JP7434767B2 - Gas-barrier vapor-deposited film, and laminates, packaging materials, and packages using the gas-barrier vapor-deposited film - Google Patents

Description

The present invention provides an excellent gas barrier vapor-deposited film that has gas barrier properties against oxygen and water vapor, as well as high retortability and high barrier properties, and can be suitably used as a packaging material for electronic devices such as electronic paper, food, medicine, pet food, etc. , and a laminate, packaging material, and package using the gas-barrier vapor-deposited film.

In the fields of electronic devices such as electronic paper, food, and pharmaceuticals, we need higher barrier properties that are unaffected by temperature and humidity to prevent the contents from deteriorating and maintain their functions and properties. There is a need for a multilayer film with barrier properties that can stably exhibit barrier properties, and a multilayer structure consisting of a resin base material, a barrier layer made of a thin vapor-deposited film of silicon oxide, aluminum oxide, etc., and a barrier coating layer are laminated. Laminated films have also been developed.

For example, Patent Document 1 describes a base material made of a plastic material, a first evaporated thin film layer provided on the base material, and a evaporated thin film layer provided on the first evaporated thin film layer containing at least a water-soluble polymer. A laminate comprising a gas barrier intermediate layer formed by applying a coating agent containing the gas barrier layer, and a second vapor-deposited thin film layer provided on the intermediate layer, further comprising the base material and the first vapor-deposited thin film layer. A gas barrier laminate is disclosed in which a primer layer consisting of a polyol, an isocyanate compound, and a silane coupling agent is provided between the layers.

Patent Document 2 describes a base film made of synthetic resin, a flattening layer laminated on at least one surface of the base film, and an inorganic oxide or Flattening formed by a sol-gel method using a gas barrier layer formed from an inorganic nitride and a composition containing another metal alkoxide and/or its hydrolyzate, which is laminated on the outer surface of this gas barrier layer. A high barrier sheet comprising a layer is disclosed.

Patent Document 3 discloses that a metal oxide layer, a resin layer, and a metal layer are laminated on the surface of a resin film in this order or in the reverse order, and the metal oxide layer is made of SiOx (1.0≦x≦ A gas barrier multilayer film made of silicon oxide shown in 2.0) is disclosed.

However, the barrier laminated film with the multilayer structure described above not only increases costs such as raw material costs and equipment operating costs due to the increased manufacturing process, but also requires quality checks for each layer and quality based on that. Complex tasks such as management corrections and history management are required.

Therefore, there is a demand for a barrier film with excellent barrier properties that solves the above manufacturing problems and does not cause a decrease in productivity.

WO2002/083408 publication Japanese Patent Application Publication No. 2005-324469 Japanese Patent Application Publication No. 2008-6762

The present invention was made to solve the above-mentioned problems, and provides a gas barrier vapor-deposited film that has excellent gas barrier properties, high retortability, and high barrier properties without having a multilayer structure as in the prior art. Another object of the present invention is to provide a laminate, a packaging material, and a package using the vapor-deposited gas-barrier film and the vapor-deposited gas-barrier film.

In order to achieve the above object, the gas barrier vapor-deposited film of the present invention includes a polyethylene terephthalate film, an inorganic oxide vapor-deposited film layer, and a barrier coating layer, and the inorganic oxide vapor-deposited film layer contains aluminum oxide as a main component. The barrier coating layer is laminated adjacent to the polyethylene terephthalate film, and the barrier coating layer is laminated adjacent to the surface of the inorganic oxide vapor-deposited film layer on the opposite side of the polyethylene terephthalate film. It is formed from a resin composition containing a water-soluble resin, and the moisture content of the laminated part consisting only of the polyethylene terephthalate film, the inorganic oxide vapor-deposited film layer, and the barrier coating layer is 0.33% by mass or more, 0. .45% by mass or less.
In addition, the laminated film of the present invention is a laminated film having barrier properties in which an aluminum oxide vapor-deposited film containing aluminum oxide as a main component is formed on the surface of a plastic base material. A transition region of the deposited film that defines the adhesion strength with the main deposited film is formed, and the transition region is etched using time-of-flight secondary ion mass spectrometry (TOF-SIMS). The metamorphosis defined using TOF-SIMS for an aluminum oxide vapor deposited film containing elemental bonds Al ₂ O ₄ H that metamorphoses into detected aluminum hydroxide and defined by etching using TOF-SIMS. The metamorphism rate of the transition region defined by the ratio of the transition region to be 5% or more and 60% or less.

Secondary ion mass spectrometry (SIMS) is an analysis method for element concentration distribution in which a primary ion beam is irradiated onto the surface of a sample to be analyzed, and secondary ions sputtered and emitted from the sample surface are analyzed by mass analysis. It is. In this secondary ion mass spectrometry, the secondary ion intensity is detected while sputtering is progressing. Therefore, by converting the transition time into depth for data on the time course of the ion intensity of secondary ions, that is, ions of the detected element or molecular ions combined with the detected element, it is possible to The concentration distribution of the detected element can be known.

In the present invention, conversion of transit time to depth is achieved by measuring the depth of the depression formed on the sample surface by primary ion irradiation using a surface roughness meter, and calculating the depth of the depression and the transit time. This is done by calculating the average sputtering speed and converting the irradiation time (i.e. transition time) into depth (sputtering amount) on the assumption that the sputtering speed is constant.

In the present invention, the aluminum oxide vapor-deposited film of the laminated film is repeatedly soft-etched at the above-described constant rate with a Cs (cesium) ion gun, while using time-of-flight secondary ion mass spectrometry (TOF-SIMS). By measuring the ions derived from the aluminum oxide deposited film and the ions derived from the plastic base material, we determined the transition that defines the adhesion strength between the base film surface and the formed deposited film, which is mainly composed of the aluminum oxide deposited film. A region is formed. The transition region contains elemental bonds Al ₂ O ₄ H that transforms into aluminum hydroxide, which is detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS). The ratio of the metamorphosed transition region defined using time-of-flight secondary ion mass spectrometry to the aluminum oxide deposited film defined by etching using secondary ion mass spectrometry (TOF-SIMS) This is based on the knowledge that a laminated film with barrier properties and improved adhesion strength can be identified by specifying the transformation rate of the transition region that transforms into aluminum hydroxide as defined by .

Specifically, the present invention etches the aluminum oxide vapor deposited film from the outermost surface using Cs using a time-of-flight secondary ion mass spectrometer, and the element bonding at the interface between the aluminum oxide vapor deposition film and the plastic base material. We measured the elemental bonds of the vapor-deposited film and obtained actual measurement graphs for each of the measured elements and elemental bonds (Fig. 3 graph analysis diagram). In order to narrow the transition region of the interface as much as possible, we focused on the elemental bond Al ₂ O ₄ H. 2) Find the peak in the graph representing the elemental bond Al ₂ O ₄ H, define the transition region from that peak to the interface, and 3) Find the (element bond Al ₂ O ₄ H) The transformation rate of the transition region to aluminum hydroxide is calculated as (transition region from the peak to the interface/aluminum oxide vapor deposited film)×100 (%).

In the present invention, by setting the transformation rate of the transition region of the aluminum oxide vapor-deposited film to 5% or more and 60% or less, a barrier coating layer is further formed on the laminated film, and the plastic base material of the gas-barrier vapor-deposited film and the oxidation Even after hot water treatment at 135°C for 40 minutes (high retort treatment) or hot water treatment at 121°C for 40 minutes (semi-retort treatment), the adhesion strength at the interface with the aluminum vapor-deposited film was 2.1N/2. 15 mm or more, delamination does not occur during molding or retort processing of a retort pouch, adhesion is improved, and a gas barrier vapor-deposited film having retort resistance can be produced.

In the present invention, by setting the transformation rate of the transition region of the aluminum oxide vapor-deposited film to 5% or more and 60% or less, the oxygen permeability and water vapor permeability after high retort treatment and semi-retort treatment are respectively 0.2 cc. /m2・24hr or less, 0.9g/m2・24hr or less, gas barrier vapor-deposited film that exhibits sufficient barrier properties to the extent that there is no deterioration in the quality or shelf life of the contents after retort processing. can be manufactured.
Therefore, the aluminum oxide vapor-deposited film of the present invention not only can improve the adhesion at the interface with the plastic substrate, but also has excellent barrier properties such as moist heat resistance and hot water resistance after retort treatment, and can improve retort resistance. It is.
Furthermore, the gas barrier vapor-deposited film of the present invention comprises a resin base material and an aluminum oxide vapor-deposited film in which element bonding structures represented by Al ₃ are locally distributed in a specific ratio on the resin base material. have.
The proportion of the elemental bonding structure represented by Al ₃ is detected by etching the gas barrier vapor-deposited film using time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is preferable that the intensity ratio Al ₃ /Al ₂ O ₃ ×100 is 1 or more and 20 or less.

