JP6809622B1 - Gas barrier film and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having improved oxygen barrier property and good printability, and a method for producing the same. SOLUTION: An oxygen barrier film 20 is formed on a resin base material 10 and at least one surface 12 of the resin base material 10, and a base layer 30 and an inorganic oxide layer are formed between the resin base material 10 and the oxygen barrier film 20. A gas barrier film 1 comprising any one or both of 40, and one surface 12 having a black area ratio of 0.15% or less as measured by the following measuring method. <Measurement method> An arbitrary region of 1281 μm square on one surface of the resin base material is photographed with an optical microscope, a photographed image of 1024 × 1024 pixel is acquired, and the photographed image has 256 gradations using image analysis software. Converted to a monochrome image, the value obtained by subtracting 30 from the most frequent value of the brightness in the monochrome image is set as the threshold value, the value below the threshold value is black, the value above the threshold value is white, and the brightness is binarized. The ratio of the total area of the black area is defined as the black area ratio. [Selection diagram] Fig. 1

Description

The present invention relates to a gas barrier film and a method for producing the same.

Gases (water vapor, oxygen, etc.) that modify the contents enter into the packaging materials used for packaging foods, pharmaceuticals, etc. in order to suppress deterioration and putrefaction of the contents and maintain their functions and quality. That is, gas barrier property is required. Therefore, a film material having a gas barrier property (gas barrier film) is used as these packaging materials.

As the gas barrier film, a film in which a gas barrier layer made of a material having a gas barrier property is provided on the surface of a resin base material is known. As the gas barrier layer, a metal foil, a metal vapor deposition film, and a film formed by a wet coating method are known. As the film, a resin film formed of a coating agent containing a resin such as a water-soluble polymer and polyvinylidene chloride, or a coating agent containing a water-soluble polymer and an inorganic layered mineral, which exhibits oxygen barrier properties, is formed. An inorganic layered mineral composite resin film has been known (Patent Document 1). Further, as the gas barrier layer, a gas barrier layer (Patent Document 2) in which a vapor-deposited thin film layer made of an inorganic oxide, a gas barrier composite film containing an aqueous polymer, an inorganic layered compound and a metal alkoxide are sequentially laminated, and a polycarboxylic acid-based weight are used. A gas barrier layer (Patent Document 3) containing a polyvalent metal salt of a carboxylic acid, which is a reaction product of a coalesced carboxy group and a polyvalent metal compound, has been proposed.

In order to improve the gas barrier property, for example, in Patent Document 4, a film is formed on at least one surface of the base material, and the surface roughness parameter Rt / Ra of the surface of the film is 20 or less. Has been proposed. Here, Rt is the distance between the maximum peak and the deepest valley of the surface roughness curve. Ra is the center line average roughness. According to the gas barrier film of Patent Document 4, the gas barrier property is improved.

Japanese Patent No. 6191221 Japanese Unexamined Patent Publication No. 2000-259494 Japanese Patent No. 4373797 Japanese Unexamined Patent Publication No. 9-150484

However, the oxygen barrier property of a gas barrier film in which a film formed by a wet coating method, a vapor deposition method, or a sputtering method is provided on the surface of a resin base material may not be stable depending on the production lot. Specifically, the oxygen barrier property of the gas barrier film may be inferior to the original oxygen barrier property, that is, the oxygen barrier property assumed from the material constituting the film and the thickness of the film. In particular, when the thickness of the film becomes thin, such a problem tends to occur easily. Therefore, it is necessary to make the thickness of the gas barrier layer thicker than necessary, which causes problems of poor productivity and excessive material cost.

Further, the surface of the gas barrier film may be printed. Therefore, the gas barrier film is required to be easy to print on the surface (printability).

The present invention has been made in view of the above circumstances, and even if the thickness of the film for imparting oxygen barrier property is thin, the original oxygen barrier property is sufficiently exhibited and excellent gas barrier property is exhibited. An object of the present invention is to provide a gas barrier film having good printability and a method for producing the same.

In order to investigate the cause of the above problem, the present inventors have observed the surface and cross section of the gas barrier film having poor oxygen barrier properties in detail with an optical microscope or an electron microscope. As a result of cross-sectional electron microscope observation with a focused ion / electron beam processing observation device at the location where the anti-blocking agent (hereinafter, also referred to as "AB agent") added to prevent blocking of the resin base material is present. It was confirmed that a defect having a width of several μm was generated in the film at the portion where the AB agent protruded high. It is considered that this defect became a gas permeation route and the oxygen barrier property was not sufficiently exhibited.

On the surface of the resin base material, there are protrusions of various sizes due to the AB agent. The protrusion height and protrusion density of the AB agent vary depending on the production lot of the resin base material, and when the surface of the resin base material is coated with the gas barrier film, the film is not locally formed at the position of the large convex portion. It is probable that a defect occurred and the oxygen barrier property became unstable.

In addition, by observing in detail the transfer failure of fine dots (sometimes called missing dots) that occurs in the highlight printing part of the gas barrier film with a microscope, the above-mentioned AB agent is likely to cause missing dots at high protrusions. I confirmed that it was.

Therefore, the present inventors have devised a method for accurately grasping a wide range of surface conditions of a resin base material, which affects the oxygen barrier property and printability of a gas barrier film, in a short time, and an optical microscope on the surface of the resin base material. When the image is binarized and the total area ratio of the black region of 100 μm ² or more (hereinafter referred to as the black area ratio) is 0.15% or less, the oxygen barrier performance is excellent and the gas barrier film is on. It has been found that the printability is improved, and the present invention has been reached.

The present invention has the following aspects.

[1] Either the resin base material, the oxygen barrier film provided on at least one surface side of the resin base material, or the base layer or the inorganic oxide layer provided between the resin base material and the oxygen barrier film. A gas barrier film comprising one or both, and one surface of a resin base material having a black area ratio of 0.15% or less as measured by the following measuring method.
<Measurement method>
An arbitrary region of 1281 μm square on one surface of the resin substrate is photographed with an optical microscope, a photographed image of 1024 × 1024 pixels is acquired, and the photographed image is converted into a monochrome image of 256 gradations using image analysis software. Then, the value obtained by subtracting 30 from the most frequent value of the brightness in the monochrome image is set as the threshold value, the value below the threshold value is set to black, the value above the threshold value is set to white, and the brightness is binarized. The black region having a size of 100 μm ² or more in the 1281 μm square region The ratio of the total area is defined as the black area ratio.

[2] A gas barrier film in which the resin base material contains an anti-blocking agent.

[3] The resin base material is a gas barrier film which is one selected from polypropylene, polyethylene terephthalate, and nylon.

[4] A gas barrier film having a thickness of an underlayer of 0.01 to 1 μm.

[5] The base layer contains an organic polymer as a main component, and the organic polymer is at least one of a polyacrylic resin, a polyol resin, a polyurethane resin, a polyamide resin, and a reaction product of these resins. Gas barrier film containing one.

[6] A gas barrier film having an inorganic oxide layer having a thickness of 1 to 200 nm.

[7] A gas barrier film in which the inorganic oxide layer is aluminum oxide or silicon oxide.

[8] A gas barrier film having a thickness of an oxygen barrier film of 0.05 to 1 μm.

[9] The oxygen barrier film is a film containing at least one of a metal alkoxide, a hydrolyzate of a metal alkoxide, and a reaction product of the metal alkoxide or a hydrolyzate of the metal alkoxide, and a water-soluble polymer. the film.

[10] A gas barrier in which the oxygen barrier film further comprises at least one reaction product of the silane coupling agent, the hydrolyzate of the silane coupling agent, and the hydrolyzate of the silane coupling agent or the silane coupling agent. Sex film.

[11] A gas barrier film in which the oxygen barrier film contains a polyvalent metal salt of carboxylic acid, which is a reaction product of a carboxyl group of a polycarboxylic acid polymer (A) and a polyvalent metal compound (B).

[12] The method for producing a gas barrier film according to any one of [1] to [11], wherein the black area ratio of the surface of the resin base material raw material is measured by the following measuring method, and at least one of them is used. A step of preparing a resin base material raw material having a black area ratio of a surface of 0.15% or less as a resin base material, and a coating agent being applied to at least one surface of the resin base material to form at least an oxygen barrier film. A method for producing a gas barrier film, which comprises a step of forming.
<Measurement method>
An arbitrary region of 1281 μm square on one surface of the resin substrate is photographed with an optical microscope, a photographed image of 1024 × 1024 pixels is acquired, and the photographed image is converted into a monochrome image of 256 gradations using image analysis software. and, to a value obtained by subtracting the 30 mode of the luminance in a monochrome image with a threshold value, black less than the threshold, and binarizes the luminance above the threshold as white, of 100 [mu] m ² or more sizes in 1281μm square regions of black area The ratio of the total area is defined as the black area ratio.

According to the gas barrier film of the present invention, even if the thickness of the oxygen barrier film is thin, there is little variation in performance between production lots, and the original oxygen barrier property is stably exhibited, thereby achieving excellent gas barrier property. It can be exhibited and the printability can be improved.

It is sectional drawing of the gas barrier film of one Embodiment of this invention. It is a photographed image which image | photographed one surface of the resin base material of one Embodiment of this invention with an optical microscope. This is an example of a histogram used when calculating the black area ratio.

An embodiment of the gas barrier film of the present invention will be described.

FIG. 1 is a schematic cross-sectional view of the gas barrier film 1 according to the first embodiment of the present invention. The dimensional ratio in FIG. 1 is different from the actual one for convenience of explanation.

