Gas barrier film and packaging film

Abstract

The present invention relates to a gas barrier film (1A) comprising: a base material layer (10) and a gas barrier layer (20) provided on at least one surface of the base material layer (10); and containing an inorganic oxide film including silicon (Si) and oxygen (O). The average value of the atomic number density of hydrogen (H), measured by a recoil particle detection method for the gas barrier layer (20), in a range from a position corresponding to 10% to a position corresponding to 50% of the film thickness of the gas barrier layer (20) in the depth direction from the surface of the gas barrier layer (20), is 1.0 × 1022 atoms / cm3 or less.

Description

Gas barrier films and packaging films

[0001] The present invention relates to a gas barrier film, and more particularly to a gas barrier film suitable for packaging food, pharmaceuticals, precision electronic components, etc. This application claims priority based on Japanese Patent Application No. 2025-068012, filed in Japan on April 17, 2025, the contents of which are incorporated herein by reference.

[0002] Packaging materials used for packaging bags containing contents such as food and pharmaceuticals require gas barrier properties to block oxygen, water vapor, and other gases from permeating the packaging material, in order to suppress deterioration of the contents and maintain their function or properties. Gas barrier packaging materials that possess gas barrier properties include gas barrier films, which are made by laminating a metal foil such as aluminum as a gas barrier layer to a base material.

[0003] Other gas barrier films are known in which an inorganic oxide film, such as aluminum oxide or silicon oxide, is formed as a gas barrier layer on a substrate film made of polymer material by vacuum deposition or sputtering (see, for example, Patent Documents 1 and 2).

[0004] These films possess both transparency and gas barrier properties, which cannot be obtained with metal foils, and are therefore suitable for use as packaging materials. Among these films, gas barrier films equipped with a gas barrier layer formed by depositing silicon dioxide are particularly widely used as food packaging films. Furthermore, when silicon dioxide is used as a deposition material and deposited by a heating method, the film formation rate is fast, and productivity can be increased.

[0005] As a gas barrier film that enhances the gas barrier properties of a gas barrier film compared to a gas barrier film having a gas barrier layer formed by depositing silicon dioxide, a gas barrier film having a gas barrier layer in which other metal oxides are added to silicon dioxide is known. As such a gas barrier film, for example, a gas barrier film has been proposed in which an inorganic oxide thin film, in which other inorganic substances or inorganic oxides are added to silicon dioxide, is laminated on a plastic film (see, for example, Patent Document 3).

[0006] Japanese Unexamined Patent Publication No. 60-049934 Japanese Unexamined Patent Publication No. 3-100164 Japanese Unexamined Patent Publication No. 6-016848

[0007] However, gas barrier films with a silicon dioxide-containing gas barrier layer had the problem that variations in water vapor barrier properties tended to be relatively large.

[0008] Based on the above circumstances, the present invention aims to provide a gas barrier film that can suppress variations in water vapor barrier properties.

[0009] One aspect of the present invention comprises a base layer and a gas barrier layer provided on at least one surface of the base layer, the gas barrier layer being an inorganic oxide film containing silicon (Si) and oxygen (O), wherein the average value of the number density of hydrogen (H) in the gas barrier layer, measured by a recoil particle detection method, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer is 1.0 × 10⁻¹⁴. ２２ atoms / cm ３ The following is a gas barrier film.

[0010] Aspect 2 of the present invention is a gas barrier film according to aspect 1 of the present invention, wherein the average value of the silicon (Si) to oxygen (O) composition ratio O / Si of the gas barrier layer, measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 1.00 or more and 1.90 or less.

[0011] A third aspect of the present invention is a gas barrier film according to the first aspect of the present invention, wherein the inorganic oxide film further comprises tin (Sn).

[0012] Aspect 4 of the present invention is a gas barrier film according to aspect 3 of the present invention, wherein the average value of the silicon (Si) to tin (Sn) composition ratio Sn / (Si+Sn), measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 0.03 or more and 0.80 or less.

[0013] Aspect 5 of the present invention is a gas barrier film according to aspect 3 of the present invention, wherein the average value of the composition ratio O / (Si + Sn) of silicon (Si), tin (Sn), and oxygen (O) of the gas barrier layer, measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 1.00 or more and 1.90 or less.

[0014] Aspect 6 of the present invention is a gas barrier film according to aspect 1 or 3 of the present invention, wherein the thickness of the gas barrier layer is 1 to 200 nm.

[0015] Aspect 7 of the present invention is a gas barrier film according to aspect 1 or 3 of the present invention, wherein the water vapor transmission rate is 3.0 g / (m²). ２ The value is less than 0.3 (day), and the standard deviation of the water vapor transmission rate is less than 0.3.

[0016] Aspect 8 of the present invention is a gas barrier film according to aspect 1 or 3 of the present invention, further comprising an overcoat layer formed on the side opposite to the substrate layer with respect to the gas barrier layer.

[0017] Aspect 9 of the present invention is a gas barrier film according to aspect 8 of the present invention, wherein the overcoat layer comprises at least one component selected from the group consisting of metal alkoxides, hydrolysates of metal alkoxides, reaction products of metal alkoxides, and reaction products of hydrolysates of metal alkoxides, and a water-soluble polymer.

[0018] Aspect 10 of the present invention is a gas barrier film according to aspect 8 of the present invention, wherein the overcoat layer comprises at least one component selected from the group consisting of a silane coupling agent, a hydrolysate of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolysate of a silane coupling agent.

[0019] Embodiment 11 of the present invention is a gas barrier film according to Embodiment 1 or 3 of the present invention, further comprising an undercoat layer formed between the substrate layer and the gas barrier layer, wherein the undercoat layer comprises at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins, ultraviolet curable resins and electron beam curable resins.

[0020] Aspect 12 of the present invention is a gas barrier film according to aspect 1 or 3 of the present invention, further comprising an undercoat layer formed between the substrate layer and the gas barrier layer, wherein the undercoat layer is made of a cured product of a composition containing an acrylic polyol resin and an isocyanate compound.

[0021] Aspect 13 of the present invention is a packaging film comprising a gas barrier film according to aspect 1 or 3 of the present invention and a sealant layer provided on the gas barrier film.

[0022] Embodiment 14 of the present invention comprises a base layer and a gas barrier layer provided on at least one surface of the base layer, the gas barrier layer being made of an inorganic oxide film containing silicon (Si) and oxygen (O), wherein the inorganic oxide film further contains tin (Sn), and the average value of the silicon (Si) to tin (Sn) composition ratio Sn / (Si+Sn) of the gas barrier layer, measured by Rutherford backscattering analysis of the gas barrier layer, in the range from the surface of the gas barrier layer to a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction, is 0.15 or more and 0.20 or less, and the gas barrier layer The average value of the composition ratio O / (Si+Sn) of silicon (Si), tin (Sn), and oxygen (O), measured by Rutherford backscattering analysis, in the range from the surface of the gas barrier layer to a depth corresponding to 20% to 80% of the thickness of the gas barrier layer, is 1.40 or more and 1.45 or less. The average value of the atomic number density of hydrogen (H), measured by recoil particle detection of the gas barrier layer, in the range from a depth corresponding to 10% to 50% of the thickness of the gas barrier layer, in the range from the surface of the gas barrier layer to a depth corresponding to 4.1 × 10⁻¹⁰ ２１ atoms / cm3 or more 6.0×10 ２１ atoms / cm ３ The following is a gas barrier film.

[0023] According to the present invention, it is possible to provide a gas barrier film that can suppress variations in water vapor barrier properties.

[0024] This is a schematic cross-sectional view of a gas barrier film according to the first embodiment of the present invention. This is a schematic diagram showing an example of a manufacturing apparatus for the gas barrier film. This is a schematic cross-sectional view of a gas barrier film according to the second embodiment of the present invention. This is a schematic cross-sectional view of a gas barrier film according to the third embodiment of the present invention.

[0025] Embodiments of the present invention will be described in detail below. For ease of understanding, the same reference numerals are used for identical components in each drawing, and redundant explanations are omitted. In this specification, the "~" indicating a numerical range means that the numbers before and after it are included as the lower and upper limits, respectively, unless otherwise specified. Furthermore, if only the upper limit of a numerical range represented by "~" has a unit specified, it means that the lower limit also has the same unit.

[0026] <First Embodiment> [Gas Barrier Film] A gas barrier film according to the first embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will be described. Figure 1 is a schematic cross-sectional view showing an example of a gas barrier film according to this embodiment. As shown in Figure 1, the gas barrier film 1A comprises a base layer 10 and a gas barrier layer 20 provided on one surface of the base layer 10 (the main surface located on the upper side in Figure 1). In the following description, the side on which the gas barrier layer 20 is located may be referred to as the upper side of the gas barrier film 1A, and the opposite side may be referred to as the lower side. This is for the convenience of explanation and is unrelated to the orientation of the gas barrier film when it is actually used.

[0027] The base layer 10 may contain and be composed of a synthetic resin. There are no particular restrictions on the synthetic resin used to form the base layer 10, and various known synthetic resins can be used. Examples of synthetic resins include polyolefins, polyesters (e.g., polyethylene terephthalate and polyethylene naphthalate), polyimides, polyamides (e.g., nylon-6, nylon-66), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, polyethersulfone, acrylic, and cellulose (e.g., triacetylcellulose and diacetylcellulose). These may be used individually or in combination of two or more. The synthetic resin used to form the base layer 10 may be appropriately selected according to the application and required physical properties. For example, when the gas barrier film 1A is used as packaging to protect contents that are extremely sensitive to moisture, such as electronic components and optical components, it is preferable to use materials with high gas barrier properties, such as polyethylene naphthalate, polyimides, and polyethersulfone.

[0028] The thickness of the base layer 10 is not particularly limited and can be appropriately set to, for example, 9 to 300 μm depending on the application. As long as the thickness of the base layer 10 is within this range, the base layer 10 has appropriate flexibility and can be wound into a roll, making it easy to handle.

[0029] In this specification, the thickness of the base layer 10 refers to the dimension in the direction perpendicular to the main surface of the base layer 10. The thickness of the base layer 10 may be determined by, for example, the value obtained by measuring at any point in the cross-section of the base layer 10, or by measuring at several points in any location and using the average value of these measurements. The definition of thickness shall be the same for other members below.

[0030] The base material layer 10 may be in the form of a long material or a single sheet, but a long material is preferably used. The length of the long base material layer 10 in the longitudinal direction is not particularly limited, but for example, a resin film of 10 m or more is preferably used. The upper limit of the length is not limited and may be, for example, about 10 km.

