] The number of silicon atoms relative to the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer and the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer at each distance. In the silicon distribution curve, oxygen distribution curve and carbon distribution curve showing the relationship between the ratio, the atomic number ratio of oxygen and the atomic number ratio of carbon, respectively, the conditions (i) and (ii):
(I) In the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer, the formula (5):
Atomic number ratio of oxygen> Atomic number ratio of silicon> Atomic number ratio of carbon (5)
The gas barrier film according to any one of [4] to [6] above, wherein (ii) the carbon distribution curve satisfies at least one extremum.
[8] The gas barrier film according to any one of [1] to [7], which has the inorganic thin film layers on both sides of the base material layer.
[9] A flexible electronic device having the gas barrier film according to any one of the above [1] to [8].
[10] When the surface of the inorganic thin film layer is measured by the ATR method of infrared spectroscopy, the peak intensity (I ₁ ^{) existing at 950 to 950 cm -1} and the peak intensity (I 1) existing at 1240 to 1290 cm ^-1. intensity ratio between ₂₎ is in the range of formula (2), gas barrier film according to any one of [1] to [8].
0.01 ≤ I ₂ / I ₁ <0.05 (2)
[11] wherein, when the inorganic thin film layer surface was measured by ATR method infrared spectroscopy, a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the peak intensity _{(I 3} present in 770～830Cm ^-1 The gas barrier film according to any one of [1] to [8] and [10], wherein the strength ratio with) is in the range of the formula (3).
0.25 ≤ I ₃ / I ₁ ≤ 0.50 (3)
[12] wherein, when the inorganic thin film layer surface was measured by ATR method infrared spectroscopy, a peak exists in 770～830Cm ^-1 intensity _{(I 3),} the peak intensity _{(I 4} present in 870～910Cm ^-1 The gas barrier film according to any one of [1] to [8], [10] and [11], wherein the strength ratio with) is in the range of the formula (4).
0.70 ≤ I ₄ / I ₃ <1.00 (4)

According to the present invention, it is possible to suppress the deterioration of the gas barrier property of the gas barrier film over time, particularly under high temperature and high humidity.

It is sectional drawing which shows an example of the gas barrier film of this invention. It is sectional drawing which shows the other example of the gas barrier film of this invention. It is sectional drawing which shows the further other example of the gas barrier film of this invention. It is a schematic diagram for demonstrating the existence area of a defect. It is a schematic diagram which shows the manufacturing apparatus of the gas barrier film used in an Example and a comparative example.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

The gas barrier film of the present invention has at least a base material layer containing at least a flexible base material and an inorganic thin film layer, and the adhesion between the base material layer and the inorganic thin film layer by ASTM D3359 is high. 2B or more, the inorganic thin film layer has at least one cut end face and has at least one defect selected from the group consisting of peeling and cracking, or has no such defect, where the said. When the inorganic thin film layer has the defect, the region where the inorganic thin film layer exists is within a range of 120 μm or less in the normal direction from the cut end face. In the gas barrier film of the present invention, the adhesion between the base material layer and the inorganic thin film layer is high, and even if the inorganic thin film layer has a defect selected from the group consisting of peeling and cracking, the region where the defect exists. When is within a predetermined range, deterioration of the gas barrier property over time is suppressed, especially under high temperature and high humidity. When defects such as cracks occur in the cut gas barrier film, if the adhesion between the base material layer and the inorganic thin film layer is low, the defects propagate in the plane under high temperature and high humidity conditions, for example, and have barrier properties. May be significantly reduced. According to the present invention, since the gas barrier film has a base material layer having a predetermined adhesiveness and an inorganic thin film layer, even if defects are generated due to stress applied to the gas barrier film at the time of cutting, it is suppressed to a minimum. Furthermore, it is possible to suppress a decrease in gas barrier property over time.

The gas barrier film of the present invention has at least a base material layer containing at least a flexible base material and an inorganic thin film layer, and the adhesion between the base material layer and the inorganic thin film layer by ASTM D3359 is 2B. That is all. If the adhesion between the base material layer and the inorganic thin film layer is lower than 2B, defects such as cracks and peeling are likely to occur in the inorganic thin film layer when the gas barrier film is cut, and the desired gas barrier property cannot be obtained. In addition, defects generated in the cut gas barrier film are likely to propagate over time, especially under high temperature and high humidity, and it is not possible to suppress a decrease in gas barrier property over time. The adhesion between the base material layer and the inorganic thin film layer is preferably 3B or more, more preferably 4B or more, and further preferably 5B or more.

The adhesion between the base material layer and the inorganic thin film layer means the adhesion between the inorganic thin film layer and the layer contained in the base material layer adjacent to the inorganic thin film layer. For example, in one aspect of the present invention, when the flexible base material contained in the base material layer is adjacent to the inorganic thin film layer, the adhesion between the base material layer and the inorganic thin film layer is, in other words, the flexible group. Adhesion between the material and the inorganic thin film layer. This embodiment is shown in FIG. 1, for example, in which the flexible base material 20 contained in the base material layer 2 is adjacent to and in close contact with the inorganic thin film layer 3 in the gas barrier film 1. Further, in another aspect of the present invention, when the base material layer contains a flexible base material and an organic layer A described later, and the organic layer A contained in the base material layer and the inorganic thin film layer are adjacent to each other, the base material is used. The adhesion between the layer and the inorganic thin film layer is, in other words, the adhesion between the organic layer A and the inorganic thin film layer. This embodiment is shown in FIG. 2, for example, in the gas barrier film 1, the base material layer 2 has a flexible base material layer 20 and an organic layer A21, and the organic layer A21 is adjacent to and in close contact with the inorganic thin film layer 3. There is. Here, the adhesion measurement is performed according to ASTM D3359.

In the barrier film of the present invention, the inorganic thin film layer has at least one cut end face. For example, when the barrier film of the present invention is obtained through at least one cutting step in at least an inorganic thin film layer, the inorganic thin film layer has at least one cut end face.

In the barrier film of the present invention, the inorganic thin film layer has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, wherein the inorganic thin film layer has the defect. When, the existing region is within a range of 120 μm or less in the normal direction from the cut end face. Since the barrier film of the present invention has high adhesion between the base material layer and the inorganic thin film layer, defects such as peeling and cracking are unlikely to occur in the inorganic thin film layer even if the gas barrier film is cut, for example. Further, even when the inorganic thin film layer has a defect selected from the group consisting of exfoliation and cracking, the defect propagates over time, especially under high temperature and high humidity, as long as the region where the inorganic thin film layer exists is within the above range. It is possible to prevent this from happening and suppress the deterioration of the gas barrier property. If there is a defect selected from the group consisting of peeling and cracking in the range exceeding 120 μm in the normal direction from the cut end face, sufficient gas barrier property cannot be obtained, and the gas barrier property deteriorates over time under high temperature and high humidity. Cannot be sufficiently suppressed. From the viewpoint of easily enhancing the gas barrier property, the region where the defect exists is preferably in the range of 100 μm or less in the normal direction from the cut end face, more preferably in the range of 50 μm or less, and more preferably in the range of 30 μm or less. It is even more preferably within the range of 10 μm or less, and most preferably within the range of 5 μm or less.

The region where the defect is selected from the group consisting of peeling and cracking is the cut end face of the inorganic thin film layer, using a microscope (for example, "DIGITAL MICROSCOPE KH7700" manufactured by Hirox Co., Ltd.) at an appropriate magnification (for example, 210). It can be evaluated by observing at double). Specifically, for peeling and cracking generated from the cut end face, the maximum length in the normal direction (perpendicular to the cross section) is measured from the cut end face, and the length is set as the region where the defect exists. When the inorganic thin film layer has two or more cut end faces, the above observation is performed for all the cut end faces.

The evaluation of the region of existence of the defect selected from the group consisting of exfoliation and cracking will be further described with reference to FIG. FIG. 4 shows a schematic diagram of a gas barrier film having a base material layer 2 made of a flexible base material 20 and an inorganic thin film layer 3, which is one aspect of the laminated film of the present invention. The inorganic thin film layer 3 in the gas barrier film shown in FIG. 4 has four cut end faces (four side surface portions). In this case, the size of the defect generated from the cut end face is observed using a microscope, and the distance a (5 in FIG. 4) of the maximum length is measured. In the gas barrier film of the present invention, the distance a in FIG. 4 is 120 μm or less.

The gas barrier film of the present invention has at least a base material layer containing at least a flexible base material and an inorganic thin film layer. The inorganic thin film layer may be laminated on at least one surface of the base material layer, and may be laminated on both sides of the base material layer. The inorganic thin film layer is not particularly limited as long as it is a layer of an inorganic material having a gas barrier property, and a known layer of an inorganic material having a gas barrier property can be appropriately used. Examples of inorganic materials include metal oxides, metal nitrides, metal oxynitrides, metal acid carbides and mixtures containing at least two of them. The inorganic thin film layer may be a single-layer film, or may be a multilayer film in which two or more layers including at least the above-mentioned inorganic thin film layer are laminated.

The inorganic thin film layer has at least silicon atoms (Si) and oxygen atoms from the viewpoint of easily exhibiting higher gas barrier properties (particularly water vapor permeation prevention property), bending resistance, ease of manufacturing, and low manufacturing cost. It preferably contains (O) and a carbon atom (C). The inorganic thin film layer may be one layer or a plurality of layers. Further, the step of forming the inorganic thin film layer may be performed once or may be performed a plurality of times. When it is performed a plurality of times, it may be performed under the same conditions or under different conditions.

