Gas barrier films, packaging films, packaging materials, packaging bags and packaging products

Abstract

To provide a gas barrier film that has good and stable water vapor barrier properties while incorporating a gas barrier layer containing silicon dioxide. [Solution] The gas barrier film according to the present invention comprises a substrate layer and a gas barrier layer made of an inorganic oxide containing Si, Ga, and O, provided on one or both sides of the substrate layer, wherein the surface of the gas barrier layer is measured by X-ray photoelectron spectroscopy, and Si 2p Peak, Ga 3d Peak and O 1s The Ga / (Si+Ga) ratio, calculated using the peak area intensity, is between 0.05 and 0.80, and the O / (Si+Ga) ratio is between 1.00 and 1.80.

Description

[Technical Field]

[0001] The present invention relates to gas barrier films, packaging films, packaging materials, packaging bags, and packaging products. [Background technology]

[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] Another configuration of gas barrier films is 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 one 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). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Unexamined Patent Publication No. 60-49934 [Patent Document 2] Japanese Patent Application Publication No. 3-100164 [Patent Document 3] Japanese Patent Application Publication No. 6-16848 [Overview of the Initiative] [Problems that the invention aims to solve]

[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] One aspect of the present invention aims to provide a gas barrier film that can suppress variations in water vapor barrier properties. [Means for solving the problem]

[0009] One aspect of the present invention is, A base layer and A gas barrier layer made of an inorganic oxide containing Si, Ga, and O is provided on one or both sides of the substrate layer, Equipped with, The surface of the gas barrier layer, measured by X-ray photoelectron spectroscopy, is composed of Si 2p Peak, Ga 3d Peak and O 1s This gas barrier film has a Ga / (Si+Ga) ratio of 0.05 to 0.80 and an O / (Si+Ga) ratio of 1.00 to 1.80, calculated using the peak area intensity. [Effects of the Invention]

[0010] According to one aspect of the present invention, a gas barrier film can be provided that can suppress variations in water vapor barrier properties. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view showing an example of a gas barrier film according to the first embodiment of the present invention. [Figure 2] This is a schematic diagram showing an example of a gas barrier film manufacturing apparatus. [Figure 3] This is a schematic cross-sectional view showing an example of a gas barrier film according to a second embodiment of the present invention. [Figure 4] This is a schematic cross-sectional view showing an example of a gas barrier film according to a third embodiment of the present invention. [Modes for carrying out the invention]

[0012] 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. Also, the scale of each component in the drawings may differ from the actual scale. In this specification, the "~" indicating a numerical range means that the values ​​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.

[0013] <First Embodiment> [Gas barrier film] A gas barrier film according to a 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 upper main surface in Figure 1).

[0014] In Figure 1, the direction from the substrate layer 10 of the gas barrier film 1A toward the gas barrier layer 20 is sometimes referred to as "up" or "upward," and the opposite direction as "down" or "downward," but this does not represent a universal up-down relationship.

[0015] 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.

[0016] There are no particular restrictions on the thickness of the base layer 10, and it can be set appropriately depending on the application, for example, it may be about 9 to 300 μm. If 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.

[0017] In this specification, the thickness of the base layer 10 refers to the length of the base layer 10 in the direction perpendicular to the main surface of the base layer 10. The thickness of the base layer 10 may be, for example, the thickness measured at any point in the cross-section of the base layer 10, or it may be the average of several measurements taken at any point. Hereafter, the definition of thickness will be defined similarly for other components.

[0018] The base material layer 10 may be in the form of a long material or a single sheet, but a long material is preferred. 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 preferred. There is no upper limit to the length, and for example, it may be about 10 km long.

[0019] The base layer 10 may optionally contain additives such as antistatic agents, ultraviolet absorbers, plasticizers, or lubricants.

[0020] 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, as well as chemical modification treatments such as acid or alkali treatment, in order to improve adhesion with the gas barrier layer 20.

[0021] Since the surface of the base layer 10 contributes 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 base layer 10 be as smooth as possible.

[0022] 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 containing silicon (Si), gallium (Ga), and oxygen (O).

[0023] X-ray photoelectron spectroscopy (hereinafter sometimes referred to as "XPS") can be used to analyze the gas barrier layer 20. XPS is a technique that irradiates the object to be measured with soft X-rays and analyzes the energy of photoelectrons emitted from the surface of the object, and can analyze the composition of a region at a depth of several nanometers from the surface of the object.

[0024] If the gas barrier layer 20 does not contain metal elements other than silicon and gallium, the Si content of the surface of the gas barrier layer 20 is measured by XPS. 2p Peak and Ga 3dThe elemental composition ratio Ga / (Si + Ga) calculated using the peak-to-peak area intensity is within the range of 0.05 to 0.80, more preferably within the range of 0.10 to 0.50, and even more preferably within the range of 0.15 to 0.40.