[0031] The base layer 10 may optionally contain additives such as antistatic agents, ultraviolet absorbers, plasticizers, or lubricants.

[0032] The surface of the substrate layer 10 may be subjected to physical treatments such as corona treatment, flame treatment, plasma treatment, or easy-adhesion treatment, or chemical modification treatments such as acid or alkali treatment, in order to improve adhesion with the gas barrier layer 20.

[0033] The surface of the substrate layer 10 is related to the density during the initial growth stage of vacuum deposition when forming the gas barrier layer 20. From this viewpoint, it is preferable that the surface of the substrate layer 10 be as smooth as possible.

[0034] The gas barrier layer 20 is a layer that plays a major role in the gas barrier properties exhibited by the gas barrier film 1A, and is a film made of an inorganic oxide film containing silicon (Si) and oxygen (O).

[0035] Rutherford backscattering analysis (hereinafter sometimes referred to as "RBS") can be used to analyze the gas barrier layer 20. RBS is a technique that irradiates the object to be measured with an ion beam such as helium (He) and analyzes the energy and intensity of the ions scattered behind the object by Rutherford scattering. RBS can analyze the composition and density of the object in the depth direction nondestructively.

[0036] In this embodiment, if the gas barrier layer 20 does not contain metal elements other than silicon (Si), it is preferable that the average value of the silicon (Si) to oxygen (O) composition ratio O / Si, measured by RBS, in the range from a position corresponding to 20% to 80% of the film thickness of the gas barrier layer 20 in the depth direction from the surface of the gas barrier layer 20 is 1.00 or more and 2.00 or less. Here, 0% in the depth direction means the surface of the gas barrier layer 20, and 100% in the depth direction means the interface position where the gas barrier layer 20 is in contact with the substrate layer 10. Considering the water vapor barrier properties and transparency of the gas barrier film 1A as a whole, it is more preferable that the average value of O / Si is 1.20 or more and 1.90 or less, and even more preferable that it is 1.30 or more and 1.80 or less. When the composition ratio O / Si measured by RBS is within the above range, the film composed of silicon (Si) and oxygen (O) in the main part of the depth direction of the gas barrier layer 20 has a dense structure that prevents the permeation of gas molecules and is a highly transparent film.

[0037] Furthermore, the average value of the O / Si composition ratio in the range from 20% to 80% of the film thickness of the gas barrier layer 20 in the depth direction from the surface of the gas barrier layer 20 can be calculated, for example, using seven measurement points taken at 10% film thickness intervals within this range. The number of measurement points is not limited to seven, but from the viewpoint of suppressing the influence of measurement variability, it is preferable to calculate the average value of the O / Si composition ratio using five or more measurement points. In addition, in RBS measurement, the boundary position between the base layer 10 and the gas barrier layer 20 (i.e., 100% depth) is defined as the position where the elemental concentration of elements such as silicon (Si), which is not included in the base layer 10 but is included only in the gas barrier layer 20, is half the average value in the range of 20% to 80% depth.

[0038] For example, RBS measurement can be performed under the following conditions. (RBS Analysis and ERDA Analysis of Gas Barrier Layer) The gas barrier layer is measured by RBS and ERDA. HRBS500 (manufactured by Kobe Steel, Ltd.) is used as the measuring apparatus. Fitting analysis is performed on the spectra measured by RBS and ERDA to obtain the element concentration and areal density in the depth direction. At this time, the density of the base material layer is assumed to be the density of the resin. The interface between the base material layer and the gas barrier layer is assumed to be a position that is 1 / 2 of the average value of 7 points when the Si concentration is measured in 10% increments from the surface up to 80%. Further, from the depth of each measurement point in the depth direction (unit: m) and the areal density at each measurement point (unit: atoms / cm ２ ), and the H concentration at each measurement point (unit: at%), the atomic number density of H at each measurement point (unit: atoms / cm ３ ) was calculated. At this time, the RBS measurement conditions are as follows. Incident ion: He ＋ (450 keV) Detected ion: Scattered He ＋ Scattering angle: 90° Incident angle: 45° In addition, the ERDA measurement conditions are as follows. Incident ion: N ＋ (480 keV) Detected ion: Recoiled H ＋ Scattering angle: 30° Incident angle: 70°

[0039] The surface of a gas barrier layer is affected by influences from other layers it comes into contact with and by oxidation from oxygen in the atmosphere. Therefore, the composition of the gas barrier layer surface tends to vary. On the other hand, the composition in the 20% to 80% depth range, which corresponds to the middle of the gas barrier layer's thickness, tends to be more stable. The inventors have found that by adjusting the composition ratio O / Si in the 20% to 80% depth range of the gas barrier layer to within this range, more stable water vapor barrier properties can be ensured. In measuring the O / Si composition ratio, the electron beam or X-rays applied to the sample during measurement can destroy the sample's own composition. Therefore, depending on the measurement method, it can be difficult to measure the true state of the sample. RBS is a non-destructive analysis method. Therefore, it can measure the true state of the sample. Consequently, by adjusting the composition ratio O / Si in the 20% to 80% depth range measured by RBS to within the above range, a gas barrier film exhibiting stable water vapor barrier properties can be manufactured.

[0040] The gas barrier layer 20 may be a film made of an inorganic oxide film containing silicon (Si), tin (Sn), and oxygen (O). When the gas barrier layer 20 is an inorganic oxide film containing silicon (Si), tin (Sn), and oxygen (O), the average value of the composition ratio Sn / (Si+Sn) of silicon (Si) and tin (Sn), measured by RBS, in the range of 20% to 80% depth of the gas barrier layer 20 is preferably 0.03 or more and 0.80 or less, more preferably 0.05 or more and 0.50 or less, and even more preferably 0.10 or more and 0.30 or less. In particular, from the viewpoint of optimizing the balance between water vapor barrier properties and refractive index to the highest degree, the average value is especially preferably 0.15 or more and 0.20 or less.

[0041] By ensuring that the composition ratio Sn / (Si+Sn) measured by RBS is within the above range, it is ensured that the gas barrier layer 20 is a dense film containing tin (Sn) in the main part in the depth direction. As a result, in addition to good water vapor barrier properties, the refractive index of the gas barrier layer 20 can be made to be about the same as the typical refractive index of 1.50 to 1.60 of the underlayer provided on the substrate. Therefore, good gas barrier properties and good optical properties can be achieved simultaneously.

[0042] When the gas barrier layer 20 is an inorganic oxide film containing silicon (Si), tin (Sn), and oxygen (O), the average value of the composition ratio O / (Si+Sn) of silicon (Si), tin (Sn), and oxygen (O), measured by RBS, in the range of 20% to 80% depth of the gas barrier layer 20 is preferably 1.00 or more and 2.00 or less. Considering the transparency of the gas barrier film 1A as a whole, it is more preferably 1.20 or more and 1.90 or less, and even more preferably 1.30 or more and 1.80 or less. In particular, from the viewpoint of achieving an extremely high level of both film density and transparency, the average value is especially preferably 1.40 or more and 1.45 or less.

[0043] The gas barrier layer 20 may contain at least one metal element (A) other than silicon (Si) or silicon (Si) and tin (Sn). The metal element (A) is not particularly limited. Examples of metal elements (A) include aluminum (Al), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), zinc (Zn), gallium (Ga), germanium (Ge), ytrim (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), indium (In), barium (Ba), hafnium (Hf), tungsten (W), tantalum (Ta), and bismuth (Bi). Among these, magnesium (Mg), aluminum (Al), gallium (Ga), tungsten (W), molybdenum (Mo), indium (In), and bismuth (Bi) are preferred because they provide good gas barrier properties and transparency when an oxide film is formed. More preferably, the metal element (A) is magnesium (Mg), aluminum (Al), or tungsten (W). Furthermore, the metal element (A) may be a combination of multiple types, not just one type. By including one or more metal elements (A) in addition to silicon (Si) and tin (Sn) in the gas barrier layer 20, it becomes possible to improve the gas barrier properties with respect to the base layer 10, improve temperature and humidity resistance, and adjust the refractive index.

[0044] The method for forming the gas barrier layer 20 is not particularly limited. Known film formation methods such as vacuum deposition, ion plating, sputtering, and plasma chemical vapor deposition (PECVD) can be used to form the gas barrier layer 20, but vacuum deposition is particularly preferred due to its superior productivity. For the vacuum deposition method, resistance heating, high-frequency induction heating, electron beam heating, etc., can be used as the material heating means. Furthermore, by combining plasma-assisted methods, ion beam-assisted methods, etc., the gas barrier layer 20 can be formed more densely, improving its barrier properties.

[0045] The gas barrier layer 20 formed by vacuum deposition has the advantage of easily achieving both gas barrier properties and elasticity. In particular, in packaging applications, external factors such as bending and stretching during processing of the packaging material, and impacts during transportation, can cause cracks in the gas barrier layer 20, potentially significantly reducing its gas barrier properties. Therefore, elasticity is required for the gas barrier layer 20. Films formed by vacuum deposition are formed through relatively large island-like structures during the film growth process. Therefore, films formed by vacuum deposition are slightly less dense than those formed by other methods such as sputtering, but they have excellent elasticity. In particular, when forming a film made of inorganic oxides containing silicon (Si), tin (Sn), and oxygen (O), a denser continuous film is more easily formed compared to a film made of inorganic oxides containing only silicon (Si) and oxygen (O), but the gas barrier properties tend to deteriorate due to insufficient elasticity. By forming an inorganic oxide film containing tin by vacuum deposition, the balance between density and elasticity can be controlled. In other words, from the viewpoint of achieving both gas barrier properties and stability, it is preferable to employ a vacuum deposition method as the method for forming the gas barrier layer 20 according to this embodiment.