That is, the present invention is characterized by the following points.
1. A gas barrier vapor-deposited film comprising a base layer made of a resin film, an inorganic oxide vapor-deposited film layer, and a barrier coating layer,
The inorganic oxide vapor-deposited film layer contains aluminum oxide as a main component and is laminated adjacent to the resin film,
The barrier coating layer is laminated adjacent to the surface of the inorganic oxide vapor-deposited film layer opposite to the resin film, and is formed from a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. It has been
Gas barrier property, characterized in that the moisture content of the laminated part consisting only of the resin film, the inorganic oxide vapor-deposited film layer, and the barrier coating layer is 0.33% by mass or more and 0.45% by mass or less Deposited film.
2. 2. The gas barrier vapor-deposited film as described in 1 above, wherein the resin film has a moisture content of 0.22% by mass or more and 0.33% by mass or less.
3. The vapor-deposited inorganic oxide film containing aluminum oxide as a main component includes a transition region that defines the adhesion strength between the surface of the base material made of the resin film and the vapor-deposited inorganic oxide film containing aluminum oxide as the main component. is formed,
The transition region contains elemental bonds Al ₂ O ₄ H that are metamorphosed into aluminum hydroxide, detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS),
The metamorphosed transition region defined using TOF-SIMS with respect to the aluminum oxide vapor deposited film defined by etching the barrier coating layer and the aluminum oxide vapor deposited film using TOF-SIMS. The gas barrier vapor-deposited film according to 1 above, wherein the transformation rate of the transition region defined by the ratio of is 5% or more and 60% or less.
4. In the inorganic oxide vapor deposited film containing aluminum oxide as a main component, elemental bonding structures represented by Al ₃ are distributed,
Intensity ratio Al ₃ /Al 2 O of the maximum Al ₃ concentration element bonding structure portion in the aluminum oxide vapor deposited film when the gas barrier vapor deposited film is analyzed by time-of-flight secondary ion mass spectrometry (TOF- _SIMS ) _{3. The gas barrier vapor-deposited film according to 1 or 2 above, wherein 3} ×100 is 1 or more and 20 or less.
5. The maximum Al ₃ concentration element bonding structure portion is located at a depth of 4% or more and 45% or less of the film thickness of the aluminum oxide vapor deposited film from the opposite surface of the aluminum oxide vapor deposited film to the resin base material. 4. The gas barrier vapor-deposited film according to 4 above.
6. 6. The gas barrier vapor deposited film according to any one of 1 to 5 above, wherein the surface of the resin film is an oxygen plasma treated surface.
7. 7. The gas barrier vapor-deposited film described in 6 above, wherein an aluminum oxide vapor-deposited film is laminated in-line on the oxygen plasma treated surface.
8. Gas barrier vapor deposition according to any one of 1 to 7 above, characterized in that the mass ratio of hydroxyl group-containing water-soluble resin/metal alkoxide in the resin composition is 5/95 or more and 20/80 or less. film.
9. 9. The gas barrier vapor-deposited film according to any one of items 1 to 8 above, wherein the barrier coating layer has a thickness of 150 nm or more and 800 nm or less.
10. 10. The gas barrier vapor-deposited film according to any one of 1 to 9 above, wherein the resin film is a polyethylene terephthalate film produced by performing a polyethylene terephthalate synthesis step and a film forming step in-line.
11. 10. The gas barrier vapor-deposited film according to any one of 1 to 9 above, wherein the resin film is a polyethylene terephthalate film.
12. 10. The gas barrier vapor-deposited film according to any one of 1 to 9 above, wherein the resin film includes a recycled polyethylene terephthalate film.
13. 10. The gas barrier vapor-deposited film according to any one of 1 to 9 above, wherein the resin film is a polybutylene terephthalate film.
14. 10. The gas barrier vapor-deposited film according to any one of 1 to 9 above, wherein the resin film is a biomass-derived polyester film.
15. The gas barrier vapor-deposited film according to any one of claims 1 to 9, wherein the resin film is a high stiffness PET film.
16. The barrier coating layer is formed from a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin having a degree of saponification of 90% or more and 100% or less. The gas barrier vapor deposited film described above.
17. A gas barrier laminate comprising the gas barrier vapor-deposited film according to any one of items 1 to 16 above and a sealant layer.
18. 18. A gas barrier packaging material produced from the gas barrier laminate described in 17 above.
19. 19. A gas barrier packaging body produced from the gas barrier packaging material described in 18 above.
20. 19. The gas barrier packaging body according to 19 above, which is used for retort sterilization packaging.
21. A manufacturing method for manufacturing a gas barrier vapor-deposited film, comprising:
An inorganic oxide vapor-deposited film containing aluminum oxide as the main component is laminated on the surface of a base material layer made of a resin film by physical vapor deposition,
Next, a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin is applied adjacent to the inorganic oxide vapor-deposited film and dried to form a barrier coating layer,
Producing the gas barrier vapor-deposited film, wherein the moisture content of the laminated portion consisting only of the polyethylene terephthalate film, the inorganic oxide vapor-deposited film, and the barrier coating layer is 0.33% by mass or more and 0.45% by mass or less. A method for producing a gas barrier vapor-deposited film, characterized in that:
22. 22. The method for producing a gas barrier vapor-deposited film as described in 21 above, wherein the resin film has a water content of 0.22% by mass or more and 0.33% by mass or less.
23. A method for producing a gas barrier laminate, comprising laminating a sealant layer on the surface of the gas barrier vapor-deposited film according to any one of items 1 to 16 above, by a dry lamination method or an extrusion lamination method.
24. A method for quality control of a gas barrier vapor deposited film in a method for producing a gas barrier vapor deposited film, the method comprising:
When the moisture content of the laminated part consisting only of the resin film, the inorganic oxide vapor-deposited film, and the barrier coating layer is measured, and the moisture content is less than 0.33% by mass or greater than 0.45% by mass. The water content is reduced to 0.33% by mass or more and 0.45% by mass or less by performing at least one or two or more treatments selected from the group consisting of heat treatment, humidification treatment, and constant temperature treatment at room temperature. A method for controlling the quality of a vapor-deposited film with gas barrier properties, characterized by adjusting the quality.
25. 25. The method for quality control of a gas barrier vapor-deposited film as described in 24 above, wherein the heat treatment is performed in an environment of 30° C. or higher and 120° C. or lower.
26. 26. The quality control method for a gas barrier vapor-deposited film as described in 24 or 25 above, wherein the humidification treatment is performed in an environment with a relative humidity of 30% RH or more and 100% RH or less.
27. 27. The quality control method for a gas barrier vapor-deposited film according to any one of 24 to 26 above, characterized in that the room temperature standing treatment is performed in an environment of 5° C. or higher and lower than 30° C.
28. A method for quality control of a gas barrier laminate in a method for producing a gas barrier laminate, in which the quality of the gas barrier laminate is controlled by the quality control method for a gas barrier vapor deposited film according to any one of 24 to 27 above. A quality control method for gas barrier laminates, characterized by:

According to the present invention, a gas barrier vapor deposited film having excellent gas barrier properties, high retortability and high barrier properties without adopting a multilayer structure, a gas barrier vapor deposited film, and a laminate using the gas barrier vapor deposited film, gas barrier properties A vapor-deposited film, packaging material, and package are obtained.
In addition, in the present invention, in order to minimize the transition region at the interface with the plastic substrate where aluminum hydroxide is formed in the aluminum oxide vapor-deposited film and to optimize the ratio of modification to aluminum hydroxide, the elemental bond Al ₂ Focusing on O ₄ H, by setting the transformation rate of the transition region of the aluminum oxide vapor-deposited film in the laminated film to 60% or less and increasing the ratio of the aluminum oxide film, which contains relatively less aluminum hydroxide, water molecules due to retort treatment can be reduced. This greatly suppresses microscopic destruction of the deposited film and destruction of the interface with the plastic base material.
Thereby, it is possible to provide a laminated film with improved adhesion and unprecedented retort resistance, and a gas barrier vapor-deposited film including the layered film. On the other hand, if there is almost no aluminum hydroxide near the plastic base material interface, a dense aluminum oxide film will not be formed and a film with poor water vapor barrier will be formed, so the metamorphosis rate is set to 5% or more.
The gas barrier vapor-deposited film of the present invention has an adhesion strength of 2.1 N/15 mm or more at the interface between the plastic substrate and the aluminum oxide vapor-deposited film even after high retort treatment and semi-retort treatment, and It has barrier performance with oxygen permeability and water vapor permeability of 0.2 cc/m2/24 hr or less and 0.9 g/m2/24 hr or less after semi-retorting, and has excellent retort resistance.
Furthermore, according to the present invention, a gas barrier vapor-deposited film with excellent barrier properties can be obtained without adopting a multilayer structure, so a gas barrier film that is advantageous in terms of production can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing an example of a gas-barrier vapor-deposited film of the present invention. FIG. 1 is a cross-sectional view showing an example of a gas barrier laminate of the present invention. FIG. 1 is a plan view showing an example of an apparatus for forming an inorganic oxide vapor-deposited film layer containing aluminum oxide as a main component in the present invention. FIG. 1 is a diagram showing an example of an apparatus for forming an aluminum oxide vapor-deposited film in the present invention. 1 is an example of a graphical analysis diagram of analysis results by time-of-flight secondary ion mass spectrometry of an aluminum oxide vapor-deposited film laminated film on which a barrier coating layer is laminated according to the present invention. FIG. 2 is a graph analysis diagram showing an example of measurement results of a barrier resin film by TOF-SIMS in the present invention. FIG. 3 is a diagram showing a test piece for measuring peel strength. FIG. 3 is a diagram showing a method of measuring peel strength. It is a figure which shows the change of tensile strength at the time of measuring peel strength.

The present invention will be described below with reference to the drawings. However, the present invention is not limited to these specifically illustrated forms or various specifically described structures.

In each figure, the sizes and proportions of members may be changed or exaggerated for ease of understanding. Further, for ease of viewing, parts unnecessary for explanation or repetitive symbols may be omitted.

<Gas barrier vapor deposited film>
As shown in FIG. 1, the gas barrier vapor-deposited film 1 of the present invention has a base layer 2 made of a polyethylene terephthalate film, an inorganic oxide vapor-deposited film layer 3, and a barrier coating layer 4, each of which is arranged in this order. are stacked directly adjacent to each other.

What we focused on in the present invention is the moisture content of the laminated portion consisting of polyethylene terephthalate, the inorganic oxide vapor-deposited film layer, and the barrier coating layer after the barrier coating layer has been formed.

The vapor-deposited gas barrier film of the present invention has a moisture content of 0.33% by mass or more and 0.45% by mass or less, and when the moisture content is within this range, good gas barrier properties can be exhibited.

In the present invention, the moisture content is measured by a Karl Fischer moisture measuring device. The detailed measurement method is as described in the example, but the important point is that the moisture content is calculated from the formula: (amount of water coming out of the sample [g])/(sample weight [g]) It is.

When the water content is smaller than the above range, water can participate in the reaction at the interface between the inorganic oxide vapor-deposited film and the polyethylene terephthalate film, and/or water can participate in the reaction at the interface between the barrier coating layer and the inorganic oxide vapor-deposited film. This is a state in which water is insufficient, and the gas barrier properties of the vapor-deposited gas barrier film tend to be insufficient.

In addition, if the water content is higher than the above range, the influence of water is too large on the reaction at the interface during vapor deposition, and the quality of the inorganic oxide vapor-deposited film may not be homogeneous. In this case, the water remaining in the barrier coating layer may complicate the reaction between the metal alkoxide and the hydroxyl group-containing water-soluble resin, causing the barrier properties of the barrier coating layer to deteriorate, and the gas barrier properties of the gas barrier vapor-deposited film to become unstable. There is a possibility that this could easily happen.

Further, although not shown in the drawings, the gas barrier vapor-deposited film 1 of the present invention may have various functional layers laminated thereon, if necessary.