[0025] In addition, Ga and Si in "Ga / (Si + Ga)" are the atomic weights of Ga (unit: atomic %) and Si (unit: atomic %) determined from the XPS measurement results. "Ga / (Si + Ga)" is the ratio of the atomic weight of gallium to the sum of the atomic weights of silicon and gallium (Si + Ga). The atomic weight of silicon can be calculated based on the area intensity of the XPS spectrum of Si 2p The maximum value of the peak of the XPS spectrum of Si can be found, for example, in the range of about 98.8 to 104.0 eV. The atomic weight of gallium can be calculated based on the area intensity of the XPS spectrum of Ga 2p The maximum value of the peak of the XPS spectrum of Ga can be found, for example, in the range of about 18.0 to 21.6 eV. In XPS, since the detection sensitivity varies depending on the element and the electronic state, the atomic weight is calculated by the relative sensitivity factor method using the relative sensitivity coefficient specific to the XPS apparatus used for the measurement with respect to the area intensity of the target XPS spectrum. Also, the maximum value of the peak of each XPS spectrum of Si 3d and Ga 3d may vary due to charging or the like and is not necessarily limited to the above range. 2p and Ga 3d The area intensity is the integrated value of the peak of the XPS spectrum corresponding to the type of atomic bond within a predetermined binding energy range measured in XPS measurement, and for example, it means the area of the region surrounded by the baseline determined by the Shirley method and the curve of the XPS spectrum. The area intensity of the XPS spectrum of Si

[0026] is, for example, the integrated value of the XPS spectrum of Si in the binding energy range of about 100.0 to 107.0 eV. 2p The area intensity of the XPS spectrum of Ga 2p is the integrated value of the XPS spectrum of Ga in the binding energy range of about 18.0 to 21.6 eV. 3dThe peaks in the XPS spectrum are, for example, Bi in the binding energy range of approximately 17.5–24.5 eV. 4f This is the integrated value of the XPS spectrum.

[0027] Gallium oxide, an oxide of gallium, forms a stable glass network structure when combined with silicon oxide. The network structure formed by the combination of gallium oxide and silicon oxide reduces the intermolecular gaps compared to a network structure composed only of silicon and oxygen bonds, because gallium is incorporated into the network structure composed of silicon and oxygen bonds. Therefore, the gas barrier layer 20 can have a denser structure than when formed only of silicon oxide, making it more difficult for water vapor to permeate and improving water vapor barrier properties. If Ga / (Si+Ga) is less than 0.05, the entire film of the gas barrier layer 20 is less likely to have a dense structure, and variations in the ease of water vapor permeation are likely to occur, so it may not be possible to stably improve the water vapor barrier properties of the entire film of the gas barrier layer 20. If Ga / (Si+Ga) exceeds 0.80, a stable network structure cannot be formed in the gas barrier layer 20, making it easier for water vapor to permeate. As a result, good and stable water vapor barrier properties and other gas barrier properties may not be obtained for the entire gas barrier layer 20 film.

[0028] Furthermore, the Si of the gas barrier layer 20, as measured by XPS, 2p Peak, Ga 3d Peak and O 1s The elemental composition ratio O / (Si+Ga) calculated using the peak area intensity is in the range of 1.00 to 1.80, more preferably in the range of 1.20 to 1.70, and even more preferably in the range of 1.40 to 1.65. If O / (Si+Ga) is less than 1.00, the transparency of the gas barrier layer 20 decreases, and if O / (Si+Ga) exceeds 1.80, sufficient water vapor barrier properties cannot be obtained for the entire film of the gas barrier layer 20.

[0029] Note that in "O / (Si+Ga)", O represents the atomic weight of oxygen (unit: atomic %) obtained from the XPS measurement results. "O / (Si+Ga)" is the ratio of the atomic weight of oxygen to the sum of the atomic weights of silicon and gallium (Si+Ga). The atomic weight of oxygen is measured by XPS. 1s It can be calculated based on the area intensity of the XPS spectrum. 1s The maximum peak value of the XPS spectrum is observed, for example, in the range of approximately 532.0–533.5 eV. 1s The area intensity of the XPS spectrum is, for example, the O in the binding energy range of approximately 528.0 to 536.5 eV. 1s This is the integrated value of the XPS spectrum.

[0030] In XPS, the detection sensitivity differs depending on the element and electronic state. Therefore, the atomic weight of O is calculated using the relative sensitivity factor method with respect to the area intensity of the target XPS spectrum, similar to how the atomic weights of Bi and Si are determined. 1s The maximum peak value of the XPS spectrum may vary depending on factors such as charging, and is not necessarily limited to the range mentioned above.

[0031] In general XPS, sputter etching with argon (Ar) ions is sometimes used for analysis of the film, but this can damage the bonds between metal elements and oxygen, making it difficult to obtain accurate elemental composition ratios or peak area ratios. Therefore, in this embodiment, Bi / (Si+Bi) and O / (Si+Bi) of the gas barrier layer 20 are defined by measurements taken on the surface of the gas barrier layer 20.