In this case, the inorganic thin film layer has a general formula of SiO _α C _β [in the formula, α and β represent positive numbers less than 2 independently of each other. ] Can be the main component. Here, "the main component" means that the content of the component is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the mass of all the components constituting the inorganic thin film layer. It means that it is. Inorganic thin layer may contain one kind of compound represented by the general formula _SiO α _C β, may contain a general formula SiO _alpha C _beta in two or more compounds represented. One or more of α and β in the above general formula may be a constant value or may change in the film thickness direction of the inorganic thin film layer.

Further, the inorganic thin film layer contains elements other than silicon atom, oxygen atom and carbon atom, for example, one or more atoms of hydrogen atom, nitrogen atom, boron atom, aluminum atom, phosphorus atom, sulfur atom, fluorine atom and chlorine atom. It may be contained.

When the average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer is expressed by C / Si, the inorganic thin film layer has high density and defects such as fine voids and cracks. From the viewpoint of reducing the amount of C / Si, it is preferable that the range of C / Si satisfies the formula (1).
0.02 <C / Si <0.50 (1)
From the same viewpoint, C / Si is more preferably in the range of 0.03 <C / Si <0.45, further preferably in the range of 0.04 <C / Si <0.40, and 0. It is particularly preferable that the range is 05 <C / Si <0.35.

Further, the inorganic thin film layer has high density when the average atomic number ratio of oxygen atoms (O) to silicon atoms (Si) in the inorganic thin film layer is expressed by O / Si, and fine voids, cracks, etc. From the viewpoint of reducing the number of defects, it is preferably in the range of 1.50 <O / Si <1.98, more preferably in the range of 1.55 <O / Si <1.97, and 1.60 <O. It is more preferably in the range of /Si <1.96, and particularly preferably in the range of 1.65 <O / Si <1.95.

The average atomic number ratios C / Si and O / Si were measured in XPS depth profile under the following conditions, and from the obtained distribution curves of silicon atoms, oxygen atoms, and carbon atoms, the averages in the thickness direction of each atom were obtained. After determining the atomic concentration, the average atomic number ratios C / Si and O / Si can be calculated.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent value): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI Co., Ltd., model name "Quantera SXM"
Irradiated X-rays: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

When performing infrared spectroscopy with respect to the surface of the inorganic thin film layer (ATR method), a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the peak intensity existing in 1240~1290cm ^-1 _{(I 2} ) And the intensity ratio (I ₂ / I ₁ ) preferably satisfy the formula (2).
0.01 ≤ I ₂ / I ₁ <0.05 (2)

_{The peak intensity ratio I 2} / I ₁ calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio _{of Si-CH 3} to Si-O-Si in the inorganic thin film layer. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (2) has high denseness and easily reduces defects such as fine voids and cracks, so that it is easy to improve the gas barrier property and the impact resistance. The peak intensity ratio I ₂ / I ₁ is more preferably in the range of _{0.02 ≦ I 2} / I ₁ <0.04 from the viewpoint of easily maintaining the high density of the inorganic thin film layer.

When the inorganic thin film layer _{satisfies the peak intensity ratio I 2} / I ₁ , the gas barrier film of the present invention becomes moderately slippery and blocking is easily reduced. If the peak intensity ratio I ₂ / I ₁ is too large, it means that there is too much Si—C, and in this case, the flexibility tends to be poor and slipperiness tends to occur. Further, if the peak intensity ratio I ₂ / I ₁ is too small, the flexibility tends to decrease due to the excessive amount of Si—C.

Infrared spectroscopy of the surface of the inorganic thin film layer is performed by a Fourier transform infrared spectrophotometer (FT / IR-460Plus, manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an ATR attachment (PIKE MIRacle) using a germanium crystal for the prism. Can be measured by.

When performing infrared spectroscopy with respect to the surface of the inorganic thin film layer (ATR method), a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the peak intensity _{(I 3} present in 770～830Cm ^-1 ) And the intensity ratio (I ₃ / I ₁ ) preferably satisfy the formula (3).
0.25 ≤ I ₃ / I ₁ ≤ 0.50 (3)

_{The peak intensity ratio I 3} / I ₁ calculated from infrared spectroscopy (ATR method) is considered to represent the relative ratio of Si—C, Si—O, etc. to Si—O—Si in the inorganic thin film layer. .. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (3) is easy to improve the bending resistance and the impact resistance because carbon is introduced while maintaining high denseness. The peak intensity ratio I ₃ / I _{1 is preferably in the range of 0.25 ≤ I 3} / I ₁ ≤ 0.50, preferably 0.30 ≤ I, from the viewpoint of maintaining a balance between the compactness and the bending resistance of the inorganic thin film layer. _{The range of 3} / I ₁ ≤ 0.45 is more preferable.

The thin film layer, when subjected infrared spectrometry the inorganic thin film layer surface (ATR method), a peak exists in 770～830Cm ^-1 intensity _{(I 3),} peaks present in 870～910Cm ^-1 It is preferable that the strength ratio with the strength (I _{4) satisfies the formula (4).}
0.70 ≤ I ₄ / I ₃ <1.00 (4)

_{The peak intensity ratio I 4} / I ₃ calculated from infrared spectroscopy (ATR method) is considered to represent the ratio of peaks related to Si—C in the inorganic thin film layer. It is considered that the inorganic thin film layer satisfying the relationship represented by the formula (4) is easy to improve the bending resistance and the impact resistance because carbon is introduced while maintaining high denseness. Regarding the range of the peak intensity ratio I ₄ / I _{3 , the range of 0.70 ≦ I 4} / I ₃ <1.00 is preferable, and 0.80 from the viewpoint of maintaining the balance between the compactness and the bending resistance of the inorganic thin film layer. The range of ≦ I ₄ / I ₃ <0.95 is more preferable.

The thickness of the inorganic thin film layer is preferably 5 to 3000 nm from the viewpoint of making it difficult to crack when the inorganic thin film layer is bent. Further, as will be described later, when the inorganic thin film layer is formed by the plasma CVD method using glow discharge plasma, the inorganic thin film layer is formed while being discharged through the substrate, so that the thickness is 10 to 2000 nm. Is more preferable, and 100 to 1000 nm is even more preferable.

The inorganic thin film layer can preferably have a high average density of ^{1.8 g / cm 3 or more.} Here, the "average density" of the inorganic thin film layer is the number of atoms of silicon, the number of atoms of carbon, the number of atoms of oxygen obtained by the Rutherford Backscattering Spectrometry (RBS), and the hydrogen forward scattering method (Hydrogen Forward). The weight of the inorganic thin film layer in the measurement range is calculated from the number of atoms of hydrogen obtained by scattering spectroscopy (HFS), and divided by the volume of the inorganic thin film layer in the measurement range (the product of the ion beam irradiation area and the film thickness). It is required by doing. When the average density of the inorganic thin film layer is at least the above lower limit, the density is high and the structure is preferable because it is easy to reduce defects such as fine voids and cracks. In a preferred embodiment of the present invention in which the inorganic thin film layer is composed of a silicon atom, an oxygen atom, a carbon atom and a hydrogen atom, the average density of the inorganic thin film layer is preferably less than ^{2.22 g / cm 3.}

In a preferred embodiment of the present invention in which the inorganic thin film layer contains at least a silicon atom (Si), an oxygen atom (O) and a carbon atom (C), the distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer. And the curve showing the relationship with the atomic ratio of silicon atoms at each distance is called a silicon distribution curve. Here, the surface of the inorganic thin film layer refers to the surface of the gas barrier film of the present invention. Similarly, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of oxygen atoms at each distance is called an oxygen distribution curve. Further, a curve showing the relationship between the distance from the surface of the inorganic thin film layer in the film thickness direction and the atomic ratio of carbon atoms at each distance is called a carbon distribution curve. The atomic ratio of silicon atom, the atomic ratio of oxygen atom, and the atomic ratio of carbon atom mean the ratio of the number of atoms to the total number of silicon atom, oxygen atom, and carbon atom contained in the inorganic thin film layer.

From the viewpoint of easily suppressing the deterioration of the gas barrier property due to bending, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer is continuous in the film thickness direction of the inorganic thin film layer. It is preferable to change the target. Here, the fact that the atomic number ratio of carbon atoms changes continuously in the film thickness direction of the inorganic thin film layer does not include, for example, a portion of the carbon distribution curve in which the atomic ratio of carbon changes discontinuously. Represents.

It is preferable that the silicon distribution curve, oxygen distribution curve and carbon distribution curve of the inorganic thin film layer satisfy the following conditions (i) and (ii) from the viewpoint of film flexibility and barrier property.
(I) The condition represented by the formula (5) is satisfied in the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer.
(Atom ratio of oxygen)> (Atom ratio of silicon)> (Atom ratio of carbon) (5) (ii) The carbon distribution curve has at least one extreme value.