[Polyethylene terephthalate film]
In the present invention, the polyethylene terephthalate film may have a single layer or a multilayer structure of two or more layers. In the case of a multilayer structure, the polyethylene terephthalate film may have a layer of the same composition or a layer of a different composition. It's okay.

The moisture content of the laminated part of the present invention is influenced by the moisture content of the polyethylene terephthalate film before inorganic oxide deposition.

The moisture content of general polyethylene terephthalate films used for industrial purposes is approximately 0.1 to 1% by mass, but in the present invention, the moisture content is 0.22% by mass or more and 0.33% by mass or less. Preferably, polyethylene terephthalate film is used.

Polyethylene terephthalate films with a water content of 0.22% by mass or more and 0.33% by mass or less can be selected and used, but even if the polyethylene terephthalate film is outside this numerical range, it cannot be heated, humidified, or room temperature treated. By performing one or more treatments selected from the group consisting of constant temperature treatment, the numerical value can be brought within or close to the above range and used as a base material.

In addition, polyethylene terephthalate films include polyethylene terephthalate films manufactured by melting and forming polyethylene terephthalate resin pellets, and polyethylene terephthalate films manufactured by performing the polyethylene terephthalate synthesis process and film forming process in-line. Terephthalate films can also be used.

The former polyethylene terephthalate film is advantageous in that it is easy to obtain a polyethylene terephthalate film having a water content of 0.22% by mass or more and 0.33% by mass or less, and the latter polyethylene terephthalate film is advantageous in terms of cost.

Furthermore, polyethylene terephthalate films are often provided with a thin film called an easy-adhesion layer made of urethane-based, polyester-based, or acrylic-based resin to improve adhesion to objects to be laminated. Such polyethylene terephthalate films can also be used in the present invention.

When producing the gas-barrier vapor-deposited film of the present invention, an inorganic oxide vapor-deposited film layer can be provided on the thin film of the easily adhesive layer. Since the easy-adhesive layer is an extremely thin film compared to the polyethylene terephthalate film, it does not affect the moisture content of the laminated portion consisting of the polyethylene terephthalate film, the inorganic oxide vapor-deposited film, and the barrier coating layer.

Furthermore, the polyethylene terephthalate film can contain various additives as long as its properties are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducers, mold release agents, antioxidants, and ions. Examples include exchange agents and color pigments, which are added depending on the purpose.
The thickness of the polyethylene terephthalate film used as the base layer is preferably 5 μm or more and 100 μm or less, more preferably 5 μm or more and 25 μm or less.

[Base material layer]
The base material layer of the gas barrier vapor-deposited film may have a single layer structure or a multilayer structure of two or more layers.
For the base material layer, any known resin film or sheet can be used without particular limitation. (Hereinafter, it will be referred to as resin film.) For example, polyester resins such as polyethylene terephthalate, biomass-derived polyester, polybutylene terephthalate, polyethylene naphthalate, recycled polyethylene terephthalate, and polyethylene furanoate; polyamide resin 6, polyamide resin Films made of polyamide resins such as 66, polyamide resin 610, polyamide resin 612, polyamide resin 11, and polyamide resin 12; polyolefin resins such as α-olefin polymers such as polyethylene and polypropylene can be used.
Among the above resins, polyester resins are preferably used, and among the polyester resins, polyethylene terephthalate film and polybutylene terephthalate film are particularly preferably used.

(Polybutylene terephthalate film (PBT))
Polybutylene terephthalate film has a high heat distortion temperature, excellent mechanical strength and electrical properties, and good moldability, so it is suitable for use in packaging bags that contain food and other contents during retort processing. This can prevent the packaging bag from deforming or reducing its strength.

Polybutylene terephthalate film has high strength. Therefore, when a polybutylene terephthalate film is used, the packaging bag can be provided with puncture resistance, as in the case where the packaging material constituting the packaging bag includes a nylon film.
In addition, polybutylene terephthalate film hydrolyzes in a high temperature and high humidity environment, resulting in a decrease in adhesion strength and barrier properties after retort treatment, but it has the property of being less likely to absorb moisture than nylon. Therefore, even when the polybutylene terephthalate film is disposed on the outer surface of the packaging material, it is possible to prevent the lamination strength between the packaging materials of the packaging bag from decreasing. Because of these properties, polybutylene terephthalate film is preferably used in retort packaging bags because it can replace the conventional packaging material made of polyethylene terephthalate film and nylon film.

The polybutylene terephthalate film is a film containing polybutylene terephthalate (hereinafter also referred to as PBT) as a main component, and is preferably a resin film containing 60% by mass or more of PBT. Polybutylene terephthalate films can be divided into two types based on their structure.

The content of PBT in the polybutylene terephthalate film according to the first aspect is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 75% by mass or more, and most preferably 80% by mass or more. .
The dicarboxylic acid component of PBT used as a main component is preferably 90 mol% or more of terephthalic acid, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100 mol% or more. It is mole%.
As a glycol component, 1,4-butanediol is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 97 mol% or more.

The polybutylene terephthalate film may contain polyester resins other than PBT. Examples of polyester resins other than PBT include polyester resins such as PET, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polypropylene terephthalate (PPT), as well as isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, and biphenyl dicarboxylic acid. , PBT resin copolymerized with dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, azelaic acid, and sebacic acid, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, neopentyl glycol, 1,5 Examples include PBT resins in which diol components such as -pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, and polycarbonate diol are copolymerized.

The amount of polyester resin other than PBT added is preferably 40% by mass or less. If the amount of polyester resin other than PBT exceeds 40% by mass, the mechanical properties of PBT may be impaired, and impact strength, pinhole resistance, and drawing formability may become insufficient.

The layer structure of the polybutylene terephthalate film according to the first aspect is produced by casting a multilayered resin by a casting method, and is composed of a multilayer structure including a plurality of unit layers. Each of the plurality of unit layers contains PBT as a main component. For example, each of the plurality of unit layers contains 60% by mass or more of PBT. Note that in the plurality of unit layers, the (n+1)th unit layer is directly stacked on the nth unit layer. That is, no adhesive layer or bonding layer is interposed between the plurality of unit layers. Such a polybutylene terephthalate film consists of a multilayer structure including at least 10 or more unit layers, preferably 60 or more layers, more preferably 250 or more layers, still more preferably 1000 or more layers.

The polybutylene terephthalate film according to the second aspect is composed of a single layer containing polyester having PBT as a main repeating unit. A polyester having PBT as the main repeating unit, for example, has 1,4-butanediol or its ester-forming derivative as a glycol component and terephthalic acid or its ester-forming derivative as a dibasic acid component as its main components. , homo- or copolymer-type polyesters obtained by condensing them. The content of PBT in the second configuration is preferably 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.

The polybutylene terephthalate film according to the second aspect may contain a polyester resin other than PBT in a range of 30% by mass or less. By including the polyester resin, PBT crystallization can be suppressed and the stretchability of the polybutylene terephthalate film can be improved. As the polyester resin to be mixed with PBT, a polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homotype mainly composed of ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component can be preferably used.

The polybutylene terephthalate film according to the second configuration can be manufactured by a tubular method or a tenter method. The unstretched original fabric may be stretched simultaneously in the machine direction and the transverse direction, or sequentially in the machine direction and the transverse direction, by a tubular method or a tenter method. Among these, the tubular method is particularly preferably employed because it can produce a stretched film with good balance of physical properties in the circumferential direction.

(Polyester film derived from biomass)
The biomass-derived polyester film is composed of a resin composition containing as a main component a polyester consisting of diol units and dicarboxylic acid units, and the resin composition has diol units that are biomass-derived ethylene glycol and dicarboxylic acid units. is a fossil fuel-derived dicarboxylic acid, 50 to 95% by mass of the entire resin composition,
It preferably contains 50 to 90% by mass.

Biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, so polyester films synthesized using biomass-derived ethylene glycol are mechanically comparable to conventional fossil fuel-derived polyester films. There is no inferiority in terms of physical properties such as physical properties.
Therefore, since the laminated film of the present invention and the gas barrier vapor-deposited film using the same have a layer made of a carbon-neutral material, the laminated film manufactured from conventional raw materials obtained from fossil fuels and the gas barrier vapor-deposited film using the same have a layer made of carbon-neutral material. Compared to vapor-deposited films, it can significantly reduce the amount of fossil fuel used and reduce environmental impact.

Biomass-derived ethylene glycol is made from ethanol produced from biomass such as sugarcane and corn (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method. Moreover, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.

Dicarboxylic acid derived from fossil fuels is used as the dicarboxylic acid unit of the polyester. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid, and examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters, and butyl esters. Examples include esters. Among these, terephthalic acid is preferred, and as the aromatic dicarboxylic acid derivative, dimethyl terephthalate is preferred.

The polyester that may be contained in a proportion of 5 to 45% by mass in the resin composition forming the biomass-derived polyester film includes fossil fuel-derived polyester, recycled polyester of fossil fuel-derived polyester products, and biomass-derived polyester products. Made of recycled polyester.

The resin composition containing the polyester obtained as described above preferably contains 10 to 19% of biomass-derived carbon based on the total carbon in the polyester as measured by radiocarbon (14C). Since carbon dioxide in the atmosphere contains 14C at a certain rate (105.5 pMC), the 14C content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known. It is also known that fossil fuels contain almost no 14C. Therefore, by measuring the proportion of 14C contained in all carbon atoms in polyester, the proportion of carbon derived from biomass can be calculated.

In the present invention, the biomass-derived carbon content Pbio is defined as follows, where the content of 14C in polyester is P14C.
Pbio(%)=P14C/105.5×100
Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymerization of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, so only biomass-derived ethylene glycol can be used. When Pbio is used, the biomass-derived carbon content Pbio in the polyester is 20%.
In the present invention, the content of biomass-derived carbon as measured by radiocarbon (14C) is preferably 10 to 19% of the total carbon in the resin composition.
If the biomass-derived carbon content in the resin composition is less than 10%, the effect as a carbon offset material will be poor. On the other hand, as mentioned above, the biomass-derived carbon content in the resin composition is preferably close to 20%, but due to problems in the film manufacturing process and physical properties, the resin may contain recycled polyester or Since it is preferable to include additives, the actual upper limit is 18%.

(Recycled polyethylene terephthalate)
As the resin base material of the present invention, one containing polyethylene terephthalate (hereinafter, polyethylene terephthalate is also referred to as PET) recycled by mechanical recycling can be used.
Specifically, the resin base material includes PET obtained by mechanically recycling a PET bottle, and the diol component of this PET is ethylene glycol, and the dicarboxylic acid component includes terephthalic acid and isophthalic acid.