[0032] The method for forming the gas barrier layer 20 is not particularly limited, and general film deposition methods such as vacuum deposition, ion plating, sputtering, and plasma chemical vapor deposition (PECVD) can be used. Among these, vacuum deposition is preferred due to its superior productivity.

[0033] When using vacuum deposition, the heating method for the inorganic oxide containing silicon, gallium, and oxygen, which forms the gas barrier layer 20, can be, for example, resistance heating, high-frequency induction heating, or electron beam heating. Furthermore, by combining this with plasma-assisted or ion beam-assisted methods, the gas barrier layer 20 can be formed more densely, improving its water vapor barrier properties.

[0034] When forming the gas barrier layer 20 by vacuum deposition, a combination of silicon oxide and gallium oxide powder materials can be used. When the silicon oxide and gallium oxide powder materials are heated in a vacuum, both silicon oxide and gallium oxide vaporize when heated to approximately 1500-2000°C, so a film consisting of an inorganic oxide containing silicon, gallium, and oxygen can be easily formed as the gas barrier layer 20.

[0035] The gas barrier layer 20 may contain at least one metal element (A) in addition to silicon and gallium. The metal element (A) is not particularly limited and includes, for example, magnesium (Mg), aluminum (Al), calcium (Ca), scandium (Sc), titanium (Ti), vanadium (V), zinc (Zn), germanium (Ge), ytrim (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), barium (Ba), hafnium (Hf), tungsten (W), tantalum (Ta), and bismuth (Bi). The metal element (A) may be contained not only as one type but also in combination of multiple types. Among these, magnesium, aluminum, tungsten, indium, tin, and bismuth are preferred because they provide good gas barrier properties and transparency when an oxide film is formed. More preferably, magnesium, aluminum, tungsten, tin, and bismuth are preferred. By including one or more metal elements (A) in addition to silicon and gallium, the gas barrier layer 20 can improve gas barrier properties such as water vapor barrier properties with respect to the substrate layer 10, improve temperature and humidity durability, or adjust optical properties such as refractive index.

[0036] The thickness of the gas barrier layer 20 varies depending on the configuration and deposition method used, but a general thickness is acceptable, for example, it may be set appropriately within the range of 1 to 200 nm. If the thickness of the gas barrier layer 20 is 1 nm or more, a uniform film is easily obtained, and because 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 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.

[0037] 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, and 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.

[0038] 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.

[0039] The vacuum deposition chamber 102 is a space in which vapor 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, and is configured to be able to form a vacuum state.

[0040] 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.

[0041] 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.

[0042] The winding roll 105 winds up the plastic film PF that is conveyed from the film-forming roll 104.

[0043] The electron beam gun 106 is a heating means for heating the deposition material VM in the deposition chamber 102.

[0044] The gas adsorption device 107 is a device that has the function of condensing or adsorbing gases such as water vapor, and is not particularly limited as long as it is a device capable of condensing or adsorbing 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 from the viewpoint of obtaining sufficient performance in condensing or adsorbing gases.

[0045] 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 water vapor around the deposition material VM in the film formation chamber 102.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] The water vapor transmission rate of gas barrier film 1A is 2.0 g / (m²). 2It is preferable that it be less than 1.90 g / (m²) 2 It is more preferable that it be less than or equal to 1.80 g / (m²). 2 It is even more preferable that it be 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. Therefore, 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.

[0050] 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".

[0051] Furthermore, the standard deviation of the water vapor transmission rate of the gas barrier film 1A is preferably less than 0.1, more preferably 0.09 or less, and even more preferably 0.08 or less. 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 value. 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.

[0052] The standard deviation of water vapor transmission may be calculated using measurements taken at multiple locations (e.g., three locations) in the MD direction at the center of a film sample on the surface of the gas barrier layer 20 of the gas barrier film 1A, or at the center of film samples from different lots (e.g., one location for each of three lots).

[0053] Thus, the gas barrier film 1A has a gas barrier layer 20 composed of a film made of an inorganic oxide containing Si, Ga, and O, and the surface of the gas barrier layer 20 is measured by XPS, and Si 2p Peak, Ga 3d Peak and O 1s The Ga / (Si+Ga) ratio, calculated using the peak area intensity, is set to 0.05 to 0.80, and the O / (Si+Ga) ratio is set to 1.00 to 1.80. As a result, the gas barrier layer 20 can have a dense network structure throughout almost its entire surface that suppresses water vapor permeation, thereby reducing variations in water vapor barrier properties across the entire surface of the gas barrier layer 20 and improving the uniformity of water vapor barrier properties across the entire surface of the gas barrier layer 20. Therefore, the gas barrier film 1A can suppress variations in water vapor barrier properties.

