Gas barrier film and manufacturing method

Abstract

In the gas barrier film provided with a base material layer and a gas barrier layer formed on the base material layer and containing silicon oxide, in an infrared absorption spectrum from the surface side of the gas barrier layer, the ratio of the peak area of an absorption peak from 3100 cm <-1 > to 3700 cm <-1 > derived from an OH bond to the peak area of an absorption peak from 720 cm <-1 > to 1320 cm <-1 > derived from an Si-O-Si bond is 0.25 or less.

Description

Technical Field

[0001] This invention relates to gas barrier films, and more specifically, to gas barrier films suitable for packaging food, pharmaceuticals, precision electronic components, etc. A method for manufacturing the gas barrier film is also disclosed.

[0002] This application claims priority based on Japanese Patent Application No. 2023-180257 filed on October 19, 2023, the contents of which are incorporated herein by reference. Background Technology

[0003] In packaging materials used for food and pharmaceuticals, from the viewpoint of preventing the deterioration of the contents and maintaining their function and properties, it is required to have gas barrier properties that block oxygen, water vapor, and other gases that cause deterioration and permeate through the packaging material. Furthermore, as a gas-barrier packaging material, gas barrier films using metal foils such as aluminum, which are less affected by temperature and humidity, are known to be used as gas barrier layers.

[0004] Other components of gas barrier films include films formed by vapor deposition of inorganic oxides such as silicon oxide and aluminum oxide on a substrate film made of polymer materials through vacuum evaporation or sputtering (see, for example, Patent Document 1). These gas barrier films have transparency and the ability to block gases such as oxygen and water vapor.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 60-049934 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] The inventors discovered that when the barrier layer is composed of a silicon oxide vapor-deposited film, the deviation in water vapor barrier properties tends to be relatively large. To mitigate this, the inventors conducted in-depth research, thus completing this invention.

[0010] In view of the above, the objective is to provide a gas barrier film having a gas barrier layer containing silicon oxide and stable water vapor barrier properties.

[0011] Methods for solving problems

[0012] [1] The first aspect of the present invention is a barrier film having a substrate layer and a barrier layer containing silicon oxide formed on the substrate layer.

[0013] In the infrared absorption spectrum from the surface side of the barrier layer, the 3100 cm⁻¹ region from the OH bond... -1 Above 3700cm -1The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is less than 0.25.

[0014] [2] According to the gas barrier film described in [1], wherein, in the infrared absorption spectrum from the surface side of the gas barrier layer, the 830 cm⁻¹ of the Si-OH bond is... -1 Above 910cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is less than 0.025.

[0015] [3] According to the gas barrier film described in [1] or [2], wherein, in the infrared absorption spectrum from the surface side of the gas barrier layer, the 2100 cm⁻¹ of the Si-H bond is... -1 Above 2200cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The ratio of the peak areas of the following absorption peaks is less than 0.003.

[0016] [4] According to any one of [1] to [3], the gas barrier film, wherein the Si content on the surface of the gas barrier layer is measured by X-ray photoelectron spectroscopy (XPS). 3+ Si 2+ Si + The peak of Si (b=Si) 3+ Si 2+ Si + The total peak of Si relative to the Si2p peak (a=Si) 4+ Si 3+ Si 2+ Si + The value of b / a in the ratio of Si is greater than 0.122.

[0017] [5] According to any one of [1] to [4], the gas barrier film, wherein the ratio of the number of oxygen (O) atoms to the number of silicon (Si) atoms (O / Si) as determined by X-ray photoelectron spectroscopy (XPS) on the surface of the gas barrier layer is more than 1.41 and less than 1.9.

[0018] [6] The gas barrier membrane according to any one of [1] to [5], wherein the thickness of the gas barrier layer is more than 10 nm and less than 60 nm.

[0019] [7] The gas barrier film according to any one of [1] to [6] further comprises an overcoat layer formed on the gas barrier layer.

[0020] [8] According to the gas barrier membrane of [7], wherein the outer coating comprises at least one of a metal alkoxide, a hydrolysis product of a metal alkoxide, a reaction product of a metal alkoxide, and a reaction product of a hydrolysis product of a metal alkoxide; and a water-soluble polymer.

[0021] [9] According to the gas barrier membrane of [7] or [8], wherein the outer coating comprises at least one of a silane coupling agent, a hydrolysis product of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolysis product of a silane coupling agent.

[0022]

[10] The gas barrier film according to any one of [1] to [9] further comprises an undercoat layer disposed between the substrate layer and the gas barrier layer, the undercoat layer comprising at least one of a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin.

[0023]

[11] The gas barrier film according to any one of [1] to

[10] further comprises an undercoating layer disposed between the substrate layer and the gas barrier layer, the undercoating layer being composed of a cured product comprising a composition of an acrylic polyol resin having an organic acid group and a polyisocyanate.

[0024] The second aspect of the present invention is the method for manufacturing the gas barrier membrane involved in the first aspect.

[0025] In this manufacturing method, a film-forming apparatus is prepared, which includes a film-forming chamber and a roll-out / roll-up chamber, and has gas adsorption devices (devices for condensing / adsorbing gases (water vapor)) in both the film-forming chamber and the roll-out / roll-up chamber; a roll-shaped substrate layer is mounted on a roll-out roller disposed in the roll-out / roll-up chamber; the gas adsorption devices in the film-forming chamber and the roll-out / roll-up chamber are activated, and with the partial pressure value of m / z18 in the film-forming chamber set to 0.05 Pa or less, a vapor deposition material made of a mixture of Si material and SiO2 material is used to form a gas barrier layer on the substrate layer passing through the film-forming chamber.

[0026] The effects of the invention

[0027] According to the present invention, a gas barrier film having a gas barrier layer containing silicon oxide and stable water vapor barrier properties can be provided. Attached Figure Description

[0028] [ Figure 1 [Illustration] is a schematic cross-sectional view of the gas barrier membrane according to the first embodiment of the present invention.

[0029] [ Figure 2[Illustration] is a schematic diagram showing an example of an apparatus for manufacturing the gas barrier film.

[0030] [ Figure 3 [Illustration] is a schematic cross-sectional view of the gas barrier membrane according to the second embodiment of the present invention.

[0031] [ Figure 4 [ ] is a schematic cross-sectional view showing a modified example of the gas barrier membrane. Detailed Implementation

[0032] The following is for reference Figure 1 The first embodiment of the present invention will be described.

[0033] Figure 1 This is a schematic cross-sectional view of the gas barrier film 1 according to this embodiment. The gas barrier film 1 includes a substrate layer 10 and a gas barrier layer 20 disposed on one surface of the substrate layer 10.