Mechanical recycling here generally means that collected polyethylene terephthalate resin products such as PET bottles are crushed, washed with alkali to remove dirt and foreign matter from the surface of the PET resin product, and then dried for a certain period of time under high temperature and reduced pressure. In this method, contaminants remaining inside the PET resin are diffused and decontaminated, dirt is removed from resin products made of PET resin, and the product is returned to PET resin again.

Hereinafter, in this specification, polyethylene terephthalate made from recycled PET bottles will be referred to as "recycled polyethylene terephthalate (hereinafter also referred to as recycled PET)", and polyethylene terephthalate that has not been recycled will be referred to as "virgin polyethylene terephthalate (hereinafter also referred to as virgin PET)". )”.

Among the PET contained in the resin base material, the content of the isophthalic acid component is preferably 0.5 mol% or more and 5 mol% or less, and 1.0 mol% in the total dicarboxylic acid components constituting the PET. More preferably, the content is 2.5 mol% or less.
If the content of the isophthalic acid component is less than 0.5 mol%, the flexibility may not be improved, while if it exceeds 5 mol%, the melting point of PET may decrease and the heat resistance may become insufficient.

Note that PET may be biomass PET in addition to ordinary fossil fuel-derived PET. "Biomass PET" includes biomass-derived ethylene glycol as a diol component and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid component. This biomass PET may be formed only of PET that uses biomass-derived ethylene glycol as a diol component and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid component, or it may be formed only of PET that uses biomass-derived ethylene glycol and fossil fuel-derived diol as a dicarboxylic acid component. It may be formed of PET having a diol component and a dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component.

PET used for PET bottles can be obtained by a conventionally known method of polycondensing the diol component and dicarboxylic acid component described above.

Specifically, the general method of melt polymerization is to perform an esterification reaction and/or transesterification reaction between the above diol component and dicarboxylic acid component, and then perform a polycondensation reaction under reduced pressure, or an organic solvent. It can be produced by a known solution heating dehydration condensation method using.

The amount of the diol component used when producing the above PET is substantially equimolar to 100 moles of the dicarboxylic acid or its derivative, but in general, it is used by esterification and/or transesterification reaction and/or polycondensation reaction. Since distillation occurs during the reaction, it is used in an excess of 0.1 mol % or more and 20 mol % or less.
Further, the polycondensation reaction is preferably carried out in the presence of a polymerization catalyst. The timing of adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added at the time of charging the raw materials or at the start of pressure reduction.

PET made from recycled PET bottles is polymerized and solidified as described above, and then undergoes solid phase polymerization as necessary to further increase the degree of polymerization and remove oligomers such as cyclic trimers. You may go.
Specifically, solid phase polymerization involves chipping PET, drying it, pre-crystallizing the PET by heating at a temperature of 100°C or higher and 180°C or lower for about 1 to 8 hours, and then pre-crystallizing the PET at 190°C. This is carried out by heating at a temperature of 230° C. or lower in an inert gas atmosphere or under reduced pressure for 1 hour to several tens of hours.

The intrinsic viscosity of PET contained in recycled PET is preferably 0.58 dl/g or more and 0.80 dl/g or less. If the intrinsic viscosity is less than 0.58 dl/g, the mechanical properties required of the PET film as a resin base material may be insufficient. On the other hand, if the intrinsic viscosity exceeds 0.80 dl/g, productivity in the film forming process may be impaired. Note that the intrinsic viscosity is measured at 35° C. using an orthochlorophenol solution.

The recycled PET preferably contains recycled PET in a proportion of 50% by weight or more and 95% by weight or less, and may contain virgin PET in addition to recycled PET.
Virgin PET may be PET in which the diol component as described above is ethylene glycol and the dicarboxylic acid component contains terephthalic acid and isophthalic acid, or PET in which the dicarboxylic acid component does not contain isophthalic acid. Good too.
Moreover, the resin base material layer may contain polyester other than PET. For example, the dicarboxylic acid component may include, in addition to aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids and the like.

Specifically, aliphatic dicarboxylic acids include chains usually having 2 to 40 carbon atoms, such as oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. or alicyclic dicarboxylic acids.
Examples of derivatives of aliphatic dicarboxylic acids include lower alkyl esters such as methyl esters, ethyl esters, propyl esters and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride. .
Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred as the aliphatic dicarboxylic acid, and those containing succinic acid as a main component are particularly preferred. As the aliphatic dicarboxylic acid derivative, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred.

The resin base material made of such PET may be a single layer or a multilayer.
When using recycled PET as described above for the resin base material, the resin base material may have three layers: an upper layer which is the outermost layer, a middle layer, and a lower layer close to the sealant layer.
In this case, it is preferable that the middle layer be a layer made only of recycled PET or a mixed layer of recycled PET and virgin PET, and that the upper and lower layers be made layers made only of virgin PET.

In this way, by using only virgin PET for the upper and lower layers, it is possible to prevent recycled PET from coming out from the front or back surface of the resin base layer. Therefore, the hygiene of the laminate can be ensured.
Moreover, the resin base material layer may be a resin base material layer provided with two layers, a middle layer and a lower layer, without providing the above-mentioned upper layer. Furthermore, the resin base material layer may be a resin base material layer provided with two layers, an upper layer and a middle layer, without providing a lower layer. In these cases as well, it is preferable that the middle layer be a layer made only of recycled PET or a mixed layer of recycled PET and virgin PET, and that the upper and lower layers be made layers made only of virgin PET.

When mixing recycled PET and virgin PET to mold one layer, there are methods such as feeding them separately to a molding machine, or feeding them after mixing by dry blending or the like. Among these, a method of mixing by dry blending is preferred from the viewpoint of easy operation.

PET constituting the resin base material can contain various additives in the manufacturing process or after the manufacturing process to the extent that its properties are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducers, mold release agents, antioxidants, and ions. Examples include exchange agents and colored pigments.
The additive is preferably contained in the entire resin composition containing PET in a range of 5% by mass or more and 50% by mass or less, preferably 5% by mass or more and 20% by mass or less.

The resin base material can be formed by forming a film using the above-mentioned PET, for example, by a T-die method. Specifically, after drying the above-mentioned PET, it is supplied to a melt extruder heated to a temperature (Tm) above the melting point of PET to Tm + 70°C to melt the resin composition. A film can be formed by extruding the extruded sheet into a sheet through a die such as the above, and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like.
As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, etc. can be used depending on the purpose.

The film obtained as described above is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto a cooling drum as described above is then heated by roll heating, infrared heating, etc., and stretched in the longitudinal direction to form a longitudinally stretched film. This stretching is preferably carried out using the difference in circumferential speed between two or more rolls. Longitudinal stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower.
Further, the longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. When the stretching ratio is less than 2.5 times, the thickness unevenness of the PET film becomes large and it is difficult to obtain a good film.

The longitudinally stretched film is then sequentially subjected to transverse stretching, heat setting, and heat relaxation to become a biaxially stretched film. The transverse stretching is usually performed at a temperature range of 50°C or higher and 100°C or lower. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, although it depends on the required characteristics of this use. If it is less than 2.5 times, the thickness of the film becomes uneven and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.

After the transverse stretching, heat setting is subsequently performed, and the preferred temperature range for heat setting is Tg+70 to Tm-10°C of PET. Further, the heat setting time is preferably 1 second or more and 60 seconds or less. Furthermore, for applications requiring a reduction in thermal shrinkage rate, a thermal relaxation treatment may be performed as necessary.

The thickness of the PET film obtained as described above is arbitrary depending on its use, but is usually about 5 μm or more and 100 μm or less, preferably 5 μm or more and 25 μm or less.
In addition, the breaking strength of the PET film is 5 kg/mm2 or more and 40 kg/mm2 or less in the MD direction, and 5 kg/mm2 or more and 35 kg/mm2 or less in the TD direction, and the breaking elongation is
It is 50% or more and 350% or less in the MD direction, and 50% or more and 300% or less in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1% or more and 5% or less.

Note that virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET. Here, "fossil fuel PET" is one in which the diol component is a fossil fuel-derived diol and the dicarboxylic acid component is a fossil fuel-derived dicarboxylic acid. Recycled PET may also be obtained by recycling PET resin products formed using fossil fuel PET, or may be obtained by recycling PET resin products formed using biomass PET. There may be.

A high stiffness PET film is a stretched plastic film that has a loop stiffness of 0.0017 N/15 mm or more in the machine direction (MD) and the vertical direction (TD) and contains PET of 51% by mass or more. The thickness of the high stiffness PET film is preferably 5 μm or more, more preferably 7 μm or more. Further, the thickness of the high stiffness PET film is preferably 25 μm or less, more preferably 20 μm or less.

[Inorganic oxide vapor deposited film layer]
The inorganic oxide vapor deposited film layer according to the present invention is a thin film of an inorganic oxide containing aluminum oxide as a main component, and contains trace amounts of aluminum compounds such as aluminum nitrides, carbides, and hydroxides alone or in mixtures thereof. , metal oxides such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, magnesium oxide, titanium oxide, tin oxide, indium oxide, zinc oxide, zirconium oxide, or metal nitrides, carbides and their It can include mixtures and the like.

A substance represented by Al ₂ O ₄ H is distributed in the inorganic oxide vapor deposited film according to the present invention, and its abundance varies depending on the depth position of the inorganic oxide vapor deposited film.
The abundance rate of the substance represented by Al ₂ O ₄ H can be expressed as the abundance ratio with Al ₂ O ₃ (aluminum oxide), and specifically, time-of-flight secondary ion mass spectrometry (TOF) It can be expressed by the intensity ratio Al ₂ O ₄ H/Al 2 O ₃ , which is the ratio of the intensity of Al _{2 O 4} H detected by -SIMS) to the intensity of Al ₂ O ₃ .

The inorganic oxide vapor deposited film according to the present invention has Al ₂ O ₄ H and Al in the same etching cycle, which is obtained by etching the barrier coating layer and the inorganic oxide vapor deposited film layer using TOF-SIMS. There is a portion where the maximum value of the intensity ratio with ₂ O ₃ is 0.25 or more and 0.65 or less.
In the present invention, this portion is referred to as the maximum intensity ratio portion, and the maximum value of the intensity ratio of Al ₂ O ₄ H/Al ₂ O ₃ in this portion is referred to as the maximum intensity ratio Al ₂ O ₄ H/Al ₂ O ₃ . Because of such a compositional structure, the inorganic oxide vapor deposited film according to the present invention has improved denseness and gas barrier properties.
If the maximum intensity ratio Al ₂ O ₄ H/Al ₂ O ₃ is smaller than the above range, there are too few elemental bonding structures represented by Al ₂ O ₄ H in the deposited film, resulting in insufficient gas barrier properties. It tends to be difficult to express. Further, when the amount is larger than the above range, the amount of Al(OH)3 present becomes too large, and the composition of the inorganic oxide vapor-deposited film is easily deteriorated by water vapor, resulting in poor water vapor barrier properties.