[0054] Therefore, the gas barrier film 1A can stably exhibit excellent water vapor barrier properties across the entire surface of the gas barrier layer 20 by suppressing variations in water vapor barrier properties across the entire surface of the gas barrier layer 20.

[0055] Furthermore, the gas barrier layer 20 can have a dense mesh structure throughout its entirety that suppresses the permeation of water vapor, thereby enhancing the water vapor barrier properties of the gas barrier layer 20.

[0056] 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. Therefore, gas barrier film 1A can be suitably used as a packaging film for packaging materials and the like.

[0057] [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.

[0058] (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 more isocyanate compound with a main component such as a polyester polyol, polyether polyol, acrylic polyol, or carbonate polyol. Each polyol may be used individually or in combination of two or more. From the viewpoint of heat resistance, the adhesive layer may be composed of a two-component curing type urethane adhesive.

[0059] To improve adhesion, the polyurethane resin described above may contain carbodiimide compounds, oxazoline compounds, epoxy compounds, phosphorus compounds, or silane coupling agents. Furthermore, from an environmental perspective, the adhesive may use a polymer component derived from biomass or a biodegradable component. In addition, the adhesive may have gas barrier properties.

[0060] The amount of adhesive to be applied is not particularly limited and may be selected arbitrarily as appropriate, but from the viewpoint of obtaining the desired adhesive strength, conformability, and workability, for example, 0.5 to 10 g / m 2 That is also acceptable.

[0061] (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; 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.

[0062] The sealant layer may or may not be stretched, but it may not be stretched in order to lower the melting point and facilitate heat sealing.

[0063] The thickness of the sealant layer is not particularly limited, but may be appropriately selected depending on the application, for example, it 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.

[0064] The packaging film according to this embodiment, having a gas barrier film according to this embodiment, suppresses variations in water vapor barrier properties across the entire surface of the film, and can have good and stable water vapor barrier properties. Therefore, it can be suitably used in the manufacture of packaging bags for storing contents such as pharmaceuticals and food. Thus, 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.

[0065] [Packaging materials] 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.

[0066] The packaging material according to this embodiment is formed of a packaging film equipped with a gas barrier film according to this embodiment. Therefore, the packaging material according to this embodiment has reduced variation in water vapor barrier properties across its entire surface and 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. Thus, 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.

[0067] [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 as described above. Various contents such as food and pharmaceuticals can be contained in the packaging bag.

[0068] The 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, or by overlapping two packaging films or packaging materials so that the sealant layers face each other, and then heat-sealing all four sides.

[0069] 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 its contents.

[0070] [Packaging products] 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 manufacturing the packaging film or packaging material with the contents placed between opposing surfaces of the packaging film or packaging material.

[0071] 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.

[0072] In addition, the following modifications may be made in this embodiment.

[0073] For example, the gas barrier film 1A may have gas barrier layers 20 on both sides of the substrate layer 10, one side and the other side (the main downward surface in Figure 1). In this case, the two gas barrier layers may be the same or different.

[0074] 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. Examples of plasma treatments for the substrate layer 10 include RIE (Reactive Ion Etching), corona treatment, hollow anode plasma treatment, and planar plasma treatment. 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. Known discharge gases such as argon, oxygen, nitrogen, and helium can be used as the gas species for plasma treatment.

[0075] <Second Embodiment> A gas barrier film according to a second embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will now be described. 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.

[0076] Figure 3 is a schematic cross-sectional view showing an example of a gas barrier film according to this embodiment. As shown in Figure 3, the gas barrier film 1B is provided with an overcoat layer 30 on a different surface of the gas barrier layer 20 than the base layer 10, in the gas barrier film 1A according to the first embodiment shown in Figure 1. That is, the gas barrier film 1B is provided with an overcoat layer 30 on the gas barrier layer 20 in the gas barrier film 1A according to the first embodiment shown in Figure 1, and the gas barrier layer 20 and the overcoat layer 30 are laminated on the base layer 10 in this order from the base layer 10 side.

[0077] 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.

[0078] 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.

[0079] 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" refers to a wet film, and "film" refers to a dried film.

[0080] 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 products 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 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.

[0081] Examples of metal alkoxides and their hydrolysates included in organic-inorganic composite films include those represented by the general formula: M(OR)n (where M is a metal element, R is an alkyl group, and n is the valence of the metal), such as tetraethoxysilane [Si(OC2H5)4] and triisopropoxyaluminum [Al(OC3H7)3], as well as their hydrolysates. The film may contain one of these metal alkoxides or their hydrolysates alone, or two or more in combination.