The gas barrier film 1 has a resin base material 10, a base layer 30, an inorganic oxide layer 40, and an oxygen barrier film 20. Either the base layer 30 or the inorganic oxide layer 40 may be omitted.

The base layer 30 is laminated in contact with one surface 12 of the resin base material 10, and the inorganic oxide layer 40 is laminated on the surface opposite to the surface of the base layer 30 in contact with the resin base material 10. The inorganic oxide layer 40 is laminated in contact with the base layer 30, and the oxygen barrier film 20 is located in contact with the surface opposite to the surface of the inorganic oxide layer 40 in contact with the base layer 30. When the base layer 30 is not provided, the inorganic oxide layer 40 is laminated on one surface 12 of the resin base material 10. When the inorganic oxide layer 40 is not provided, the oxygen barrier coating 20 is laminated on the base layer 30.

<Resin base material>
The resin base material 10 contains a resin. Examples of the resin constituting the resin base material 10 include olefin resins such as polyethylene, polypropylene, olefin polymers having 2 to 10 carbon atoms, and propylene-ethylene copolymers; polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Polyethylene resins such as Nylon 6, aliphatic polyamides such as nylon 66, and polyamide resins such as aromatic polyamides such as polymethoxylylen adipamide; polystyrene, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl Vinyl-based resins such as alcohol and ethylene-vinyl alcohol copolymers; acrylic resins such as polymethylmethacrylate and polyacrylonitrile (meth) acrylic monomers alone or copolymers; cellophane; polycarbonate, polyimide, etc. Examples include engineering plastics. One of these resins may be used alone, or two or more of these resins may be used in combination.

Examples of the resin base material 10 include a single-layer film composed of a single resin, a single-layer film using a plurality of resins, and a laminated film. Further, a laminated base material in which the above resin is laminated on another base material (metal, wood, paper, ceramics, etc.) may be used. The resin base material 10 may have a single layer or two or more layers. As the resin base material 10, polyolefin-based resin films (particularly polypropylene films and the like), polyester-based resin films (particularly polyethylene terephthalate-based resin films), polyamide-based resin films (particularly nylon films) and the like are preferable.

The resin base material 10 may be an unstretched film or a uniaxial or biaxially stretched oriented film. As the resin base material 10, a biaxially stretched polypropylene film (OPP) is particularly preferable from the viewpoint of excellent water vapor barrier property. The OPP may be a film processed from at least one polymer selected from homopolymers, random copolymers and block copolymers. Homopolymers are polypropylenes consisting of propylene alone. The random copolymer is polypropylene in which propylene, which is the main monomer, and a small amount of comonomer different from propylene are randomly copolymerized to form a homogeneous phase. Block copolymers are polypropylenes that form a heterogeneous phase by block-polymerizing propylene, which is the main monomer, and the above-mentioned comonomer, or by polymerizing in a rubber-like manner. When the resin base material 10 is OPP, the OPP may be one layer or two or more layers.

One surface 12 of the resin base material 10 is subjected to surface treatment such as chemical treatment, solvent treatment, corona treatment, low temperature plasma treatment, ozone treatment, etc. in order to improve the adhesion to the base layer 30 and the inorganic oxide layer 40. It may be applied.

The resin base material 10 may contain additives such as fillers, antiblocking agents, antistatic agents, plasticizers, lubricants, and antioxidants. Any one of these additives may be used alone, or two or more thereof may be used in combination.

When the resin base material 10 contains an anti-blocking agent (hereinafter, also referred to as “AB agent”), unevenness derived from the AB agent is formed on one surface 12 of the resin base material 10. By containing the AB agent, the resin base material 10 can impart convexity to the surface of the resin base material 10 and suppress the occurrence of blocking of the film. That is, the blocking resistance of the film can be enhanced by containing the AB agent in the resin base material 10. Therefore, the film can be easily wound up and the processing characteristics of the film can be improved. Therefore, the resin base material 10 preferably contains an AB agent. On the other hand, when a large convex portion is formed on one surface 12 of the resin base material 10, the base layer 30, the inorganic oxide layer 40, and the oxygen barrier film 20 formed on the convex portion have a gas permeation path. Defects are likely to occur. Therefore, the oxygen barrier property of the gas barrier film 1 may be lowered.

When the resin base material 10 contains an AB agent, the AB agent is dispersed in the resin base material 10. On one surface 12 or the other surface 14 of the resin base material 10, there are a plurality of protrusions locally derived from the AB agent. On one surface 12 and the other surface 14, the AB agent may be exposed or may be covered with a resin.

The AB agent is solid particles, and examples thereof include organic particles and inorganic particles. Examples of the organic particles include polymethylmethacrylate particles, polystyrene particles, polyamide particles and the like. These organic particles can be obtained by, for example, emulsion polymerization or suspension polymerization. Examples of the inorganic particles include silica particles, zeolite, talc, kaolinite, and feldspar. Any one of these AB agents may be used alone, or two or more thereof may be used in combination.

Considering the appearance, transparency, shedding possibility of the AB agent, and anti-blocking performance of the gas barrier film 1, the average particle size of the AB agent is preferably 0.1 to 5 μm, for example. The average particle size of the AB agent is the weight average diameter measured by the Coulter method.

When the resin base material 10 contains an AB agent, the content of the AB agent is preferably 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the resin constituting the resin base material 10, for example. When the content of the AB agent is at least the above lower limit value, it is easy to improve the processing characteristics of the film used as the raw material of the resin base material 10. When the content of the AB agent is not more than the above upper limit value, it is easy to suppress the deterioration of the oxygen barrier property of the gas barrier film 1.

The black area ratio of one surface 12 of the resin base material 10 is 0.15% or less, more preferably 0.12% or less, still more preferably 0.10% or less. When the black area ratio is not more than the above upper limit value, the oxygen barrier property of the gas barrier film 1 can be more easily improved. In addition, when the black area ratio is not more than the above upper limit value, the printability of the gas barrier film 1 tends to be improved. The lower limit of the black area ratio is not particularly limited and is 0% or more.

Here, "improving printability" means that when gravure printing is performed on the oxygen barrier film 20 of the gas barrier film, ink is missing in the highlight portion (printing portion having a low halftone dot area ratio). It means to suppress (sometimes called missing dots). The black area ratio is adjusted, for example, according to the material of the AB agent contained in the resin base material 10, the average particle size and content, the characteristics of the resin forming one surface 12 of the resin base material 10, the film manufacturing conditions, and the like. it can.

When the brightness of the surface of the resin base material 10 is binarized and the portion (black spot) that appears black is observed with an electron microscope, protrusions are present. The larger the size of the black spots, the higher the height of the protrusions tends to be. Especially, in the presence of black spots (projections) having a size of 100 μm ² or more, coating film defects of the oxygen barrier film and ink loss in printing occur. It was easy to occur. That is, the smaller the black area ratio, the less protrusions on one surface 12 of the resin base material 10 have an adverse effect on the oxygen barrier property and printability, and the oxygen barrier property of the gas barrier film 1 is further improved. Printability can be improved.

The black area ratio in the present specification can be measured by the following measuring method.
<Measurement method>
An arbitrary region of 1281 μm square on one surface 12 of the resin base material 10 is photographed with an optical microscope to obtain a photographed image of 1024 × 1024 pixel. An example of the captured image is shown in FIG.

FIG. 2 is a photographed image of one surface 12 of the resin base material 10 taken with an optical microscope. In FIG. 2, 100 represents a flat portion and 110 represents a protrusion. Examples of the protrusion 110 include foreign matter, an AB agent, undissolved resin, and the like. As shown in FIG. 2, the flat portion 100 appears gray and the protrusion 110 appears black. The brightness of the flat portion 100 corresponds to the mode value of the brightness described later.

Next, using image analysis software, the acquired 1024 × 1024 pixel captured image is converted into a monochrome image having 256 gradations. A histogram is created by plotting the brightness distribution in the converted monochrome image. An example of the histogram is shown in FIG.

In FIG. 3, the horizontal axis represents the brightness converted into a monochrome image having 256 gradations. The brightness in a monochrome image is an integer from 0 to 255. The vertical axis represents the frequency of brightness. In FIG. 3, the minimum value of the distributed luminance is 26, and the maximum value is 255. The mode of brightness is the value of brightness most distributed in a monochrome image. P in FIG. 3 represents the mode of luminance. In FIG. 3, P = 160.

Next, the value obtained by subtracting 30 from the mode value of the brightness is set as the threshold value, the value below the threshold value is set to black, and the value above the threshold value is set to white, and the brightness in the monochrome image is binarized. In the monochrome image of FIG. 3, the threshold value at the boundary between black and white is a value (P-30) obtained by subtracting 30 from the mode value of luminance. In FIG. 3, the threshold is 130. That is, in FIG. 3, the luminance is less than 130 as “black” and the luminance as 130 or more is “white”, and the binarization process is performed.

From the viewpoint of improving the accuracy of the value of the black area ratio, it is preferable that the luminance histogram of the acquired image has a sharp shape. Here, the "sharp shape" is also referred to as, for example, the width of the histogram at half the height (H / 2) of the peak height H at the mode P of the histogram (hereinafter, also referred to as "half width". ) It can be judged by the size of W. The half width W is, for example, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less. When the full width at half maximum W is not more than the above upper limit value, the histogram has a sharp shape, and the accuracy of the value of the black area ratio can be improved. The lower limit of the full width at half maximum W is not particularly limited, but is substantially 2 or more.