Furthermore, it is preferable that the maximum strength ratio portion exists near the interface between the inorganic oxide vapor-deposited film and the base layer resin.
The maximum intensity ratio portion is 0 nm or more from the center of the interface to the inorganic oxide vapor deposited film layer side, 6
More preferably, it exists at a depth of nm or less.
By being present at the above depth position, the denseness of the deposited film is improved and the adhesion to the base material layer is further improved.

Furthermore, in order to obtain the above maximum strength ratio, the base material layer on which the inorganic oxide vapor deposited film layer is formed has a moisture content of 0.1% by mass or more and 0.33% by mass or less. Preferably.
The moisture content in the present invention is measured by a Karl Fischer moisture measuring device. The detailed measurement method is as described in the Examples, but the point is that the water content is calculated from (amount of water coming out of the sample [g])/(sample weight [g]). The test piece can be measured whether it is in the form of a film or granules.
Gas barrier properties of vapor-deposited films depend on the water content of the resin film used as the base layer, and good barrier properties are exhibited when the water content is low (0.1% by mass or more and less than 0.22% by mass). However, the inorganic oxide vapor deposited film of the present invention can exhibit good barrier properties.

Furthermore, by using the inorganic oxide vapor-deposited film of the present invention as a gas barrier vapor-deposited film using a resin film with a high water content (0.22% by mass or more and 0.33% by mass or less), the barrier performance can be further improved. can be raised.
The thickness of the inorganic oxide vapor-deposited film layer is preferably 5 nm or more and 100 nm or less. If it is smaller than the above range, the barrier properties tend to be insufficient, and if it is larger than the above range, the rigidity of the inorganic oxide vapor-deposited film layer becomes too strong and peeling tends to occur.

(Oxygen plasma pretreatment)
As shown in FIG. Partition walls 35a to 35c are formed therein. The partition walls 35a to 35c form a substrate transfer chamber 12A, a plasma pretreatment chamber 12B, and a film formation chamber 12C, and in particular, a plasma pretreatment chamber 12B and a film formation chamber are defined as spaces surrounded by the partition walls 35a to 35c. 12C is formed, and each chamber is further formed with an exhaust chamber therein as required.

Inside the plasma pretreatment chamber 12B, a part of the plasma pretreatment roller 20 that conveys the plastic substrate S to be pretreated and enables plasma treatment is provided so as to be exposed to the substrate conveyance chamber 12A. The plastic base material S is moved to the plasma pretreatment chamber 12B while being wound up.

The plasma pretreatment chamber 12B and the film forming chamber 12C are provided in contact with the substrate transfer chamber 12A, and are capable of moving the plastic substrate S without exposing it to the atmosphere. Further, the pretreatment chamber 12B and the substrate transfer chamber 12A are connected through a rectangular hole, and a part of the plasma pretreatment roller 20 protrudes toward the substrate transfer chamber 12A through the rectangular hole. A gap is formed between the wall of the transfer chamber and the pretreatment roller 20, and the substrate S can be moved from the substrate transfer chamber 12A to the film forming chamber 12C through the gap.
The structure is similar between the base material transfer chamber 12A and the film forming chamber 12C, and the plastic base material S can be moved without being exposed to the atmosphere.

The base material transport chamber 12A serves as a winding means for winding up into a roll the plastic base material S on which a vapor deposited film is formed on one side, which has been moved to the base material transport chamber 12A again by the film forming roller 23. A take-up roller is provided so that the plastic base material S on which the vapor-deposited film is formed can be taken up.

When producing a laminated film having an aluminum oxide deposited film with barrier properties with improved adhesion according to the present invention, the plasma pretreatment chamber 12B separates a space in which plasma is generated from other regions, and separates an opposing space from another region. By being configured to efficiently evacuate, the plasma gas concentration can be easily controlled and productivity can be improved.
The pretreatment pressure for forming the reduced pressure can be set and maintained at about 0.1 Pa to 100 Pa. Particularly, in order to obtain a metamorphosis rate in the preferable transition region of the aluminum oxide vapor deposited film of the present invention, oxygen plasma pretreatment is performed. The processing pressure is preferably 1 to 20 Pa.

The conveyance speed of the plastic substrate S is not particularly limited, but from the viewpoint of production efficiency, it can be at least 200 to 1000 m/min, especially in order to obtain the transformation rate of the transition region of the aluminum oxide vapor deposited film of the present invention. The transport speed for oxygen plasma pretreatment is preferably 300 to 800 m/min.

The plasma pretreatment roller 20 constituting the plasma pretreatment device prevents the plastic substrate S from shrinking or breaking due to heat during plasma treatment by the plasma pretreatment means, and prevents the plastic substrate S from shrinking or being damaged by the heat generated during the plasma treatment by the plasma pretreatment means. The objective is to apply it uniformly and over a wide range of areas.
Preferably, the temperature of the pretreatment roller 20 can be adjusted to a constant temperature between -20° C. and 100° C. by adjusting the temperature of a temperature adjusting medium circulating within the pretreatment roller.

The plasma pretreatment means includes a plasma supply means and a magnetic formation means. The plasma pretreatment means cooperates with the plasma pretreatment roller 20 to confine oxygen plasma P near the surface of the plastic substrate S.

The plasma pretreatment means is provided so as to cover a part of the pretreatment roller 20. Specifically, plasma supply means and magnetic formation means constituting the plasma pretreatment means are arranged along the surface near the outer periphery of the pretreatment roller 20 to supply the pretreatment roller 20 and the plasma raw material gas, and to generate the plasma P. The plasma supply nozzles 22a to 22c, which also serve as electrodes for generating plasma P, and a magnetic formation means having a magnet 21 and the like to promote generation of plasma P are installed to form a gap sandwiched between them.
Thereby, the plasma supply nozzles 22a to 22c are opened in the space of the gap to inject plasma toward the surface of the substrate, making the inside of the gap a plasma formation area, and furthermore, the pretreatment roller 20 and the plastic substrate S are connected to each other. By forming a region with high plasma density in the vicinity of the surface, the plastic base material S is configured so that the oxygen plasma pretreatment of the present invention, which forms a plasma-treated surface on one side, can be performed.

The plasma supply means of the plasma pretreatment means includes a raw material volatilization supply device 18 connected to a plasma supply nozzle provided outside the decompression chamber 12, and a raw material gas supply line that supplies raw material gas from the device. The plasma raw material gas to be supplied is oxygen alone or a mixed gas of oxygen gas and an inert gas, and is supplied from the gas storage section through a flow rate controller while measuring the flow rate of the gas. Examples of the inert gas include one or more mixed gases selected from the group consisting of argon, helium, and nitrogen.

These supplied gases are mixed at a predetermined ratio as necessary to form a plasma raw material gas alone or a mixed gas for plasma formation, and are supplied to the plasma supply means. The single or mixed gas is supplied to the plasma supply nozzles 22a to 22c of the plasma supply means, and is supplied near the outer periphery of the pretreatment roller 20 where the supply ports of the plasma supply nozzles 22a to 22c are open.
The nozzle opening is directed toward the plastic substrate S on the pretreatment roller 20, and is arranged and configured so that the oxygen plasma P can be uniformly diffused and supplied to the entire surface of the plastic substrate S. A uniform plasma pretreatment can be applied to a large area of the material S.

In order to obtain the metamorphosis rate in the transition region of the aluminum oxide vapor deposited film of the present invention, the oxygen plasma pretreatment is performed with a mixing ratio of oxygen gas and the inert gas, oxygen gas/inert gas, of 6/1 to 1/1. is preferable, 3/2.5 to 3/1 is more preferable, and 3/2 to 3/1 is even more preferable.
By setting the mixing ratio to 6/1 to 1/1, the energy for forming a film of vapor-deposited aluminum on the plastic film substrate increases, and by setting the mixing ratio to 3/2.5 to 3/1, aluminum hydroxide is formed near the interface of the substrate, ie, the metamorphism rate of the transition region is reduced.

The plasma supply nozzles 22a to 22c function as opposing electrodes of the pretreatment roller 20, and are designed to have an electrode function, and are supplied between the pretreatment roller 20 and the high frequency voltage, low The plasma raw material gas supplied is excited by a potential difference caused by a frequency voltage or the like, and plasma P is generated and supplied.

Specifically, the plasma supply means of the plasma pretreatment means is equipped with a plasma pretreatment roller as a plasma power source, applies an AC voltage with a frequency of 10 Hz to 2.5 GHz between it and a counter electrode, and controls input power or , it is possible to perform impedance control, etc., and apply any voltage between it and the plasma pretreatment roller 20, and it is possible to physically or chemically modify the surface properties of the base material. A power source 32 is provided that can apply a bias voltage to bring the oxygen plasma P to a positive potential.
The plasma intensity per unit area adopted in the present invention is 50 to 8000 W・sec/m2, and below 50 W・sec/m2, no effect of plasma pretreatment is seen, and above 8000 W・sec/m2, Plasma tends to cause deterioration of the base material, such as wear, damage, discoloration, and firing of the base material. In particular, the plasma intensity of the oxygen plasma pretreatment is preferably 100 to 1000 W·sec/m2, more preferably 100 to 500 W·sec/m2, in order to obtain the metamorphism rate in the transition region of the aluminum oxide deposited film of the present invention. .
By applying a bias voltage perpendicular to the plastic substrate and providing the plasma intensity described above, the adhesion to the aluminum oxide vapor deposited film can be stably strengthened compared to conventional methods.

The plasma pretreatment means includes magnetic formation means. As magnetism forming means, an insulating spacer and a base plate are provided inside the magnet case, and a magnet 21 is provided on this base plate. An insulating shield plate is provided in the magnet case, and an electrode is attached to this insulating shield plate.
Therefore, the magnet case and the electrode are electrically insulated, and even if the magnet case is installed and fixed in the decompression chamber 12, the electrode can be kept at an electrically floating level.