[0082] In the organic-inorganic composite film, the total content of at least one component from among metal alkoxides, their hydrolysates or reaction products, and the reaction products of metal alkoxide hydrolysates may be, for example, 40 to 70% by mass. From the viewpoint of further improving 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, and the reaction products of metal alkoxide hydrolysates in the organic-inorganic composite film may be 50% by mass. From a similar viewpoint, the upper limit of the total content of at least one component from among metal alkoxides, their hydrolysates or reaction products, and the reaction products of metal alkoxide hydrolysates in the organic-inorganic composite film may be 65% by mass.

[0083] 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. From the viewpoint of further improving the gas barrier properties of the overcoat layer 30, it is preferable that the water-soluble polymer includes a polyvinyl alcohol-based polymer.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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. One of these may be included alone, or two or more may be included in combination.

[0088] 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.

[0089] 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.

[0090] In an organic-inorganic composite film, the total content of the silane coupling agent, its hydrolysate or reaction product, and at least one of the reaction products of the hydrolysate of the silane coupling agent is preferably, for example, 1 to 15% by mass, and more preferably 2 to 12% by mass. When the total content of the silane coupling agent, its hydrolysate or reaction product, and at least one of the reaction products of the hydrolysate of the silane coupling agent is 1 to 15% by mass, the gas barrier properties of the organic-inorganic composite film can be further improved.

[0091] 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.

[0092] Thus, the gas barrier film 1B has an overcoat layer 30 on top of the gas barrier layer 20, and by making the overcoat layer 30 out of the organic-inorganic composite film described above, it maintains excellent water vapor barrier properties even when subjected to boiling or retort sterilization.

[0093] <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 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.

[0094] Figure 4 is a schematic cross-sectional view showing an example of a gas barrier film according to this embodiment. As shown in Figure 4, the gas barrier film 1C, in the gas barrier film 1B according to the second embodiment shown in Figure 3, has an undercoat layer 40 between the base layer 10 and the gas barrier layer 20, and 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.

[0095] In addition, the gas barrier film 1C may have an undercoat layer 40 between the substrate layer 10 and the gas barrier layer 20, as in the gas barrier film 1A according to the first embodiment shown in Figure 1.

[0096] Alternatively, the gas barrier film 1C may have a gas barrier layer 20 and an undercoat layer 40 as a set on both the upper and lower surfaces of the base layer 10, and the undercoat layer 40, gas barrier layer 20, and overcoat layer 30 may be laminated on both the upper and lower surfaces of the base layer 10 in this order from the base layer 10 side.

[0097] 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.

[0098] 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 curing resins and electron beam curing resins can be used.

[0099] 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.

[0100] 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, which have hydroxyl groups at their terminals and side chains and react with isocyanate groups of isocyanate compounds.

[0101] (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.

[0102] 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.

[0103] The other monomers mentioned above may be monomers copolymerizable with other monomers besides (meth)acrylic acid derivative monomers, such as styrene monomer, cyclohexylmaleimide monomer, or phenylmaleimide monomer.

[0104] The other monomers mentioned above may themselves have hydroxyl groups at their terminals and side chains.

[0105] 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 it using a composite of an acrylic polyol resin obtained by polymerizing a monomer having a carboxyl group and an isocyanate compound.

[0106] 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 mgKOH / g to 250 mgKOH / g. Here, the hydroxyl value (unit: mgKOH / 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.

[0107] 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.

[0108] 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-type nurate, the adduct-type obtained by reacting with 1,1,1-trimethylolpropane, or the biuret-type obtained by reacting with biuret.

[0109] 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.

[0110] 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.

[0111] 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; and 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.

[0112] 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, while 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. It is also desirable that the organic polymer resin contains at least a thermoplastic resin. If the hydroxyl value or acid value is 10 mgKOH / g or higher, 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 lower, 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.

[0113] Monomers that can be used in the UV-curable or electron-beam-curable resin forming the undercoat layer 40 include, for example, monofunctional monomers such as ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, and N-vinylpyrrolidone. Polyfunctional monomers such as polytrimethylolpropane (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 that can be used in this UV-curable or electron-beam-curable resin include urethane acrylate, epoxy acrylate, and polyester acrylate.

[0114] When using two or more organic polymer resins selected from the above-mentioned thermosetting resins, thermoplastic resins, ultraviolet curing resins, and electron beam curing resins as the undercoat layer 40, the mixing ratio is not particularly limited and may be arbitrarily selected as appropriate.

[0115] The undercoat layer 40 may further contain, as appropriate, any additives in addition to the organic polymer resin. Examples of additives include antioxidants, weathering agents, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, plasticizers, antistatic agents, colorants, fillers, surfactants, and silane coupling agents.

[0116] 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 furthermore, transparency and coating accuracy are also insufficient.

[0117] A general coating method can be used to form the undercoat layer 40. Examples of coating methods include well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and organic vapor deposition.

[0118] 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, in combination.

[0119] Alternatively, the undercoat layer 40 may be formed by transferring a film that has been 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.