[0046] When depositing the gas barrier layer 20 by vacuum deposition, the deposition environment is set so that the partial pressure value of m / z 18 measured with a partial pressure gauge (quadrupole mass spectrometer using a Faraday cup) is 0.05 Pa or less during deposition. If the partial pressure value of m / z 18 measured with the mass spectrometer during deposition exceeds 0.05 Pa, it is undesirable because it indicates a large amount of water molecules in the deposition atmosphere, resulting in a large amount of H bonding to Si. Here, m / z (more precisely, italicized) is defined as a dimensionless quantity obtained by dividing the mass of an ion by the unified atomic mass unit, and then further dividing that dimensionless quantity by the absolute value of the ion's charge number. It is the value used on the horizontal axis of the mass spectrum measured by a mass spectrometer. m / z is defined as an academic term by the International Union of Pure and Applied Sciences (IUPAC). m / z 18 refers to H related to water. ２ O ＋ The m / z value is derived from the ion. In addition to m / z 18, there are also fragment ions such as m / z 17 as ions related to water, but in this invention, H, which has the strongest spectral intensity, is used. ２ O ＋ The m / z 18 pressure originating from ions was used as an indicator. A typical method for adjusting the partial pressure of m / z 18 during film formation is to provide a mechanism for adsorbing gas in the film formation environment. For example, when forming a gas barrier layer using a film formation apparatus consisting of a film formation chamber and an unwinding / winding chamber, a gas (water vapor) condensation and adsorption device (hereinafter referred to as "gas adsorption device") is provided in the film formation chamber of the film formation apparatus, and also in the unwinding / winding chamber, particularly near the unwinding roll. This provides both the effect of reducing water vapor in the film formation chamber and the effect of reducing water vapor originating from moisture released from the substrate. As a result, the partial pressure of m / z 18 during film formation can be kept below 0.05 Pa. Meissner coils, cryopaneers, cryopumps, sorption pumps, ion pumps, and getter pumps are preferably used as gas adsorption devices. Meissner coils and cryopaneers are more preferably used because they allow for a larger adsorption area. For example, when using a Meissner coil or cryopanel, the cooling temperature is preferably -100°C or lower, and more preferably -110°C or lower, in order to obtain sufficient performance in condensing and adsorbing gases.

[0047] By adjusting the partial pressure of m / z 18 during film formation to the above range, the amount of water molecules present in the atmosphere during inorganic oxide film formation is reduced compared to a typical deposition process, resulting in a lower amount of OH in the inorganic oxide film. Furthermore, the amount of OH and H in water molecules that can bond with Si is also reduced. As a result of the reduced amount of Si-OH and Si-H bonds, the intermolecular gaps in the inorganic oxide film are reduced. Consequently, the entire surface of the gas barrier layer 20 becomes denser, improving the stability of the water vapor barrier properties exhibited.

[0048] The inventors further discovered that, in the case of an inorganic oxide film containing silicon (Si), tin (Sn), and oxygen (O), adjusting the partial pressure at m / z 18 during film formation to the above range significantly reduces the intermolecular gaps in the formed inorganic oxide film compared to a general vapor deposition process. The inclusion of tin (Sn) allows Sn to enter between the molecules of the formed inorganic oxide film, reducing the intermolecular gaps compared to a film made of SiOx. This also reduces the number of unbonded bonds. In addition, adjusting the partial pressure at m / z 18 during film formation to a predetermined range reduces the number of bonds terminated at Si-OH and Si-H. By achieving both of these, the amount of space for hydrogen and moisture to penetrate across the entire surface of the gas barrier layer 20 is reduced, allowing the gas barrier layer 20 to exhibit high water vapor barrier properties and further enhance its stability.

[0049] To analyze the above state in the gas barrier layer 20, the rebound particle detection method (hereinafter sometimes referred to as "ERDA") can be used. ERDA is a method that irradiates the object to be measured with helium (He) ions and analyzes the hydrogen (H) ions scattered in front of the object, allowing for non-destructive analysis of the hydrogen (H) concentration at a depth of several tens of nanometers from the surface of the object. Therefore, there is little fluctuation in hydrogen (H) due to damage during measurement, and the hydrogen concentration in the film can be analyzed relatively accurately.

[0050] The average value of the hydrogen (H) atomic number density of the gas barrier layer 20, measured by ERDA, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer 20 in the depth direction from the surface of the gas barrier layer 20, is 1.0 × 10⁻⁶. ２２ atoms / cm３ The following is true: 1.0 × 10 ２０ atoms / cm ３ The above 9.0 x 10 ２1 atoms / cm ３ It is more preferable that the following conditions apply: 1.0 × 10 ２０ atoms / cm ３ The above 8.0 x 10 ２1 atoms / cm ３ It is even more preferable that the following be the case. In particular, from the viewpoint of minimizing the possibility of hydrogen and moisture entering and completely suppressing variations in water vapor barrier properties, the average value is 4.0 × 10 ２１ atoms / cm ３ The above 6.0 x 10 ２１ atoms / cm ３ The following is particularly preferable: When the atomic number density of hydrogen (H) measured by ERDA is within the above range, it means that in the main part of the gas barrier layer 20 in the depth direction, there is less hydrogen (H) in the structure of the gas barrier layer 20 compared to when it is formed by a general deposition process. The area near the interface between the surface of the gas barrier layer and the substrate is susceptible to the influence of moisture in the atmosphere, and accurate measurement is difficult near the interface between the surface of the gas barrier layer and the substrate. On the other hand, the main part in the depth direction is not affected by moisture in the atmosphere from the surface side and the substrate side. In other words, when the atomic number density of hydrogen (H) measured by ERDA is within the above range, it means that the formed gas barrier layer has a dense structure with a small amount of Si-OH bonds and Si-H bonds. Such a gas barrier layer 20 exhibits stable water vapor barrier properties.

[0051] The average number density of hydrogen (H) atoms in the range from 10% to 50% depth from the surface of the gas barrier layer 20 can be calculated, for example, using measurements taken at multiple points spaced apart to correspond to 10% of the thickness of the gas barrier layer 20. Furthermore, it is preferable to calculate the average value using five or more measurements to suppress the influence of variability in the measurements taken at multiple points.

[0052] In this embodiment, the gas barrier layer 20 is preferably amorphous. Because the gas barrier layer 20 is an amorphous film, it is a film without grain boundaries, which occur in the case of a polycrystalline film, thus reducing the permeation paths of gas molecules. Whether or not the gas barrier layer 20 is amorphous can be evaluated by known methods. For example, it can be evaluated by checking whether or not the X-ray diffraction pattern obtained by X-ray diffraction has crystalline diffraction peaks.

[0053] The thickness of the gas barrier layer 20 varies depending on the configuration and film deposition method used, but a general thickness is acceptable. The thickness of the gas barrier layer 20 may be appropriately set within the range of 1 to 200 nm, for example. If the thickness of the gas barrier layer 20 is 1 nm or more, a film with uniform thickness is easily obtained, and since the thickness is sufficient, the gas barrier layer 20 can fully exhibit gas barrier properties, particularly water vapor barrier properties. If the thickness of the gas barrier layer 20 is 200 nm or less, cracks due to external factors such as bending or stretching are less likely to occur after film deposition, and gas barrier properties, particularly water vapor barrier properties, can be maintained. The thickness of the gas barrier layer 20 is preferably in the range of 5 to 150 nm, and more preferably in the range of 10 to 120 nm.

[0054] The method for manufacturing the gas barrier film 1A is not particularly limited and can be manufactured using a general gas barrier film manufacturing apparatus (hereinafter simply referred to as "gas barrier film manufacturing apparatus"). An example of a gas barrier film manufacturing apparatus is shown in Figure 2. As shown in Figure 2, the gas barrier film manufacturing apparatus 100 includes an unwinding and winding chamber 101, a film deposition chamber 102, an unwinding roll 103, a film deposition roll 104, a winding roll 105, an electron beam gun 106, and a gas adsorption device 107. The gas barrier film manufacturing apparatus 100 may have an unwinding roll 103, a film deposition roll 104, and a winding roll 105 in the unwinding and winding chamber 101, and an electron beam gun 106 in the vacuum film deposition chamber 102. The unwinding and winding chamber 101 and the film deposition chamber 102 are separated by a partition wall. The unwinding and winding chamber 101 and the film deposition chamber 102 each have an exhaust system such as an exhaust port (not shown). In the gas barrier film manufacturing apparatus 100, when in use, the plastic film PF which will become the base layer 10 is set on the unwinding roll 103 in the unwinding and winding chamber 101, and a container 108 containing the vapor deposition material VM for forming the gas barrier layer 20 is set in the film formation chamber 102.

[0055] The unwinding and winding chamber 101 is a space that houses the unwinding roll 103, the film-forming roll 104, and the winding roll 105. In the unwinding and winding chamber 101, the plastic film PF is unwound, and after a gas barrier layer 20 is formed on the surface of the plastic film PF, it is wound up.

[0056] The vacuum deposition chamber 102 is a space in which deposition particles VP are deposited onto the plastic film PF exposed from the unwinding and winding chamber 101 by the deposition roll 104 to form a gas barrier layer 20. The deposition chamber 102 is configured to be able to form a vacuum state.

[0057] The unwinding roll 103 is a roll for setting the plastic film PF, and unwinds the plastic film PF into the unwinding and winding chamber 101.

[0058] The film-forming roll 104 is positioned so that a portion of it is exposed into the film-forming chamber 102, and a portion of the plastic film PF unwound from the unwinding roll 103 is exposed into the film-forming chamber 102.

[0059] The winding roll 105 winds up the plastic film PF that is conveyed from the film-forming roll 104.

[0060] The electron beam gun 106 is a heating means for heating the deposition material VM in the deposition chamber 102.

[0061] The gas adsorption device 107 is a device that has the function of condensing or adsorbing gases such as water vapor. The gas adsorption device 107 is not particularly limited as long as it is a device that can condense or adsorb gases. As the gas adsorption device 107, for example, a Meissner coil, a cryopanel, a cryopump, a sorption pump, an ion pump, and a getter pump are preferably used, and a Meissner coil and a cryopanel are more preferably used because they can increase the adsorption area. For example, when using a Meissner coil or a cryopanel, it is preferable that the cooling temperature is -100°C or lower in order to obtain sufficient performance in condensing or adsorbing gases.

[0062] The gas adsorption device 107 may include a gas adsorption device 107A provided in the unwinding and winding chamber 101 and a gas adsorption device 107B provided in the film formation chamber 102. The gas adsorption device 107A may be provided near the unwinding roll 103 in the unwinding and winding chamber 101. This makes it easier to adsorb water vapor originating from moisture released from the plastic film PF. The gas adsorption device 107B may be provided as a set in the film formation chamber 102 via a container 108 containing the deposition material VM. This makes it easier to reduce the amount of water vapor around the deposition material VM in the film formation chamber 102. That is, it makes it easier to set the partial pressure value of m / z 18 during film formation to 0.05 Pa or less.

[0063] After the plastic film PF is set on the unwinding roll 103 in the unwinding and winding chamber 101, the plastic film PF is pulled out from the unwinding roll 103, passes through the film deposition roll 104 exposed in the film deposition chamber 102, and is then wound onto the winding roll 105. Inside the film deposition chamber 102, the deposition material VM, heated by the electron beam from the electron beam gun 106, becomes vapor deposition particles VP and is deposited onto the plastic film PF. As a result, a gas barrier layer 20 made of the deposition material VM is formed on the plastic film PF.