[0034] The substrate layer 10 is formed of synthetic resin. There are no particular limitations on the material of the substrate layer 10; various known materials can be used. Specific examples include polyolefins (polyethylene, polypropylene, etc.), polyesters (polyethylene terephthalate, polyethylene naphthalate, etc.), polyimides, polyamides (nylon-6, nylon-66, etc.), polystyrene, vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol, polycarbonate, polyethersulfone, acrylics, and cellulose (triacetyl cellulose, diacetyl cellulose, etc.). In practice, it is preferable to select materials appropriately based on the intended use or required properties. For packaging containing contents that are extremely sensitive to moisture, such as electronic or optical components, materials that inherently possess high gas barrier properties, such as polyethylene naphthalate, polyimides, and polyethersulfone, are preferred. In the case of packaging material applications, polyethylene terephthalate, polyethylene, and polypropylene are preferred.

[0035] The thickness of the substrate layer 10 is particularly preferred to provide flexibility and processability when used in packaging materials, and can be set to approximately 9 μm to 100 μm. More preferably, it is 9 μm to 90 μm, 9 μm to 70 μm, 9 μm to 50 μm, or 9 μm to 30 μm. Substrate layers 10 with thicknesses within this range have moderate flexibility and can also be wound into rolls, thus facilitating handling.

[0036] The substrate layer 10 can be in the form of a strip or a single sheet, but a strip is preferred. There is no particular limitation on the longitudinal length of the strip substrate layer 10; for example, a resin film of 10m or more is preferred. It should be noted that there is no upper limit to the length; for example, it can be around 10km.

[0037] Depending on the requirements, the surface of the substrate layer 10 may contain additives such as antistatic agents, ultraviolet absorbers, plasticizers, and lubricants. Furthermore, to improve adhesion, the surface of the substrate layer 10 may undergo physical treatments such as corona treatment, flame treatment, plasma treatment, or easy-bonding treatment; or chemical modification treatments such as acid or alkali treatment. The surface of the substrate layer 10 contributes to the density during the initial growth stage of vacuum film formation when forming the gas barrier layer; from this viewpoint, it is preferable to have a surface as smooth as possible.

[0038] The gas barrier layer 20 is the layer that plays a major role in the gas barrier properties of the gas barrier film 1, and is a film composed of inorganic oxides containing at least silicon oxide (SiOx).

[0039] In the gas barrier layer 20 according to this embodiment, the ratio of the number of oxygen (O) atoms to the number of silicon (Si) atoms (O / Si) is at least 1.0 to 1.9 or less on the surface of the gas barrier layer 20. Considering the transparency of the gas barrier film 1 as a whole, O / Si is more preferably 1.3 or more. From the viewpoint of balancing barrier properties and transparency, O / Si is preferably 1.3 to 1.9 or less, more preferably 1.4 to 1.9 or less, 1.41 to 1.9 or less, 1.45 to 1.9 or less, 1.5 to 1.9 or less, 1.6 to 1.9 or less, 1.7 to 1.9 or less, 1.41 to 1.85 or less, 1.41 to 1.8 or less, 1.45 to 1.85 or less, or 1.45 to 1.85 or less.

[0040] The O / Si ratio of the barrier layer 20 can be evaluated using analytical apparatus such as XPS (X-ray photoelectron analysis). In analytical apparatus such as XPS, sputtering etching using argon (Ar) ions is sometimes used for analysis of the film. However, since the transparent oxide film containing silicon (Si) is reduced, the correct ratio of silicon (Si) atoms to oxygen (O) atoms (O / Si) cannot be obtained. Therefore, it is preferable to analyze the surface of the layer.

[0041] There are no restrictions on the method for forming the barrier layer 20. For example, known film formation methods such as vacuum evaporation, ion plating, sputtering, and plasma-enhanced chemical vapor deposition (PECVD) can be used. However, from the perspective of superior productivity, vacuum evaporation is particularly preferred. As the material heating method for vacuum evaporation, resistance heating, high-frequency induction heating, and electron beam heating can be used. Furthermore, when combined with plasma-assisted methods or ion beam-assisted methods, the barrier layer 20 can be densely formed, improving barrier properties.

[0042] When forming the barrier layer 20 using vacuum evaporation, the partial pressure of m / z 18 measured by a pressure divider (using a quadrupole mass spectrometer with a Faraday cup) during film formation is set to be below 0.05 Pa. When the partial pressure of m / z 18 measured by the mass spectrometer during film formation exceeds 0.09 Pa, the amount of water molecules in the evaporation atmosphere is high, resulting in an increased amount of OH in the inorganic oxide film. Additionally, the amount of OH or H bonded to Si also increases, which is undesirable.

[0043] Here, m / z (italicized precisely) is defined as a dimensionless quantity obtained by dividing the mass of an ion by a uniform atomic mass unit, and then further dividing by the absolute value of the ion's charge number. It is the value used on the horizontal axis of a mass spectrum measured using a mass spectrometer. m / z is designated as an academic term by the International Union of Pure and Applied Sciences (IUPAC). m / z18 is derived from H2O related to water. + The m / z of the ion. Besides m / z 18, there are also fragment ions such as m / z 17 that are associated with water, but in this invention, H₂O, which has the strongest spectral intensity, is used. + The m / z 18 of the ion is used as an indicator.

[0044] A typical method for adjusting the partial pressure of m / z18 during film formation is to install a gas adsorption mechanism in the film formation environment. For example, by installing a device for condensing / adsorbing gas (water vapor) (hereinafter referred to as a "gas adsorption device") in the film formation chamber of the film formation apparatus, the water vapor in the film formation chamber can be reduced. This allows the partial pressure of m / z18 during film formation to be suppressed to below 0.05 Pa. Furthermore, by also installing a gas adsorption device in the winding chamber, particularly near the winding roll, the water vapor released from the substrate can be reduced. Moisture released from the substrate can sometimes hinder the initial film growth of the gas barrier layer. By controlling the water vapor released from the substrate, a dense gas barrier layer can be created during initial film growth, achieving not only water vapor barrier properties in the initially formed film but also stable water vapor barrier properties throughout the entire gas barrier layer.

[0045] As a gas adsorption device, Meissner coils, cryogenic plates, cryogenic pumps, sorption pumps, ion pumps, and getter pumps are preferred. From the perspective of increasing the adsorption area, Meissner coils and cryogenic plates are more preferred. For example, when using Meissner coils or cryogenic plates, from the viewpoint of fully obtaining the performance of condensing / adsorbing gases, the cooling temperature is preferably below -100°C, and more preferably below -110°C.

[0046] The inventors have discovered that by adjusting the O / Si value and the partial pressure of m / z18 during film formation to a specified range, the intermolecular gaps in the formed inorganic oxide film are smaller than those of a typical vapor deposition process. In such an inorganic oxide film, there is less room for adsorbed water to enter, and the amount of OH in the inorganic oxide film is reduced. Furthermore, due to the reduction in dangling bonds, the amount of OH and H that can bond with Si is also reduced; therefore, by using it as a gas barrier layer 20, the stability of the water vapor barrier effect can be improved.