[0120] 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 scope of the invention and its equivalents as described in the claims. [Examples]

[0121] The embodiment will be described in more detail below with reference to examples and comparative examples, but this embodiment is not limited to these examples and comparative examples.

[0122] <Fabrication of gas barrier film> [Example 1] A 12 μm thick PET film was used as the substrate layer. In the deposition chamber, a mixture of SiO and Ga2O3 was evaporated, adjusting the ratio so that the elemental composition ratio Ga / (Si+Ga) of the deposition material was 0.20. A gas barrier layer (40 nm thick) consisting of an inorganic oxide containing Si, Ga, and O was formed on one side of the substrate layer by electron beam deposition. A gas barrier film was thus fabricated. (XPS analysis of gas barrier layer) Si x Ga y O (1-x-y) The film composition of the surface of a gas barrier layer was measured by XPS. An X-ray photoelectron spectrometer (JPS-9010MX, JEOL Ltd.) was used for XPS. AlKα was used as the X-ray source, and the analyzer transmission energy was set to 10 eV. To avoid the influence of noise, each narrow spectrum was scanned and integrated more than 30 times. The results of the XPS measurement of the surface of the gas barrier layer showed that Ga / (Si+Ga) was 0.32 and O / (Si+Ga) was 1.40.

[0123] [Example 2] Except for using a mixed material of Si, SiO2, and Ga2O3 whose elemental composition ratio Ga / (Si+Ga) of the deposition material was adjusted to 0.05, the procedure was the same as in Example 1. x Ga y O (1-x-y) A gas barrier layer (film thickness 30 nm) consisting of a film was formed to create a gas barrier film. x Ga y O (1-x-y) The gas barrier layer 20, which consists of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) of 0.05 and an O / (Si+Ga) of 1.50.

[0124] [Example 3] Except for using a mixed material of Si, SiO, and Ga2O3 whose elemental composition ratio Ga / (Si+Ga) of the deposition material was adjusted to 0.20, the procedure was the same as in Example 1. x Ga y O (1-x-y)A gas barrier layer 20 (film thickness 35 nm) consisting of a film was formed to create a gas barrier film. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.21 and an O / (Si+Ga) ratio of 1.05.

[0125] [Example 4] Except for using a mixed material of SiO2 and Ga2O3 with an elemental composition ratio Ga / (Si+Ga) of 0.15 for the deposition material, the procedure was the same as in Example 1, but with respect to Si x Ga y O (1-x-y) A gas barrier layer (film thickness 35 nm) consisting of a film was formed to create a gas barrier film. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.15 and an O / (Si+Ga) ratio of 1.80.

[0126] [Example 5] Except for using a mixed material of Si, SiO2, and Ga2O3 whose elemental composition ratio Ga / (Si+Ga) of the deposition material was adjusted to 0.50, the procedure was the same as in Example 1. x Ga y O (1-x-y) A gas barrier layer (film thickness 40 nm) consisting of a film was formed to create a gas barrier film. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.50 and an O / (Si+Ga) ratio of 1.65.

[0127] [Example 6] A gas barrier film was prepared using the same procedure as in Example 1, except that the film thickness was set to 20 nm. x Ga y O (1-x-y)The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.30 and an O / (Si+Ga) ratio of 1.43.

[0128] [Example 7] A gas barrier film was prepared using the same procedure as in Example 1, except that the film thickness was set to 50 nm. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.31 and an O / (Si+Ga) ratio of 1.42.

[0129] [Example 8] A gas barrier film was prepared using the same procedure as in Example 1, except that the film thickness was set to 100 nm. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.28 and an O / (Si+Ga) ratio of 1.39.

[0130] [Example 9] A coating agent, prepared by mixing liquids (1) and (2) below in a weight ratio of 6:4, was applied to the gas barrier layer of the gas barrier film of Example 1 using the gravure coating method and dried to form an overcoat layer with a thickness of 0.4 μm. (1) Solution: Add 89.6g of hydrochloric acid (0.1N) to 10.4g of tetraethoxysilane, stir for 30 minutes to hydrolyze, and obtain a hydrolyzed solution with a solid content of 3 wt% (in terms of SiO2). (2) Solution: 3 wt% water / isopropyl alcohol solution of polyvinyl alcohol (water:isopropyl alcohol weight ratio 90:10)

[0131] [Example 10] In Example 1, a coating agent with a solid content of 5 wt%, prepared by mixing an aqueous solution of polyvinyl alcohol, a hydrolysis solution of tetraethoxysilane, and a hydrolysis solution of a 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate silane coupling agent in a dry solid content weight ratio of 30:60:10, was applied to the gas barrier layer of a gas barrier film by gravure coating and dried to form an overcoat layer with a thickness of 0.4 μm. This produced a gas barrier film.