[0064] In the gas barrier film manufacturing apparatus 100 shown in Figure 2, an electron beam deposition method using an electron beam gun 106 is used to heat the deposition material VM. However, the deposition material VM may also be heated and evaporated using a resistance heating method or a high-frequency induction heating method. Furthermore, the resistance heating method may involve directly resistively heating a crucible filled with the deposition material VM, or it may be a different method.

[0065] The configuration of the gas barrier film manufacturing apparatus is not limited to the configuration shown in Figure 2 above. If necessary, a plasma pretreatment device may be installed in the unwinding and winding chamber 101, or a reaction gas introduction device may be installed in the film deposition chamber. The arrangement of the unwinding roll 103, film deposition roll 104, and winding roll 105 is also not particularly limited and may be placed in any location as appropriate.

[0066] The water vapor transmission rate of gas barrier film 1A is 3.0 g / (m²). ２ It is preferable that the amount is less than 2.0 g / (m²) per day. ２ It is more preferable that the amount is less than or equal to 1.50 g / (m²) per day. ２ It is even more preferable that the value is less than or equal to (day). The water vapor transmission rate of the gas barrier film 1A largely depends on the water vapor transmission rate of the gas barrier layer 20. As a result, by lowering the water vapor transmission rate of the gas barrier layer 20, the water vapor transmission rate of the gas barrier film 1A can be lowered. By lowering the water vapor transmission rate of the gas barrier layer 20 and making the water vapor transmission rate of the gas barrier film 1A less than the above preferred value, the water vapor transmission rate of the gas barrier film 1A can be lowered, and the water vapor barrier properties of the gas barrier film 1A can be improved.

[0067] Furthermore, the water vapor transmission rate can be measured, for example, using a general water vapor transmission rate measuring device, or it may be measured in accordance with JIS K 7129-2 "Plastics - Films and sheets - Method for determining water vapor transmission rate - Part 2: Infrared sensor method".

[0068] Furthermore, the standard deviation of the water vapor transmission rate of the gas barrier film 1A is preferably less than 0.30, more preferably less than 0.20, and even more preferably less than 0.15. The standard deviation of the water vapor transmission rate of the gas barrier film 1A is also largely dependent on the standard deviation of the water vapor transmission rate of the gas barrier layer 20. Therefore, by lowering the standard deviation of the water vapor transmission rate of the gas barrier layer 20, the standard deviation of the water vapor transmission rate of the gas barrier film 1A is set to less than the above preferred values. This makes it possible to keep the variation in the water vapor transmission rate throughout the gas barrier film 1A small, and improves the uniformity of the water vapor barrier properties throughout the gas barrier film 1A.

[0069] The standard deviation of water vapor transmission may be calculated using measurements taken on the surface of the gas barrier layer 20 of the gas barrier film 1A, for example, at multiple locations (e.g., three locations) in the MD direction at the center of a film sample, or at the center of film samples from different lots (e.g., one location for each of three lots).

[0070] As described above, gas barrier film 1A has good and stable water vapor barrier properties, and therefore can be used as a packaging material for packaging bags containing contents such as pharmaceuticals, food, nutritional supplements, beverages, cosmetics, precision electronic components, industrial chemicals, and pesticides. When gas barrier film 1A is used as a packaging material, deterioration of the contents is suppressed, and a packaging product with excellent preservation stability of the contents' function or properties can be obtained. For this reason, gas barrier film 1A can be suitably used as a packaging film for packaging materials and the like.

[0071] [Packaging Film] A packaging film using the gas barrier film according to this embodiment will be described. The packaging film according to this embodiment comprises the gas barrier film according to this embodiment and a sealant layer provided on the gas barrier film, and the sealant layer may be provided on the gas barrier layer side of the gas barrier film according to this embodiment via an adhesive layer.

[0072] (Adhesive Layer) The adhesive layer adheres the gas barrier film and the sealant layer according to this embodiment. Examples of adhesives constituting the adhesive layer include polyurethane resins obtained by reacting a bifunctional or higher isocyanate compound with a main component such as polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol. Various polyols may be used individually or in combination of two or more. The adhesive layer may be composed of a two-component curing type urethane adhesive to obtain heat resistance.

[0073] To improve adhesion, the polyurethane resin described above may contain carbodiimide compounds, oxazoline compounds, epoxy compounds, phosphorus compounds, or silane coupling agents. Furthermore, to be environmentally conscious, the adhesive may use a polymer component derived from biomass or a biodegradable component. Additionally, the adhesive may have gas barrier properties.

[0074] The amount of adhesive applied is not particularly limited and may be selected arbitrarily as appropriate, but to obtain the desired adhesive strength, conformability, and processability, for example, 0.5 to 10 g / m ２ That is also acceptable.

[0075] (Sealant layer) The sealant layer contains a polyolefin resin. Examples of polyolefin resins include ethylene-based resins such as low-density polyethylene resin (LDPE), medium-density polyethylene resin (MDPE), linear low-density polyethylene resin (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-α-olefin copolymer, and ethylene-(meth)acrylic acid copolymer; propylene-based resins such as homopolypropylene resin (PP), propylene-ethylene random copolymer, propylene-ethylene block copolymer, and propylene-α-olefin copolymer; or mixtures thereof. The material of the sealant layer can be appropriately selected from the above-mentioned polyolefin resins depending on the type of material of the components constituting the gas barrier film, the application of the gas barrier film, and the temperature conditions when the packaging bag formed using the gas barrier film is subjected to boiling or retorting.

[0076] The sealant layer may or may not be stretched, but it is preferable that the sealant layer not be stretched in order to lower the melting point and facilitate heat sealing.

[0077] The thickness of the sealant layer is not particularly limited, but may be selected as appropriate depending on the application. For example, the thickness of the sealant layer may be 15 μm or more, 30 μm or more, or 50 μm or more, or it may be 200 μm or less, 150 μm or less, or 100 μm or less.

[0078] The packaging film according to this embodiment includes a gas barrier film according to this embodiment. This suppresses variations in water vapor barrier properties across the entire surface of the film, resulting in good and stable water vapor barrier properties, making it suitable for use in the manufacture of packaging bags for storing contents such as pharmaceuticals and food. Therefore, by using the packaging film according to this embodiment in the manufacture of packaging bags, the storage stability of the contents of the packaging bags can be improved.

[0079] [Packaging Material] A packaging material using the gas barrier film according to this embodiment will be described. The packaging material according to this embodiment can be formed from a packaging film equipped with the gas barrier film according to this embodiment.

[0080] The packaging material according to this embodiment is formed of a packaging film equipped with a gas barrier film according to this embodiment. As a result, variations in water vapor barrier properties are suppressed across the entire surface of the packaging material according to this embodiment, and it can have good and stable water vapor barrier properties, making it suitable for use in the manufacture of packaging bags for storing contents such as pharmaceuticals and food. Therefore, by using the packaging material according to this embodiment in the manufacture of packaging bags, the storage stability of the contents of the packaging bags can be improved.

[0081] [Packaging Bag] A packaging bag using the gas barrier film according to this embodiment will be described. The packaging bag according to this embodiment has a packaging film or packaging material equipped with the gas barrier film according to this embodiment. The packaging bag according to this embodiment is made by manufacturing a bag from the packaging film or packaging material equipped with the gas barrier film according to this embodiment described above. Various contents such as food and pharmaceuticals can be contained in the packaging bag.

[0082] A packaging bag may be formed by folding a single packaging film or packaging material in half so that the sealant layers face each other, and then heat-sealing three sides. Alternatively, a packaging bag may be formed by overlapping two packaging films or packaging materials so that the sealant layers face each other, and then heat-sealing all four sides.

[0083] Since the packaging bag according to this embodiment is formed from a packaging film or packaging material equipped with the gas barrier film according to this embodiment, variations in water vapor barrier properties are suppressed across the entire surface of the packaging bag, and it can have good and stable water vapor barrier properties. Therefore, the packaging bag according to this embodiment can improve the storage stability of the contents, etc.

[0084] [Packaging Product] A packaging product using the gas barrier film according to this embodiment will be described. The packaging product according to this embodiment comprises a packaging bag equipped with the gas barrier film according to this embodiment and contents. The packaging product according to this embodiment can contain contents inside the packaging bag by forming the packaging bag with the contents placed between opposing surfaces of the packaging film or packaging material.

[0085] Since the packaging product according to this embodiment is formed from a packaging bag equipped with the gas barrier film according to this embodiment, variations in water vapor barrier properties are suppressed across the entire surface of the packaging bag, and good and stable water vapor barrier properties can be achieved. Therefore, the packaging product according to this embodiment can improve the storage stability of the contents, and the contents can be stored while maintaining their quality for a longer period of time.

[0086] In addition, the following modifications may be made in this embodiment.

[0087] For example, the gas barrier film 1A may have a gas barrier layer 20 on both the main surface of the substrate layer 10 and the other surface (the lower surface located at the bottom in Figure 1). In this case, the two gas barrier layers may be the same or different.

[0088] Furthermore, the substrate layer 10 may be subjected to plasma treatment. By laminating the gas barrier layer 20 onto the plasma-treated surface, the adhesion and gas barrier properties between the substrate layer 10 and the gas barrier layer 20 are enhanced. As plasma treatment of the substrate layer 10, for example, RIE (Reactive Ion Etching), corona treatment, hollow anode plasma treatment, and planar plasma treatment can be used. In addition to various known plasma treatments, various known surface treatments such as ozone treatment and ion beam treatment can also be used as plasma treatments for the substrate layer 10, as they produce similar effects to plasma treatment. As the type of gas used for plasma treatment, known discharge gases such as argon, oxygen, nitrogen, and helium can be used.

[0089] <Second Embodiment> A gas barrier film according to a second embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will be described. Note that components common to the gas barrier film 1A according to the first embodiment shown in Figure 1 are denoted by the same reference numerals, and redundant explanations are omitted.

[0090] Figure 3 is a schematic cross-sectional view showing the gas barrier film 1B according to this embodiment. As shown in Figure 3, the gas barrier film 1B differs from the first embodiment in that the gas barrier layer 20 has an overcoat layer 30 on a different surface from the base layer 10. That is, the gas barrier film 1B is provided by laminating the gas barrier layer 20 and the overcoat layer 30 on the base layer 10 in this order from the base layer 10 side.

[0091] The overcoat layer 30 is a layer containing an organic polymer resin and has the function of protecting the gas barrier layer 20 and suppressing the occurrence of cracks due to abrasion or bending.