A power supply wiring 31 is connected to the electrode, and the power supply wiring 31 is connected to a power source 32. Further, a temperature regulating medium pipe for cooling the electrode and the magnet 21 is provided inside the electrode.
The magnet 21 is provided so that the oxygen plasma P from the plasma supply nozzles 22a to 22c, which serve as electrodes and plasma supply means, is applied to the substrate S in a concentrated manner. By providing the magnet 21, the reactivity near the surface of the base material becomes high, and it becomes possible to form a good plasma pretreated surface at high speed.

The magnet 21 has a magnetic flux density of 10 Gauss to 10,000 Gauss at the surface position of the plastic base material S. If the magnetic flux density on the surface of the plastic base material S is 10 Gauss or more,
It becomes possible to sufficiently increase the reactivity near the base material surface, and a good pretreated surface can be formed at high speed.

Because ions and electrons formed during plasma pretreatment move according to the arrangement structure of the magnet 21 of the electrode, for example, when performing plasma pretreatment on a plastic substrate S with a large area of 1 m ² or more. Also, electrons, ions, and decomposed products of the base material are uniformly diffused over the entire electrode surface, making it possible to uniformly and stably perform the desired pretreatment with the desired plasma intensity even when the plastic base material S has a large area. It is something.

[Method for forming inorganic oxide vapor deposited film layer]
Since the inorganic oxide vapor deposited film layer contains aluminum oxide as a main component, the following description will be made assuming that the inorganic oxide vapor deposited film is an aluminum oxide vapor deposited film.

As the vapor deposition method for forming the aluminum oxide vapor deposited film, various vapor deposition methods can be applied from among physical vapor deposition and chemical vapor deposition. Physical vapor deposition methods can be selected from the group consisting of vapor deposition, sputtering, ion plating, ion beam assist, and cluster ion beam methods, and chemical vapor deposition methods include plasma CVD, plasma polymerization, and thermal It can be selected from the group consisting of CVD method and catalytic reaction type CVD method. In the present invention, physical vapor deposition is preferred.
Formation of the inorganic oxide vapor deposited film layer of the present invention will be explained using FIG. 3.

The resin film is conveyed by the conveyance roller 14 of the vapor-deposited substrate conveyance chamber 12A to the depressurized vapor-deposited film-forming chamber 12C in the vapor-deposited film-forming apparatus 12.
The transported resin film is wound around a film forming roller 23 for vapor deposition processing.
Then, the target of the vapor deposition source 24 placed opposite the film forming roller 23 is evaporated to form a vapor deposited film on the surface of the resin film, which is then sequentially wound up by the winding roller 15 into a roll.

The vapor deposition film forming means 24 is of a resistance heating type, uses a wire made of aluminum metal as an evaporation source, and forms an aluminum oxide vapor deposition film on the surface of the resin film while supplying oxygen to oxidize the aluminum vapor.
Oxygen may be supplied alone or as a mixed gas with an inert gas such as argon, but it is preferable that the amount of oxygen can be adjusted.
Further, evaporation of aluminum can be performed, for example, by arranging a plurality of wire rods made of aluminum metal in the axial direction of the roller 23 in a boat-shaped (referred to as "boat type") vapor deposition container, and heating the wire rods using a resistance heating method.

In this way, aluminum metal is evaporated while adjusting the heat and amount of heat supplied, and by adjusting the amount of oxygen supplied, the reaction between aluminum and oxygen is controlled to form an aluminum oxide vapor deposited film. can do.

In the present invention, the inorganic oxide vapor-deposited film can be subjected to heat treatment, if necessary.
The heat treatment conditions are preferably an oxygen concentration of 18% to 25%, a temperature of 50° C. or more and 100° C. or less, and 72 hours or more and 350 hours or less.
If the temperature is lower than the above-mentioned temperature range, the heat treatment effect is difficult to exhibit, and in order to obtain a sufficient effect, a long treatment time is required, resulting in deterioration of productivity. If the temperature is higher than the above temperature range, the resin layer will easily deteriorate.
When the time is shorter than the above-mentioned time range, it is difficult to exhibit the heat treatment effect, and when the time is longer than the above-mentioned time range, the resin layer portion is likely to deteriorate and productivity is deteriorated.

By performing the heat treatment, the constituent compounds of the film are reacted after the inorganic oxide vapor-deposited film is formed, and a composition in which the maximum strength ratio portion of the present invention exists can be obtained.
The heat treatment is carried out in order to achieve a composition of the inorganic oxide deposited film in which the maximum strength ratio portion of the present invention exists through the reaction of the constituent compounds of the inorganic oxide deposited film, and may be repeated several times as necessary. May be repeated.
As mentioned above, this heat treatment changes the composition of the inorganic oxide deposited film, and changes aluminum oxide, which has incomplete stoichiometry during conventional deposition, to oxidation with perfect stoichiometry. This is different from the heat treatment used to make aluminum.

Further, the heat treatment conditions vary depending on the moisture content of the resin film that is the base layer of the gas barrier vapor deposited film and the form of the gas barrier vapor deposited film (roll or sheet).
Even gas-barrier vapor-deposited films that are based on resin films with low moisture content that do not have good barrier properties can be heat-treated to create a composition that has the maximum strength ratio of the present invention, thereby improving barrier performance. can be done.

Judging from the above points comprehensively, all of the following manufacturing conditions 1 to 4 must be satisfied in order to produce a vapor-deposited film so that the transformation rate in the transition region is within the range of 5% to 60%. is preferred.
Manufacturing conditions 1
The thickness of the transparent vapor deposition layer is 8 nm or more.
Manufacturing conditions 2
The mixing ratio of oxygen gas and inert gas in the oxygen plasma treatment is 3/2.5 or more and 3/1 or less.
Manufacturing conditions 3
The pretreatment pressure in the oxygen plasma treatment is 1 Pa or more and 20 Pa or less.
Manufacturing conditions 4
The plasma intensity in the oxygen plasma treatment is 100 W·sec/m 2 or more and 500 W·sec/m 2 or less.

[How to determine maximum intensity ratio Al ₂ O ₄ H/Al ₂ O ₃ and depth position]
In the present invention, the Al ₂ O ₄ H intensity and Al ₂ O ₃ intensity in the inorganic oxide deposited film, as well as their respective depth positions, are measured using TOF-SIMS, and the maximum intensity ratio Al ₂ O The value of ₄ H/Al ₂ O ₃ is calculated and the depth position is also specified.

TOF-SIMS (Time-of-Flight secondary ion mass spectrometry)
Secondary ion mass spectrometry (Secondary Ion Mass Spectrometry) is a method in which a primary ion beam is irradiated from a primary ion gun onto the surface of a solid sample to be analyzed. (proportional to the square root) to perform mass separation and mass analysis.
Here, by detecting the secondary ion intensity while sputtering is progressing, the data on the time course of the ion intensity of the secondary ions, that is, the ions of the detected element or the molecular ions combined with the detected element, is analyzed by detecting the transition time. By converting to depth, it is possible to know the concentration distribution of the detected element in the depth direction of the sample surface.
Then, the depth of the depression formed on the sample surface by primary ion irradiation is measured in advance using a surface roughness meter, and the average sputtering rate is calculated from the depth of the depression and the transit time. Under the assumption that the sputtering speed is constant, it is possible to calculate the depth (sputter amount) from the irradiation time (ie, transition time) or the number of irradiation cycles.

In the present invention, a Cs (cesium) ion gun is preferably used to measure the barrier coating layer of the gas barrier resin film and the inorganic oxide vapor deposited film at a constant speed in order to measure deep areas. While repeating soft etching, the intensity ratio of each ion was determined by measuring Al ₂ O ₄ H and Al ₂ O ₃ ions originating from the inorganic oxide vapor deposited film layer and C6 ions originating from the resin film base layer. It can be calculated.
It has sufficient strength against aluminum oxide and has a depth that can be used to approximate the concentration distribution of Al ₂ O ₄ H by separating the ion species to be measured by the present invention from a plurality of ion species derived from aluminum oxide. Cs ions are suitable for obtaining a high density distribution.
Using Cs, etching was performed from the outermost surface of the barrier coating layer, and the elemental bonds at the interface between the barrier coating layer, the aluminum oxide deposited film, and the resin film base material, and the elemental bonds in the deposited film were analyzed and measured. Each graph of the elements and element bonds shown in FIG. 5 is obtained. In the graph, first, the position where the strength of SiO ₂ (mass number 59.96), which is a constituent element of the barrier coating layer, is half that of the barrier coating layer is defined as the interface between the barrier coating layer and the aluminum oxide vapor deposited film. Next, the position that is half of the layer of C6 (mass number 72.00), which is the constituent material of the resin film base material, is set as the interface between the resin film base material and the aluminum oxide vapor-deposited film, and the position is the second from the first interface. The aluminum oxide vapor deposited film extends up to the interface.

Next, a graph representing the measured elemental bond Al ₂ O ₄ H (mass number 118.93) is obtained, but if the component of the barrier coating layer has the same mass number as Al ₂ O ₄ H (mass number 118.93), , it is necessary to separate 118.93 corrugations.
In the case of the present invention, a reactant AlSiO 4 having the same mass as Al ₂ O ₄ H (mass number 118.93) is generated at the interface between the barrier coating layer and the aluminum oxide layer, so that AlSiO _{4 and} Al ₂ O ₄ H Separate the waveforms. Such waveform separation is performed by appropriately setting target compounds depending on the material of the barrier coating layer.

One method for waveform separation is to perform nonlinear curve fitting on a profile with a mass number of 118.93 obtained by TOF-SIMS using a Gaussian function, and to separate overlapping waveforms using the least squares method Levenberg Marquardt algorithm. It's a method.
By performing the above overlapping waveform separation operation, the depth within the inorganic oxide deposited film, Al ₂ O ₄ H intensity, and Al ₂ O ₃ intensity in each cycle were obtained, and the intensity ratio Al ₂ O ₄ H / Al ₂ O By determining ₃ , it is possible to know the value of the maximum intensity ratio and the depth distance from the interface in the inorganic oxide vapor deposited film layer.

[Barrier coating layer]
The barrier coating layer mechanically and chemically protects the inorganic oxide vapor-deposited film layer and improves the barrier performance of the gas-barrier vapor-deposited film. Ru.

The barrier coating layer is formed from a barrier coating layer coating agent made of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. In the barrier coating layer, the metal alkoxide produces a condensation reaction product, but it may also produce a co-condensate with the hydroxyl group-containing water-soluble resin.