From the above binarized image of 1281 × 1281 μm (1024 × 1024pixel), the ratio of the total area of the black region having a size of 100 μm ² or more is defined as the black area ratio. Further, the black area ratio is an arithmetic mean value of the values obtained in any three regions.

As the optical microscope, the optical microscope "OLS-4000" manufactured by Olympus Corporation is preferable. As the image analysis software, "Scion ImageJ" manufactured by Scion is preferable.

The image acquisition conditions will be described.
(Image acquisition conditions)
Resin on a slide glass using a black film double-sided tape (Teraoka Seisakusho, 7694) with the side (one side 12) on which the coating agent of the resin base material 10 for which the black area ratio is to be applied is facing up. The base material 10 is attached. Using an optical microscope (OLS-4000, manufactured by Olympus Corporation), an objective lens (MPFLN10) with a magnification of 10 times is used to capture an image with a range of 1281 μm × 1281 μm from any three locations on the resin substrate 10 on a slide glass. It is acquired as an image of 1024 × 1024 pixels. The amount of light when taking an image is arbitrary, but it is preferable to adjust the amount of light so that the mode value of the image brightness falls within the range of 80 to 200 at 256 gradations.

The image analysis conditions are as follows.
(Image analysis conditions)
-Discard color information: 8 bits.
-Bilingual threshold: A value obtained by subtracting 30 from the mode of brightness.
-Scale setting: Set Scale Distance in pixel: 1024, Known distance: 1281, Unit of length: μm
-Area measurement: Analysis Particles Size: Check 100-Infinity (μm ² ) and Particle Holes.
Under the above image analysis conditions,% Area values are calculated for each of the captured images acquired from any three locations of the resin base material 10, and the arithmetic mean value of these% Area values is defined as the black area ratio.

The black area ratio in the present specification is calculated by observing one surface 12 of the resin base material 10 in a plane. Therefore, as compared with the conventional measurement of surface roughness, the surface condition can be observed with a surface instead of a line.

Conventional surface roughness values vary depending on the method and range of measurement. If the measurement area is small, the roughness may be underestimated because a small number of protrusions are not measured. Also, even when measuring the roughness in a straight line range of a certain length, such as the average roughness of the center line, if a large protrusion is measured, the roughness will be overestimated, but if not, the roughness will be overestimated. After all, the roughness is underestimated.

By defining the state of the surface of the resin base material by the black area ratio as described in the present specification, it is possible to evaluate the state of the surface of the resin base material by reducing the variation in the state of the surface of the resin base material. Therefore, the variation in the oxygen barrier property can be suppressed, and the oxygen barrier property of the gas barrier film 1 can be more easily improved.

The management of the black area ratio by the binarization treatment of the optical microscope image is suitable for the control method of oxygen barrier property and printability because the measurement range is wide and the protrusions can be found by a simple method.

The thickness of the resin base material 10 is not particularly limited, and is appropriately selected depending on the price and application while considering the suitability as a packaging material and the suitability for laminating other films. The thickness of the resin base material 10 is practically preferably 3 μm to 200 μm, more preferably 5 μm to 120 μm, further preferably 6 μm to 100 μm, and particularly preferably 10 μm to 30 μm.

<Underground layer>
The base layer 30 is provided between the resin base material 10 and the inorganic oxide layer 40 or the oxygen barrier film 20.

The base layer 30 is a layer containing an organic polymer as a main component, and is sometimes called a primer layer. By providing the base layer 30, the film forming property and the adhesion strength of the inorganic oxide layer 40 or the oxygen barrier film 20 can be improved.

The content of the organic polymer in the base layer 30 may be, for example, 70% by mass or more, or 80% by mass or more. Examples of the organic polymer include polyacrylic resin, polyester resin, polycarbonate resin, polyurethane resin, polyamide resin, polyolefin resin, polyimide resin, melamine resin, phenol resin, etc., and the resin base material 10 and the inorganic oxide layer 40 or oxygen. Considering the heat resistance and water resistance of the adhesion strength to the barrier film 20, it is preferable to contain at least one of a polyacrylic resin, a polyol resin, a polyurethane resin, a polyamide resin, or a reaction product of these organic polymers. .. Further, the base layer 30 may contain a silane coupling agent, an organic titanate or a modified silicone oil.

More preferably, the organic polymer has a urethane bond formed by a reaction between a polyol having two or more hydroxyl groups at the polymer terminal and an isocyanate compound, and / or two or more at the polymer terminal. Examples thereof include organic polymers containing reaction products of polyols having a hydroxyl group and organic silane compounds such as a silane coupling agent or a hydrolyzate thereof.

Examples of the polyols include at least one selected from acrylic polyols, polyvinyl acetals, polystill polyols, polyurethane polyols and the like. The acrylic polyol may be obtained by polymerizing an acrylic acid derivative monomer, or may be obtained by copolymerizing an acrylic acid derivative monomer and another monomer. Examples of the acrylic acid derivative monomer include ethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and the like. Examples of the monomer copolymerized with the acrylic acid derivative monomer include styrene and the like.

The isocyanate compound has an effect of enhancing the adhesion between the resin base material 10 and the inorganic oxide layer 40 or the oxygen barrier film 20 by the urethane bond generated by reacting with the polyol. That is, the isocyanate compound functions as a cross-linking agent or a curing agent. Examples of the isocyanate compound include monomers such as aromatic toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), aliphatic xylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI). Classes, polymers thereof, and derivatives thereof. The above-mentioned isocyanate compounds may be used alone or in combination of two or more.

Examples of the silane coupling agent include vinyl trimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-. Examples thereof include methacryloxypropylmethyldimethoxysilane. The organic silane compound may be a hydrolyzate of these silane coupling agents. The organic silane compound may contain one of the above-mentioned silane coupling agent and its hydrolyzate alone or in combination of two or more.

The base layer 30 can be formed by blending the above-mentioned components in an organic solvent at an arbitrary ratio to prepare a mixed solution, and using the mixed solution prepared on one surface 12 of the resin base material 10. The mixed solution is, for example, a curing accelerator such as a tertiary amine, an imidazole derivative, a metal salt compound of a carboxylic acid, a quaternary ammonium salt, or a quaternary phosphonium salt; an antioxidant such as a phenol-based, sulfur-based, or phosphite-based antioxidant; It may contain a leveling agent; a flow conditioner; a catalyst; a cross-linking reaction accelerator; a filler and the like.

The mixed solution is prepared from the resin base material 10 by using a well-known printing method such as an offset printing method, a gravure printing method, or a silk screen printing method, or a well-known coating method such as roll coating, knife edge coating, or gravure coating. Can be coated on top. After coating, the base layer 30 can be formed by heating to, for example, 50 to 200 ° C., drying and / or curing.

The thickness of the base layer 30 is not particularly limited and may be, for example, 0.005 to 5 μm. The thickness may be adjusted according to the application or required properties.
The thickness of the base layer 30 is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5 μm. When the thickness of the base layer 30 is 0.01 μm or more, sufficient adhesion strength between the resin base material 10 and the inorganic oxide layer 40 or the oxygen barrier film 20 can be obtained, and the oxygen barrier property is also good. When the thickness of the base layer 30 is 1 μm or less, it is easy to form a uniform coated surface, and the drying load and the manufacturing cost can be suppressed.

<Inorganic oxide layer>
Examples of the inorganic oxide layer 40 include aluminum oxide, silicon oxide, magnesium oxide, titanium oxide, tin oxide, zinc oxide, and indium oxide. In particular, aluminum oxide or silicon oxide has excellent productivity and heat resistance. It is preferable because it has excellent oxygen barrier property and water vapor barrier property in moisture resistance. The inorganic oxide layer 40 may contain one of these types alone or in combination of two or more types.

The thickness of the inorganic oxide layer 40 is preferably 1 to 200 nm. If the thickness is 1 nm or more, excellent oxygen barrier property and water vapor barrier property can be obtained, and if the thickness is 200 nm or less, the production cost can be kept low. At the same time, cracks due to external forces such as bending and pulling are unlikely to occur, and deterioration of the barrier property can be suppressed.

The inorganic oxide layer 40 can be formed by a known film forming method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a plasma vapor deposition method (CVD).

<Oxygen barrier film>
The oxygen barrier film 20 may be known as an oxygen barrier film formed by the wet coating method. The oxygen barrier film 20 is obtained by forming a coating film made of a coating agent on the base layer 30 or the inorganic oxide layer 40 by a wet coating method and drying the coating film. The coating film is a wet film, and the film is a dry film.

As the oxygen barrier film 20, a film containing at least one of a metal alkoxide and a hydrolyzate thereof, or a reaction product thereof, and a water-soluble polymer (organic-inorganic composite film) is preferable. Further, a film further containing at least one of a silane coupling agent and a hydrolyzate thereof is preferable.

Examples of the metal alkoxide contained in the organic-inorganic composite film and its hydrolyzate include tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ] and triisopropoxyaluminum [Al (OC ₃ H ₇ ) ₃ ]. Examples thereof include those represented by the formula M (OR) n and their hydrolysates. One of these may be contained alone or in combination of two or more.

The total content of at least one of the metal alkoxide and its hydrolyzate, or its reaction product, in the organic-inorganic composite membrane is, for example, 40 to 70% by mass. From the viewpoint of further reducing the oxygen permeability, the lower limit of the total content of at least one of the metal alkoxide and its hydrolyzate or its reaction product in the organic-inorganic composite film may be 50% by mass. From the same viewpoint, the upper limit of the total content of at least one of the metal alkoxide and its hydrolyzate or its reaction product in the organic-inorganic composite membrane may be 65% by mass.