[0047] The aforementioned state of the gas barrier layer 20 can be evaluated by using FT-IR (Fourier Transform Infrared Spectroscopy) to analyze and calculate the amount of OH, Si-OH, and Si-H.

[0048] Specifically, in the infrared absorption spectrum obtained by FT-IR analysis, using the software provided with the device, the absorption spectra from Si-O-Si bonds (720 cm⁻¹) were analyzed. -1 ~1320cm -1 The peak area of ​​) and the peak area from OH bonds (3100) -1 ~3700cm -1 The peak area of ​​) and the origin of Si-OH bonds (830 -1 ~910cm -1 The peak area of ​​) and the peak area from Si-H bonds (2100 -1 ~2200cm -1 A baseline is drawn connecting the two ends of the defined range at the peak area of ​​the spectrum, and the area enclosed by the spectrum and the baseline is calculated. At this time, the region below the baseline is ignored and not included in the area. FT-IR analysis is mostly performed using the ATR method, but the inventors' research revealed that data before corrections such as ATR correction or baseline correction more accurately reflects the properties of the barrier layer 20. Therefore, the values ​​of the parameters mentioned later are defined as the values ​​of the uncorrected data obtained through FT-IR analysis.

[0049] Detailed information will be provided in the following examples. The inventors have discovered through research that: • From OH bond (3100) -1 ~3700cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The ratio of peak area to peak area is below 0.25. • From Si-OH bonds (830) -1 ~910cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The ratio of peak area to peak area is below 0.025. • From Si-H bonds (2100) -1 ~2200cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The ratio of the peak areas of () to the peak areas of () is below 0.003. These are all independent indicators that the gas barrier layer 20 has few inter-molecular gaps and is dense as a membrane.

[0050] OH bonds are an indicator related to the amount of moisture adsorbed in the gas barrier layer 20. It is believed that moisture adsorption originates from OH bonds (3100...). -1 ~3700cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The smaller the ratio of peak area to water content, the less water is adsorbed in the structure of the barrier layer 20.

[0051] The Si-OH bond is an indicator related to the amount of moisture adsorbed and the amount of dangling Si bonds in the gas barrier layer 20. It is believed that the Si-OH bond (830...) -1 ~910cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The smaller the ratio of the peak areas of the gas barrier layer 20, the less water adsorption and dangling Si bonds there are in the structure of the gas barrier layer 20.

[0052] Si-H bonds are an indicator related to the amount of dangling bonds in Si within the barrier layer 20. It is believed that the Si-H bonds (2100...) -1 ~2200cm -1 The peak area of ​​) is relative to that from Si-O-Si bonds (720 cm⁻¹) -1 ~1320cm -1 The smaller the ratio of the peak areas of the two layers, the fewer the number of dangling bonds of Si in the structure of the barrier layer 20.

[0053] The three indicators mentioned above, based on OH bonds, Si-OH bonds, and Si-H bonds, all reflect the amount of defects in the Si-O-Si structure. However, the size of the defects they reflect decreases in the order of OH bonds, Si-OH bonds, and Si-H bonds. Furthermore, to reduce the peak area from these bonds in the order of OH bonds, Si-OH bonds, and Si-H bonds, the partial voltage at m / z 18 needs to be carefully controlled.

[0054] In particular, by reducing the peak area from both Si-OH and Si-H bonds, a dense barrier layer can be created during the initial film growth, which not only achieves the water vapor barrier properties of the initially formed film, but also provides stable water vapor barrier properties for the entire barrier layer.

[0055] The gas barrier membrane of the present invention exhibits stable gas barrier properties by having a gas barrier layer 20 that satisfies at least one of the above-mentioned indicators. Furthermore, in mass production processes, it is possible to manufacture high-quality gas barrier membranes with high-level stable gas barrier properties and high efficiency.

[0056] The chemical bonding state of the barrier layer 20 can also be analyzed using X-ray photoelectron spectroscopy (hereinafter sometimes referred to as "XPS"). XPS is a method that analyzes the energy of photoelectrons emitted from the surface of an object by irradiating it with X-rays. It can analyze the composition and chemical bonding state of elements in a region a few nm deep from the surface of the object. It is known that there are 5 chemical bonding states related to silicon oxide in the inorganic oxide film layer 13, except for SiO2 (Si... 4+ In addition to ), there is also Si. 3+ Si 2+ Si + These three secondary oxide components and Si. Si was determined using XPS. 2p In the narrow spectrum case, SiO2 was observed near 103.5–104.5 eV, and Si was observed at positions approximately 1 eV apart at energy levels lower than SiO2. 3+ Si 2+ Si + And Si.

[0057] In addition, Si was measured using XPS with commonly used X-ray sources of MgKα or AlKα and a path energy of around 10 eV. 2p In the narrow spectrum, the peaks of each bond are not separated and are observed in a synthetic form. Therefore, in Si 2p In the narrow spectrum, a peak was detected near 103.5–104.5 eV in the case of SiO2 films, but in the case of silicon oxide films dominated by SiO2 and containing multiple other chemically bonded states, the peak shifted to the range of 101–103.5 eV. Furthermore, compared to the case of SiO2 films, in the case of silicon oxide films dominated by SiO2 and containing multiple other chemically bonded states, Si… 2p The peak's full width at half maximum (FWHM) broadens. It should be noted that due to the peak shift caused by charged hydrocarbons, C2C2 detected from surface contaminants needs to be used. 1s Peak correction is performed. In this invention, C detected from surface contaminating hydrocarbons... 1sThe peak value is 284.6 eV. In addition, in XPS, sputtering etching using argon (Ar) ions is sometimes used for depth-oriented analysis. However, reduction or mixing may occur due to collisions of argon (Ar) ions, which may change the chemical bonding state of the original silicon oxide film. Therefore, it is preferable to analyze the surface without using sputtering etching.

[0058] The surface of the barrier layer 20 in this embodiment, measured using X-ray photoelectron spectroscopy (XPS), shows Si content. 3+ Si 2+ Si + The peak of Si (b=Si) 3+ Si 2+ Si + (Si) relative to Si 2p The total peak of the peak (a=Si) 4+ Si 3+ Si 2+ Si + The ratio of silicon dioxide (SiO2) to silicon oxide (B / a) is preferably greater than 0.122. When the value of b / a is greater than 0.122, since it is a silicon oxide film containing more chemically bonded states other than SiO2, it becomes a dense structure, which can reduce the permeation path of gas molecules. When it is 0.153 or less, sufficient transparency can be obtained. From the viewpoint of balancing barrier properties and transparency, b / a is preferably 0.123 or more and 0.153 or less, more preferably 0.123 or more and 0.148 or less, 0.123 or more and 0.147 or less, 0.123 or more and 0.145 or less, 0.123 or more and 0.143 or less, 0.123 or more and 0.138 or less, 0.123 or more and 0.133 or less, 0.126 or more and 0.147 or less, 0.128 or more and 0.147 or less, 0.128 or more and 0.145 or less, or 0.128 or more and 0.143 or less.