The carbon distribution curve of the inorganic thin film layer is preferably substantially continuous. The fact that the carbon distribution curve is substantially continuous means that the carbon distribution curve does not include a portion where the atomic ratio of carbon changes discontinuously. Specifically, it is preferable to satisfy the formula (6) when the distance from the surface of the thin film layer in the film thickness direction is x [nm] and the atomic ratio of carbon is C.
| DC / dx | ≤0.01 (6)

Further, the carbon distribution curve of the inorganic thin film layer preferably has at least one extremum. The extreme value here is a maximum value or a minimum value of the atomic ratio of each element with respect to the distance from the surface of the inorganic thin film layer in the film thickness direction. The extreme value is the atomic ratio at the point where the atomic ratio of the element changes from increasing to decreasing or the atomic ratio of the element changes from decreasing to increasing when the distance from the surface of the inorganic thin film layer in the film thickness direction is changed. Is the value of. The extreme value can be obtained, for example, based on the measured atomic ratio at a plurality of measurement positions in the film thickness direction. The atomic ratio measurement position is set so that the interval in the film thickness direction is, for example, 20 nm or less. For the positions showing extreme values in the film thickness direction, for discrete data groups including the measurement results at each measurement position, for example, the measurement results at three or more different measurement positions are compared, and the measurement results increase or decrease. It can be obtained by finding the position where it turns to or the position where it turns from decrease to increase. The position showing the extremum can also be obtained, for example, by differentiating the approximate curve obtained from the above-mentioned discrete data group. When the section where the atomic ratio increases or decreases monotonically from the position showing the extreme value is, for example, 20 nm or more, the atomic ratio and the extreme value at the position moved by 20 nm in the film thickness direction from the position showing the extreme value. The absolute value of the difference is, for example, 0.03 or more.

In the inorganic thin film layer formed so as to satisfy the condition that the carbon distribution curve has at least one extremum as described above, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending satisfies the above condition. It will be less than when it is not. That is, by satisfying the above conditions, the effect of suppressing the deterioration of the gas barrier property due to bending can be obtained. When the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is two or more, the amount of increase is smaller than that of the case where the number of extreme values of the carbon distribution curve is one. .. Further, when the inorganic thin film layer is formed so that the number of extreme values of the carbon distribution curve is three or more, the amount of increase is larger than that of the case where the number of extreme values of the carbon distribution curve is two. Less. When the carbon distribution curve has two or more extrema, the distance from the surface of the inorganic thin film layer in the film thickness direction at the position showing the first extremum and the second extremum adjacent to the first extremum. The absolute value of the difference from the distance from the surface of the inorganic thin film layer in the film thickness direction at the position indicating the value is preferably in the range of 1 nm or more and 200 nm or less, and further preferably in the range of 1 nm or more and 100 nm or less. preferable.

Further, it is preferable that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve of the inorganic thin film layer is larger than 0.01. In the inorganic thin film layer formed so as to satisfy the above conditions, the amount of increase in the gas permeability after bending with respect to the gas permeability before bending is smaller than that in the case where the conditions are not satisfied. That is, by satisfying the above conditions, the effect of suppressing the deterioration of the gas barrier property due to bending can be obtained. When the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 0.02 or more, the above effect is high, and when it is 0.03 or more, the above effect is further high.

The lower the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the absolute value is preferably less than 0.05 (less than 5 at%), more preferably less than 0.04 (less than 4 at%), and less than 0.03 (3 at%). Less than) is particularly preferred.

In addition, in the oxygen carbon distribution curve, when the sum of the atomic ratios of oxygen atoms and the atomic ratios of carbon atoms at each distance is taken as the "total atomic ratio", the absolute value of the difference between the maximum and minimum values of the total atomic ratio is The lower the value, the better the gas barrier property of the inorganic thin film layer tends to be. From this point of view, the total atomic ratio is preferably less than 0.05, more preferably less than 0.04, and particularly preferably less than 0.03.

When the inorganic thin film layer has a substantially uniform composition in the surface direction of the inorganic thin film layer, the gas barrier property of the inorganic thin film layer can be made uniform and improved. The substantially uniform composition means the number of extreme values existing in the film thickness direction at any two points on the surface of the inorganic thin film layer in the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve. Is the same, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same as each other or the difference is within 0.05.

The inorganic thin film layer formed so as to satisfy the above conditions can exhibit the gas barrier property required for, for example, a flexible electronic device using an organic EL element.

The method for processing the gas barrier film of the present invention includes a Thomson type punching machine, a super cutter, and a cross cutter from the viewpoint of processing the inorganic thin film layer, which is harder than the base material layer made of an organic substance, so as not to cause cracks. Cutting with a guillotine cutting, shear cutter, rotary die cutter, press cutter, etc., or processing by ablation using various lasers is preferable. Further, the machined end face can be machined. Examples of the method for cutting the machined end face include a method of cutting the outer peripheral end portion of the polarizing plate with a rotary blade as disclosed in Patent Document 3 (Japanese Unexamined Patent Publication No. 2001-54445), and the above-mentioned method. In the method for processing a gas barrier film of the present invention, a method for continuously cutting the outer peripheral end portion of a polarizing plate by a fly-cut method as disclosed in Patent Document 4 (Japanese Unexamined Patent Publication No. 2003-220512) is used. Is also preferably adopted. By cutting the outer peripheral end face by such a method, it is possible to suppress the occurrence of at least one defect selected from the group consisting of peeling and cracking that occurs on the cut end face.

When processing the gas barrier film of the present invention, a protective film or a cover film with an adhesive such as OCA is attached from the viewpoint of processing the inorganic thin film layer, which is harder than the base material layer made of an organic substance, so as not to cause cracks. It may be combined. In particular, as a protective film or a cover film with an adhesive such as OCA, a PET film is preferable from the viewpoint of film rigidity.

In a preferred embodiment of the present invention in which the inorganic thin film layer contains at least silicon atoms, oxygen atoms and carbon atoms, the layer of the inorganic material containing such atoms tends to increase the denseness and has defects such as fine voids and cracks. From the viewpoint of easy reduction, it is preferable to form the film by the chemical vapor deposition method (CVD method), and above all, it is more preferable to form the plasma by the plasma chemical vapor deposition method (PECVD method) using glow discharge plasma or the like. preferable.

An example of a raw material gas used in the chemical vapor deposition method is an organosilicon compound containing a silicon atom and a carbon atom. Examples of such organic silicon compounds are hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane. , Ppropylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoint of the handleability of the compound and the gas barrier property of the obtained inorganic thin film layer. As the raw material gas, one of these organosilicon compounds may be used alone, or two or more thereof may be used in combination.

Further, a reaction gas capable of reacting with the raw material gas to form an inorganic compound such as an oxide or a nitride can be appropriately selected and mixed with the raw material gas. As the reaction gas for forming the oxide, for example, oxygen or ozone can be used. Further, as the reaction gas for forming the nitride, for example, nitrogen or ammonia can be used. These reaction gases can be used alone or in combination of two or more. For example, in the case of forming an oxynitride, the reaction gas for forming an oxide and the nitride are formed. Can be used in combination with a reaction gas for. The flow rate ratio of the raw material gas and the reaction gas can be appropriately adjusted according to the atomic ratio of the inorganic material to be formed.
The C / Si value can be controlled by adjusting the flow rate ratio of the raw material gas and the reaction gas. For example, when hexamethyldisiloxane (HMDSO) is used as the raw material gas and oxygen is used as the reaction gas, the ratio of oxygen flow rate to HMDSO flow rate O ₂ / HMDSO is set to the range of 5 to 25, and the C / Si value is set. It can be controlled within the above range.

If necessary, a carrier gas may be used to supply the raw material gas into the vacuum chamber. Further, in order to generate plasma discharge, a discharge gas may be used, if necessary. As such a carrier gas and a gas for discharge, known ones can be used as appropriate, and for example, a rare gas such as helium, argon, neon, or xenon; hydrogen can be used.

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

FIG. 5 is a schematic diagram showing an example of a manufacturing apparatus used for manufacturing an inorganic thin film layer contained in a gas barrier film, and is a schematic diagram of an apparatus for forming an inorganic thin film layer by a plasma chemical vapor deposition method. In FIG. 5, the dimensions and ratios of the components are appropriately different in order to make the drawings easier to see. The manufacturing apparatus shown in FIG. 5 includes a delivery roll 6, a take-up roll 13, a transfer roll 7, a gas supply pipe 10, a plasma generation power supply 11, a magnetic field forming apparatus 11 installed inside the film forming rolls 8 and 9, respectively. Has twelve. In the apparatus of FIG. 5, the film-forming rolls 11 and 12 also serve as electrodes, and are roll-shaped electrodes described later.

Among the components of the manufacturing apparatus, at least the film forming roll, the gas supply pipe, and the magnetic field forming apparatus are arranged in a vacuum chamber (not shown) when forming the inorganic thin film layer. This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

By using this device, by controlling the power supply for plasma generation, it is possible to generate the discharge plasma of the film-forming gas supplied from the gas supply pipe in the space between the two film-forming rolls, and the generated discharge. Plasma CVD film formation can be performed by a continuous film formation process using plasma.

The film 14 before film formation is installed on the delivery roll in a wound state, and the film is fed while being unwound in the long direction. Further, a take-up roll is provided on the end side of the film, and after the film is formed, the film is taken up while being towed and stored in a roll shape.

It is preferable that the two film forming rolls extend in parallel and are arranged to face each other. Both rolls are made of a conductive material and carry the film while rotating. It is preferable to use two film forming rolls having the same diameter, and for example, it is preferable to use one having a diameter of 5 cm or more and 100 cm or less.

When the inorganic thin film layer is formed, the base material layer is conveyed to the surface of the pair of roll-shaped electrodes while being in close contact with each other, plasma is generated between the pair of electrodes, and the raw material is decomposed in the plasma to be flexible. It is preferable to form an inorganic thin film layer on the substrate. In the pair of electrodes, magnets are preferably arranged inside the electrodes so that the magnetic flux density is high on the surfaces of the electrodes and the flexible base material. As a result, the plasma tends to be constrained at high density on the electrodes and the flexible substrate when the plasma is generated.