The water-soluble polymer contained in the organic-inorganic composite film is not particularly limited, and examples thereof include polyvinyl alcohol-based polymers, polysaccharides such as starch, methyl cellulose and carboxymethyl cellulose, and acrylic polyol-based polymers. From the viewpoint of further improving the oxygen gas barrier property, the water-soluble polymer preferably contains a polyvinyl alcohol-based polymer. The number average molecular weight of the water-soluble polymer is, for example, 40,000 to 180,000.

The polyvinyl alcohol-based water-soluble polymer can be obtained, for example, by saponifying (including partially saponifying) polyvinyl acetate. This water-soluble polymer may have tens of percent of acetic acid groups remaining, or may have only a few percent of acetic acid groups remaining.

The content of the water-soluble polymer in the organic-inorganic composite membrane is, for example, 15 to 50% by mass. The lower limit of the content of the water-soluble polymer in the organic-inorganic composite membrane may be 20% by mass from the viewpoint of further reducing the oxygen permeability. The upper limit of the content of the water-soluble polymer in the organic-inorganic composite membrane may be 45% by mass from the viewpoint of further reducing the oxygen permeability.

Examples of the silane coupling agent and its hydrolyzate contained in the organic-inorganic composite membrane include a silane coupling agent having an organic functional group. Examples of such a silane coupling agent and its hydrolyzate include ethyltrimethoxysilane, vinyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, and γ. Included are-methacryloxypropyltrimethoxysilane, γ-methacryloxyprepylmethyldimethoxysilane, and hydrolyzates thereof. One of these may be contained alone or in combination of two or more.

As at least one of the silane coupling agent and its hydrolyzate, it is preferable to use one having an epoxy group as the organic functional group. Examples of the silane coupling agent having an epoxy group include γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The silane coupling agent having an epoxy group and its hydrolyzate may have an organic functional group different from the epoxy group, such as a vinyl group, an amino group, a methacryl group or a ureyl group.

The silane coupling agent having an organic functional group and its hydrolyzate have the oxygen barrier property of the oxygen barrier film 20 and the underlying layer 30 or inorganic oxidation due to the interaction between the organic functional group and the hydroxyl group of the water-soluble polymer. The adhesiveness with the material layer 40 can be further improved. In particular, the epoxy group of the silane coupling agent and its hydrolyzate and the hydroxyl group of polyvinyl alcohol interact with each other to form an oxygen barrier film having particularly excellent oxygen barrier properties and adhesiveness to the base layer 30 or the inorganic oxide layer 40. 20 can be formed.

The total content of at least one of the silane coupling agent and its hydrolyzate, or its reaction product, in the organic-inorganic composite membrane is, for example, 1 to 15% by mass. From the viewpoint of further reducing the oxygen permeability, the lower limit of the total content of at least one of the silane coupling agent and its hydrolyzate or its reaction product in the organic-inorganic composite film may be 2% by mass. .. From the same viewpoint, the upper limit of the total content of at least one of the silane coupling agent and its hydrolyzate or its reaction product in the organic-inorganic composite membrane may be 12% by mass.

The organic-inorganic composite film may contain a crystalline inorganic layered compound having a layered structure. Examples of the inorganic layered compound include clay minerals typified by kaolinite, smectite, mica and the like. One of these may be used alone, or two or more thereof may be used in combination. The particle size of the inorganic layered compound is, for example, 0.1 to 10 μm. The aspest ratio of the inorganic layered compound is, for example, 50 to 5000.

As the inorganic layered compound, a smectite group clay mineral is preferable because a film having excellent oxygen barrier properties and adhesion strength can be formed by the inclusion of a water-soluble polymer between layers of the layered structure (intercalation). Specific examples of smectite clay minerals include montmoritronite, hectorite, saponite, and water-swellable synthetic mica.

Further, as another preferable example of the oxygen barrier film 20, a polyvalent metal salt of a carboxylic acid, which is a reaction product of a carboxy group of a polycarboxylic acid-based polymer (A) and a polyvalent metal compound (B), is contained. Examples thereof include a film (a polycarboxylic acid polyvalent metal salt film). In this case, even if it is a polycarboxylic acid polyvalent metal salt film formed by applying a coating agent in which a polycarboxylic acid-based polymer (A) and a polyvalent metal compound (B) are mixed and heating and drying, the film may be formed. A coating agent containing a polycarboxylic acid polymer (A) as a main component is applied and dried to form an A film, and then a coating agent containing a polyvalent metal compound (B) as a main component is applied and dried. It may be a polyvalent metal salt film of a polycarboxylic acid formed by forming a B film and performing a cross-linking reaction between A / B layers.

[Polycarboxylic acid polymer (A)]
The polycarboxylic acid-based polymer is a polymer having two or more carboxy groups in the molecule. Examples of the polycarboxylic acid-based polymer include (co) polymers of ethylenically unsaturated carboxylic acids; copolymers of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated monomers; alginic acid and carboxymethyl cellulose. , Pectin and other acidic polysaccharides having a carboxyl group in the molecule. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. Examples of the ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid include saturated carboxylic acid vinyl esters such as ethylene, propylene and vinyl acetate, alkyl acrylates, alkyl methacrylates and alkyl itaconates. , Vinyl chloride, vinylidene chloride, styrene, acrylamide, acrylonitrile and the like. One of these polycarboxylic acid-based polymers may be used alone, or two or more thereof may be mixed and used.

Among the above, at least one polymerizable component selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, itaconic acid, fumaric acid and crotonic acid from the viewpoint of the gas barrier property of the obtained gas barrier film 1. A polymer containing a structural unit derived from a monomer is preferable, and a polymer containing a structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid is contained. Polymers are particularly preferred. In the polymer, the proportion of the structural unit derived from at least one polymerizable monomer selected from the group consisting of acrylic acid, maleic acid, methacrylic acid and itaconic acid is preferably 80 mol% or more. More preferably, it is 90 mol% or more (however, the total of all the constituent units constituting the polymer is 100 mol%). The polymer may be a homopolymer or a copolymer. When the polymer is a copolymer containing a structural unit other than the above-mentioned structural unit, the other structural unit may be, for example, an ethylenically unsaturated monopolymer copolymerizable with the above-mentioned ethylenically unsaturated carboxylic acid. Examples include structural units derived from polymers.

The number average molecular weight of the polycarboxylic acid-based polymer is preferably in the range of 2,000 to 10,000,000, more preferably 5,000 to 1,000,000. If the number average molecular weight is less than 2,000, the obtained gas barrier film cannot achieve sufficient water resistance, and moisture may deteriorate the gas barrier property and transparency, or whitening may occur. On the other hand, if the number average molecular weight exceeds 10,000,000, the viscosity of the coating agent when forming the oxygen barrier film 20 becomes high, and the coatability may be impaired. The number average molecular weight is a polystyrene-equivalent number average molecular weight determined by gel permeation chromatography (GPC).

When a coating agent containing the polycarboxylic acid polymer (A) as a main component is applied and dried to form an A film and then a B film is formed, the polycarboxylic acid polymer is a part of the carboxy group. May be pre-neutralized with a basic compound. By neutralizing a part of the carboxy group of the polycarboxylic acid polymer in advance, the water resistance and heat resistance of the A film can be further improved. As the basic compound, at least one basic compound selected from the group consisting of polyvalent metal compounds, monovalent metal compounds and ammonia is preferable. As the polyvalent metal compound, a compound exemplified in the description of the polyvalent metal compound (B) described later can be used. Examples of the monovalent metal compound include sodium hydroxide, potassium hydroxide and the like.

Various additives can be added to the coating agent containing the polycarboxylic acid polymer (A) as the main component, and a cross-linking agent, a curing agent, a leveling agent, a defoaming agent, and an anti-blocking agent are used as long as the barrier performance is not impaired. , Antistatic agent, dispersant, surfactant, softener, stabilizer, film-forming agent, thickener and the like.

The solvent used for the coating agent containing the polycarboxylic acid polymer (A) as a main component is preferably an aqueous medium. Aqueous media include water, water-soluble or hydrophilic organic solvents, or mixtures thereof. Aqueous media usually contain water or water as the main component. The content of water in the aqueous medium is preferably 70% by mass or more, more preferably 80% by mass or more. Examples of the water-soluble or hydrophilic organic solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, cellosolves, carbitols and nitriles of acetonitrile. Can be mentioned.

[Multivalent metal compound (B)]
The polyvalent metal compound is not particularly limited as long as it is a compound that reacts with the carboxyl group of the polycarboxylic acid-based polymer to form a polyvalent metal salt of the polycarboxylic acid, and is zinc oxide particles, magnesium oxide particles, magnesium methoxydo. , Copper oxide, calcium carbonate and the like. These may be used alone or in combination of a plurality. Zinc oxide is preferable from the viewpoint of the oxygen barrier property of the oxygen barrier film.

Zinc oxide is an inorganic material having an ultraviolet absorbing ability, and the average particle size of zinc oxide particles is not particularly limited, but from the viewpoint of gas barrier property, transparency, and coating suitability, the average particle size is preferably 5 μm or less. It is more preferably 1 μm or less, and particularly preferably 0.1 μm or less.