[0059] The gas barrier layer 20 in this embodiment is preferably amorphous. While grain boundaries are generated in the case of polycrystalline films, since the gas barrier layer 20 is an amorphous film, it becomes a film without grain boundaries, thus reducing the permeation path of gas molecules. Whether the gas barrier layer 20 is amorphous can be evaluated using known methods. For example, the presence of crystalline diffraction peaks can be evaluated by using X-ray diffraction patterns obtained from analytical apparatus such as XRD (X-ray diffraction device).

[0060] The thickness of the gas barrier layer 20 varies depending on the formation / film formation method used, but it can generally be appropriately set within the range of 1 to 200 nm. When the thickness of the gas barrier layer 20 is less than 1 nm, a uniform film or insufficient film thickness may not be obtained, and it may not fully perform its function as a gas barrier layer. When the thickness of the gas barrier layer 20 exceeds 200 nm, cracks may occur after film formation due to external factors such as bending and stretching, thereby losing its barrier properties. Preferably, it is in the range of 5 to 150 nm, more preferably in the ranges of 10 to 120 nm, 10 to 60 nm, 10 to 50 nm, 10 to 45 nm, and 10 to 40 nm.

[0061] Figure 2 This is a schematic diagram illustrating an example of a manufacturing apparatus for a gas-barrier film according to an embodiment of the present invention. In manufacturing, a film-forming apparatus 100 is used, comprising a film-forming chamber 40 equipped with a vacuum and a take-up / take-up chamber 50 equipped with a take-up roller 42. The film-forming chamber 40 and the take-up / take-up chamber 50 are separated by a partition wall and have independent exhaust systems. A gas adsorption device 48 is provided in the film-forming chamber 40, and a gas adsorption device 49 having the same function as the gas adsorption device 48 is also provided near the take-up roller 42 in the take-up / take-up chamber 50. The gas adsorption device 49 can be any device that condenses / adsorbs gases, and can be the same material as the gas adsorption device 48 or a different material.

[0062] A plastic film 41, which will become the substrate layer 10, is placed on a take-up roller 42. The plastic film 41, drawn from the take-up roller 42, passes through a film-forming roller 43 exposed inside the film-forming chamber 40, and is then wound onto a take-up roller 44. A vapor deposition material 45 for forming the gas barrier layer 20 is provided inside the film-forming chamber 40, and an electron beam gun 46, serving as a vapor deposition unit, is also provided. The vapor deposition material 45, heated by the electron beam, becomes vapor deposition particles 47 and is deposited onto the plastic film. Thus, the gas barrier layer 20 is formed on the plastic film 41.

[0063] The vapor-deposited material 45 comprises a mixture of Si and SiO2 materials. The Si material contains elemental Si and / or materials containing Si elements other than SiO2. By appropriately adjusting the ratio of Si material to SiO2 material, the O / Si ratio of the barrier layer can be adjusted.

[0064] exist Figure 2 In this paper, electron beam evaporation using an electron beam gun 46 is shown as a method for heating the evaporation material 45. However, resistance heating or high-frequency induction heating can also be used to evaporate the evaporation material 45. Resistance heating can be a method of directly heating the crucible containing the material, or other methods. Regardless of the method, the device must be configured to exhibit a high film formation rate.

[0065] The apparatus for manufacturing barrier layer vapor-deposited films is not limited to this form. Depending on the needs, the plasma pretreatment device can be placed in the roll-up / rewind-off chamber, or the reactive gas introduction device can be placed in the film formation chamber. There are also no particular restrictions on the configuration of the rollers.

[0066] In this embodiment, the following changes can also be made.

[0067] • Gas barrier layers are provided on both sides of the substrate layer 10. In this case, the two gas barrier layers can be the same or different.

[0068] • By performing plasma treatment on the substrate layer 10 and then stacking a barrier layer 20 on the plasma-treated surface, the adhesion and barrier properties between the substrate layer 10 and the barrier layer 20 are improved. As for the plasma treatment of the substrate layer 10, in addition to various known plasma treatments such as RIE (Reactive Ion Etching), corona treatment, hollow anode plasma treatment, and planar plasma treatment, various known surface treatments such as ozone treatment and ion beam treatment can also be used to achieve the same effect as plasma treatment. The gas used for plasma treatment can be any known discharge gas such as argon, oxygen, nitrogen, or helium.

[0069] Reference Figure 3 The second embodiment of the present invention will now be described. In the following description, configurations that are common to those already described will be marked with the same symbols and repeated descriptions will be omitted.

[0070] Figure 3 This is a schematic cross-sectional view of the gas barrier film 2 according to this embodiment. The gas barrier film 2 also includes an outer coating layer 30 disposed on the gas barrier layer 20.

[0071] The outer coating 30 is a layer containing organic polymer resin, which has the function of protecting the gas barrier layer 20 and preventing cracks caused by friction or bending.

[0072] Various known gas barrier films can also be used as the outer coating 30. In this case, the barrier properties of the gas barrier film as a whole can be further improved.

[0073] The outer coating 30 is obtained, for example, by forming a coating film composed of a coating agent on the gas barrier layer 20 using a wet coating method and then drying the coating film. It should be noted that, in this specification, "coating film" refers to a wet film and "film coating" refers to a dry film.

[0074] The outer coating 30 may be a film containing at least one of a metal alkoxide and its hydrolysis product or its reaction product; and a film containing a water-soluble polymer (hereinafter sometimes referred to as an "organic-inorganic composite film"). Furthermore, it preferably contains at least one of a silane coupling agent and its hydrolysis product.

[0075] Metal alkoxides and their hydrolysis products contained in organic-inorganic composite membranes, such as tetraethoxysilane [Si(OC2H5)4] and triisopropoxyaluminum [Al(OC3H7)3], are derived from the general formula M(OR). n The substance and its hydrolysis products are represented. It may contain one of them alone, or two or more in combination.

[0076] The total content of at least one of the metal alkoxides and their hydrolysis products or reaction products in the organic-inorganic composite membrane can be set to, for example, 40-70% by mass. From the viewpoint of further improving gas barrier properties, the lower limit of the total content of at least one of the metal alkoxides and their hydrolysis products or reaction products in the organic-inorganic composite membrane can be set to 50% by mass. From the same viewpoint, the upper limit of the total content of at least one of the metal alkoxides and their hydrolysis products or reaction products in the organic-inorganic composite membrane can be set to 65% by mass.