[0132] [Example 11] 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 a 0.2 μm thick undercoat layer. A gas barrier layer was formed on the undercoat layer using the same procedure as in Example 1 to produce a gas barrier film. x Ga y O (1-x-y) The gas barrier layer, consisting of a film, was measured by XPS as described in Example 1, and the results showed a Ga / (Si+Ga) ratio of 0.30 and an O / (Si+Ga) ratio of 1.42.

[0133] [Comparative Example 1] Except for using a gallium-free SiO material, a gas barrier layer (film thickness 40 nm) made of an SiOx film was formed using the same procedure as in Example 1, and a gas barrier film was fabricated. x Since the gas barrier layer, which consists of a film, does not contain gallium, the Ga / (Si+Ga) value of the gas barrier layer measured by XPS as described in Example 1 was 0.00, and the O / (Si+Ga) value was 1.55.

[0134] [Comparative Example 2] Except for using a mixed material of SiO and Ga2O3 with an elemental composition ratio Ga / (Si+Ga) of 0.03 for the deposition material, the procedure was the same as in Example 1, but with a different approach. x Ga y O (1-x-y) A gas barrier layer (film thickness 30 nm) consisting of a film was formed to create a gas barrier film. x Gay O (1-x-y) As a result of measuring the gas barrier layer made of the film by XPS described in Example 1, Ga / (Si+Ga) was 0.03 and O / (Si+Ga) was 1.52.

[0135] [Comparative Example 3] Oxygen was supplied into the film formation chamber, and in an oxygen atmosphere where the flow rate was adjusted so that the pressure (total pressure) of the film formation chamber was in the range of 10 -2 Pa, a mixed material of SiO2 and Ga2O3 with the ratio adjusted so that the elemental composition ratio Ga / (Si+Ga) of the evaporation material was 0.30 was used. Except for this point, Si x Ga y O (1-x-y) A gas barrier layer 20 (film thickness 30 nm) made of the film was formed to produce a gas barrier film. Si x Ga y O (1-x-y) As a result of measuring the gas barrier layer made of the film by XPS described in Example 1, Ga / (Si+Ga) was 0.30 and O / (Si+Ga) was 1.92.

[0136] [Comparative Example 4] Oxygen was supplied into the film formation chamber, and in an oxygen atmosphere where the flow rate was adjusted so that the pressure (total pressure) of the film formation chamber was in the range of 10 -2 Pa, a mixed material of SiO2 and Ga2O3 with the ratio adjusted so that the elemental composition ratio Ga / (Si+Ga) of the evaporation material was 0.03 was used. Except for this point, Si x Ga y O (1-x-y) A gas barrier layer (film thickness 30 nm) made of the film was formed to produce a gas barrier film. Si x Ga y O (1-x-y) As a result of measuring the gas barrier layer made of the film by XPS described in Example 1, Ga / (Si+Ga) was 0.02 and O / (Si+Ga) was 1.89.

[0137] Table 1 shows the presence or absence of an undercoat layer, the thickness and elemental ratio composition of the gas barrier layer, and the presence or absence of an overcoat layer for the gas barrier films of each example and comparative example.

[0138] [evaluation] The following evaluations were performed on the gas barrier films of each example and comparative example.

[0139] (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 / (m²)) was used to measure the water vapor transmission rate. 2 Using a 3D model, the water vapor transmission rate (WVTR) was measured at three locations every 1000m 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). Table 1 shows the measurement results for each WVTR measurement point and the calculated standard deviation.

[0140]

number

[0141] [Table 1]

[0142] Table 1 shows that the gas barrier films in Comparative Examples 1 to 4 exhibited inferior water vapor barrier stability compared to the gas barrier films in each example. This is thought to be because the gas barrier layer either did not contain gallium, the Ga / (Si+Ga) ratio on the surface of the gas barrier layer was less than 0.05, or the O / (Si+Ga) ratio on the surface of the gas barrier layer was greater than 1.80.

[0143] On the other hand, the gas barrier films in each example all showed a WVTR of 2.0 g / (m²) at all measurement points. 2The values ​​were less than 0.5 days, and the standard deviation of WVTR was less than 0.1. Therefore, it was confirmed that if the Ga / (Si+Ga) on the surface of the gas barrier layer of the gas barrier film in each example is 0.05 to 0.80 and the O / (Si+Ga) is 1.00 to 1.80, the gas barrier film can suppress variations in water vapor barrier properties across the entire surface of the gas barrier layer. Thus, it can be said that the gas barrier film in each example can have stable water vapor barrier properties across the entire surface of the gas barrier layer.