When a coating agent containing a polyvalent metal compound (B) as a main component is applied and dried to form a film, in addition to zinc oxide particles, various types are required as long as the effects of the present invention are not impaired. Additives may be included. Examples of the additive include a resin that is soluble or dispersible in a solvent used for a coating agent, a dispersant that is soluble or dispersible in the solvent, a surfactant, a softener, a stabilizer, a film-forming agent, a thickener, and the like. May be contained.

Among the above, the solvent used for the coating agent preferably contains a resin that is soluble or dispersible in the solvent. As a result, the coatability and film forming property of the coating agent are improved. Examples of such resins include alkyd resins, melamine resins, acrylic resins, urethane resins, polyester resins, phenol resins, amino resins, fluororesins, epoxy resins, isocyanate resins and the like.

Further, it is preferable to contain a dispersant that is soluble or dispersible in the solvent used for the coating agent. This improves the dispersibility of the multivalent metal compound. As the dispersant, an anionic surfactant or a nonionic surfactant can be used. Examples of the surfactant include (poly) carboxylate, alkyl sulfate ester salt, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate, and aromatics. Phosphoric acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, alkylallyl sulfate ester, polyoxyethylene alkyl phosphate ester, sorbitan alkyl ester, glycerin fatty acid ester, sorbitan fatty acid ester, sugar fatty acid Various surfactants such as esters, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan alkyl esters, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives, polyoxyethylene sorbitol fatty acid esters, polyoxy fatty acid esters, polyoxyethylene alkyl amines, etc. Be done. These surfactants may be used alone or in combination of two or more.

When the coating agent containing the polyvalent metal compound (B) as a main component contains an additive, the mass ratio of the polyvalent metal compound to the additive (polyvalent metal compound: additive) is 30: It is preferably in the range of 70 to 99: 1, preferably in the range of 50:50 to 98: 2.

Examples of the solvent used for the coating agent containing the polyvalent metal compound (B) as a main component include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol and dimethyl sulf. Examples thereof include foxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate and butyl acetate. In addition, these solvents may be used alone or in combination of two or more. Among these, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone and water are preferable from the viewpoint of coatability. From the viewpoint of manufacturability, methyl alcohol, ethyl alcohol, isopropyl alcohol and water are preferable.

When a coating agent in which a polycarboxylic acid-based polymer (A) and a polyvalent metal compound (B) are mixed is applied and dried to form a polyvalent metal salt film of the polycarboxylic acid, the above-mentioned polycarboxylic acid-based Using the polymer (A), the above-mentioned polyvalent metal compound (B), water or alcohols as a solvent, a resin or dispersant that can be dissolved or dispersed in the solvent, and an additive if necessary, are mixed. A polyvalent metal salt film of a polycarboxylic acid can be formed by applying and drying the coating agent by a known coating method. Examples of the coating method include casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method, metering bar coating method, and chamber doctor combined coating method. The curtain coat method and the like can be mentioned.

The thickness of the oxygen barrier film 20 is set according to the required oxygen barrier property, and may be, for example, 0.05 to 5 μm. The thickness of the oxygen barrier film 20 is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm. When the thickness of the oxygen barrier film 20 is 0.05 μm or more, sufficient oxygen barrier properties can be easily obtained. When the thickness of the oxygen barrier film 20 is 1 μm or less, it is easy to form a uniform coated surface, the drying load and the manufacturing cost can be suppressed, and the black area ratio, which is a feature of the present invention, is 0.15% or less. The usefulness of using the resin base material 10 having the surface of the above is increased.

As the oxygen barrier film 20, the organic-inorganic composite film and the gas barrier film having the polycarboxylic acid polyvalent metal salt film show excellent oxygen barrier properties even after boil treatment or retort sterilization treatment. , Has sufficient adhesion strength and sealing strength as a packaging material for boiling and retort treatment by laminating with a sealant film, and also has transparency, bending resistance and stretch resistance not found in metal foils and metal vapor deposition films. It has the advantage that there is no risk of generating harmful substances such as dioxin.

[Manufacturing method of gas barrier film]
In the gas barrier film 1, the base layer 30 or the inorganic oxide layer 40 or both the base layer 30 and the inorganic oxide layer 40 are formed on one surface 12 of the resin base material 10, and then the base layer 30 or the inorganic oxide is formed. It can be produced by forming an oxygen barrier film 20 on the layer 40.

The method for producing the gas barrier film 1 of the present invention includes, for example, a sorting step, a base layer forming step, an inorganic oxide layer forming step, and an oxygen barrier film forming step.

Examples of the sorting step include a step of sorting a resin base material raw material having a surface black area ratio of 0.15% or less as a resin base material. The black area ratio of the surface of the resin base material raw fabric is measured by the same method as the method for measuring the black area ratio of one surface 12 of the resin base material 10 described above.

As the resin base material 10, a commercially available product may be used, or a product manufactured by a known method may be used.

As a base layer forming step, for example, a coating agent is applied to at least one surface 12 of the resin base material 10 by a wet coating method to form a coating film, and the coating film is dried (solvent is removed). Examples thereof include a step of forming the formation 30.

As a method for applying the coating agent, a known wet coating method can be used. Examples of the wet coating method include a roll coating method, a gravure coating method, a reverse coating method, a die coating method, a screen printing method, and a spray coating method.

As a method for drying the coating film made of the coating agent, known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. The drying temperature of the coating film is preferably, for example, 50 to 200 ° C. The drying time varies depending on the thickness of the coating film, the drying temperature, and the like, but is preferably 1 second to 5 minutes, for example.

The inorganic oxide layer forming step includes, for example, the vacuum deposition method, the sputtering method, the ion plating method, or the plasma vapor deposition method (CVD) described above on one surface 12 of the resin base material 10 or the base layer 30. ) And the like to form the inorganic oxide layer 40.

As an oxygen barrier film forming step, for example, a coating agent is applied on the base layer 30 or the inorganic oxide layer 40 by a wet coating method to form a coating film, and the coating film is dried (solvent is removed). ) To form the oxygen barrier film 20.

As a method for applying the coating agent, a known wet coating method can be used. Examples of the wet coating method include a roll coating method, a gravure coating method, a reverse coating method, a die coating method, a screen printing method, and a spray coating method.

As a method for drying the coating film made of the coating agent, known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. The drying temperature of the coating film is preferably, for example, 50 to 200 ° C. The drying time varies depending on the thickness of the coating film, the drying temperature, and the like, but is preferably 1 second to 5 minutes, for example.

The oxygen barrier film 20 may be formed by applying and drying once, or may be formed by repeating application and drying a plurality of times with the same kind of coating agent or different kinds of coating agents.

In the base layer forming step, the inorganic oxide layer forming step, and the oxygen barrier film forming step, the base layer 30, the inorganic oxide layer 40, or the oxygen barrier film 20 is formed on one surface 12 of the resin base material 10. At this time, the black area ratio of one surface 12 is 0.15% or less. Further, the base layer 30, the inorganic oxide layer 40, or the oxygen barrier film 20 may be formed on both surfaces of the resin base material 10. In that case, the black area ratio of the other surface 14 of the resin base material 10 is 0.15% or less.

When the base layer 30, the inorganic oxide layer 40, or the oxygen barrier film 20 is formed on both surfaces of the resin base material, the black area ratio of both surfaces of the resin base material is 0.15% or less. If there is, the oxygen barrier property is further enhanced and the printability is good, which is preferable.

When the method for producing the gas barrier film 1 of the present invention includes a sorting step, a resin base material having a surface black area ratio of 0.15% or less can be efficiently applied. Therefore, by having the sorting step, the gas barrier film 1 having further improved oxygen barrier properties can be efficiently produced. In addition, by having the sorting step, the gas barrier film 1 having good printability can be efficiently produced.

The gas barrier film 1 of the present invention may further have a printing layer, a protective layer, a light-shielding layer, an adhesive layer, a heat-sealing heat-sealing layer, another functional layer, and the like, if necessary.

When the gas barrier film 1 of the present invention has a heat-sealing heat-sealing layer, the heat-sealing layer is arranged on at least one outermost surface layer of the gas barrier film 1. Since the gas barrier film 1 has a heat-sealing layer, the gas barrier film 1 can be sealed by a heat seal (for example, a package or a lid).

The heat-sealing layer is, for example, a polyurethane-based or polyester on a laminate obtained by forming the base layer 30, the inorganic oxide layer 40, and the oxygen barrier film 20 of the present embodiment on one or both sides of a resin base material. It can be laminated by a known dry laminating method, extrusion laminating method or the like using a known adhesive such as a system or a polyether system.

<Effect>
The gas barrier film 1 of the present invention binarizes the brightness in a monochrome image and calculates the total area ratio (black area ratio) of a black region having a size of 100 μm ² or more. Oxygen barrier property on at least one surface of the resin base material 10 having a black area ratio of 0.15% or less via the base layer 30 or the inorganic oxide layer 40 or both the base layer 30 and the inorganic oxide layer 40. The film 20 is laminated.

In the gas barrier film 1 of the present invention, the oxygen barrier film 20 is formed on the surface of the resin base material 10 having a black area ratio of 0.15% or less via the base layer 30 and / or the inorganic oxide layer 40. Since it is formed, film defects due to large protrusions on the surface of the base material are less likely to occur, and the oxygen barrier property is more likely to be improved. In addition, it is easy to improve the printability of the gas barrier film 1.

Therefore, by using the gas barrier film 1 of the present invention as a packaging material, the quality retention of the contents can be improved at low cost.