[0077] There are no particular limitations on the water-soluble polymers contained in the organic-inorganic composite membrane; examples include polyvinyl alcohol-based polymers, acrylic polyol-based polymers, and polysaccharides such as starch / methylcellulose / carboxymethylcellulose. From the viewpoint of further improving gas barrier properties, polymers containing polyvinyl alcohol-based polymers are preferred. The number-average molecular weight of the water-soluble polymer can be set, for example, between 40,000 and 180,000.

[0078] Water-soluble polymers based on polyvinyl alcohol can be obtained, for example, by saponifying (including partially saponifying) polyvinyl acetate. These water-soluble polymers can be those with tens of percent of acetic acid groups remaining, or those with only a few percent of acetic acid groups remaining.

[0079] The content of water-soluble polymers in the organic-inorganic composite membrane can be set to, for example, 15-50% by mass. When the content of water-soluble polymers is 20-45% by mass, the gas barrier properties of the organic-inorganic composite membrane can be further improved, and therefore this is preferred.

[0080] Silane coupling agents and their hydrolysis products contained in organic-inorganic composite membranes can be categorized as having organic functional groups. Examples of such silane coupling agents and their hydrolysis products include ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and their hydrolysis products. One of these agents may be contained alone, or two or more may be contained in combination.

[0081] At least one of the silane coupling agent and its hydrolysis product is preferably a substance having an epoxy group as an organic functional group. Examples of epoxy-containing silane coupling agents include γ-epoxypropoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Epoxy-containing silane coupling agents and their hydrolysis products may also have organic functional groups different from epoxy groups, such as vinyl, amino, methacryl, or urea groups.

[0082] Silane coupling agents with organic functional groups and their hydrolysis products can further improve the gas barrier properties of the outer coating 30 and its 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 adhesion between the outer coating 30 and the gas barrier layer 20 can be improved through the interaction between the epoxy groups of the silane coupling agent and its hydrolysis products and the hydroxyl groups of polyvinyl alcohol.

[0083] The total content of at least one of the silane coupling agent and its hydrolysis product or reaction product in the organic-inorganic composite membrane can be set to, for example, 1 to 15% by mass. When the total content of at least one of the silane coupling agent and its hydrolysis product or reaction product is 2 to 12% by mass, the gas barrier properties of the organic-inorganic composite membrane can be further improved, and therefore it is preferred.

[0084] The thickness of the outer coating 30 can be set according to the required gas barrier properties, for example, it can be set to 0.05 to 5 μm. The thickness of the outer coating 30 is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. If the thickness of the outer coating 30 is 0.05 μm or more, sufficient oxygen barrier properties are easily obtained. If the thickness of the outer coating 30 is 1 μm or less, a uniform coating surface is easily formed, which can suppress drying load and manufacturing costs.

[0085] The gas barrier membrane with the above-mentioned organic-inorganic composite coating as the outer coating 30 can maintain excellent gas barrier properties even after boiling or steam sterilization treatment.

[0086] In the gas barrier membranes described in the above embodiments, for example, it is also possible to use... Figure 4As shown in the modified example, a primer layer 15 is further provided between the substrate layer 10 and the gas barrier layer 20. That is, Figure 4 The gas barrier membrane 2A shown is a modified example according to the second embodiment, but it can also be used with... Figure 1 The same modifications are made to the first embodiment shown. Alternatively, a combination of a base coating layer 15 and a gas barrier layer 20 may be provided on both sides of the substrate layer 10.

[0087] The primer layer 15 is disposed on the substrate layer 10 to improve the adhesion between the substrate layer 10 and the gas barrier layer 20, prevent the gas barrier layer 20 from peeling off, and thus protect it from mechanical damage such as scratches and abrasions. The material of the primer layer 15 is not particularly limited and can include thermosetting resins, thermoplastic resins, UV-curable resins, electron beam-curable resins, etc.

[0088] Examples of thermosetting resins that form the base coating 15 include thermosetting urethane resins, phenolic resins, urea-melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins, which are composed of acrylic polyol resins and isocyanate prepolymers. Among these, the adhesion between the substrate layer 10 and the gas barrier layer 20 can be improved by using a composite formed from an acrylic polyol resin containing hydroxyl and / or organic acid groups and an isocyanate compound having at least two NCO groups within its molecule.

[0089] Acrylic polyol resins are substances that, in polymers obtained by polymerizing (meth)acrylic acid derivative monomers or by copolymerizing (meth)acrylic acid derivative monomers with other monomers, have hydroxyl groups at their ends and side chains, and react with the NCO groups of isocyanate compounds. (Meth)acrylic acid derivative monomers have hydroxyl groups at their ends and side chains. Examples of (meth)acrylic acid derivative monomers include hydroxyethyl (meth)acrylate and hydroxybutyl (meth)acrylate.

[0090] The aforementioned monomers can be copolymerized with (meth)acrylic acid derivative monomers having hydroxyl groups at the ends and on the side chains. Examples of these other monomers include (meth)acrylic acid derivative monomers with alkyl side chains, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and tert-butyl (meth)acrylate; (meth)acrylic acid derivative monomers with carboxyl side chains, such as (meth)acrylic acid; and (meth)acrylic acid derivative monomers with aromatic rings or cyclic structures, such as benzyl (meth)acrylate and cyclohexyl (meth)acrylate. Besides (meth)acrylic acid derivative monomers, styrene monomers, cyclohexylmaleimide monomers, and phenylmaleimide monomers can also be considered. These other monomers may also themselves have hydroxyl groups at the ends and on the side chains.

[0091] The acrylic polyol resin is particularly preferably a polymer obtained by polymerizing monomers of (meth)acrylic acid derivatives such as (meth)acrylic acid with carboxyl groups on the side chains. When forming the base coating 15, a gas barrier laminate with higher water vapor barrier properties can be obtained by using a composite of an acrylic polyol resin obtained by polymerizing monomers with carboxyl groups and an isocyanate compound.

[0092] There are no particular limitations on the hydroxyl-containing acrylic polyol resin that can be used in the base coating 15, but a hydroxyl value of 50 mg KOH / g or more and 250 mg KOH / g or less is preferred. Here, the hydroxyl value (mg KOH / g) is an indicator of the amount of hydroxyl groups in the acrylic polyol resin, representing the number of mg of potassium hydroxide required to acetylate the hydroxyl groups in 1 g of acrylic polyol resin. Furthermore, there are no particular limitations on the weight-average molecular weight of the acrylic polyol resin, but specifically, it is preferably 3000 or more and 200000 or less. Particularly preferred is 5000 or more and 100000 or less. Even more preferred is 5000 or more and 40000 or less.