The gas barrier film of the present invention has a base material layer containing at least a flexible base material. The flexible base material is a flexible base material capable of holding an inorganic thin film tank. As the flexible base material, a resin film containing at least one kind of resin as a resin component can be used. The flexible base material is preferably a transparent resin base material.

Examples of the resin that can be used for the resin film include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefins; polyamide resins; polycarbonate resins. Examples thereof include a polystyrene resin; a polyvinyl alcohol resin; a saponified product of an ethylene-vinyl acetate copolymer; a polyacrylonitrile resin; an acetal resin; a polyimide resin; and a polyether sulfide (PES). As the flexible base material, one of the above resins may be used, or two or more kinds of resins may be used in combination. Among these, from the viewpoint of easily enhancing properties such as transparency, heat resistance, and linear expandability, it is preferable to use a resin selected from the group consisting of polyester resin and polyolefin resin, and the group consisting of PET, PEN, and cyclic polyolefin. It is more preferable to use a resin selected from.

The flexible base material may be an unstretched resin base material, or the unstretched resin base material may be uniaxially stretched, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, or tubular simultaneous biaxial stretching. The stretched resin base material may be stretched in the flow direction (MD direction) of the resin base material and / or in the direction perpendicular to the flow direction of the resin base material (TD direction) by a known method such as stretching. The flexible base material may be a laminate in which two or more layers of the above-mentioned resin are laminated.

The thickness of the flexible base material may be appropriately set in consideration of stability in manufacturing a gas barrier film, etc., but from the viewpoint of facilitating the transfer of the flexible base material in vacuum, 5 to 5 It is preferably 500 μm. Further, when the inorganic thin film layer is formed by the plasma CVD method, the thickness of the flexible substrate is more preferably 10 to 200 μm, further preferably 15 to 100 μm. Here, the thickness of the flexible base material is measured by a dial gauge or an interferometric thickness gauge.

The flexible substrate may be a retardation film such as a λ / 4 retardation film or a λ / 2 retardation film, in which the refractive indexes of the two orthogonal components in the plane are different from each other. As the material of the retardation film, orientation solidification of cellulose-based resin, polycarbonate-based resin, polyarylate-based resin, polyester-based resin, acrylic resin, polysulfone-based resin, polyether sulfone-based resin, cyclic olefin-based resin, and liquid crystal compound. An example can be a layer or the like. Among them, a polycarbonate-based resin film is preferably used because a uniform film can be obtained at a low cost. As the film forming method, a solvent casting method or a precision extrusion method capable of reducing the residual stress of the film can be used, but the solvent casting method is preferably used from the viewpoint of uniformity. The stretching method is not particularly limited, and vertical uniaxial stretching between rolls, tenter horizontal uniaxial stretching, etc., which can obtain uniform optical characteristics, can be applied.

When the flexible substrate is a λ / 4 retardation film, the in-plane retardation Re (550) at a wavelength of 550 nm can be 100 to 180 nm, preferably 110 to 170 nm, and more preferably 110 to 170 nm. It is 120 to 160 nm.

When the flexible substrate is a λ / 2 retardation film, the in-plane retardation Re (550) at a wavelength of 550 nm can be 220 to 320 nm, preferably 240 to 300 nm, and more preferably 240 nm. It is 250 to 280 nm.

When the flexible substrate is a retardation film, the retardation value may exhibit a reverse wavelength dispersibility that increases with the wavelength of the measurement light, and the retardation value decreases with the wavelength of the measurement light. It may show a positive wavelength dispersion characteristic, or may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes depending on the wavelength of the measured light.

When the flexible base material is a retardation film exhibiting reverse wavelength dispersibility, the flexible base material is Re (λ) when the phase difference at the wavelength λ of the flexible base material is expressed as Re (λ). (450) / Re (550) <1 and Re (650) / Re (550)> 1 can be satisfied.

The flexible substrate is preferably colorless and transparent from the viewpoint of being able to transmit and absorb light. More specifically, the total light transmittance is preferably 80% or more, and more preferably 85% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less, and further preferably 1% or less.

Flexible base material, from the viewpoint that it either be used on the substrate of the organic devices and energy devices, it is preferable that an insulating, electrical resistivity is preferably 10 ⁶ [Omega] cm or more.

The surface of the flexible base material may be subjected to a surface activation treatment for cleaning the surface from the viewpoint of adhesion to the inorganic thin film layer or the like. Examples of such surface activation treatment include corona treatment, plasma treatment, and frame treatment.

In the gas barrier film of the present invention, the base material layer contains another layer in addition to the above-mentioned flexible base material for the purpose of improving adhesion and / or flatness with the inorganic thin film layer. May be good. Further, the gas barrier film of the present invention may contain a layer other than the base material layer. Examples of the other layers include organic layers such as an easy-slip layer, a flattening layer, and an anti-blocking layer. The organic layer is also referred to as "organic layer A" below. The organic layer A may be laminated on the surface of the flexible base material contained in the base material layer on the inorganic thin film layer side, or may be laminated on the surface opposite to the inorganic thin film layer side. It may be laminated on both sides of the flexible substrate. From the viewpoint of adhesion and water vapor barrier property, the base material layer preferably has an organic layer A laminated on the surface of the flexible base material on the side of the inorganic thin film layer. Here, the organic layer A is preferably a flattening layer.

For the organic layer A, a resin composition containing a monomer and / or an oligomer of a photocurable resin such as an ultraviolet ray or an electron beam curable resin is applied onto a flexible substrate, dried as necessary, and then ultraviolet rays or electrons. It can be formed by curing by irradiation with a line. The resin composition may contain additives such as a solvent, a photopolymerization initiator, a thermal polymerization initiator, an antioxidant, an ultraviolet absorber, and a plasticizer, if necessary.

Examples of coating methods include various conventionally used coating methods such as spray coating, spin coating, bar coating, curtain coating, dipping method, air knife method, slide coating, hopper coating, reverse roll coating, and gravure coating. Examples include methods such as extraction application.

For the flattening layer, for example, an acrylate resin can be used. The acrylate resin is preferably a photocurable resin. The photocurable resin is a resin in which polymerization is started by ultraviolet rays, electron beams, or the like, and curing proceeds. Further, a resin other than the acrylate resin may be contained to the extent that the effect is not impaired. Specific examples thereof include polyester resin, isocyanate resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, phenol resin, urea melamine resin, styrene resin, alkyl titanate and the like, and one or more of these are included together. But it may be. Further, by changing the drying conditions and the curing conditions of the flattening layer, the flatness of the surface can be improved and the flattening layer can be used as an easy-slip layer or an anti-blocking layer.

As the flattening layer, when the temperature change of the elastic modulus of the flattening layer surface is evaluated by a rigid pendulum type physical property tester (for example, RPT-3000W manufactured by A & D Co., Ltd.), the flattening layer surface. It is preferable that the temperature at which the elastic modulus of the pendulum decreases by 50% or more is 150 ° C. or higher.

For the slippery layer, for example, a resin composition containing inorganic particles can be used. Examples of the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like.

For the anti-blocking layer, for example, a resin composition containing inorganic particles can be used. Examples of the inorganic particles include silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like.

The gas barrier film of the present invention may contain other layers in addition to the above-mentioned base material layer and inorganic thin film layer. Examples of the other layer include the organic layer A. The organic layer A that can be contained in a portion other than the base material layer of the gas barrier film of the present invention is also referred to as "organic layer B" below. Examples of the organic layer B include an easy-to-slip layer, a flattening layer, an anti-blocking layer, a matting agent layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light-shielding layer, an antireflection layer, a hard coat layer, and stress relaxation. Examples thereof include a layer, an antifogging layer, an antifouling layer, a layer to be printed, and an easy-adhesion layer. Regarding the specific structure of the layer, the matters described for the organic layer A also apply to the organic layer B. The organic layer B may be laminated on the surface of the inorganic thin film layer opposite to the base material layer, or may be laminated on the inorganic thin film layer, for example. From the viewpoint of water vapor barrier property, the gas barrier film of the present invention preferably further has an organic layer B on the surface of the inorganic thin film layer opposite to the base material layer.

Examples of the organic layer B include a layer composed of the resin described for the organic layer A and a layer containing an additive for exerting each function in the resin described for the organic layer A, and examples thereof include a gas barrier. It is appropriately selected depending on the intended use and usage of the sex film.

Examples of the method for laminating the organic layer B include the method described for the organic layer A above.

Further, the organic layer B may be a layer formed by using a composition containing an inorganic polymer such as polysilazane. By forming the inorganic polymer layer, the permeation of water vapor can be prevented at a high level, and when applied to an electronic device such as an organic EL element, the generation of dark spots can be suppressed for a long period of time. can.

The inorganic polymer layer can be adjusted to a desired film thickness by one coating, or can be applied multiple times to adjust to a desired film thickness. When the coating is applied a plurality of times, it is more effective to carry out the curing treatment for each coating from the viewpoint of securing the diffusion path of the gas generated by the curing and compensating for defects such as cracks.

The inorganic polymer layer can be formed by applying a coating liquid containing an inorganic polymer such as polysilazane on the inorganic thin film layer, drying the coating film, and then curing the formed coating film. As the coating liquid, one in which an inorganic polymer is dissolved or dispersed in a solvent can be used. The concentration of the inorganic polymer in the coating liquid may be appropriately adjusted according to the thickness of the inorganic polymer layer and the pot life of the coating liquid, but is usually 0.2 to 35% by mass.