In addition, by using the gas barrier film 1 of the present invention as a packaging material, printing can be easily and beautifully performed.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

The materials used in each of the following examples are shown below.
[Material used]
<Resin base material>
α1: Biaxially stretched polypropylene film (trade name: M-1, thickness 20 μm, single-sided corona treatment, manufactured by Mitsui Chemicals Tohcello Co., Ltd.).
α2: Biaxially stretched polypropylene film (trade name: ME-1, thickness 20 μm, single-sided corona treatment, manufactured by Mitsui Chemicals Tohcello Co., Ltd.).
α3: Biaxially stretched polypropylene film (trade name: TS18TI-TPN, thickness 18 μm, single-sided corona treatment, Max Speciality Films Limited).
α4: Biaxially stretched polypropylene film (trade name: P2111, thickness 20 μm, single-sided corona treatment, manufactured by Toyobo Co., Ltd.).
α5: Biaxially stretched polypropylene film (trade name: P2171, thickness 20 μm, single-sided corona treatment, manufactured by Toyobo Co., Ltd.).
α6: Biaxially stretched polypropylene film (trade name: P2102, thickness 20 μm, single-sided corona treatment, manufactured by Toyobo Co., Ltd.).
α7: Biaxially stretched polypropylene film (trade name: P2161, thickness 20 μm, single-sided corona treatment, manufactured by Toyobo Co., Ltd.).
α8: Biaxially stretched polypropylene film (trade name: VPH2011, thickness 20 μm, single-sided corona treatment, average particle size of AB agent 2 μm on the corona-treated surface side, manufactured by AJ Plast).
α9: Biaxially stretched polypropylene film (trade name: VPH2011, thickness 20 μm, single-sided corona treatment, average particle size of AB agent 4 μm on the corona-treated surface side, manufactured by AJ Plast).
α10: Biaxially stretched polypropylene film (trade name: PB210J, thickness 20 μm, single-sided corona treatment, manufactured by Futamura Chemical Co., Ltd.).
α11: Polyethylene terephthalate film (trade name: P60, thickness 12 μm, single-sided corona treatment, manufactured by Toray Industries, Inc.).
α12: Polyethylene terephthalate film (trade name: E5102, thickness 12 μm, single-sided corona treatment, manufactured by Toyobo Co., Ltd.).

<Manufacturing example 1>
Using Acrydic CL-1000 (manufactured by DIC Co., Ltd.) as an acrylic polyol and TDI type curing agent Coronate 2030 (manufactured by Toso Co., Ltd.) as an isocyanate compound, the compounding ratio of the acrylic polyol and the isocyanate compound is solidified. The mixture was blended so as to have a weight-to-weight ratio of 6: 4, and a mixed solution (solid content: 2% by mass) for forming the base layer 30 was prepared using a diluting solvent (ethyl acetate).

<Manufacturing example 2>
58.9 parts by mass of distilled water was added to 20 parts by mass of an aqueous polyacrylic acid solution having a number average molecular weight of 200,000 (Aron A-10H manufactured by Toagosei Co., Ltd., solid content concentration 25% by mass) for dilution. Then, 0.44 parts by mass of aminopropyltrimethoxysilane (manufactured by APTMS Aldrich) was added and stirred to obtain a uniform solution, and a coating agent containing a polycarboxylic acid-based polymer as a main component was prepared.

<Manufacturing example 3>
A coating agent containing a polyvalent metal compound as a main component is prepared by mixing 100 parts by mass of a zinc oxide fine particle aqueous dispersion (ZE143 manufactured by Sumitomo Osaka Cement) and 2 parts by mass of a curing agent Liofol HAERTER UR 5889-21 (manufactured by Henkel). did.

<Manufacturing example 4>
An aqueous solution in which a polyvinyl alcohol resin (PVA trade name: Poval PVA-105, manufactured by Kuraray Co., Ltd., polyvinyl alcohol with a saponification degree of 98 to 99% and a polymerization degree of 500) is dissolved, and tetraethoxysilane (TEOS), γ-glycidoxypropyl. Prepare an aqueous solution obtained by hydrolyzing trimethoxysilane (GPTMS trade name: KBM-403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) with 0.02 mol / L hydrochloric acid, and PVA: TEOS: GPTMS by weight ratio before hydrolysis. The aqueous solution was blended so as to be 40:50:10. Further, a diluting solvent was added so that the solvent component of the blended aqueous solution had a mass ratio of water: isopropyl alcohol of 90:10 to prepare a coating agent (5% by mass) for forming an organic-inorganic composite film.

[Measurement of black area ratio of resin base material]
For the surface of the resin base material α1 to 12 on the corona-treated surface side, the black area ratio was determined according to the above-mentioned image acquisition conditions and image analysis conditions. The results are shown in Table 1. An optical microscope OLS-4000 manufactured by Olympus Corporation and a 10x objective lens (MPFLN10) were used for measuring the black area ratio, and Section ImageJ manufactured by Section Co., Ltd. was used as image analysis software.

[Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-4]
A coating film was formed by applying the mixed solution for forming a base layer prepared in Production Example 1 to the corona-treated surface of the resin substrate shown in Table 1 using a gravure printing machine, and placed in an oven at 100 ° C. By passing through for 10 seconds and drying, a base layer having a thickness of 0.1 μm was formed. Next, on the formed base layer, a coating agent containing the polycarboxylic acid-based polymer prepared in Production Example 2 as a main component was applied using a gravure printing machine to form a coating film, and the mixture was placed in an oven at 100 ° C. A polycarboxylic acid-based polymer film having a thickness of 0.2 μm was formed by passing the mixture for 10 seconds and drying, and further prepared in Production Example 3 using a gravure printing machine on the polycarboxylic acid-based polymer film. A coating agent containing a polyvalent metal compound as a main component is applied to form a coating film, which is then passed through an oven at 100 ° C. for 10 seconds and dried to form a polyvalent metal compound film having a thickness of 0.2 μm. , An oxygen barrier film composed of a polycarboxylic acid polyvalent metal salt film was formed to obtain gas barrier films of Examples 1-1 to 1-8 and Comparative Examples 1-1 to 1-4.

<Printability evaluation>
Using a gravure printing machine on the oxygen barrier film of the gas barrier film of each example, ink ink (trade name: N920LPGT, manufactured by Toyo Ink Co., Ltd.) is applied at a halftone dot density of 5% to 50% (in 5% increments). Gradation printing was performed. The ink viscosity was 14 seconds (Zahn cup # 3, 25 ° C.).
The printing speed was 150 m / min and the drying temperature was 50 ° C. The surface after printing was observed with an optical microscope, and the missing dots were counted. The judgment was ◯ if there were less than 5 missing dots in the 6 mm square area, Δ if there were 5 to 20 spots, and × if there were 21 or more spots. The determination results are shown in Table 1.

The "missing dots" refers to a state in which the ink is poorly deposited on the film substrate and the dots (halftone dots) are not partially transferred. The smaller the number of missing dots until the halftone dot density is low, the better the printability of the highlighted portion.

<Evaluation of oxygen barrier property and water vapor barrier property after retort treatment>
The gas barrier film of each example was bonded to CPP (polypropylene film) using an adhesive to prepare a gas barrier laminated film for retort treatment having a gas barrier film / adhesive / CPP composition. The adhesive used was Mitsui Chemicals polyurethane's two-component curable adhesive, Takelac A620 (main agent) / Takenate A65 (curing agent), and the CPP used was Toray Film-processed polypropylene film, Trefan ZK93KM (60 μm). Then, it was dry-laminated with a multi-coater TM-MC manufactured by HIRANO TECSEED and cured at 40 ° C. for 3 days. The oxygen barrier film of the gas barrier film was arranged so as to be on the adhesive side.

An A5 size 4-way seal pouch was prepared from the obtained gas barrier laminated film, filled with 150 ml of tap water as the content, and heat sterilized (retort treatment) for 30 minutes in hot water at 120 ° C. did.

For the gas barrier laminated film after retort treatment, oxygen permeability (cm ³ /) under an atmosphere of 30 ° C. and 70% RH using an oxygen permeability measuring device (trade name: OXTRAN-2 / 20, manufactured by MOCON). ^{(m 2 · day · atm)} ) was measured. The water vapor transmission rate measuring device: (trade name PERMATRAN-W-3/33, MOCON Inc.), 40 ° C., under an atmosphere of RH 90%, the water vapor transmission rate of ^{(g / (m 2 · day} )) It was measured. The measurement results are shown in Table 1.

From the results shown in Table 1, the gas barrier films of Examples 1-1 to 1-8 have a black area ratio of 0.15% or less, and have an oxygen permeability in an atmosphere of 30 ° C. and a relative humidity of 70%. When the value was 2 cm ³ / (m ² · day · atm) or less, good oxygen barrier property was obtained.

On the other hand, the gas barrier films of Comparative Examples 1-1 to 1-4 is a black area ratio of 0.15% or more, the value of the oxygen permeability ^{2cm 3 / (m 2 · day} · atm) at greater than black When the area ratio was higher than 0.15%, the oxygen permeability was increased, and a better oxygen barrier property was not obtained as compared with Examples 1-1 to 1-8.

From the results shown in Table 1, the gas barrier films of Examples 1-1 to 1-8 had a halftone dot density of 30% or more and a printability of "◯".

On the other hand, the gas barrier films of Comparative Examples 1-1 to 1-4 had a printability of "x" at a halftone dot density of 30%.

As described above, it was found that the printability was good when the black area ratio was 0.15% or less.

[Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4]
A coating film was formed by applying the mixed solution for forming a base layer prepared in Production Example 1 to the corona-treated surface of the resin substrate shown in Table 2 using a gravure printing machine, and placed in an oven at 100 ° C. By passing through for 10 seconds and drying, a base layer having a thickness of 0.1 μm was formed. Next, a mixed material containing two or more kinds of metallic silicon, silicon monoxide, and silicon dioxide is evaporated using a vacuum vapor deposition apparatus by an electron beam heating method, and the mixture is composed of silicon oxide having a thickness of 30 nm on the base layer. An inorganic oxide layer was formed. Subsequently, the coating agent for forming the organic-inorganic composite film prepared in Production Example 4 is applied onto the formed inorganic oxide layer using a gravure printing machine to form a coating film, and the coating agent is formed in an oven at 100 ° C. By passing through for seconds and drying, an oxygen barrier film composed of an organic-inorganic composite film having a thickness of 0.3 μm is formed, and the gas barrier properties of Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-4 are obtained. I got a film.

[Example 2-7]
A gas barrier film of Example 2-7 was obtained in the same manner as in Examples 2-3 except that an inorganic oxide layer was directly formed on the corona-treated surface of the resin base material α8 without providing a base layer.

<Printability evaluation>
Using a gravure printing machine on the oxygen barrier film of the gas barrier film of each example, ink ink (trade name: N920LPGT, manufactured by Toyo Ink Co., Ltd.) is applied at a halftone dot density of 5% to 50% (in 5% increments). Gradation printing was performed. The ink viscosity was 14 seconds (Zahn cup # 3, 25 ° C.).
The printing speed was 150 m / min and the drying temperature was 50 ° C. The surface after printing was observed with an optical microscope, and the missing dots were counted. The judgment was ◯ if there were less than 5 missing dots in the 6 mm square area, Δ if there were 5 to 20 spots, and × if there were 21 or more spots. The determination results are shown in Table 2.

The "missing dots" refers to a state in which the ink is poorly deposited on the film substrate and the dots (halftone dots) are not partially transferred. The smaller the number of missing dots until the halftone dot density is low, the better the printability of the highlighted portion.

<Evaluation of oxygen barrier property and water vapor barrier property after retort treatment>
The gas barrier film of each example was bonded to CPP (polypropylene film) using an adhesive to prepare a gas barrier laminated film for retort treatment having a gas barrier film / adhesive / CPP composition. The adhesive used was Mitsui Chemicals polyurethane's two-component curable adhesive, Takelac A620 (main agent) / Takenate A65 (curing agent), and the CPP used was Toray Film-processed polypropylene film, Trefan ZK93KM (60 μm). Then, it was dry-laminated with a multi-coater TM-MC manufactured by HIRANO TECSEED and cured at 40 ° C. for 3 days. The oxygen barrier film of the gas barrier film was arranged so as to be on the adhesive side.

An A5 size 4-way seal pouch was prepared from the obtained gas barrier laminated film, filled with 150 ml of tap water as the content, and heat sterilized (retort treatment) for 30 minutes in hot water at 120 ° C. did.

For the gas barrier laminated film after retort treatment, oxygen permeability (cm ³ /) under an atmosphere of 30 ° C. and 70% RH using an oxygen permeability measuring device (trade name: OXTRAN-2 / 20, manufactured by MOCON). ^{(m 2 · day · atm)} ) was measured. The water vapor transmission rate measuring device: (trade name PERMATRAN-W-3/33, MOCON Inc.), 40 ° C., under an atmosphere of RH 90%, the water vapor transmission rate of ^{(g / (m 2 · day} )) It was measured. The measurement results are shown in Table 2.

From the results shown in Table 2, the gas barrier films of Examples 2-1 to 2-7 have a black area ratio of 0.15% or less, and have an oxygen permeability in an atmosphere of 30 ° C. and a relative humidity of 70%. the value is ^{3cm 3 / (m 2 · day} · atm) or less, good oxygen barrier properties were obtained.

On the other hand, the gas barrier films of Comparative Examples 2-1 to 2-4 is a black area ratio of 0.15% or more, the value of the oxygen permeability ^{5cm 3 / (m 2 · day} · atm) at greater than black When the area ratio was higher than 0.15%, the oxygen permeability was increased, and a better oxygen barrier property was not obtained as compared with Examples 2-1 to 2-7.

From the results shown in Table 2, the gas barrier films of Examples 2-1 to 2-7 had a halftone dot density of 30% or more and a printability of "○".

On the other hand, the gas barrier film of Comparative Examples 2-1 to 2-4 had a printability of "x" at a halftone dot density of 30%.

As described above, it was found that the printability was good when the black area ratio was 0.15% or less.

[Examples 3-1 to 3-7 and Comparative Example 3-1]
A coating film was formed by applying the mixed solution for forming a base layer prepared in Production Example 1 to the corona-treated surface of the resin substrate shown in Table 3 using a gravure printing machine, and placed in an oven at 100 ° C. By passing through for 10 seconds and drying, a base layer having a thickness of 0.1 μm was formed. Next, a mixed material containing two or more kinds of metallic silicon, silicon monoxide, and silicon dioxide is evaporated using a vacuum vapor deposition apparatus by an electron beam heating method, and the mixture is composed of silicon oxide having a thickness of 30 nm on the base layer. An inorganic oxide layer was formed. A coating agent containing the polycarboxylic acid-based polymer prepared in Production Example 2 as a main component is applied onto the subsequently formed inorganic oxide layer using a gravure printing machine to form a coating film at 100 ° C. A polycarboxylic acid-based polymer film having a thickness of 0.2 μm is formed by passing the film through the oven for 10 seconds and dried, and further, using a gravure printing machine on the polycarboxylic acid-based polymer film, Production Example 3 A coating agent containing the polyvalent metal compound as the main component prepared in step 2 is applied to form a coating film, which is then passed through an oven at 100 ° C. for 10 seconds and dried to form a 0.2 μm-thick polyvalent metal compound film. It was formed to form an oxygen barrier film composed of a polyvalent metal salt film of a polycarboxylic acid, and gas barrier films of Examples 3-1 to 3-7 and Comparative Example 3-1 were obtained.

[Example 3-8]
The gas barrier film of Example 3-8 was obtained in the same manner as in Example 3-4 except that the inorganic oxide layer was directly formed on the corona-treated surface of the resin base material α8 without providing a base layer.

<Printability evaluation>
Using a gravure printing machine on the oxygen barrier film of the gas barrier film of each example, ink ink (trade name: N920LPGT, manufactured by Toyo Ink Co., Ltd.) is applied at a halftone dot density of 5% to 50% (in 5% increments). Gradation printing was performed. The ink viscosity was 14 seconds (Zahn cup # 3, 25 ° C.).
The printing speed was 150 m / min and the drying temperature was 50 ° C. The surface after printing was observed with an optical microscope, and the missing dots were counted. The judgment was ◯ if there were less than 5 missing dots in the 6 mm square area, Δ if there were 5 to 20 spots, and × if there were 21 or more spots. The determination results are shown in Table 3.

The "missing dots" refers to a state in which the ink is poorly deposited on the film substrate and the dots (halftone dots) are not partially transferred. The smaller the number of missing dots until the halftone dot density is low, the better the printability of the highlighted portion.

<Evaluation of oxygen barrier property and water vapor barrier property after retort treatment>
The gas barrier film of each example was bonded to CPP (polypropylene film) using an adhesive to prepare a gas barrier laminated film for retort treatment having a gas barrier film / adhesive / CPP composition. The adhesive used was Mitsui Chemicals polyurethane's two-component curable adhesive, Takelac A620 (main agent) / Takenate A65 (curing agent), and the CPP used was Toray Film-processed polypropylene film, Trefan ZK93KM (60 μm). Then, it was dry-laminated with a multi-coater TM-MC manufactured by HIRANO TECSEED and cured at 40 ° C. for 3 days. The oxygen barrier film of the gas barrier film was arranged so as to be on the adhesive side.

An A5 size 4-way seal pouch was prepared from the obtained gas barrier laminated film, filled with 150 ml of tap water as the content, and heat sterilized (retort treatment) for 30 minutes in hot water at 120 ° C. did.

For the gas barrier laminated film after retort treatment, oxygen permeability (cm ³ /) under an atmosphere of 30 ° C. and 70% RH using an oxygen permeability measuring device (trade name: OXTRAN-2 / 20, manufactured by MOCON). ^{(m 2 · day · atm)} ) was measured. The water vapor transmission rate measuring device: (trade name PERMATRAN-W-3/33, MOCON Inc.), 40 ° C., under an atmosphere of RH 90%, the water vapor transmission rate of ^{(g / (m 2 · day} )) It was measured. The measurement results are shown in Table 3.

From the results shown in Table 3, the gas barrier films of Examples 3-1 to 3-8 had a black area ratio of 0.15% or less, and had an oxygen permeability in an atmosphere of 30 ° C. and a relative humidity of 70%. When the value was 2 cm ³ / (m ² · day · atm) or less, good oxygen barrier property was obtained.

On the other hand, the gas barrier film of Comparative Example 3-1 is a black area ratio of 0.15% or more, the value of the oxygen permeability at ^{4.7cm 3 / (m 2 · day} · atm), Example 3 No good oxygen barrier property was obtained as compared with 1-3-8.

From the results shown in Table 3, the gas barrier films of Examples 3-1 to 3-8 had a halftone dot density of 30% or more and a printability of “◯”.

On the other hand, the gas barrier film of Comparative Example 3-1 had a printability of "x" at a halftone dot density of 30%.