[0092] Various known gas barrier coatings can be used as the overcoat layer 30. In this case, the gas barrier film 1B can further improve the water vapor barrier properties of the gas barrier film as a whole.

[0093] The overcoat layer 30 is obtained, for example, by forming a coating film made of a coating agent on the gas barrier layer 20 by a wet coating method and drying this coating film. In this specification, "coating film" means a wet film, and "film" means a dry film.

[0094] The overcoat layer 30 may be a film (hereinafter sometimes referred to as an "organic-inorganic composite film") comprising a metal alkoxide, its hydrolysate or reaction product thereof, at least one component from the reaction product of the hydrolysate of the metal alkoxide, and a water-soluble polymer. That is, the overcoat layer 30 may be an organic-inorganic composite film comprising at least one component selected from the group consisting of a metal alkoxide, a hydrolysate of the metal alkoxide, a reaction product of the metal alkoxide, and a reaction product of the hydrolysate of the metal alkoxide, and a water-soluble polymer. Furthermore, the overcoat layer 30 may further contain at least one of a silane coupling agent and its hydrolysate.

[0095] Examples of metal alkoxides and their hydrolysates contained in organic-inorganic composite films include tetraethoxysilane [Si(OC) ２ H ５ ) ４ ] and triisopropoxyaluminum [Al(OC ３ H ７ ) ３ General formulas such as: M(OR) ｎ Examples include those represented by (where M is a metal element, R is an alkyl group, and n is the valence of the metal), and their hydrolysates. Metal alkoxides and their hydrolysates may contain one of these alone, or two or more in combination.

[0096] In the organic-inorganic composite film, the total content of at least one component from among metal alkoxides, their hydrolysates or reaction products thereof, and the reaction products of metal alkoxide hydrolysates may be, for example, 40 to 70% by mass. To further improve the gas barrier properties of the overcoat layer 30, the lower limit of the total content of at least one component from among metal alkoxides, their hydrolysates or reaction products thereof, and the reaction products of metal alkoxide hydrolysates in the organic-inorganic composite film may be 50% by mass. For a similar purpose, the upper limit of the total content of at least one component from among metal alkoxides, their hydrolysates or reaction products thereof, and the reaction products of metal alkoxide hydrolysates in the organic-inorganic composite film may be 65% by mass.

[0097] The water-soluble polymer contained in the organic-inorganic composite film is not particularly limited, and examples include polyvinyl alcohol-based polymers and acrylic polyol-based polymers, as well as polysaccharides such as starch, methylcellulose, and carboxymethylcellulose. To further improve the gas barrier properties of the overcoat layer 30, it is preferable that the water-soluble polymer includes a polyvinyl alcohol-based polymer.

[0098] The number-average molecular weight of the water-soluble polymer is not particularly limited and any number may be selected as appropriate, for example, it may be between 40,000 and 180,000.

[0099] Polyvinyl alcohol-based water-soluble polymers can be obtained, for example, by saponifying (including partial saponification) polyvinyl acetate. These water-soluble polymers may contain several tens of percent of acetate groups, or only a few percent of acetate groups.

[0100] The content of water-soluble polymers in the organic-inorganic composite film is preferably 15 to 50% by mass, and more preferably 20 to 45% by mass. A water-soluble polymer content of 15 to 50% by mass is preferable because it further improves the gas barrier properties of the organic-inorganic composite film.

[0101] Examples of silane coupling agents and their hydrolysates included in organic-inorganic composite films include silane coupling agents having organic functional groups. Examples of such silane coupling agents and their hydrolysates include ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidooxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and their hydrolysates. The organic-inorganic composite film may contain one of these individually or a combination of two or more.

[0102] It is preferable that at least one of the silane coupling agent and its hydrolysate has an epoxy group as an organic functional group. Examples of silane coupling agents having an epoxy group include γ-glycidooxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The silane coupling agent having an epoxy group and its hydrolysate may also have an organic functional group other than the epoxy group, such as a vinyl group, an amino group, a methacrylic group, or a ureyl group.

[0103] Silane coupling agents having organic functional groups and their hydrolysates can further improve the gas barrier properties of the overcoat layer 30 and the adhesion to the gas barrier layer 20 through the interaction of their organic functional groups with the hydroxyl groups of water-soluble polymers. In particular, the interaction between the epoxy groups of the silane coupling agent and its hydrolysates and the hydroxyl groups of polyvinyl alcohol can further improve the adhesion between the overcoat layer 30 and the gas barrier layer 20.

[0104] The thickness of the overcoat layer 30 can be appropriately set according to the required gas barrier properties. For example, it is preferably 0.05 to 5 μm, more preferably 0.05 to 1 μm, and even more preferably 0.1 to 0.5 μm. If the thickness of the overcoat layer 30 is 0.05 μm or more, the overcoat layer 30 can obtain sufficient oxygen barrier properties. If the thickness of the overcoat layer 30 is 5 μm or less, the overcoat layer 30 can easily form a uniform coated surface, reducing drying load and manufacturing costs.

[0105] Thus, the gas barrier film 1B includes an overcoat layer 30 on top of the gas barrier layer 20. By making the overcoat layer 30 out of the organic-inorganic composite film described above, excellent water vapor barrier properties are maintained even after boiling or retort sterilization.

[0106] <Third Embodiment> A gas barrier film according to a third embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will now be described. Components common to the other embodiments already described will be denoted by the same reference numerals, and redundant descriptions will be omitted.

[0107] Figure 4 is a schematic cross-sectional view showing the gas barrier film 1C according to this embodiment. As shown in Figure 4, the gas barrier film 1C differs from the gas barrier film 1B according to the second embodiment in that it has an undercoat layer 40 between the base layer 10 and the gas barrier layer 20. That is, the gas barrier film 1C is provided by laminating the undercoat layer 40, the gas barrier layer 20 and the overcoat layer 30 on the base layer 10 in this order from the base layer 10 side.

[0108] In addition, the gas barrier film 1C may have an undercoat layer 40 between the base layer 10 and the gas barrier layer 20 in the gas barrier film 1A according to the first embodiment shown in Figure 1. That is, the overcoat layer 30 may be omitted.

[0109] Furthermore, if the gas barrier film 1C has gas barrier layers 20 provided on both the upper and lower surfaces of the base layer 10, the undercoat layer 40 may be provided on only one of the two gas barrier layers 20, and the overcoat layer 30 may be provided on only one of the two gas barrier layers 20. Moreover, the undercoat layer 40 and gas barrier layer 20 may be provided on one of the upper and lower surfaces of the base layer 10, and the gas barrier layer 20 and overcoat layer 30 may be provided on the other surface.

[0110] The gas barrier film 1C enhances the adhesion between the substrate layer 10 and the gas barrier layer 20 by providing an undercoat layer 40 between the substrate layer 10 and the gas barrier layer 20, thereby suppressing the peeling of the gas barrier layer 20. Furthermore, the undercoat layer 40 prevents the substrate layer 10 from coming into contact with the outside during transport or other processes before the formation of the gas barrier layer 20, thus protecting the substrate layer 10 from mechanical damage such as scratches or abrasions, and minimizing any impact on the performance of the gas barrier layer 20. For this reason, the gas barrier film 1C can stably exhibit the performance of the gas barrier layer 20.

[0111] The material of the undercoat layer 40 is not particularly limited and any material may be selected as appropriate, but for example, organic polymer resins such as thermosetting resins, thermoplastic resins, ultraviolet curable resins, and electron beam curable resins can be used.

[0112] Examples of thermosetting resins used to form the undercoat layer 40 include thermosetting urethane resins composed of acrylic polyol resin and isocyanate prepolymer, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. Among these, the adhesion between the substrate layer 10 and the gas barrier layer 20 can be improved by forming the undercoat layer 40 using a composite of an acrylic polyol resin containing a hydroxyl group and an isocyanate compound having at least two isocyanate groups in its molecule.

[0113] Acrylic polyol resins are polymer compounds obtained by polymerizing (meth)acrylic acid derivative monomers, or polymer compounds obtained by copolymerizing (meth)acrylic acid derivative monomers with other monomers, and are resins that have hydroxyl groups at their terminals and side chains and react with isocyanate groups of isocyanate compounds.

[0114] (Meth)acrylic acid derivative monomers have hydroxyl groups at their terminal and side chains. Examples of (meth)acrylic acid derivative monomers include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.

[0115] The other monomers mentioned above are monomers copolymerizable with (meth)acrylic acid derivative monomers having hydroxyl groups at the terminal and side chains. Examples of the other monomers mentioned above include, for example, (meth)acrylic acid derivative monomers having alkyl groups in the side chains, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and t-butyl (meth)acrylate; (meth)acrylic acid derivative monomers having carboxyl groups in the side chains, such as (meth)acrylic acid; and (meth)acrylic acid derivative monomers having aromatic rings or cyclic structures in the side chains, such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate.

[0116] The other monomers mentioned above may be monomers copolymerizable with monomers other than (meth)acrylic acid derivative monomers, such as styrene monomers, cyclohexylmaleimide monomers, or phenylmaleimide monomers.

[0117] The other monomers mentioned above may themselves have hydroxyl groups at their terminals and side chains.

[0118] The acrylic polyol resin is preferably a polymer compound obtained by polymerizing a (meth)acrylic acid derivative monomer having a carboxyl group in its side chain, such as (meth)acrylic acid. When forming the undercoat layer 40, the gas barrier film 1C can have higher water vapor barrier properties by forming the undercoat layer 40 using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxyl group and an isocyanate compound.

[0119] The acrylic polyol resin containing hydroxyl groups that can be used for the undercoat layer 40 is not particularly limited, but it is preferable that the hydroxyl value is 50 mg KOH / g to 250 mg KOH / g. Here, the hydroxyl value (unit: mg KOH / g) is an indicator of the amount of hydroxyl groups in the acrylic polyol resin, and represents the number of mg of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of acrylic polyol resin.

[0120] Furthermore, the weight-average molecular weight (Mw) of the acrylic polyol resin is not particularly limited, but is preferably 3,000 to 200,000, more preferably 5,000 to 100,000, and even more preferably 5,000 to 40,000.

[0121] As isocyanate compounds, those having two or more isocyanate groups in their molecule are used. Examples of monomeric isocyanates include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), and tetramethylxylylene diisocyanate (TMXDI); and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Polymers or derivatives of these monomeric isocyanates can also be used as isocyanate compounds. Examples of polymers or derivatives of monomer-based isocyanates include the trimer-nurate type, the adduct type obtained by reacting with 1,1,1-trimethylolpropane, or the biuret type obtained by reacting with biuret.