[0093] As isocyanate compounds, those with two or more NCO groups in their molecules are used. Examples of mono-system isocyanates include aromatic isocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), and tetramethylxylene diisocyanate (TMXDI); and aliphatic isocyanates such as hexamethylene diisocyanate (HDI), diisocyanate-methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H12MDI). Polymers or derivatives of these mono-system isocyanates can also be used. Examples include trimer ureate types, adduct types reacting with 1,1,1-trimethylolpropane, and biuret types reacting with biuret.

[0094] Isocyanate compounds can be selected from the above-mentioned isocyanate compounds or their polymers and derivatives, and one or more of them can be used in combination.

[0095] As an example of the base coating layer 15, it is formed by coating a solution consisting of the aforementioned acrylic polyol resin, the aforementioned isocyanate compound, and a solvent onto the substrate layer 10, and then allowing it to react and cure. The equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound to the hydroxyl group of the acrylic polyol resin is preferably 0.3 to 2.5 or less. The solvent used here can be any solvent capable of dissolving the aforementioned acrylic polyol resin and isocyanate compound. Examples of solvents include methyl acetate, ethyl acetate, butyl acetate, cyclohexanone, acetone, methyl ethyl ketone, dioxolane, tetrahydrofuran, etc. It should be noted that, in practice, one or more of these solvents can be used in combination.

[0096] The thermoplastic resin forming the base coating 15 can be appropriately selected from polyols having two or more hydroxyl groups, such as acrylic polyols, polyester polyols, polycarbonate polyols, polyether polyols, polycaprolactone polyols, epoxy polyols, polyethylene-based resins such as polyvinyl acetate or polyvinyl chloride, polyvinylidene chloride resins, polystyrene resins, polyethylene resins, polypropylene resins, and polyurethane resins. Furthermore, they can be mixed in any ratio. The hydroxyl value of the polyol is not particularly limited, but is preferably 10 mg KOH / g or more and 250 mg KOH / g or less.

[0097] The UV-curable or electron-beam-curable resin used to form the base coating 15 is not particularly limited, but preferably includes a resin with a hydroxyl value in the range of 10 to 100 mg KOH / g. Furthermore, the organic polymer resin is not particularly limited, but preferably includes a resin with an acid value in the range of 10 to 100 mg KOH / g. Here, acid value (mg KOH / g) represents the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc., contained in 1 g of sample. Additionally, the organic polymer resin preferably includes at least a thermoplastic resin. When the hydroxyl value or acid value is less than 10 mg KOH / g, the chemical bonding force between the functional groups and the surface of the gas barrier layer 20 weakens, and the adhesion between the functional groups and the gas barrier layer 20 tends to decrease. When the hydroxyl value or acid value exceeds 100 mg KOH / g, hydroxyl-containing precipitates generated by the decomposition of the base coating 15 during durability tests such as damp heat resistance tests tend to hinder the adhesion between the base coating 15 and the gas barrier layer 20.

[0098] Monomers that can be used to form the UV-curable or electron-beam-curable resin of the base coating 15 include, for example, monofunctional monomers such as ethyl methacrylate, ethylhexyl methacrylate, styrene, methylstyrene, and N-vinylpyrrolidone; and 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. Oligomers that can be used in this UV-curable or electron-beam-curable resin include urethane acrylates, epoxy acrylates, and polyester acrylates.

[0099] The proportion of the organic polymer resin used to form the base coating 15 is not particularly limited when two or more of the following are selected from thermosetting resins, thermoplastic resins, UV-curable resins, and electron beam-curable resins.

[0100] In addition to organic polymer resins, the base coating 15 may also contain additives as needed. Examples of additives include antioxidants, weather resistant agents, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, silane coupling agents, etc.

[0101] The thickness of the base coating 15 is preferably 0.05 μm to 10.0 μm. Particularly preferred is 0.05 μm to 5.0 μm. When the thickness is less than 0.05 μm, the adhesion between the substrate layer 10 and the gas barrier layer 20 becomes insufficient. When the thickness is greater than 10.0 μm, the influence of internal stress increases, the gas barrier layer 20 cannot be neatly stacked, the barrier effect becomes insufficient, and the transparency and coating precision also become insufficient.

[0102] As a method for forming the base coating layer 15, conventional coating methods can be used. For example, known methods such as dip coating, roller coating, gravure coating, reverse coating, air knife coating, comma coating, mold coating, screen printing, spraying, gravure offset coating, and organic vapor deposition can be used. Regarding the drying method, one or more methods of applying heat, such as hot air drying, hot roller drying, high-frequency irradiation, infrared irradiation, UV irradiation, and electron beam irradiation, can be used in combination. Alternatively, transfer methods such as adhesive transfer, heat transfer, and UV transfer can be used to transfer the film obtained by pre-coating other resin substrates by the above-described forming methods onto the substrate layer 10.

[0103] The gas barrier membranes according to various embodiments of the present invention will be further described using examples and comparative examples. The scope of the present invention is not limited to the specific details of the examples and comparative examples.

[0104] (Example 1)

[0105] A 20 μm thick biaxially stretched polypropylene film was used as the substrate layer. The partial pressure of m / z18 in the film-forming chamber, as measured by a manometer, was adjusted to 0.02 Pa by using Meissner coils (cooling temperature: -120°C) located near the roll-out rollers in both the film-forming chamber and the roll-out / take-out chamber. Inside the film-forming chamber, a SiOx vapor deposition material with an appropriately adjusted Si to SiO2 ratio was sublimated, and a barrier layer composed of silicon oxide (SiOx) (40 nm thick, O / Si 1.7) was formed on the substrate layer by electron beam evaporation.

[0106] The gas barrier membrane described in Example 1 was fabricated using the above methods.

[0107] (Example 2)

[0108] The partial pressure of m / z18 was adjusted to 0.01 Pa, and the ratio of Si material to SiO2 material was appropriately adjusted so that the O / Si ratio of the gas barrier layer was 1.3. Otherwise, the gas barrier film involved in Example 2 was fabricated by the same steps as in Example 1.

[0109] (Example 3)

[0110] The partial pressure of m / z18 was adjusted to 0.04 Pa, and the ratio of Si material to SiO2 material was appropriately adjusted so that the O / Si ratio of the gas barrier layer was 1.8. Otherwise, the gas barrier film involved in Example 3 was fabricated by the same steps as in Example 1.

[0111] (Example 4)

[0112] Except for adjusting the partial pressure of m / z18 to 0.01 Pa, the gas barrier membrane involved in Example 4 was prepared by the same steps as in Example 1.

[0113] (Example 5)

[0114] Except for adjusting the partial pressure of m / z18 to 0.04 Pa, the gas barrier membrane involved in Example 5 was prepared by the same steps as in Example 1.