More specific examples of the inorganic polymer polysilazane include perhydropolysilazane (PHPS) and organopolysilazane.

As the solvent, a solvent that does not react with the inorganic polymer to be used, is suitable for dissolving or dispersing the inorganic polymer, and does not adversely affect the inorganic thin film layer can be appropriately selected and used. Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, and ethers such as halogenated hydrocarbon solvents, aliphatic ethers and alicyclic ethers. More specific examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, toluene and xylene, halogenated hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. Two or more kinds of these solvents may be mixed and used.

When polysilazane is used as the inorganic polymer, an amine catalyst, a Pt compound such as Pt acetylacetonate, a Pd compound such as propionic acid Pd, and a Rh compound such as Rh acetylacetonate are used in the coating liquid in order to promote the modification to silicon nitride. It is also possible to add a metal catalyst such as.

The amount of the catalyst added to polysilazane is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and 0.5 to 2% by mass based on the total amount of the coating liquid. Is even more preferable. By setting the amount of the catalyst added within the above range, it is possible to suppress excessive silanol formation, a decrease in film density, an increase in film defects, etc. due to the rapid progress of the reaction.

Drying may be performed under conditions where the solvent in the coating liquid can be removed. Further, for example, the coating liquid may be applied and dried at the same time on a heated hot plate.

Examples of the curing treatment method for the formed coating film include a plasma CVD method, an ion implantation treatment method, an ultraviolet irradiation method, a vacuum ultraviolet irradiation method, an oxygen plasma irradiation method, and a heat treatment method, in which an inorganic polymer in the coating film is cured. Any method that can be used can be used. Among these, as the curing treatment method, it is preferable to use a method of irradiating the coating film with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less. Further, the method of irradiating the coating film with vacuum ultraviolet light is more preferable when polysilazane is used as the inorganic polymer.

By utilizing vacuum ultraviolet irradiation method as hardening method of the coating film containing polysilazane, it is irradiated with vacuum ultraviolet rays to the coating film, at least a portion of the polysilazane is reformed into silicon oxynitride that denoted by SiO _x N _y To. Here, when perhydropolysilazane _{having a structure represented by − (SiH 2-} NH-) _n − is used as polysilazane, oxygen is required for x> 0 when reforming to _{SiO x} N _y. A source is required, but oxygen and water taken into the coating film during the manufacturing process serve as the oxygen source.

In _{the composition of SiO x} N _y , x and y are basically in the range of 2x + 3y = 4 due to the relationship between the bonds of Si, O, and N. In the state of y = 0 where the oxidation is completely advanced, the silanol group is contained in the coating film, and the range may be in the range of 2 <x <2.5.
Since it is usually unlikely that nitriding will proceed more than the oxidation of Si, y is basically 1 or less.

The reaction mechanism in which silicon nitride is generated from perhydropolysilazane and silicon oxide is generated by irradiation with vacuum ultraviolet rays is considered as follows.

(1) Dehydrogenation and accompanying formation of Si—N bonds The Si—H bonds and N—H bonds in perhydropolysilazane are relatively easily cleaved by excitation by vacuum ultraviolet irradiation or the like, and Si under an inert atmosphere. It is considered to recombine as −N (unbonded hands of Si may be formed). That is, perhydropolysilazane is cured as SiN _y composition without oxidizing. In this case, cleavage of the polymer backbone does not occur. Cleavage of Si—H bonds and NH bonds is promoted by the presence of a catalyst and heating. Cut H is released into the epidural as H _2.

(2) Formation of Si—O—Si bond by hydrolysis and dehydration condensation The Si—N bond in perhydropolysilazane is hydrolyzed by water, and the polymer main chain is cleaved to form Si—OH. The two Si-OH are dehydrated and condensed to form a Si—O—Si bond and are cured. This is a reaction that occurs even in the atmosphere, but it is considered that water vapor generated as outgas from the resin substrate due to the heat of irradiation is the main water source during the irradiation of vacuum ultraviolet rays in an inert atmosphere. When the water content becomes excessive, Si—OH that cannot be completely dehydrated and condensed remains, resulting in a cured film having a low gas barrier property represented by the compositions of _{SiO 2.1 to SiO 2.3.}

(3) Direct oxidation by singlet oxygen, formation of Si—O—Si bond When an appropriate amount of oxygen is present in the atmosphere during vacuum ultraviolet irradiation, singlet oxygen with extremely strong oxidizing power is formed. H and N in perhydropolysilazane replace O to form Si—O—Si bonds and cure. Cleavage of the polymer backbone may result in bond recombination.

(4) Oxidation with Si-N bond cleavage by vacuum ultraviolet irradiation and excitation Since the energy of vacuum ultraviolet is higher than the binding energy of Si-N in perhydropolysilazane, the Si-N bond is cleaved and oxygen is generated in the surroundings. In the presence of an oxygen source such as ozone or water, it is considered that it is oxidized to form a Si—O—Si bond or a Si—ON bond. Cleavage of the polymer backbone may result in bond recombination.

The composition of the silicon nitride in the layer obtained by irradiating the coating film containing polysilazane with vacuum ultraviolet rays is adjusted by appropriately combining the oxidation mechanisms of (1) to (4) described above to control the oxidation state. It can be carried out.

In vacuum ultraviolet radiation, intensity of the vacuum ultraviolet rays in the coated surface of the coating film is subjected containing polysilazane is preferably in the range of 1~100000mW / cm ^2, in the range of from 30~200mW / cm ² Is more preferable. If the illuminance is 1 mW / cm ² or more, there is no concern that the reforming efficiency will decrease, and if it is 100,000 mW / cm ² or less, the coating film will not be ablated and the flexible substrate will be damaged. It is preferable because it does not exist.

In vacuum ultraviolet irradiation, the integrated light amount (integrated irradiation energy amount) of the vacuum ultraviolet emitted to the coating film containing polysilazane is 1.0 to 100 mJ / in the following formula standardized by the film thickness of the inorganic polymer layer. preferably cm in the range of ² / nm, more preferably in the range of 1.5~30mJ / ^cm 2 / nm, still in the range of 2.0~20mJ / ^cm 2 / nm It is preferably in the range of 5.0 to 20 mJ / cm ² / nm, particularly preferably. When the standardized integrated light amount is 1.0 mJ / cm ² / nm or more, the modification can be sufficiently performed. On the other hand, when the standardized integrated light amount is 100 mJ / cm ² / nm or less, the over-modification condition does not occur and the generation of cracks in the inorganic polymer layer can be prevented. Even when the inorganic polymer layer is cured a plurality of times in order to obtain a desired film thickness, it is preferable that the amount of light is within the standardized integrated light amount for each layer.

A noble gas excimer lamp is preferably used as the vacuum ultraviolet light source. Noble gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they do not chemically bond to form molecules.

However, the excited atoms of the noble gas that gained energy by electric discharge or the like can be combined with other atoms to form molecules. If the noble gas is xenon
e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172nm)
Then, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, it emits excimer light having a wavelength of 172 nm.

One of the characteristics of excimer lamps is that they are highly efficient because the radiation is concentrated on one wavelength and almost no light other than the required light is emitted. In addition, since extra light is not emitted, the temperature of the object can be kept low. Furthermore, since it does not take time to start and restart, it is possible to turn on and blink instantly.

A method using a dielectric barrier discharge is known to obtain excimer light. Dielectric barrier discharge occurs in the gas space by arranging a gas space between both electrodes via a dielectric such as transparent quartz and applying a high voltage of several tens of kHz to the electrodes, which is very similar to lightning. It is a discharge called a fine micro discharge, and when the streamer of the micro discharge reaches the tube wall (derivative), an electric charge is accumulated on the surface of the dielectric, so that the micro discharge disappears.

This micro discharge spreads over the entire tube wall and is a discharge that is repeatedly generated and extinguished. For this reason, light flicker that can be confirmed with the naked eye occurs. In addition, a streamer with a very high temperature reaches the pipe wall directly locally, which may accelerate the deterioration of the pipe wall.

As a method for efficiently obtaining excimer light emission, an electrodeless electric field discharge is also possible in addition to the dielectric barrier discharge. Electrodeless electric field discharge due to capacitive coupling, also known as RF discharge. The lamp, the electrodes, and their arrangement may be basically the same as the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. Since the electrodeless electric field discharge can obtain a uniform discharge spatially and temporally in this way, a long-life lamp without flicker can be obtained.

In the case of dielectric barrier discharge, micro discharge occurs only between the electrodes, so the outer electrode covers the entire outer surface to allow discharge in the entire discharge space, and transmits light to extract light to the outside. Must be something to do.

Therefore, an electrode made of a thin metal wire in a mesh shape is used. Since this electrode uses as thin a wire as possible so as not to block light, it is easily damaged by ozone or the like generated by vacuum ultraviolet light in an oxygen atmosphere. In order to prevent this, it is necessary to create an atmosphere of an inert gas such as nitrogen around the lamp, that is, inside the irradiation device, and to provide a window of synthetic quartz to take out the irradiation light. Synthetic quartz windows are not only an expensive consumable item, but also cause light loss.

Since the double cylindrical lamp has an outer diameter of about 25 mm, the difference in the distance to the irradiation surface cannot be ignored between the area directly under the lamp shaft and the side surface of the lamp, which causes a large difference in illuminance. Therefore, even if the lamps are arranged in close contact with each other, a uniform illuminance distribution cannot be obtained. If the irradiation device is provided with a synthetic quartz window, the distance in the oxygen atmosphere can be made uniform, and a uniform illuminance distribution can be obtained.