The mass ratio of hydroxyl group-containing water-soluble resin/metal alkoxide in the resin composition is preferably 5/95 or more and 20/80 or less, and more preferably 6/94 or more and 15/85 or less. If it is smaller than the above range, the barrier coating layer tends to be too rigid or brittle, and if it is larger than the above range, the barrier effect of the barrier coating layer tends to be insufficient. .

The thickness of the barrier coating layer is preferably 100 nm or more and 800 nm or less. If it is thinner than the above range, the barrier effect of the barrier coating layer tends to be insufficient, and if it is thicker than the above range, the rigidity becomes too strong or the brittleness tends to become large.

In the present invention, the barrier coating layer can be formed, for example, by the following method.

First, a metal alkoxide, a water-soluble resin containing a hydroxyl group, a reaction accelerator (sol-gel method catalyst, acid, etc.), and an organic solvent such as water as a solvent, alcohol such as methyl alcohol, ethyl alcohol, or isopropanol are mixed to form a resin. A coating agent for a barrier coating layer is prepared.

Next, on the inorganic oxide vapor-deposited film layer, the above coating agent for a barrier coating layer is applied by a conventional method and dried. Through this drying step, the condensation or co-condensation reaction further proceeds and a cured coating film is formed. On the first coating film, the above coating and drying operations may be further repeated to form a coating film consisting of two or more layers.

Furthermore, if necessary, heating for 3 seconds to 10 minutes at 20 to 200°C, preferably 30 to 150°C, more preferably 40 to 100°C, and at a temperature below the softening point of the resin constituting the base layer. It can be treated and dried to the moisture content defined by the present invention. Drying conditions vary depending on the form and properties of the gas barrier vapor-deposited film to be dried and the composition of the coating agent for the barrier coating layer.

As a result, a barrier coating layer using the coating agent for barrier coating layer can be formed on the inorganic oxide vapor-deposited film layer.

[Metal alkoxide]
The metal alkoxide has the general formula R ¹ _n M(OR ² ) _m (wherein R ¹ and R ² represent a hydrogen atom or an organic group having 1 to 8 carbon atoms, M represents a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M. Each of the plurality of R ¹ and R ² in one molecule may be the same or different. ).

Specific examples of the metal atom represented by M in the metal alkoxide include silicon, zirconium, titanium, aluminum, tin, lead, borane, and others. For example, alkoxy in which M is Si (silicon) Preference is given to using silanes.

Alkoxysilane is represented by the general formula R ¹ _n Si(OR ² ) _m (where n+m=4).

In the above, specific examples of OR ² include a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an i-propoxy group, a butoxy group, and a 3-methacryloxy group. Examples include alkoxy groups such as 3-acryloxy groups and phenoxy groups, and phenoxy groups.

In the above, specific examples of R ¹ include methyl group, ethyl group, n-propyl group, isopropyl group, phenyl group, p-styryl group, 3-chloropropyl group, trifluoromethyl group, vinyl group, γ-glycyl group, Examples include sidoxypropyl group, methacryl group, and γ-aminopropyl group.

Specific examples of alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, methyltriphenoxysilane, phenylphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-styryltrimethoxysilane, 3- Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane Examples include various alkoxysilanes such as ethoxysilane, 3-chloropropyltriethoxysilane, trifluoromethyltrimethoxysilane, and 1,6-bis(trimethoxysilyl)hexane, and phenoxysilane.

In alkoxysilanes, when R ¹ is an organic group having a functional group such as a vinyl group, epoxy group, methacrylic group, or amino group, it is generally called a silane coupling agent.

Specific examples of the silane coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyltriethoxysilane, Examples include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Silane is preferred.

The above-mentioned metal alkoxides may be used alone or in combination of two or more types, and it is particularly preferable to use a silane coupling agent in combination. When a silane coupling agent is used in combination, it is preferable that the silane coupling agent accounts for 2% by mass or more and 15% by mass or less of the total metal alkoxide.

[Hydroxyl group-containing water-soluble resin]
In the present invention, the hydroxyl group-containing water-soluble resin is capable of dehydration co-condensation with a metal alkoxide, and the degree of saponification is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, and 99% or more. % or more and 100% or less is more preferable. If the degree of saponification is smaller than the above range. The hardness of the barrier coating layer tends to decrease.

Specific examples of hydroxyl group-containing water-soluble resins include polyvinyl alcohol resins, polymers of bifunctional phenol compounds and bifunctional epoxy compounds, and each may be used alone, or two or more types may be used. They may be used as a mixture or may be copolymerized. Among these, polyvinyl alcohol is particularly suitable because it has excellent flexibility and affinity.

Specific examples of polyvinyl alcohol-based resins include polyvinyl alcohol obtained by saponifying polyvinyl acetate, and ethylene-vinyl alcohol copolymer obtained by saponifying a copolymer of ethylene and vinyl acetate. Coalescing can be used.

Examples of such polyvinyl alcohol include PVA-124 (saponification degree = 99%, polymerization degree = 2,400) manufactured by Kuraray Co., Ltd., and Gohsenol NM-14 (saponification degree = 99%, degree of polymerization = 1,400).

<Quality control method for gas barrier vapor deposited film>
In the present invention, the quality of the gas barrier vapor deposited film is controlled by adopting the moisture content of the laminated portion consisting only of the polyethylene terephthalate film, the inorganic oxide vapor deposited film layer, and the barrier coating layer as a control standard in the manufacturing method. Can be done.

Specifically, in the production process of the gas barrier vapor deposited film, samples for moisture content measurement were collected from the produced gas barrier vapor deposited film, which consists of only a polyethylene terephthalate film, an inorganic oxide vapor deposited film layer, and a barrier coating layer. , Measure the moisture content, compare the moisture content with the standard range of 0.33% by mass or more and 0.45% by mass or less, and consider whether or not it is necessary to implement an additional process for the gas barrier vapor-deposited film. Can be done.

For example, if the moisture content is less than 0.33% by mass, in order to increase the moisture content, humidification treatment is performed to create an environment corresponding to the measured moisture content value, with a relative humidity in the range of 30% RH or more and 100% RH or less. You can choose to do it. The above relative humidity is a range suitable for adjusting the moisture content of the product; if it is lower than the above range, it is difficult to obtain the effect of increasing the moisture content, and if it is higher than the above range, the gas barrier vapor deposited film that is the product There is a risk of blocking and mold growth.

In addition, if the moisture content exceeds 0.45% by mass, heat treatment is performed in a range of 30°C or higher and 100°C or lower in an environment that corresponds to the measured value of the moisture content in order to lower the moisture content. be able to. If it is lower than the above range, it will be difficult to obtain the effect of lowering the water content, and if it is higher than the above range, there is a risk that heat wrinkles, heat deflection, etc. will occur in the gas barrier deposited film.

Furthermore, if the measured moisture content value is only slightly out of the reference range, the slight difference can be eliminated by constant temperature treatment at room temperature. The constant temperature treatment at room temperature can be carried out at a temperature in the range of 5 to 30°C.

Note that the time for each treatment can be appropriately determined in consideration of the winding thickness of the gas-barrier vapor-deposited film, thermal conductivity, and the like.

By performing such quality control, it is possible to reduce loss of intermediate products in the manufacturing process, loss of manufacturing process time, etc., and it is possible to efficiently manufacture a gas barrier vapor-deposited film.

<Gas barrier laminate>
As shown in FIG. 2, the gas barrier laminate 5 of the present invention further includes at least a heat-sealable sealant layer 6 on the outermost surface of the gas barrier vapor-deposited film 1 of the present invention via an adhesive. , or laminated without intervening. FIG. 3 shows an example in which it is provided on the barrier coating layer 4.

The sealant layer 6 is preferably laminated on the inorganic oxide vapor-deposited film layer 3 side or the barrier coating layer 4 side of the gas-barrier vapor-deposited film 1 .

Furthermore, if necessary, functions to be imparted when used in packaging materials, such as a light-shielding layer for imparting light-shielding properties, decorative properties, a printing layer for imparting printing, a pattern layer, a laser-printed layer, and odor. The layer structure can also include various functional layers such as a deodorizing layer that decomposes or adsorbs .

[Sealant layer]
The sealant layer is a layer containing one or more heat-sealable resins and can be bonded by heating, and can be applied by dry lamination using a resin film, extrusion lamination including coextrusion, or resin coating. This is a layer formed from a film or the like.

The sealant layer may be a single layer or may have a multilayer structure of two or more layers. In the case of a multilayer structure, the compositions of the respective layers may be the same or different, and may include a layer consisting only of a heat-sealable resin or a layer not containing a heat-sealable resin. Furthermore, it can also include functional layers with various functions and adhesive layers. However, the layer constituting the outermost layer on one side of the packaging material preferably contains a resin with excellent heat sealability.

Heat-sealable resins include, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer, α- Resins such as olefin copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, elastomers, and these resins A mixed resin can be used.

In addition, the sealant layer contains antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, antiblocking agents, flame retardants, crosslinking agents, colorants, pigments, lubricants, fillers, reinforcing agents, and modifying agents. One or more kinds of various inorganic or organic additives such as resins for use in the composition can be contained as appropriate. The content can be arbitrarily determined from a trace amount to several tens of percent depending on the purpose.

<Quality control method of gas barrier laminate>
In the present invention, the quality of the gas barrier laminate can be controlled by controlling the quality of the gas barrier deposited film.

By performing this kind of quality control, it is possible to reduce the loss of the gas barrier vapor-deposited film, as well as reduce the loss of raw materials and manufacturing process time in subsequent processes, making it possible to efficiently manufacture gas barrier laminates. .

<Gas barrier packaging material>
The gas barrier packaging material of the present invention is a packaging material produced from the gas barrier laminate of the present invention.

A gas barrier packaging material can also be produced by further laminating a functional film depending on the application on the gas barrier laminate of the present invention.

For example, in the case of a packaging material for a retort, a nylon film can be laminated as a pinhole-resistant structure, and a heat-resistant sealant CPP or the like can be laminated as a heat-resistant structure. Alternatively, if it is a packaging material for liquid paper containers, paper can be laminated.

<Gas barrier packaging>
The barrier package of the present invention is a package made from the gas barrier packaging material of the present invention.

For example, gas barrier packaging bodies in the form of pillow packaging bags, three-sided seals, four-sided seals, gusset types, etc. can be produced by heat-sealing in which the sealant layer of a gas-barrier packaging material made of a multilayer film is thermally fused. In addition, if the packaging material is made from a laminate of paper, it is possible to produce a Goebel-top type liquid paper container packaging for alcoholic beverages, juices, and the like.