[0122] The isocyanate compound can be arbitrarily selected from the above-mentioned isocyanate compounds or their polymers or derivatives, and one or more types of isocyanate compounds or their polymers or derivatives can be used in combination.

[0123] The undercoat layer 40 can be formed, for example, by coating a solution consisting of the above-mentioned acrylic polyol resin and isocyanate compound, and a solvent onto the substrate layer 10 and allowing it to react and cure. The equivalent ratio (NCO / OH) of the isocyanate groups of the isocyanate compound to the hydroxyl groups of the acrylic polyol resin is preferably 0.3 to 2.5. The solvent used here can be any solvent that dissolves the above-mentioned acrylic polyol resin and isocyanate compound. Examples of solvents include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, and tetrahydrofuran. These solvents may be used individually or in combination of two or more.

[0124] Examples of thermoplastic resins that form the undercoat layer 40 include polyols having two or more hydroxyl groups, such as acrylic polyols, polyester polyols, polycarbonate polyols, polyether polyols, polycaprolactone polyols, and epoxy polyols; polyvinyl resins such as polyvinyl acetate and polyvinyl chloride; polyvinylidene chloride resins; polystyrene resins; polyethylene resins; polypropylene resins; and polyurethane resins. These may be mixed in any ratio as appropriate. The hydroxyl value of the polyol is not particularly limited, but is preferably, for example, 10 mg KOH / g to 250 mg KOH / g.

[0125] The UV-curable resin and electron-beam-curable resin forming the undercoat layer 40 are not particularly limited as long as they are organic polymer resins, but it is preferable that they contain at least a resin with a hydroxyl value in the range of 10 to 100 mgKOH / g. Furthermore, although the organic polymer resin is not particularly limited, it is desirable that it contains at least a resin with an acid value in the range of 10 to 100 mgKOH / g. Here, the acid value (unit: mgKOH / g) indicates the number of mg of potassium hydroxide required to neutralize the free fatty acids or resin acids contained in 1 g of the sample. Furthermore, it is desirable that the organic polymer resin contains at least a thermoplastic resin. If the hydroxyl value or acid value is 10 mgKOH / g or more, the chemical bonding force between the functional groups and the surface of the gas barrier layer 20 can be exerted, and adhesion to the gas barrier layer 20 can be maintained. If the hydroxyl value or acid value is 100 mgKOH / g or less, the decomposition of the undercoat layer 40 can be suppressed in durability tests such as humid heat resistance tests, and adhesion between the gas barrier layer 20 and the undercoat layer 40 can be maintained.

[0126] Monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone can be used as monomers for the UV-curable or electron-beam-curable resin that forms the undercoat layer 40. Polyfunctional monomers such as trimethylolpropane (meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, diethylene glycol (meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol (meth)acrylate can also be used. Oligomers such as urethane acrylate, epoxy acrylate, and polyester acrylate can be used as oligomers for this UV-curable or electron-beam-curable resin.

[0127] When two or more organic polymer resins selected from thermosetting resins, thermoplastic resins, ultraviolet curing resins, and electron beam curing resins are used in combination as the undercoat layer 40, the mixing ratio is not particularly limited and may be arbitrarily selected as appropriate.

[0128] The undercoat layer 40 may contain, in addition to the organic polymer resin, any additives as needed. Examples of additives include antioxidants, weathering agents, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and silane coupling agents.

[0129] The thickness of the undercoat layer 40 is preferably 0.05 to 10.0 μm, and more preferably 0.05 to 5.0 μm. If the thickness of the undercoat layer 40 is 0.05 μm or more, adhesion between the substrate layer 10 and the gas barrier layer 20 can be maintained. If the thickness of the undercoat layer 40 is 10.0 μm or less, the influence of internal stress is small, the gas barrier layer 20 is not laminated neatly, the barrier properties are not sufficiently expressed, and transparency and coating accuracy are also insufficient.

[0130] A general coating method can be used to form the undercoat layer 40. Examples of known coating methods include dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset method, and organic vapor deposition method.

[0131] The drying method for the undercoat layer 40 can be one or more heat application methods, such as hot air drying, hot roll drying, high-frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation.

[0132] Alternatively, the undercoat layer 40 may be formed by transferring a film pre-coated on another resin substrate using the above-described formation method to the substrate layer 10 using a transfer method such as adhesive transfer, thermal transfer, or UV transfer.

[0133] As described above, embodiments have been explained, but each of the above embodiments is presented as an example, and the present invention is not limited by each of the above embodiments. Each of the above embodiments can be implemented in various other forms, and various combinations, omissions, substitutions, and modifications are possible without departing from the spirit of the invention. Each of the above embodiments and its variations are included in the scope and spirit of the invention, as well as in the claims of the invention and its equivalents.

[0134] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited solely on the basis of the specific details of these examples and comparative examples.

[0135] <Fabrication of Gas Barrier Film> [Example 1] A PET film with a thickness of 12 μm was used as the substrate layer. In a roll-to-roll film deposition apparatus consisting of a deposition chamber and an unwinding / winding chamber, the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during film deposition, was adjusted to 0.02 Pa by using both a Meissner coil (cooling temperature: -120°C in both cases) installed near the unwinding roll in both the deposition chamber and the unwinding / winding chamber. ２A mixture of materials in a weight ratio of 1:10 was sublimated, and a gas barrier layer (thickness 40 nm) made of silicon oxide (SiOx) was formed on the substrate layer by electron beam deposition. This produced the gas barrier film according to Example 1.

[0136] (RBS and ERDA analysis of the gas barrier layer) The gas barrier layer was measured by RBS and ERDA. An HRBS500 (manufactured by Kobe Steel, Ltd.) was used as the measuring instrument. The elemental concentration in the depth direction and the surface density were obtained by performing fitting analysis on the spectra measured by RBS and ERDA. At this time, the density of the substrate layer was 1.49 g / cm³. ３ This was assumed. Furthermore, the interface between the substrate layer and the gas barrier layer was assumed to be at a position where the Si concentration was half the average value of seven points in the range of 8 nm to 32 nm from the surface. In addition, the depth (in m) of each measurement point in the depth direction and the surface density (in atoms / cm³) at each measurement point were specified. ２ ), and the H concentration at each measurement point (unit: at%), the atomic number density of H at each measurement point (unit: atoms / cm³) ３ The following was calculated. The measurement conditions for RBS were as follows: Incident ions: He ＋ (450 keV) Detected ion: Scattered He ＋ Scattering angle: 90° Incident angle: 45° The measurement conditions for ERDA are as follows: Incident ion: N ＋ (480 keV) Detected ion: Rebound H ＋ Scattering angle: 30° Incident angle: 70° The average value of 7 points in the range of 8 nm to 32 nm from the surface of the O / Si, calculated from the Si and O concentrations of the gas barrier layer measured by RBS, was 1.66. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface of the gas barrier layer, measured by ERDA, was 6.1 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0137] [Example 2] A gas barrier film according to Example 2 was prepared using the same procedure as in Example 1, except that the partial pressure at m / z 18 was adjusted to 0.04 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface of O / Si was 1.70. The average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H was 7.5 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0138] [Example 3] A gas barrier film according to Example 3 was prepared using the same procedure as in Example 1, except that the partial pressure at m / z 18 was adjusted to 0.01 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 8 nm to 32 nm from the surface of O / Si was 1.65. The average value of five points in the range of 4 nm to 20 nm from the surface for the atomic number density of H was 5.0 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0139] [Example 4] Si material and SiO ２ A gas barrier film according to Example 4 was prepared using the same procedure as in Example 1, except that a gas barrier layer with a thickness of 30 nm was formed by sublimating a material mixed with materials in a weight ratio of 1:4. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the O / Si surface was 1.30. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H was 5.5 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0140] [Example 5] Si material and SiO ２A gas barrier film according to Example 5 was prepared using the same procedure as in Example 1, except that a gas barrier layer with a thickness of 30 nm was formed by sublimating a material mixed with materials in a weight ratio of 1:19. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the O / Si surface was 1.80. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H was 6.2 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0141] [Example 6] SiO ２ A gas barrier film according to Example 6 was prepared using the same procedure as in Example 1, except that the material was sublimated to form a gas barrier layer with a thickness of 30 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the O / Si surface was 1.95. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H was 8.9 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0142] [Example 7] A gas barrier film according to Example 7 was prepared using the same procedure as in Example 1, except that the thickness of the gas barrier layer was 10 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 2 nm to 8 nm from the surface of O / Si was 1.67. The average value of 5 points in the range of 1 nm to 5 nm from the surface of H was 6.4 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 2 nm to 8 nm from the surface.

[0143] [Example 8] A gas barrier film according to Example 8 was prepared using the same procedure as in Example 1, except that the thickness of the gas barrier layer was set to 100 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 20 nm to 80 nm from the surface of O / Si was 1.65. In addition, the average value of five points in the range of 10 nm to 50 nm from the surface for the atomic number density of H was 5.8 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 20 nm to 80 nm from the surface.

[0144] [Example 9] A gas barrier film according to Example 9 was prepared using the same procedure as in Example 1, except that a 20 μm thick OPP film was used as the base layer. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface of O / Si was 1.66. The average value of 5 points in the range of 4 nm to 20 nm from the surface of H was 5.8 × 10⁻⁶. ２１ atoms / cm ３ The result was as follows. Furthermore, in the fitting analysis of RBS and ERDA, the density of the substrate layer was 0.90 g / cm³. ３ This was assumed.

[0145] [Example 10] A mixed solution of acrylic polyol and isocyanate was applied to a substrate layer (PET film, 12 μm thick) by gravure coating and dried to form an undercoat layer with a thickness of 0.2 μm. A gas barrier layer was formed on the undercoat layer using the same procedure as in Example 1. This produced the gas barrier film according to Example 10. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface of O / Si was 1.65. The average value of 5 points in the range of 4 nm to 20 nm from the surface of H was 5.7 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0146] [Example 11] A coating agent prepared by mixing liquid (1) and liquid (2) below in a weight ratio of 6:4 was applied to the gas barrier layer of the gas barrier film of Example 1 by gravure coating and dried to form an overcoat layer with a thickness of 0.4 μm. This produced the gas barrier film according to Example 11. Liquid (1): 10.4 g of tetraethoxysilane was mixed with 89.6 g of hydrochloric acid (0.1 N), stirred for 30 minutes to hydrolyze the mixture, resulting in a solid content of 3 wt% (SiO ２ (Converted) Hydrolysis solution (2) Solution: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water:isopropyl alcohol weight ratio 90:10)

[0147] [Example 12] On the gas barrier layer of the gas barrier film of Example 1, a coating agent with a solid content of 5 wt% was prepared by mixing an aqueous solution of polyvinyl alcohol, a hydrolysis solution of tetraethoxysilane, and a hydrolysis solution of 1,3,5-tris(3-trimethoxysilylpropyl) isocyanurate silane coupling agent in such a way that the solid content weight ratio after drying was 30:60:10. This coating agent was applied by gravure coating and dried to form an overcoat layer with a thickness of 0.4 μm. This produced the gas barrier film according to Example 12.