[0115] (Example 6)

[0116] Except for adjusting the thickness of the barrier layer to 10 nm, the barrier film involved in Example 6 was fabricated using the same steps as in Example 1.

[0117] (Example 7)

[0118] Except for adjusting the thickness of the barrier layer to 120 nm, the barrier film involved in Example 7 was fabricated using the same steps as in Example 1.

[0119] (Example 8)

[0120] On the gas barrier layer of the gas barrier film involved in Example 1, a coating agent consisting of a mixture of liquid (1) and liquid (2) in a weight ratio of 6:4 was applied by gravure coating and dried to form an outer coating with a thickness of 0.4 μm.

[0121] (1) Solution: Add 89.6 g of hydrochloric acid (0.1 N) to 10.4 g of tetraethoxysilane and stir for 30 minutes to hydrolyze it to obtain a hydrolysis solution with a solid component of 3 wt% (converted to SiO2).

[0122] (2) Liquid: 3wt% water / isopropanol solution of polyvinyl alcohol (water:isopropanol weight ratio 90:10)

[0123] The gas barrier membrane described in Example 8 was fabricated through the above process.

[0124] (Example 9)

[0125] On the gas barrier layer of the gas barrier membrane involved in Example 1, a coating agent with 5 wt% solid components, which is a mixture of an aqueous solution of polyvinyl alcohol, a hydrolyzed solution of tetraethoxysilane, and a hydrolyzed solution of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate silane coupling agent in a dry solid component weight ratio of 30:60:10, is applied by gravure coating and dried to form an outer coating with a thickness of 0.4 μm.

[0126] The gas barrier membrane described in Example 9 was fabricated through the above process.

[0127] (Example 10)

[0128] A mixed solution of acrylic polyol and isocyanate was applied to the substrate layer by gravure coating and dried to form a base layer with a thickness of 0.2 μm. A gas barrier layer 20 was formed on the base layer using the same steps as in Example 1, thereby producing the gas barrier film of Example 10.

[0129] (Comparative Example 1)

[0130] Without using Meissner coils located in the film-forming chamber and the winding-out chamber, the partial pressure of m / z18 in the film-forming chamber, measured by a manometer during film formation, was set to 0.10 Pa, and the ratio of Si material to SiO2 material was adjusted to make the O / Si ratio of the barrier layer 1.9. Otherwise, the barrier film involved in Comparative Example 1 was fabricated using the same steps as in Example 1.

[0131] (Comparative Example 2)

[0132] The partial pressure of m / z18 was adjusted to 0.04 Pa, and SiO2 material was used as the SiOx material without mixing Si material. Otherwise, the gas barrier film 1 involved in Comparative Example 2 was fabricated through the same steps as in Example 1. The O / Si ratio of the gas barrier layer in Comparative Example 2 was set to 2.0.

[0133] (Comparative Example 3)

[0134] Without using the Meissner coils located in the film-forming chamber and the winding-out chamber, the partial pressure of m / z18 in the film-forming chamber, as measured by a manometer during film formation, was set to 0.10 Pa. Otherwise, the gas barrier film involved in Comparative Example 3 was prepared by following the same steps as in Example 1.

[0135] (Comparative Example 4)

[0136] Using only the Meissner coil located in the film-forming chamber, the partial pressure of m / z18 in the film-forming chamber, as measured by a manometer, was set to 0.07 Pa. Otherwise, the gas barrier film involved in Comparative Example 4 was fabricated using the same steps as in Example 1.

[0137] The laminates involved in the examples and comparative examples were evaluated as follows. Evaluations were performed on three samples in each example.

[0138] (FT-IR analysis)

[0139] FT-IR analysis was performed using a Fourier transform infrared spectrometer (FT / IR-4600) manufactured by Nippon Spectroscopy Corporation, under the following measurement conditions.

[0140] • Measurement method: Reflection ATR method (measured from the gas barrier layer side of the barrier membrane)

[0141] • Atmosphere measurement:

[0142] • Measurement temperature: room temperature

[0143] • ATR crystal: germanium (wavenumber range 600-5500 cm⁻¹) -1 )

[0144] • Resolution: 4.0cm -1

[0145] Total number of times: 64

[0146] In the infrared absorption spectra obtained by FT-IR analysis, using the software provided with the device, the absorption spectra from Si-O-Si bonds (720-1320 cm⁻¹) were analyzed. -1 The peak area of ​​) and the peaks originating from OH bonds (3100-3700 cm⁻¹) -1The peak area of ​​) and the peak area from Si-OH bonds (830-910 cm⁻¹) -1 The peak area of ​​) and the peak area from Si-H bonds (2100-2200 cm⁻¹) -1 A baseline is drawn connecting the two ends of the defined range at the peak area of ​​the spectrum, and the area enclosed by the spectrum and the baseline is calculated. It should be noted that regions below the baseline are ignored and not included in the area. FT-IR analysis is performed using the ATR method, but the area ratios shown below are based on the uncorrected data, i.e., without ATR correction or baseline correction.

[0147] (XPS analysis of the gas barrier layer)

[0148] The composition and bonding state of the inorganic oxide film serving as the gas barrier layer were determined using an X-ray photoelectron spectroscopy system (JPS-9010MX) manufactured by JEOL Ltd. The X-ray source was MgKα, and the path energy was set to 5 eV. Si was measured in the range of 95–106 eV. 2p A narrow spectrum, measuring O in the range of 525–538 eV. 1s A narrow spectrum, measuring C in the range of 278–290 eV. 1s Narrow spectrum. Furthermore, to avoid noise interference, each narrow spectrum was scanned and accumulated more than 30 times. At this time, to avoid changes in the chemical bonding state of the silicon oxide film due to reduction or mixing caused by argon (Ar) ion collisions, the composition of the outermost surface was measured without argon etching. Additionally, corrections were made for peak shifts caused by charging, so that C detected from surface contaminant hydrocarbons... 1s The peak value is 284.6 eV.

[0149] (Evaluation of water vapor barrier performance)

[0150] For each example involving a gas barrier membrane, a water vapor transmission rate measuring device manufactured by Mocon, Inc. (product name: PERMATRAN3 / 34G, measurement conditions: 40℃-90%RH, unit: g / (m)) was used. 2 • (day), to evaluate water vapor transmission rate (WVTR).

[0151] The results are shown in Table 1.

[0152] [Table 1]

[0153] The gas barrier films involved in the embodiments are all based on the 3100 cm⁻¹ of the inorganic oxide film layer 13 calculated from the FT-IR of the OH bonds. -1 Above 3700cm -1The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is below 0.25; the 830 cm⁻¹ peak from the Si-OH bond... -1 Above 910cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is below 0.025; the 2100 cm⁻¹ peak from the Si-H bond... -1 Above 2200cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The ratio of the peak areas of the following absorption peaks is less than 0.003.