[0144] The embodiments of the present invention are, for example, as follows. <1> A base layer and A gas barrier layer made of an inorganic oxide containing Si, Ga, and O is provided on one or both sides of the substrate layer, Equipped with, The surface of the gas barrier layer, measured by X-ray photoelectron spectroscopy, is composed of Si 2p Peak, Ga 3d Peak and O 1s A gas barrier film in which the Ga / (Si+Ga) ratio, calculated using the peak area intensity, is 0.05 to 0.80, and the O / (Si+Ga) ratio is 1.00 to 1.80. <2> The gas barrier layer contains at least one element selected from the group consisting of Mg, Al, W, In, Sn, and Bi. <1> The gas barrier film described above. <3> The thickness of the gas barrier layer is 1 to 200 nm. <1> or <2> The gas barrier film described above. <4> The water vapor transmission rate is 2.0 g / (m³). 2 It is less than (day) The standard deviation of the water vapor transmission rate is less than 0.1. <1> ~ <3> A gas barrier film described in any one of the following terms. <5> The gas barrier layer is provided with an overcoat layer on a surface different from the surface facing the substrate layer. <1> ~ <4> A gas barrier film described in any one of the following terms. <6> The overcoat layer contains at least one component selected from the group consisting of a metal alkoxide, a hydrolyzate of a metal alkoxide, a reaction product of a metal alkoxide, and a reaction product of a hydrolyzate of a metal alkoxide, and a water-soluble polymer, and is the gas barrier film according to <5>. <7> The overcoat layer contains at least one component selected from the group consisting of a silane coupling agent, a hydrolyzate of a silane coupling agent, a reaction product of a silane coupling agent, and a reaction product of a hydrolyzate of a silane coupling agent, and is the gas barrier film according to <6>. <8> An undercoat layer is provided between the base material layer and the gas barrier layer. The undercoat layer contains at least one resin selected from the group consisting of a thermosetting resin, a thermoplastic resin, an ultraviolet curable resin, and an electron beam curable resin, and is the gas barrier film according to any one of <1> to <7>. <9> An undercoat layer is provided between the base material layer and the gas barrier layer. The undercoat layer is composed of a cured product of a composition containing an acrylic polyol resin and an isocyanate compound, and is the gas barrier film according to any one of <1> to <8>. <10> A gas barrier layer made of an inorganic oxide containing Si, Bi, and O is provided on one or both surfaces of the base material layer. The water vapor transmission rate is less than 2.0 g / (m 2 ·day), and the standard deviation of the water vapor transmission rate is less than 0.1, and is the gas barrier film. <11> The gas barrier film according to any one of <1> to <10>, and a sealant layer provided on the gas barrier film, and is a packaging film. <12> A packaging material including the packaging film according to <11>. <13> A packaging bag including the packaging material according to <12>. <14> The packaging bag according to <13>, and the content contained in the packaging bag, A packaged product equipped with the following features. [Explanation of Symbols]

[0145] 1A, 1B, 1C Gas Barrier Film 10 Base material layer 20 Gas barrier layer 30 Overcoat Layers 40 Undercoat Layer 100 Gas barrier film manufacturing equipment (gas barrier film manufacturing equipment) PF plastic film VM deposition materials VP vapor deposited particles

Claims

1. A base layer and A gas barrier layer made of an inorganic oxide containing Si, Ga, and O is provided on one or both sides of the substrate layer, Equipped with, The surface of the gas barrier layer, measured by X-ray photoelectron spectroscopy, is Si ２ｐ Peak, Ga ３ｄ Peak and O １ｓ A gas barrier film in which Ga / (Si+Ga), calculated using peak area intensity, is 0.05 to 0.80, and O / (Si+Ga) is 1.00 to 1.

80.

2. The gas barrier film according to claim 1, wherein the gas barrier layer contains at least one element selected from the group consisting of Mg, Al, W, In, Sn, and Bi.

3. The gas barrier film according to claim 1 or 2, wherein the thickness of the gas barrier layer is 1 to 200 nm.

4. The water vapor transmission rate is 2.0 g / (m²). ２ - less than day The gas barrier film according to claim 1 or 2, wherein the standard deviation of the water vapor transmission rate is less than 0.

1.

5. The gas barrier film according to claim 1 or 2, wherein the gas barrier layer is provided with an overcoat layer on a surface different from the surface of the gas barrier layer that faces the substrate layer.

6. The gas barrier film according to claim 5, 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 metal alkoxide hydrolysates, and a water-soluble polymer.

7. The gas barrier film according to claim 6, 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.

8. An undercoat layer is provided between the substrate layer and the gas barrier layer. The gas barrier film according to claim 1 or 2, 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.

9. An undercoat layer is provided between the substrate layer and the gas barrier layer. The gas barrier film according to claim 1 or 2, wherein the undercoat layer is made of a cured product of a composition containing an acrylic polyol resin and an isocyanate compound.

10. A gas barrier film according to claim 1 or 2, A sealant layer provided on the gas barrier film, A packaging film equipped with the following features.

11. A packaging material comprising the packaging film described in claim 10.

12. A packaging bag comprising the packaging material described in claim 11.

13. The packaging bag according to claim 12, The contents contained in the aforementioned packaging bag, A packaged product equipped with the following features.

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