When electrodeless electric field discharge is used, it is not necessary to make the external electrodes into a mesh. Glow discharge spreads over the entire discharge space simply by providing an external electrode on a part of the outer surface of the lamp. As the external electrode, an electrode that also serves as a light reflector made of an aluminum block is usually used on the back of the lamp. However, since the outer diameter of the lamp is large as in the case of dielectric barrier discharge, synthetic quartz is required to obtain a uniform illuminance distribution.

The biggest feature of the thin tube excimer lamp is its simple structure. Both ends of the quartz tube are closed, and a gas for excimer emission is enclosed inside.

The outer diameter of the tube of the thin tube lamp is about 6 to 12 mm, and if it is too thick, a high voltage is required for starting.

As the discharge form, either a dielectric barrier discharge or an electrodeless electric field discharge can be used. The shape of the electrode may be a flat surface in contact with the lamp, but by making the shape match the curved surface of the lamp, the lamp can be firmly fixed, and the electrode is in close contact with the lamp, so that the discharge is more stable. .. Moreover, if the curved surface is made a mirror surface with aluminum, it can also be used as a light reflector.

The Xe excimer lamp has excellent luminous efficiency because it emits ultraviolet rays having a short wavelength of 172 nm at a single wavelength. Since this excimer light has a large oxygen absorption coefficient, it is possible to generate radical oxygen atom species and ozone at a high concentration with a small amount of oxygen.

It is also known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate the bonds of organic substances. The high energy of active oxygen, ozone, and ultraviolet radiation can be used to modify the polysilazane layer in a short time.

Therefore, compared to low-pressure mercury lamps and plasma cleaning with wavelengths of 185 nm and 254 nm, it is possible to shorten the process time due to high throughput, reduce the equipment area, and irradiate organic materials and plastic substrates that are susceptible to heat damage. ..

Since excimer lamps have high light generation efficiency, they can be turned on with low power input. In addition, it does not emit light with a long wavelength that causes the temperature to rise due to light irradiation, and irradiates energy in the ultraviolet region, that is, in a short wavelength range, so it has the characteristic that the rise in the surface temperature of the object to be irradiated is suppressed. .. Therefore, it is suitable for reforming a material having a flexible film such as PET, which is considered to be easily affected by heat.

Since vacuum ultraviolet rays are absorbed by oxygen in the presence of oxygen, the efficiency in the ultraviolet irradiation step tends to decrease. Therefore, it is preferable to perform vacuum ultraviolet irradiation in a state where the oxygen concentration is as low as possible. That is, the oxygen concentration during vacuum ultraviolet irradiation is preferably in the range of 10 to 100,000 volume ppm, more preferably in the range of 50 to 50,000 volume ppm, and further preferably in the range of 100 to 10,000 volume ppm. Is.

When irradiating with vacuum ultraviolet rays, it is preferable to use a dry inert gas as the gas that satisfies the irradiation environment, and above all, it is preferable to use dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rates of the oxygen gas and the inert gas introduced into the irradiation environment and changing the flow rate ratio.

In the gas barrier film of the present invention, the coefficient of static friction between one surface of the gas barrier film and the other surface is preferably 0.30 or more and 2.0 or less.

The coefficient of static friction is measured by dividing a gas barrier film having an upper surface and a lower surface into two sheets and bringing the upper surface of the first gas barrier film into contact with the lower surface of the second gas barrier film. Can be done. The coefficient of static friction conforms to the inclination method of JIS P 8147 and can be measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH%.

To adjust the coefficient of static friction, the surface roughness of both sides of the gas barrier film may be adjusted. For example, when the inorganic thin film layer is provided on only one surface of the base material layer, the surface roughness of the exposed surface of the inorganic thin film layer and the surface roughness of the exposed surface of the base material layer may be adjusted. When the inorganic thin film layer is provided on both surfaces of the base material layer, the surface roughness of the exposed surface of one inorganic thin film layer and the surface roughness of the exposed surface of the other inorganic thin film layer may be adjusted. Increasing the surface roughness of at least one surface of the gas barrier film tends to reduce the coefficient of static friction between the front and back surfaces.

The surface roughness of the inorganic thin film layer can be changed, for example, according to the conditions such as the pressure (vacuum degree) in the vacuum chamber and the film thickness in the film forming conditions of the inorganic thin film layer, and the composition of the inorganic thin film layer. Further, the surface roughness of the inorganic thin film layer adjusts the surface roughness of the underlying flexible base material and the surface roughness of the intermediate layer arranged between the inorganic thin film layer and the flexible base material. Can also be adjusted by.

In order to adjust the surface roughness of the flexible substrate, a treatment such as a corona treatment may be performed.

The arithmetic average roughness Ra of the surface of the inorganic thin film layer can be 3 nm or less. The arithmetic mean roughness Ra can be obtained by attaching a gas barrier film to an epoxy plate with an adhesive and then observing the surface thereof with a white interference microscope. The arithmetic mean roughness Ra is the arithmetic average roughness according to JIS B 0601: 2001.

Further, in the gas barrier film according to the present embodiment, when a 50 mm square portion cut out from the gas barrier film is placed so that the central portion of the portion is in contact with the horizontal plane, the average distance from the horizontal plane to the four corners warped is average. The value is 2 mm or less.

This average value can be measured as follows. First, the gas barrier film is held at a temperature of 23 ° C. and a humidity of 50 RH% for 48 hours. Next, a 50 mm square portion is cut out from the gas barrier film to obtain a sample. The sample is placed on the horizontal plane so that the central portion of the sample is in contact with the horizontal plane, and a total of 4 points are obtained from the horizontal plane to the four corners. Finally, the average value of these four points is obtained.

In order to reduce the warp of the gas barrier film and improve the flatness, balance the stress of each inorganic thin film layer on the front and back surfaces, or balance the stress of the inorganic thin film layer on one side and the coating layer under it. Alternatively, the residual stress of the inorganic thin film layer itself may be reduced, or these may be combined to balance the stresses on both sides. The stress can be adjusted by the film forming pressure at the time of forming the inorganic thin film layer, the film thickness, the degree of curing shrinkage at the time of forming the coating layer, and the like.

The water vapor transmission rate of the gas barrier film of the present invention at 40 ° C. and 90% RH ^{can be 0.1 g / m 2} / day or less, and may be 0.001 g / m ² / day or less. Moisture vapor transmission rate can be measured by the Ca corrosion test method according to ISO / WD 15106-7 (Annex C).

The layer structure of the gas barrier film of the present invention is not particularly limited as long as it includes the base material layer and the inorganic thin film layer. When the gas barrier film of the present invention has an organic layer A and / or an organic layer B, it may have one organic layer A and / or one organic layer B, or two or more organic layers. It may have A and / or two or more organic layers B. When having two or more organic layers A, the same organic layer A may be provided in two or more layers, or two or more types of organic layers A may be provided in two or more layers. The same applies to the organic layer B. Further, the organic layer A and the organic layer B may be the same layer or may be different layers from each other. As an example of the layer structure, specifically, it may be a two-layer structure of a flexible base material / an inorganic thin film layer (a structure shown in FIG. 1), or a flexible base material / organic layer A /. It may have a three-layer structure such as an inorganic thin film layer (configuration shown in FIG. 2), an inorganic thin film layer / a flexible substrate / an inorganic thin film layer, or a flexible substrate / organic layer A / an inorganic thin film layer. It may have a four-layer structure such as / organic layer B (configuration shown in FIG. 3), inorganic thin film layer / flexible substrate / organic layer A / inorganic thin film layer, or inorganic thin film layer / organic layer A /. Flexible substrate / Organic layer A / Inorganic thin film layer, Organic layer B / Inorganic thin film layer / Flexible substrate / Organic layer A / Inorganic thin film layer / Organic layer B, Organic layer B / Inorganic thin film layer / Organic layer It may be composed of five or more layers such as A / flexible substrate / organic layer A / inorganic thin film layer / organic layer B. In addition to the layers described above, an additional layer C may be provided. Examples of such a layer C include a transparent conductive film layer and a color filter layer.

The gas barrier film of the present invention can be produced by a method of separately producing and bonding a base material layer and an inorganic thin film layer, a method of forming an inorganic thin film layer on the base material layer, or the like. From the viewpoint of easily increasing the denseness of the inorganic thin film layer and easily reducing defects such as fine voids and cracks, the organic layer laminated on the surface of the flexible base material or the flexible base material as described above. It is preferable to form the thin film layer on A by a known vacuum film forming method such as a CVD method using a glow discharge plasma. A further organic layer B may be formed on the laminated film thus obtained by a known method. The inorganic thin film layer is preferably formed by a continuous film forming process, and more preferably, for example, the inorganic thin film layer is continuously formed on the long base material while being continuously conveyed. Specifically, the inorganic thin film layer may be formed while transporting the flexible base material from the delivery roll to the take-up roll. After that, the feed-out roll and the take-up roll may be inverted and the base material may be conveyed in the opposite direction to form an inorganic thin film layer from above.