[0154] The WVTR deviations of the embodiments were all below ±0.5g (standard deviation below 0.5g), indicating stability.

[0155] On the other hand, Lots 1 to 2 in Comparative Examples 1 to 3 and Comparative Example 4 are: 3100 cm⁻¹ from OH bonds calculated by FT-IR of the inorganic oxide film 13. -1 Above 3700cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks exceeds 0.25; the 830 cm⁻¹ peak from the Si-OH bond... -1 Above 910cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks exceeds 0.025; the 2100 cm⁻¹ peak from the Si-H bond... -1 Above 2200cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks exceeds 0.003.

[0156] The WVTR deviations of Comparative Examples 1–4 all exceeded ±0.5g (standard deviation exceeded 0.5g), and the quality was also unstable. For the only example with a WVTR less than 1.0g (m... 2Lot3 of Comparative Example 4 (day), the 3100 cm⁻¹ of the inorganic oxide film 13, calculated by FT-IR from the OH bonds. -1 Above 3700cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is below 0.25; the 830 cm⁻¹ peak from the Si-OH bond... -1 Above 910cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is less than 0.025; and the peaks originating from the Si-H bond at 2100 cm⁻¹ -1 Above 2200cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratios of the following absorption peaks are below 0.003. Therefore, these three parameters are useful for evaluating the performance of transparent inorganic oxide films, providing information that cannot be obtained simply by looking at the O / Si ratio.

[0157] Furthermore, as can be seen from the results of the embodiments and comparative examples, when the partial pressure of m / z18 in the film-forming chamber is set to 0.05 Pa or less using a gas adsorption device, a barrier layer can be formed on the substrate layer passing through the film-forming chamber by using a vapor deposition material made of mixed Si material and SiO2 material, thereby stably manufacturing the barrier film according to this embodiment.

[0158] It is believed that, compared to Comparative Example 4, which was fabricated without using a gas adsorption device in the roll-out chamber, the gas barrier film of Example 1 improved the water vapor barrier properties of the initially formed vapor-deposited film on the substrate layer by using a gas adsorption device in the roll-out chamber. Therefore, stable water vapor barrier properties can be obtained throughout the gas barrier layer. In particular, even when the thickness of the gas barrier layer is set to 40 nm as in Example 1, suitable water vapor barrier properties can be obtained by improving the water vapor barrier properties of the initially formed vapor-deposited film.

[0159] The various embodiments and examples of the present invention have been described above. However, the specific configuration is not limited to these embodiments, and also includes changes and combinations of configurations that do not depart from the spirit of the present invention.

[0160] Explanation of symbols

[0161] 1, 2, 2A Gas Barrier Membrane

[0162] 10 Substrate layer

[0163] 15. Primer coating

[0164] 20 Gas barrier layer

[0165] 30 Outer coating

[0166] 40 film-forming chambers

[0167] 41 Plastic film

[0168] 42 winding roll

[0169] 43 Film forming roller

[0170] 44. Take-up roller

[0171] 45 Evaporation materials

[0172] 46 Electron Beam Gun

[0173] 47 vapor-deposited particles

[0174] 48, 49 Gas adsorption devices

[0175] 50 rolls unloading and retrieving room

[0176] 100 Film Forming Device

Claims

1. A gas barrier membrane, comprising: Substrate layer, and A barrier layer containing silicon oxide is formed on the substrate layer. In the infrared absorption spectrum from the surface side of the gas barrier layer, the 3100 cm⁻¹ value originates from the OH bond. -1 Above 3700cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is less than 0.

25.

2. The gas barrier membrane according to claim 1, wherein, In the infrared absorption spectrum from the surface side of the barrier layer, the 830 cm⁻¹ value originates from the Si-OH bond. -1 Above 910cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The peak area ratio of the following absorption peaks is less than 0.

025.

3. The gas barrier membrane according to claim 1 or 2, wherein, In the infrared absorption spectrum from the surface side of the barrier layer, the 2100 cm⁻¹ value originates from the Si-H bond. -1 Above 2200cm -1 The peak area of ​​the following absorption peaks is 720 cm⁻¹ from the Si-O-Si bond. -1 The above 1320cm -1 The ratio of the peak areas of the following absorption peaks is less than 0.

003.

4. The gas barrier membrane according to claim 1, wherein, On the surface of the barrier layer, Si was measured using X-ray photoelectron spectroscopy (XPS). 3+ Si 2+ Si + The peak of Si (b=Si) 3 + Si 2+ Si + The total peak of Si relative to the Si2p peak (a=Si) 4+ Si 3+ Si 2+ Si + The value of b / a in the ratio of Si is greater than 0.

122.

5. The gas barrier membrane according to claim 1, wherein, On the surface of the gas barrier layer, the ratio of the number of oxygen (O) atoms to the number of silicon (Si) atoms (O / Si), as determined by X-ray photoelectron spectroscopy (XPS), is 1.41 to 1.9 or less.

6. The gas barrier membrane according to claim 1, wherein, The thickness of the gas barrier layer is more than 10 nm and less than 60 nm.

7. The gas barrier membrane according to claim 1, It also has an outer coating layer formed on the gas barrier layer.

8. The gas barrier membrane according to claim 7, wherein, The outer coating comprises at least one of a metal alkoxide, a hydrolysis product of a metal alkoxide, a reaction product of a metal alkoxide, and a reaction product of a hydrolysis product of a metal alkoxide; and a water-soluble polymer.

9. The gas barrier membrane according to claim 7, wherein, The outer coating comprises at least one of a silane coupling agent, a hydrolysis product of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolysis product of a silane coupling agent.

10. The gas barrier membrane according to claim 1, It also includes a base coating layer disposed between the substrate layer and the gas barrier layer. The base coating comprises at least one of thermosetting resin, thermoplastic resin, ultraviolet-curable resin, and electron beam-curable resin.

11. The gas barrier membrane according to claim 1, It also includes a base coating layer disposed between the substrate layer and the gas barrier layer. The base coating is composed of a cured product comprising a composition of an acrylic polyol resin having organic acid groups and a polyisocyanate.

12. A method for manufacturing a gas barrier membrane, which is the method for manufacturing a gas barrier membrane according to claim 1, wherein, A film-forming apparatus is prepared, which has a film-forming chamber and a roll-out / roll-up chamber, and has gas adsorption devices in both the film-forming chamber and the roll-out / roll-up chamber; The substrate layer is mounted in a coil shape on the take-up and take-up chamber. The gas adsorption device in the film-forming chamber and the winding-out chamber is activated, and the partial pressure value of m / z18 in the film-forming chamber is set to below 0.05 Pa. The gas barrier layer is formed on the substrate layer passing through the film-forming chamber using a vapor deposition material made of mixed Si material and SiO2 material.

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