[0148] [Example 13] SiO material and SnO ２ Except for the fact that the materials were mixed in a weight ratio of 1.6:1 and sublimated to form a gas barrier layer with a thickness of 40 nm, the same procedure as in Example 1 was used to deposit tin-containing silicon oxide (SiSn) onto the substrate layer by electron beam deposition. ｘ O ｙ A gas barrier layer (thickness 40 nm) was formed consisting of the following. This produced the gas barrier film according to Example 13. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 8 nm to 32 nm from the surface for Sn / (Si+Sn), calculated from the Si concentration, Sn concentration, and O concentration of the gas barrier layer measured by RBS, was 0.17, and the average value of seven points in the same range for O / (Si+Sn) was 1.41. In addition, the average value of five points in the range of 4 nm to 20 nm from the surface for the atomic number density of H in the gas barrier layer, measured by ERDA, was 4.8 × 10⁻⁶.２１ atoms / cm ３ That was the case.

[0149] [Example 14] A gas barrier film according to Example 14 was prepared using the same procedure as in Example 13, except that the partial pressure at m / z 18 was adjusted to 0.04 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of 7 points in the same range for O / (Si+Sn) was 1.43. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 5.6 × 10⁻¹⁰. ２１ atoms / cm ３ That was the case.

[0150] [Example 15] A gas barrier film according to Example 15 was prepared using the same procedure as in Example 13, except that the partial pressure at m / z 18 was adjusted to 0.01 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of 7 points in the same range for O / (Si+Sn) was 1.40. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 4.0 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0151] [Example 16] Si material and SiO ２ Materials and SnO ２A gas barrier film according to Example 16 was produced in the same procedure as in Example 1, except that a material obtained by mixing the materials at a weight ratio of 1:10:1.5 was sublimated to form a gas barrier layer having a thickness of 30 nm. As a result of measuring the gas barrier layer by RBS and ERDA described in Example 1, the average value of 7 points in the range of 6 nm to 24 nm from the surface of Sn / (Si+Sn) was 0.05, and the average value of 7 points in the same range for O / (Si+Sn) was 1.65. Further, the average value of 5 points in the range of 3 nm to 15 nm from the surface of the atomic number density of H in the gas barrier layer measured by ERDA was 5.5×10 ２１ atoms / cm ３ . The interface between the base material layer and the gas barrier layer was assumed to be a position where the Si concentration becomes 1 / 2 of the average value of 7 points in the range of 6 nm to 24 nm from the surface.

[0152] [Example 17] A gas barrier film according to Example 17 was produced in the same procedure as in Example 1, except that a material obtained by mixing a Si material, a SiO ２ material, and a SnO ２ material at a weight ratio of 1:9:3 was sublimated to form a gas barrier layer having a thickness of 30 nm. As a result of measuring the gas barrier layer by RBS and ERDA described in Example 1, the average value of 7 points in the range of 6 nm to 24 nm from the surface of Sn / (Si+Sn) was 0.10, and the average value of 7 points in the same range for O / (Si+Sn) was 1.65. Further, the average value of 5 points in the range of 3 nm to 15 nm from the surface of the atomic number density of H in the gas barrier layer measured by ERDA was 5.2×10 ２１ atoms / cm ３ . The interface between the base material layer and the gas barrier layer was assumed to be a position where the Si concentration becomes 1 / 2 of the average value of 7 points in the range of 6 nm to 24 nm from the surface.

[0153] [Example 18] A Si material and a SiO ２ material and a SnO ２A material obtained by mixing the materials at a weight ratio of 1:10:5 was sublimated, and the gas barrier film according to Example 18 was produced in the same procedure as in Example 1, except that a gas barrier layer having a film thickness of 30 nm was formed. As a result of measuring the gas barrier layer by RBS and ERDA described in Example 1, the average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of 7 points in the same range for O / (Si+Sn) was 1.68. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 5.0×10 ２１ atoms / cm ３ . Note that the interface between the base material layer and the gas barrier layer was assumed to be the position where the Si concentration becomes 1 / 2 of the average value of 7 points in the range of 6 nm to 24 nm from the surface.

[0154] [Example 19] A material obtained by mixing the Si material and the SiO ２ material and the SnO ２ material at a weight ratio of 1:7:9 was sublimated, and the gas barrier film according to Example 19 was produced in the same procedure as in Example 1, except that a gas barrier layer having a film thickness of 30 nm was formed. As a result of measuring the gas barrier layer by RBS and ERDA described in Example 1, the average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.30, and the average value of 7 points in the same range for O / (Si+Sn) was 1.65. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 4.5×10 ２１ atoms / cm ３ . Note that the interface between the base material layer and the gas barrier layer was assumed to be the position where the Si concentration becomes 1 / 2 of the average value of 7 points in the range of 6 nm to 24 nm from the surface.

[0155] [Example 20] The Si material and the SiO ２ material and the SnO ２A gas barrier film according to Example 20 was prepared using the same procedure as in Example 1, except that a gas barrier layer with a thickness of 30 nm was formed by sublimating a material mixed with materials in a weight ratio of 1:4:14. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.50, and the average value of seven points in the same range for O / (Si+Sn) was 1.65. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 4.0 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0156] [Example 21] A gas barrier film according to Example 21 was prepared using the same procedure as in Example 1, except that a material prepared by mixing SiO material and Sn material in a weight ratio of 2:1 was sublimated to form a gas barrier layer with a thickness of 30 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of 7 points in the same range for O / (Si+Sn) was 1.00. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 4.5 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0157] [Example 22] Si material and SiO ２ Materials and SnO ２A gas barrier film according to Example 22 was prepared using the same procedure as in Example 1, except that a gas barrier layer with a thickness of 30 nm was formed by sublimating a material mixed with materials in a weight ratio of 1:15:7. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of seven points in the same range for O / (Si+Sn) was 1.80. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 6.5 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0158] [Example 23] SiO ２ Materials and SnO ２ A gas barrier film according to Example 23 was prepared using the same procedure as in Example 1, except that a gas barrier layer with a thickness of 30 nm was formed by sublimating a material mixed in a weight ratio of 2.5:1. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of seven points in the same range for O / (Si+Sn) was 1.95. Furthermore, the average value of five points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 7.8 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0159] [Example 24] SiO ２A gas barrier film according to Example 24 was prepared using the same procedure as in Example 13, except that the material was sublimated to form a gas barrier layer with a thickness of 10 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 2 nm to 8 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of seven points in the same range for Sn / (Si+Sn) was 1.45. Furthermore, the average value of five points in the range of 1 nm to 5 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 5.4 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0160] [Example 25] SiO ２ A gas barrier film according to Example 25 was prepared using the same procedure as in Example 13, except that the material was sublimated to form a gas barrier layer with a thickness of 60 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 12 nm to 48 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of seven points in the same range for O / (Si+Sn) was 1.40. Furthermore, the average value of five points in the range of 6 nm to 30 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 4.4 × 10⁻⁶. ２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 12 nm to 48 nm from the surface.

[0161] [Example 26] SiO ２ A gas barrier film according to Example 26 was prepared using the same procedure as in Example 13, except that the material was sublimated to form a gas barrier layer with a thickness of 120 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of seven points in the range of 24 nm to 96 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of seven points in the same range for O / (Si+Sn) was 1.40. Furthermore, the average value of five points in the range of 12 nm to 60 nm from the surface for the atomic number density of H in the gas barrier layer, as measured by ERDA, was 4.2 × 10⁻⁶.２１ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 24 nm to 96 nm from the surface.

[0162] [Example 27] A mixed solution of acrylic polyol and isocyanate was applied to a substrate layer (PET film, 12 μm thick) by gravure coating and dried to form an undercoat layer with a thickness of 0.2 μm. A gas barrier layer was formed on the undercoat layer using the same procedure as in Example 13 to produce the gas barrier film according to Example 27. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.40. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 4.5 × 10⁻⁶. ２１ atoms / cm ３ That was the case.

[0163] [Example 28] A coating agent prepared by mixing liquid (1) and liquid (2) below in a weight ratio of 6:4 was applied to the gas barrier layer of the gas barrier film of Example 13 by gravure coating and dried to form an overcoat layer with a thickness of 0.4 μm, thereby producing the gas barrier film according to Example 28. Liquid (1): 10.4 g of tetraethoxysilane was mixed with 89.6 g of hydrochloric acid (0.1 N), stirred for 30 minutes to hydrolyze the mixture, resulting in a solid content of 3 wt% (SiO ２ (Converted) Hydrolysis solution (2) Solution: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water:isopropyl alcohol weight ratio 90:10)

[0164] [Example 29] On the gas barrier layer of the gas barrier film of Example 13, a coating agent with a solid content of 5 wt% was prepared by mixing an aqueous solution of polyvinyl alcohol, a hydrolysis solution of tetraethoxysilane, and a hydrolysis solution of 1,3,5-tris(3-trimethoxysilylpropyl) isocyanurate silane coupling agent in such a way that the solid content weight ratio after drying was 30:60:10. This coating agent was applied by gravure coating and dried to form an overcoat layer with a thickness of 0.4 μm. This produced the gas barrier film according to Example 29.

[0165] [Comparative Example 1] A gas barrier film according to Comparative Example 1 was prepared using the same procedure as in Example 1, except that neither the Meissner coil installed in the deposition chamber nor the unwinding / winding chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.10 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1, and the average value of 7 points in the range of 8 nm to 32 nm from the surface of O / Si was 1.72. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface of H was 1.9 × 10⁻⁶. ２２ atoms / cm ３ That was the case.

[0166] [Comparative Example 2] A gas barrier film according to Comparative Example 2 was prepared using the same procedure as in Example 4, except that only a Meissner coil installed in the deposition chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.07 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1, and the average value of 7 points in the range of 6 nm to 24 nm from the surface of O / Si was 1.32. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H was 1.5 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0167] [Comparative Example 3] A gas barrier film according to Comparative Example 3 was prepared using the same procedure as in Example 6, except that neither the Meissner coil installed in the deposition chamber nor the unwinding / winding chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.10 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1, and the average value of 7 points in the range of 6 nm to 24 nm from the surface of O / Si was 1.96. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H was 2.5 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0168] [Comparative Example 4] A gas barrier film according to Comparative Example 4 was prepared using the same procedure as in Comparative Example 1, except that the thickness of the gas barrier layer was set to 100 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 20 nm to 80 nm from the surface of O / Si was 1.71. In addition, the average value of 5 points in the range of 10 nm to 50 nm from the surface of H was 1.8 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 20 nm to 80 nm from the surface.