The gas barrier film of the present invention is a film having excellent gas barrier properties, in which deterioration of gas barrier properties over time is suppressed, especially under high temperature and high humidity. The gas barrier film of the present invention can be used for packaging foods, industrial products, pharmaceuticals and the like, which require gas barrier properties. The present invention also provides a flexible electronic device having the gas barrier film of the present invention. The gas barrier film of the present invention can also be used as a flexible substrate for a flexible electronic device (for example, a flexible display) such as a liquid crystal display element, a solar cell, and an organic EL display, which require higher gas barrier properties. When the gas barrier film of the present invention is used as a flexible substrate for an electronic device, the element may be formed directly on the gas barrier film of the present invention, or after the element is formed on another substrate, the present invention may be formed. The gas barrier film of the above may be overlapped from above.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Film thickness]
An inorganic thin film layer and an organic layer A are formed on a flexible substrate, and a step difference between a non-deposited portion and a film-formed portion is measured using a surf coder ET200 manufactured by Kosaka Laboratory Co., Ltd., and the film thickness of each layer is measured. (T) was requested.

[X-ray photoelectron spectroscopy measurement of the surface of the inorganic thin film layer]
The atomic number ratio of the surface of the inorganic thin film layer of the gas barrier film was measured by X-ray photoelectron spectroscopy (QuantaraSXM, manufactured by ULVAC-PHI, Inc.). An AlKα ray (1486.6 eV, X-ray spot 100 μm) was used as the X-ray source, and a neutralizing electron gun (1 eV) and a low-speed Ar ion gun (10 V) were used for charge correction at the time of measurement. For post-measurement analysis, spectral analysis was performed using MultiPak V6.1A (ULVAC-PHI, Inc.), and Si 2p, O 1s, N 1s and C 1s obtained from the measured wide scan spectrum, respectively. The surface atomic number ratio of C to Si was calculated using the peak corresponding to the binding energy of. As the surface atomic number ratio, the average value of the values measured five times was adopted.

[Infrared spectroscopy of the surface of the inorganic thin film layer (ATR method)]
Infrared spectroscopy of the surface of the inorganic thin film layer of the gas barrier film is performed by a Fourier transform infrared spectrophotometer (FT / IR, manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an ATR attachment (PIKE MIRacle) that uses germanium crystals for the prism. -Measured by 460Plus).

[Optical characteristics of gas barrier film]
The total light transmittance of the gas barrier film was measured by a direct reading haze computer (model HGM-2DP) manufactured by Suga Test Instruments Co., Ltd. After performing background measurement without a sample, a gas barrier film was set in the sample holder and measurement was performed to determine the total light transmittance.

[Gas barrier property]
The gas barrier property was measured by the Ca corrosion test method in accordance with ISO / WD 15106-7 (Annex C) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH, and the water vapor transmission rate of the gas barrier property film was determined.

[Manufacturing method of inorganic thin film layer]
An inorganic thin film layer was laminated on the base material layer using the manufacturing apparatus shown in FIG. Specifically, as shown in FIG. 5, in some cases, a resin film base material having an organic layer A is attached to a delivery roll 6, and a magnetic field is applied between the film forming roll 8 and the film forming roll 9. At the same time, power is supplied to the film forming roll 8 and the film forming roll 9, respectively, and plasma is generated by discharge between the film forming roll 8 and the film forming roll 9, and the film forming gas (deposition gas) is generated in such a discharge region. A mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (which also functions as a discharge gas) as a reaction gas) is supplied, and a thin film is formed by the plasma CVD method under the following film forming conditions. An inorganic thin film layer was laminated on the base material layer.
<Film formation condition 1>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.4 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed; 3.0 m / min
Number of passes: 28 times

[Adhesion between the base material layer and the inorganic thin film layer]
Adhesion was measured according to ASTM D3359. Specifically, a gas barrier film is placed on a clean glass substrate so that the inorganic thin film layer is on the opposite side of the glass substrate, and a cutter guide and a cutter knife are used to reach the base material on the inorganic thin film layer. Make 6 x 6 (25 squares) cuts. A tape (manufactured by Nichiban Co., Ltd., cellophane tape, CT-12M) is attached flatly to the grid portion (cross cut portion) due to the cut so that air bubbles do not enter over the grid portion + 20 mm. The attached tape is peeled off at an angle of 60 ° in 0.5 to 1 second, and the state of the grid portion is observed using a microscope (for example, DIGITAL MICROSCOPE KH7700 manufactured by Hirox Co., Ltd.) to obtain adhesion. The degree was evaluated according to the following evaluation criteria.
(Evaluation criteria for adhesion)
0B: Area ratio where peeling occurred in the cross-cut part 65% or more 1B: Area ratio where peeling occurred in the cross-cut part 35% to 65%
2B: Area ratio where peeling occurred in the cross-cut part 15% to 35%
3B: Area ratio where peeling occurred in the cross-cut part 5% to 15%
4B: Area ratio where peeling occurred in the cross-cut part 5% or less 5B: Area ratio where peeling occurred in the cross-cut part 0%

[Moist heat endurance time]
Durability was evaluated using a constant temperature and humidity controller (KCL-2000W type manufactured by Tokyo University of Science, Inc.) under the conditions of 85 ° C. and 85% RH. The measurement was performed at a frequency of 24 hours, 48 hours, 72 hours, 96 hours, 192 hours, 312 hours, 504 hours, 768 hours, and 1008 hours, and the time when peeling / cracking of 200 μm or more was observed in the cross-sectional observation was moist heat. The endurance limit time was set, and the observation time immediately before that was set as the moist heat endurance time. It can be said that the longer it takes for the peeling / cracking of 200 μm or more to be observed, the higher the durability over time under high temperature and high humidity conditions, and the higher the effect of suppressing the deterioration of the gas barrier property over time.

[Evaluation of defects]
In order to observe and measure the region where peeling / cracks exist in the inorganic thin film layer and the region where peeling / cracks exist in the inorganic thin film layer after storage under high temperature and high humidity conditions, a microscope (manufactured by Hirox Co., Ltd., DIGITAL) The cut end face was observed at a magnification of 210 times using MICROSCOPE KH7700). For the length of peeling / cracking, the length of peeling / cracking, which is the maximum distance from the cut end face in the normal direction (perpendicular to the cross section), was used as the length of the region where the defect exists for all the cut end faces of the cut sample. ..

[Example 1]
One side of a cycloolefin polymer film (COP film, thickness: 50 μm, width: 350 mm, manufactured by Nippon Zeon Co., Ltd., trade name “Zeonoa (registered trademark) film, ZF-16”), which is a flexible substrate, is treated with corona. Then, coating agent 1 (manufactured by Toyochem Co., Ltd., Rio Duras (registered trademark) TYAB500LC3NS, containing particles) was applied by a gravure coating method, dried at 100 ° C. for 3 minutes, and then used with a high-pressure mercury lamp. The organic layer A1 (easy-slip layer) having a thickness of 1.5 μm was laminated by irradiating with ultraviolet rays under the condition of an integrated light amount of 500 mJ / cm ^2. Next, after corona treatment is applied to the other surface of the COP film, coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toagosei Co., Ltd.) is applied by a gravure coating method and dried at 100 ° C. for 3 minutes. Then, using a high-pressure mercury lamp ^{, ultraviolet rays are irradiated under the condition of an integrated light amount of 500 mJ / cm 2} , and an organic layer A2 (flattening layer) having a thickness of 1.8 μm is laminated to form a laminated film as a base material layer. Obtained. An inorganic thin film layer was laminated on the surface of the laminated film thus obtained on the organic layer A2 side according to the above-mentioned method for producing an inorganic thin film layer. Next, a protective film (manufactured by Sanei Kaken Co., Ltd., NSA-35H, PET 50 μm) was attached to both sides of the film on which the inorganic thin film layer was laminated, and then 50 mm × 50 mm □ manufactured by Danberu Co., Ltd. using a super straight cutter. The gas barrier film 1 was obtained by punching to the size of. When the wet and heat endurance time was measured for the obtained test piece, peeling and cracking of 200 μm or more were observed in the cross-sectional observation for 768 hours after storage.

The obtained gas barrier film has oxygen, silicon, and carbon in the order of oxygen, silicon, and carbon in the region of 90% or more in the film thickness direction of the inorganic thin film layer from the one having the largest atomic number ratio, and the carbon distribution curve in the film thickness direction. The absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve was 5% or more.

In addition, XPS depth profile measurement is performed, and the average atomic concentration in the thickness direction of each atom is obtained from the obtained distribution curves of silicon atom, oxygen atom and carbon atom, and then the average atomic number ratio C / Si and O / As a result of calculating Si, the average atomic number ratio was C / Si = 0.30 and O / Si = 1.73. Further, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changed continuously in the film thickness direction of the inorganic thin film layer.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent value): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI Co., Ltd., model name "Quantera SXM"
Irradiated X-rays: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

The inorganic thin film layer of the obtained gas barrier film was subjected to infrared spectroscopic measurement under the above conditions. From the obtained infrared absorption spectrum, a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the peak intensity existing in 1240~1290cm ^-1 _{(I 2)} and the absorption intensity ratio of _(I 2 / I ₁ ) Was obtained, and it was _{I 2} / I _{1 = 0.03.} Further, a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the determined peak intensities present in 770~830cm ^-1 _{(I 3)} and the absorption intensity ratio of the _{(I 3 / I 1),} I 3 / I ₁ = 0.36.
Also, a peak intensity existing in 770~830cm ^-1 _{(I 3),} the determined absorption intensity ratio of the peak intensity _{(I 4)} that exists in 870～910Cm ^-1 to _{(I 4 / I 3),} I 4 / I ₃ = 0.84.

The thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 μm. The water vapor transmission rate of the obtained gas barrier film under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 × 10 ⁻⁵ g / (m ² · day).