As described above, it was found that the printability was good when the black area ratio was 0.15% or less.

[Examples 4-1 to 4-5 and Comparative Example 4-1]
A coating film was formed by applying the mixed solution for forming a base layer prepared in Production Example 1 to the corona-treated surface of the resin substrate shown in Table 4 using a gravure printing machine, and placed in an oven at 100 ° C. By passing through for 10 seconds and drying, a base layer having a thickness of 0.1 μm was formed. Next, metallic aluminum was evaporated using a vacuum vapor deposition apparatus by an electron beam heating method, oxygen gas was introduced therein, and an inorganic oxide layer made of aluminum oxide having a thickness of 20 nm was formed on the base layer. A coating agent containing the polycarboxylic acid-based polymer prepared in Production Example 2 as a main component is applied onto the subsequently formed inorganic oxide layer using a gravure printing machine to form a coating film at 100 ° C. A polycarboxylic acid-based polymer film having a thickness of 0.2 μm is formed by passing the film through the oven for 10 seconds and dried, and further, using a gravure printing machine on the polycarboxylic acid-based polymer film, Production Example 3 A coating agent containing the polyvalent metal compound as the main component prepared in step 2 is applied to form a coating film, which is then passed through an oven at 100 ° C. for 10 seconds and dried to form a 0.2 μm-thick polyvalent metal compound film. It was formed to form an oxygen barrier film composed of a polyvalent metal salt film of a polycarboxylic acid, and gas barrier films of Examples 4-1 to 4-5 and Comparative Example 4-1 were obtained.

[Example 4-6]
A gas barrier film of Example 4-6 was obtained in the same manner as in Example 4-2 except that an inorganic oxide layer was directly formed on the corona-treated surface of the resin base material α8 without providing a base layer.

<Printability evaluation>
Using a gravure printing machine on the oxygen barrier film of the gas barrier film of each example, ink ink (trade name: N920LPGT, manufactured by Toyo Ink Co., Ltd.) is applied at a halftone dot density of 5% to 50% (in 5% increments). Gradation printing was performed. The ink viscosity was 14 seconds (Zahn cup # 3, 25 ° C.).
The printing speed was 150 m / min and the drying temperature was 50 ° C. The surface after printing was observed with an optical microscope, and the missing dots were counted. The judgment was ◯ if there were less than 5 missing dots in the 6 mm square area, Δ if there were 5 to 20 spots, and × if there were 21 or more spots. The determination results are shown in Table 4.

The "missing dots" refers to a state in which the ink is poorly deposited on the film substrate and the dots (halftone dots) are not partially transferred. The smaller the number of missing dots until the halftone dot density is low, the better the printability of the highlighted portion.

<Evaluation of oxygen barrier property and water vapor barrier property after retort treatment>
The gas barrier film of each example was bonded to CPP (polypropylene film) using an adhesive to prepare a gas barrier laminated film for retort treatment having a gas barrier film / adhesive / CPP composition. The adhesive used was Mitsui Chemicals polyurethane's two-component curable adhesive, Takelac A620 (main agent) / Takenate A65 (curing agent), and the CPP used was Toray Film-processed polypropylene film, Trefan ZK93KM (60 μm). Then, it was dry-laminated with a multi-coater TM-MC manufactured by HIRANO TECSEED and cured at 40 ° C. for 3 days. The oxygen barrier film of the gas barrier film was arranged so as to be on the adhesive side.

An A5 size 4-way seal pouch was prepared from the obtained gas barrier laminated film, filled with 150 ml of tap water as the content, and heat sterilized (retort treatment) for 30 minutes in hot water at 120 ° C. did.

For the gas barrier laminated film after retort treatment, oxygen permeability (cm ³ /) under an atmosphere of 30 ° C. and 70% RH using an oxygen permeability measuring device (trade name: OXTRAN-2 / 20, manufactured by MOCON). ^{(m 2 · day · atm)} ) was measured. The water vapor transmission rate measuring device: (trade name PERMATRAN-W-3/33, MOCON Inc.), 40 ° C., under an atmosphere of RH 90%, the water vapor transmission rate of ^{(g / (m 2 · day} )) It was measured. The measurement results are shown in Table 4.

From the results shown in Table 4, the gas barrier films of Examples 4-1 to 4-6 have a black area ratio of 0.15% or less, and have an oxygen permeability in an atmosphere of 30 ° C. and a relative humidity of 70%. the value is ^{1cm 3 / (m 2 · day} · atm) or less, good oxygen barrier properties were obtained. On the other hand, the gas barrier film of Comparative Example 4-1 is a black area ratio of 0.15% or more, the value of the oxygen permeability ^{1.5cm 3 / (m 2 · day} · atm), Example 4 No good oxygen barrier property was obtained as compared with 1-4-6.

From the results shown in Table 4, the gas barrier films of Examples 4-1 to 4-6 had a halftone dot density of 30% or more and a printability of "○".

On the other hand, the gas barrier film of Comparative Example 4-1 had a printability of "x" at a halftone dot density of 30%.

As described above, it was found that the printability was good when the black area ratio was 0.15% or less.

The gas barrier film of the present invention stably exhibits excellent gas barrier properties, and also exhibits excellent gas barrier properties even after retort treatment. In addition, the surface condition of the base film can be easily grasped, the quality can be stabilized even if the oxygen barrier film is thinned, and the raw material cost can be reduced.

In addition, the gas barrier film of the present invention has good printability. Therefore, the surface of the gas barrier film can be easily and beautifully printed.

The gas barrier film of the present invention can be suitably used as a packaging material, for example, and can also be suitably used as a packaging material for boiling treatment and retort treatment. By using the gas barrier film of the present invention as a packaging material, the quality retention of the contents can be improved.

The gas barrier film of the present invention can be used for applications other than packaging materials. Applications other than packaging materials include, for example, electronic device-related films, solar cell films, various functional films for fuel cells, substrate films, and the like.

1 Gas barrier film 10 Resin base material 20 Oxygen barrier film 30 Underlayer 40 Inorganic oxide layer

Claims (12)

With resin base material
An oxygen barrier film provided on at least one surface side of the resin base material and
It includes one or both of the base layer and the inorganic oxide layer provided between the resin base material and the oxygen barrier film.
One surface of the resin base material is a gas barrier film having a black area ratio of 0.15% or less as measured by the following measuring method.
<Measurement method>
An arbitrary region of 1281 μm square on one surface of the resin base material is photographed with an optical microscope to acquire a photographed image of 1024 × 1024 pixels, and the photographed image is converted into a monochrome image of 256 gradations by using image analysis software. After conversion, the value obtained by subtracting 30 from the most frequent value of the brightness in the monochrome image is set as the threshold value, the value below the threshold value is set to black, the value above the threshold value is set to white, and the brightness is binarized to obtain 100 μm ² or more in the 1281 μm square region. The ratio of the total area of the black area of the size of is defined as the black area ratio. The gas barrier film according to claim 1, wherein the resin base material contains an anti-blocking agent. The gas barrier film according to claim 1 or 2, wherein the resin base material is one selected from polypropylene, polyethylene terephthalate, and nylon. The gas barrier film according to any one of claims 1 to 3, wherein the thickness of the base layer is 0.01 to 1 μm. The base layer contains an organic polymer as a main component and contains
The organic polymer comprises at least one of a polyacrylic resin, a polyol resin, a polyurethane resin, a polyamide resin, and a reaction product of these resins, according to any one of claims 1 to 4. The gas barrier film described. The gas barrier film according to any one of claims 1 to 5, wherein the thickness of the inorganic oxide layer is 1 to 200 nm. The gas barrier film according to any one of claims 1 to 6, wherein the inorganic oxide layer is aluminum oxide or silicon oxide. The gas barrier film according to any one of claims 1 to 7, wherein the oxygen barrier film has a thickness of 0.05 to 1 μm. The oxygen barrier property coating, metal alkoxide, metal alkoxide hydrolyzate, and at least one reaction product of the hydrolyzate of metal alkoxide or metal alkoxide, a coating comprising a water-soluble polymer, claim The gas barrier film according to any one of 1 to 8. 9. The oxygen barrier film comprises at least one reaction product of a silane coupling agent, a silane coupling agent hydrolyzate, and a silane coupling agent or a silane coupling agent hydrolyzate. The gas barrier film described in. The oxygen barrier film according to claim 1 to 8, wherein the oxygen barrier film contains a polyvalent metal salt of a carboxylic acid which is a reaction product of a carboxy group of the polycarboxylic acid polymer (A) and a polyvalent metal compound (B). The gas barrier film according to any one of the above. The method for producing a gas barrier film according to any one of claims 1 to 11.
The black area ratio of the surface of the resin base material raw material is measured by the following measuring method, and the resin base material raw material having the black area ratio of at least one surface of 0.15% or less is prepared as the resin base material. Process and
A method for producing a gas barrier film, which comprises a step of applying a coating agent to at least one surface side of the resin base material to form at least the oxygen barrier film.
<Measurement method>
An arbitrary region of 1281 μm square on one surface of the resin base material is photographed with an optical microscope to acquire a photographed image of 1024 × 1024 pixels, and the photographed image is converted into a monochrome image of 256 gradations by using image analysis software. After conversion, the value obtained by subtracting 30 from the most frequent value of the brightness in the monochrome image is set as the threshold value, the value below the threshold value is set to black, the value above the threshold value is set to white, and the brightness is binarized to obtain 100 μm ² or more in the 1281 μm square region. The ratio of the total area of the black area of the size of is defined as the black area ratio.