[0169] [Comparative Example 5] A gas barrier film according to Comparative Example 5 was prepared using the same procedure as in Example 9, except that neither the Meissner coil installed in the deposition chamber nor the unwinding / winding chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.10 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1, and the average value of 7 points in the range of 8 nm to 32 nm from the surface of O / Si was 1.72. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H was 2.0 × 10⁻⁶. ２２ atoms / cm ３ That was the case.

[0170] [Comparative Example 6] A gas barrier film according to Comparative Example 6 was prepared using the same procedure as in Example 13, except that neither the Meissner coil installed in the deposition chamber nor the unwinding / winding chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.10 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 8 nm to 32 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.50. In addition, the average value of 5 points in the range of 4 nm to 20 nm from the surface for the atomic number density of H in the gas barrier layer, measured by ERDA, was 1.5 × 10⁻⁶. ２２ atoms / cm ３ That was the case.

[0171] [Comparative Example 7] A gas barrier film according to Comparative Example 7 was prepared using the same procedure as in Example 19, except that only a Meissner coil installed in the deposition chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.07 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.30, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.68. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, measured by ERDA, was 1.1 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0172] [Comparative Example 8] A gas barrier film according to Comparative Example 8 was prepared using the same procedure as in Example 21, except that only a Meissner coil installed in the deposition chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.07 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.04. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, measured by ERDA, was 1.2 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0173] [Comparative Example 9] A gas barrier film according to Comparative Example 9 was prepared using the same procedure as in Example 22, except that neither the Meissner coil installed in the deposition chamber nor the unwinding / winding chamber was used, and the partial pressure at m / z 18 in the deposition chamber, measured with a partial pressure gauge during deposition, was set to 0.10 Pa. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 6 nm to 24 nm from the surface for Sn / (Si+Sn) was 0.15, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.83. In addition, the average value of 5 points in the range of 3 nm to 15 nm from the surface for the atomic number density of H in the gas barrier layer, measured by ERDA, was 1.7 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 6 nm to 24 nm from the surface.

[0174] [Comparative Example 10] A gas barrier film according to Comparative Example 10 was prepared using the same procedure as in Comparative Example 6, except that the thickness of the gas barrier layer was 120 nm. The gas barrier layer was measured using RBS and ERDA as described in Example 1. The average value of 7 points in the range of 24 nm to 96 nm from the surface for Sn / (Si+Sn) was 0.17, and the average value of 7 points in the same range for Sn / (Si+Sn) was 1.42. In addition, the average value of 5 points in the range of 12 nm to 60 nm from the surface for the atomic number density of H in the gas barrier layer measured by ERDA was 1.3 × 10⁻⁶. ２２ atoms / cm ３ The results were as follows. Furthermore, it was assumed that the interface between the substrate layer and the gas barrier layer was located at a position where the Si concentration was half the average value of seven points in the range of 24 nm to 96 nm from the surface.

[0175] [Evaluation] The following evaluations were performed on the gas barrier films of each example and comparative example.

[0176] (Water vapor barrier properties) For each example and comparative example of the gas barrier film, a water vapor transmission rate measuring device manufactured by Mokon Corporation (product name: PERMATRAN3 / 34G, measurement conditions: 40℃-90%RH, unit: g / (m)) was used. ２ Using a 24-hour (day) system, the water vapor transmission rate (WVTR) was measured at three locations every 1000 m in the MD direction at the center of the film sample on the surface of the gas barrier layer. The standard deviation of these measurements was calculated to evaluate the water vapor barrier properties. The standard deviation was calculated based on the following formula (1). The measurement results for each WVTR measurement point and the calculated standard deviation are shown in Tables 1 and 2. Tables 1 and 2 show examples and comparative examples with similar configurations, respectively.

[0177]

[0178]

[0179]

[0180] From Tables 1 and 2, the gas barrier films of Examples 1 to 29 all have an average value of 1.0 × 10¹⁶ of the atomic number density of H measured by the recoil particle detection method of the gas barrier layer, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer. ２２ atoms / cm ３ The results were as follows: The gas barrier films according to each example had a WVTR standard deviation of less than 0.3, confirming that variations in vapor barrier properties could be kept small across the entire surface of the gas barrier film. Therefore, it can be said that the gas barrier films of each example have stable water vapor barrier properties across their entire surface.

[0181] On the other hand, the gas barrier films of Comparative Examples 1 to 10 all showed an average value of 1.0 × 10⁻¹⁰ of the number of hydrogen (H) atoms measured by a recoil particle detection method of the gas barrier layer, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer. ２２ atoms / cm ３ The values ​​exceeded [value]. The gas barrier films in each comparative example had a WVTR standard deviation of 0.3 or more, indicating inferior stability of water vapor barrier properties compared to the gas barrier films in each example.

[0182] Furthermore, the results from the examples and comparative examples demonstrate that the gas barrier film according to this embodiment can be manufactured even more stably by forming a gas barrier layer on a substrate layer passing through the film deposition chamber using a deposition material that forms an inorganic oxide film containing at least silicon (Si) and oxygen (O), or silicon (Si) and tin (Sn) and oxygen (O), while maintaining a partial pressure value of 0.05 Pa or less at m / z 18 in the film deposition chamber using a gas adsorption device.

[0183] Although embodiments and examples of the present invention have been described above, the specific configuration is not limited to these embodiments, and modifications and combinations of configurations that do not depart from the spirit of the present invention are also included.

[0184] According to the present invention, it is possible to provide a gas barrier film that can suppress variations in water vapor barrier properties.

[0185] 1A, 1B, 1C Gas barrier film 10 Substrate layer 20 Gas barrier layer 30 Overcoat layer 40 Undercoat layer 100 Gas barrier film manufacturing equipment (gas barrier film manufacturing equipment) 101 Unwinding and winding chamber 102 Film deposition chamber 103 Unwinding roll 104 Film deposition roll 105 Winding roll 106 Electron beam gun 107A, 107B Gas adsorption device PF Plastic film VM Vapor deposition material VP Vapor deposition particles

Claims

1. The material comprises a base layer and a gas barrier layer provided on at least one surface of the base layer, the gas barrier layer being made of an inorganic oxide film containing silicon (Si) and oxygen (O), wherein the average value of the number density of hydrogen (H) in the gas barrier layer, measured by a recoil particle detection method, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer is 1.0 × 10⁻¹⁴. ２２ atoms / cm ３ The following is a gas barrier film.

2. The gas barrier film according to claim 1, wherein the average value of the silicon (Si) to oxygen (O) composition ratio O / Si of the gas barrier layer, measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 1.00 or more and 1.90 or less.

3. The gas barrier film according to claim 1, wherein the inorganic oxide film further comprises tin (Sn).

4. The gas barrier film according to claim 3, wherein the average value of the silicon (Si) to tin (Sn) composition ratio Sn / (Si+Sn), measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 0.03 or more and 0.80 or less.

5. The gas barrier film according to claim 3, wherein the average value of the composition ratio O / (Si + Sn) of silicon (Si), tin (Sn), and oxygen (O), measured by Rutherford backscattering analysis of the gas barrier layer, in the range from a position corresponding to 20% to 80% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 1.00 or more and 1.90 or less.

6. The gas barrier film according to claim 1 or 3, wherein the thickness of the gas barrier layer is 1 to 200 nm.

7. Water vapor transmission rate is 3.0 g / (m³). ２ A gas barrier film according to claim 1 or 3, wherein the water vapor transmission rate is less than 0.3 days, and the standard deviation of the water vapor transmission rate is less than 0.

3.

8. The gas barrier film according to claim 1 or 3, further comprising an overcoat layer formed on the side of the gas barrier layer opposite to the substrate layer side.

9. The gas barrier film according to claim 8, wherein the overcoat layer comprises at least one component selected from the group consisting of a metal alkoxide, a hydrolysate of a metal alkoxide, a reaction product of a metal alkoxide, and a reaction product of a hydrolysate of a metal alkoxide, and a water-soluble polymer.

10. The gas barrier film according to claim 8, wherein the overcoat layer comprises at least one component selected from the group consisting of a silane coupling agent, a hydrolysate of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolysate of a silane coupling agent.

11. The gas barrier film according to claim 1 or 3, further comprising an undercoat layer formed between the substrate layer and the gas barrier layer, wherein the undercoat layer comprises at least one resin selected from the group consisting of thermosetting resins, thermoplastic resins, ultraviolet curable resins and electron beam curable resins.

12. The gas barrier film according to claim 1 or 3, further comprising an undercoat layer formed between the substrate layer and the gas barrier layer, wherein the undercoat layer is made of a cured product of a composition containing an acrylic polyol resin and an isocyanate compound.

13. A packaging film comprising: a gas barrier film according to claim 1 or 3; and a sealant layer provided on the gas barrier film.

14. A gas barrier layer comprising: a base layer; and a gas barrier layer provided on at least one surface of the base layer, the gas barrier layer comprising an inorganic oxide film containing silicon (Si) and oxygen (O), wherein the inorganic oxide film further contains tin (Sn), and the average value of the composition ratio of silicon (Si) to tin (Sn) Sn / (Si+Sn) of the gas barrier layer, measured by Rutherford backscattering analysis of the gas barrier layer, in the range from the surface of the gas barrier layer to a position corresponding to 20% to 80% of the thickness of the gas barrier layer, is 0.15 or more and 0.20 or less, and the average value of the composition ratio of silicon (Si), tin (Sn), and oxygen (O) O / (Si+Sn), measured by Rutherford backscattering analysis of the gas barrier layer, in the range from the surface of the gas barrier layer to a position corresponding to 20% to 80% of the thickness of the gas barrier layer, is 1.40 or more and 1.45 or less. The average value of the number density of hydrogen (H) atoms measured by the recoil particle detection method of the gas barrier layer, in the range from a position corresponding to 10% to 50% of the thickness of the gas barrier layer in the depth direction from the surface of the gas barrier layer, is 4.1 × 10⁻¹⁰. ２１ atoms / cm3 or more 6.0×10 ２１ atoms / cm ３ The following is a gas barrier film.

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