[Example 2]
A film on which an inorganic thin film layer obtained in the same manner as in Example 1 was laminated was subjected to laser processing (manufactured by M-Rays, small excimer laser, output 6 mJ / cm ² , frequency 500 Hz, processing speed 2 mm / sec) to 50 mm × 50 mm. A gas barrier film 2 was obtained by cutting into a size of □. When the wet and heat endurance time was measured for the obtained test piece, peeling and cracking of 200 μm or more were observed in the cross-sectional observation for 768 hours after storage.

[Example 3]
In Example 1, the gas barrier film 3 was obtained in the same manner as in Example 1 except that the following <deposition condition 2> and <deposition condition 3> were continuously carried out as the film forming conditions for the inorganic thin film layer. rice field.
When the wet and heat endurance time was measured for the obtained test piece, peeling and cracking of 200 μm or more were observed in the cross-sectional observation for 1008 hours after storage.
<Film formation condition 2>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.6 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed; 3.0 m / min
Number of passes: 4 times <Film formation condition 3>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Oxygen gas supply: 500 sccm
Vacuum degree in vacuum chamber: 1Pa
Power applied from the plasma generation power supply: 0.4 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed; 3.0 m / min
Number of passes: 24 times

The obtained gas barrier film has oxygen, silicon, and carbon in the order of oxygen, silicon, and carbon in the region of 90% or more in the film thickness direction of the inorganic thin film layer from the one having the largest atomic number ratio, and the carbon distribution curve in the film thickness direction. The absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve was 5% or more.

In addition, XPS depth profile measurement is performed, and the average atomic concentration in the thickness direction of each atom is obtained from the obtained distribution curves of silicon atom, oxygen atom and carbon atom, and then the average atomic number ratio C / Si and O / As a result of calculating Si, the average atomic number ratio was C / Si = 0.30 and O / Si = 1.73. Further, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changed continuously in the film thickness direction of the inorganic thin film layer.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent value): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI Co., Ltd., model name "Quantera SXM"
Irradiated X-rays: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

The thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 μm. The water vapor transmission rate of the obtained gas barrier film under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 × 10 ⁻⁵ g / (m ² · day).

[Comparative Example 1]
In Example 1, the coating agent 2 (Aronix (registered trademark) UV3701 manufactured by Toagosei Co., Ltd.) was applied by a gravure coating method and dried at 120 ° C. for 3 minutes in the same manner as in Example 1. , A gas barrier film 4 was obtained. When the wet and heat endurance time was measured for the obtained test piece, peeling and cracking of 200 μm or more were observed in the cross-sectional observation 48 hours after storage.

The obtained gas barrier film has oxygen, silicon, and carbon in the order of oxygen, silicon, and carbon in the region of 90% or more in the film thickness direction of the inorganic thin film layer from the one having the largest atomic number ratio, and the carbon distribution curve in the film thickness direction. The absolute value of the difference between the maximum value and the minimum value of the atomic number ratio of carbon in the carbon distribution curve was 5% or more.

In addition, XPS depth profile measurement is performed, and the average atomic concentration in the thickness direction of each atom is obtained from the obtained distribution curves of silicon atom, oxygen atom and carbon atom, and then the average atomic number ratio C / Si and O / As a result of calculating Si, the average atomic number ratio was C / Si = 0.30 and O / Si = 1.73. Further, the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changed continuously in the film thickness direction of the inorganic thin film layer.
<XPS depth profile measurement>
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide film equivalent value): 0.027 nm / sec
Spatter time: 0.5 min
X-ray photoelectron spectrometer: ULVAC-PHI Co., Ltd., model name "Quantera SXM"
Irradiated X-rays: Single crystal spectroscopy AlKα (1486.6 eV)
X-ray spot and its size: 100 μm
Detector: Pass Energy 69eV, Step size 0.125eV
Charge correction: Neutralizing electron gun (1eV), low-speed Ar ion gun (10V)

The thickness of the inorganic thin film layer of the obtained gas barrier film was 0.7 μm. The water vapor transmission rate of the obtained gas barrier film under the conditions of a temperature of 40 ° C. and a humidity of 90% RH was 5.0 × 10 ⁻⁵ g / (m ² · day).
[Comparative Example 2]
Using a cutter knife (manufactured by KOKUYO Co., Ltd., cutter knife (standard type), spare blade HA-100B), a film obtained by laminating an inorganic thin film layer obtained in the same manner as in Example 1 was used to form a film having a size of 50 mm × 50 mm □. It was cut into a size to obtain a gas barrier film 5. When the wet and heat endurance time was measured for the obtained test piece, peeling and cracking of 200 μm or more were observed in the cross-sectional observation 96 hours after storage.

With respect to the gas barrier films 1 to 5 obtained as described above, the adhesion and the wet heat endurance time were measured and the defects were evaluated according to the above measuring method. The obtained results are shown in Table 1 below.

1 Gas barrier film 2 Base material layer 20 Flexible base material 21 Organic layer A
3 Inorganic thin film layer 4 Organic layer B
5 distance a
6 Sending roll 7 Conveying roll 8 Film forming roll 9 Film forming roll 10 Gas supply pipe 11 Plasma generation power supply 12 Magnetic field generator 13 Winding roll 14 Film

Claims (12)

A gas barrier film having at least a base material layer containing at least a flexible base material and an inorganic thin film layer, wherein the base material layer is an organic layer laminated on one surface of the flexible base material. A1 includes an easy-slip layer, and the organic layer A2 laminated on the surface of the other inorganic thin film layer includes a flattening layer.
The adhesion between the base material layer and the inorganic thin film layer is 2B or more as measured according to ASTM D3359.
The inorganic thin film layer has at least one cut end face and has at least one defect selected from the group consisting of peeling and cracking, or does not have the defect, where the inorganic thin film layer is said to be said. If having a defect, the existence region state, and are within the range of not less than 120μm in the normal direction from the cut edge,
The limit time of moist heat endurance in which peeling / cracking of 200 μm or more was observed in cross-sectional observation under the conditions of 85 ° C. and 85% RH is 96 hours or more.
Gas barrier film. The gas barrier film according to claim 1, wherein the inorganic thin film layer contains at least a silicon atom, an oxygen atom, and a carbon atom. The gas barrier film according to claim 2 , wherein the atomic number ratio of carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer changes continuously in the film thickness direction of the inorganic thin film layer. .. The gas barrier film according to claim 2 or 3 , wherein the inorganic thin film layer has an average atomic number ratio of carbon atoms (C) to silicon atoms (Si) in the inorganic thin film layer in the range of the formula (1).
0.10 <C / Si <0.50 (1) The distance from the surface of the inorganic thin film layer in the film thickness direction of the inorganic thin film layer, the atomic number ratio of silicon to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the inorganic thin film layer at each distance, and oxygen. In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the atomic number ratio of carbon and the atomic number ratio of carbon, conditions (i) and (ii):
(I) In the region where the atomic number ratio of silicon, the atomic number ratio of oxygen and the atomic number ratio of carbon are 90% or more in the film thickness direction of the inorganic thin film layer, the formula (5):
Atomic number ratio of oxygen> Atomic number ratio of silicon> Atomic number ratio of carbon (5)
The gas barrier film according to any one of claims 2 to 4 , wherein the gas barrier film satisfies, and (ii) the carbon distribution curve has at least one extremum. The gas barrier film according to any one of claims 1 to 5 , which has the inorganic thin film layer on both sides of the base material layer. A flexible electronic device having the gas barrier film according to any one of claims 1 to 6. When the surface of the inorganic thin film layer was measured by ATR method infrared spectroscopy, a peak intensity existing in 950~1050cm ^-1 _{(I 1),} the peak intensity existing in 1240～1290Cm ^-1 and _{(I 2)} The gas barrier film according to any one of claims 1 to 6 , wherein the strength ratio of the above is in the range of the formula (2).
0.01 ≤ I ₂ / I ₁ <0.05 (2) Wherein when the inorganic thin film layer surface was measured by ATR method infrared spectroscopy, a peak exists in 950～1050Cm ^-1 intensity _{(I 1),} the peak intensity _{(I 3)} present in 770～830Cm ^-1 and the The gas barrier film according to any one of claims 1 to 6 and 8 , wherein the strength ratio is in the range of the formula (3).
0.25 ≤ I ₃ / I ₁ ≤ 0.50 (3) Wherein when the inorganic thin film layer surface was measured by ATR method infrared spectroscopy, a peak exists in 770～830Cm ^-1 intensity _{(I 3),} the peak intensity _{(I 4)} that exists 870～910Cm ^-1 and the The gas barrier film according to any one of claims 1 to 6 , 8 and 9 , wherein the strength ratio is in the range of the formula (4).
0.70 ≤ I ₄ / I ₃ <1.00 (4) The method for producing a gas barrier film according to any one of claims 1 to 6.
For a gas barrier film having at least a base material layer containing at least a flexible base material and an inorganic thin film layer.
After attaching protective films on both sides, cut with a Thomson type punching machine, super cutter, cross cutter, guillotine cutting, shear cutter, rotary die cutter, press cutter, or
Processed by ablation using a laser,
Here, the base material layer includes an easy-slip layer as the organic layer A1 laminated on one surface of the flexible base material, and is an organic layer laminated on the surface of the other inorganic thin film layer side. A method comprising a flattening layer as A2 and having an adhesion between the substrate layer and the inorganic thin film layer of 2B or greater as measured according to ASTM D3359. The method according to claim 11, wherein the super cutter is a super straight cutter.

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