<<Experiment 1>>
The following Examples and Comparative Examples were carried out using the polyethylene terephthalate film shown below and preparing the coating agent for a barrier coating layer shown below.

(Polyethylene terephthalate film)
- Film 1: water content 0.257% by mass, thickness 12 μm.
- Film 2: water content 0.256% by mass, thickness 12 μm.
- Film 3: water content 0.255% by mass, thickness 12 μm.
- Film 4: water content 0.228% by mass, thickness 12 μm.
- Film 5: water content 0.227% by mass, thickness 12 μm.
- Film 6: water content 0.224% by mass, thickness 12 μm.
- Film 7: water content 0.216% by mass, thickness 12 μm.

(Adjustment of barrier coating agent for barrier coating layer)
175 g of tetraethoxysilane and 9.2 g of glycidoxypropyltrimethoxysilane were added to a solution of 300 g of water, 146 g of isopropyl alcohol, and 7.3 g of 0.5N hydrochloric acid mixed and adjusted to pH 2.2 and cooled to 10°C. Solution A was prepared by mixing while stirring.

Solution B was prepared by mixing 14.7 g of polyvinyl alcohol with a degree of saponification of 99% or more and a degree of polymerization of 2400, 324 g of water, and 17 g of isopropyl alcohol.

A solution obtained by mixing liquid A and liquid B at a weight ratio of 3.5:6.5 was used as a barrier coating agent for a barrier coating layer.

[Example 1]
(Formation of aluminum oxide vapor deposited film)
First, a roll of Film 1 was prepared.

Next, an aluminum oxide vapor deposited film having a thickness of 12 nm was formed as an inorganic oxide vapor deposited film on this film 1 under the following conditions to obtain a roll of the vapor deposited film.

Next, an A4-sized vapor-deposited film was cut out from the roll, and the barrier coating layer coating agent prepared above was coated onto the aluminum oxide-deposited film using an applicator.

Thereafter, heat treatment was performed in an oven at 180° C. for 60 seconds to form a barrier coating layer with a thickness of about 400 nm on the aluminum oxide vapor deposited film, thereby obtaining a gas barrier vapor deposited film.

Then, the water content, oxygen permeability, and water vapor permeability were measured.

(Aluminum oxide film forming conditions)
・Heating means for vacuum evaporation method: Reactive resistance heating method ・Pressure: 8.1×10 ^-2 Pa
・Transportation speed: 400m/min
・Oxygen gas supply amount: 8000sccm

[Examples 2 to 6, Comparative Example 1]
A gas barrier vapor-deposited film was obtained by performing the same operation as in Example 1, except that the type of film was changed, and the water content, oxygen permeability, and water vapor permeability were measured in the same manner.

<Measurement method>
[Moisture content of gas barrier vapor deposited film]
Karl Fischer moisture measuring device (Mitsubishi Chemical Analytech Co., Ltd., CA-20)
0, VA-236S) was used to measure the moisture content of a laminated portion consisting only of a polyethylene terephthalate film, an inorganic oxide vapor-deposited film layer, and a barrier coating layer.

After storing the film consisting of about 1 g of the laminated portion for 3 days or more in an environment of 25 ± 2 ° C. and relative humidity of 45 ± 10% RH, it is folded into a strip shape so that the height is less than half the height of the measurement cell. The water content was measured under the following conditions and environment. Each sample was measured with n=3, and the average value was adopted as the water content.

Titration duration: 10 minutes End point sensitivity: 0.1μg/sec Heating temperature: 120℃
Nitrogen gas flow rate: 250ml/min Measurement environment: 25±2℃, relative humidity 45±10%RH
Karl Fischer reagent: “Aquamicron AX/CXU” manufactured by Mitsubishi Chemical Corporation

[Oxygen permeability]
Using an oxygen permeability measuring device (MOCON, OX-TRAN2/22), set the gas barrier vapor-deposited film so that the polyethylene terephthalate film side faces the oxygen supply side, and heat the film to 23°C in accordance with JIS K 7126. The oxygen permeability was measured in an environment with relative humidity of 90% RH.

[Water vapor permeability]
Using a water vapor permeability measuring device (manufactured by MOCON, PERMATRAN-W3-34G), set the gas barrier vapor-deposited film so that the polyethylene terephthalate film side faces the sensor side, and heat the film at 40°C in accordance with JIS K 7129. The water vapor permeability was measured in an environment with relative humidity of 100% RH.

[Result Summary]
The measurement results of Examples 1 to 6 and Comparative Example 1 are summarized in Table 1.

The vapor-deposited gas barrier films of Examples 1 to 6 exhibited good oxygen barrier properties and water vapor barrier properties, but the vapor-deposited gas barrier films of Comparative Example 1 had extremely poor water vapor barrier properties.

From the above, the gas barrier vapor deposited film of the present invention has a moisture content of 0.33 to 0.45% by mass as specified in the present application in the laminated portion consisting only of the polyethylene terephthalate film, the inorganic oxide vapor deposited film layer, and the barrier coating layer. Although it showed excellent oxygen barrier properties and water vapor barrier properties, the vapor-deposited gas barrier film of Comparative Example 1, which did not meet the requirements, showed poor water vapor barrier properties.

<<Experiment 2>>
[Example 1]
<Formation of aluminum oxide vapor deposited film>
First, a roll was prepared by winding up a polyester film (hereinafter referred to as PET film) having a thickness of 12 μm as a resin base material.
Next, the surface of the PET film on which the vapor deposition film is to be provided is subjected to the following plasma conditions in the pretreatment section using a continuous vapor deposition film forming apparatus in which a pretreatment section in which a plasma pretreatment device is arranged and a film formation section are separated. Plasma was introduced from a plasma supply nozzle, subjected to plasma pretreatment at a conveyance speed of 400 m/min, and was continuously conveyed in the film forming section under the following conditions using reactive resistance heating as a heating means for vacuum evaporation on the plasma treated surface. Accordingly, a 12 nm thick aluminum oxide vapor-deposited film was formed on a PET film, a roll of the gas barrier vapor-deposited film was obtained, and various evaluations were performed.
(Plasma pretreatment conditions)
・Plasma intensity: 200W・sec/m2
・Plasma forming gas ratio: oxygen/argon = 2/1
・Voltage applied between pre-treatment drum and plasma supply nozzle: 340V
・Pre-treatment section pressure: 3.8 Pa

(Aluminum oxide film forming conditions)
・Pressure: 8.1×10 ^-2 Pa
・Transportation speed: 400m/min
・Oxygen gas supply amount: 8000sccm

<Preparation of barrier coating agent for barrier coating layer>
A mixture of 307 g of water, 147 g of isopropyl alcohol, and 7.3 g of 0.5N hydrochloric acid was added to a solution adjusted to pH 2.2, and 175 g of tetraethoxysilane was added as a metal alkoxide, and 3-glycidoxypropyltrimethoxysilane was added as a silane coupling agent. Solution A was prepared by mixing 8.7 g while cooling to 10°C.
A solution B was prepared by mixing 14.7 g of polyvinyl alcohol with a polymerization degree of 2400 with a saponification value of 99% or higher, 324 g of water, and 17 g of isopropyl alcohol as a water-soluble polymer.
A solution obtained by mixing liquid A and liquid B at a weight ratio of 6.5:3.5 was used as a barrier coat composition.
The barrier coating composition prepared above was coated on the aluminum oxide vapor-deposited film of the above PET film by a spin coating method.
Thereafter, heat treatment was performed in an oven at 180° C. for 60 seconds to form a barrier coating layer with a thickness of about 400 nm on the aluminum oxide vapor deposited film, thereby obtaining a barrier film.

[Example 2]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the plasma intensity in the pretreatment was 100 W·sec/m ² .

[Example 3]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the base material was a plant-derived polyester resin and the plasma intensity of the pretreatment was 150 W·sec/m ² .
[Example 4]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the base material was polybutylene terephthalate (PBT), the plasma intensity of the pretreatment was 150 W·sec/m ² , and the vapor-deposited film thickness was 10 nm.

[Example 5]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the thickness of the vapor-deposited film was 14 nm.

[Example 6]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the thickness of the vapor-deposited film was 10 nm.

[Example 7]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the thickness of the vapor-deposited film was 14 nm.

[Example 8]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the base material was a plant-derived polyester resin, the pretreatment plasma intensity was 150 W·sec/m ² , and the vapor-deposited film thickness was 10 nm.

[Example 9]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the base material was a plant-derived polyester resin, the pretreatment plasma intensity was 150 W·sec/m ² , and the vapor-deposited film thickness was 14 nm.

[Example 10]
In Example 1, no pretreatment was performed.

[Comparative example 1]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the gas ratio O ₂ /Ar in Example 1 was changed to 4/1.

[Comparative example 2]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the pressure in Example 1 was changed to 50 Pa.

[Reference example 1]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that the plasma intensity in Example 1 was changed to 1200 W·sec/m ² .

<Evaluation method>
(Metamorphism rate of transition region)
In the present invention, the transformation rate of the transition region of the deposited film is determined by time-of-flight secondary ion mass spectroscopy while repeatedly soft etching the surface of the barrier coating layer of the gas barrier deposited film at a constant rate with a Cs (cesium) ion gun. By measuring ions derived from the barrier coating layer, ions derived from the aluminum oxide deposited film, and ions derived from the plastic base material using a TOF-SIMS method, the graphical analysis diagram shown in FIG. 4 is obtained.
Here, the unit (intensity) on the vertical axis of the graph is the measured ion intensity, and the unit (cycle) on the horizontal axis is the number of times of etching.
The time-of-flight secondary ion mass spectrometer used in the TOF-SIMS mentioned above is manufactured by ION TOF and TOF. Measurements were performed using SIMS5 under the following measurement conditions.
(TOF-SIMS measurement conditions)
・Primary ion type: Bi3++ (0.2pA, 100μs), measurement area: 150 x 150μm2
・Et gun type: Cs (1keV, 60nA), Et area: 600 x 600μm2, Et rate: 3sec/Cycle
In addition, in order to measure ions derived from aluminum oxide, which is the measurement target, an ion gun usually needs to separate ions derived from other components from among multiple ions derived from aluminum oxide, and In the present invention, Cs ions were selected because it is necessary to select a material having high strength, and in particular, for the purpose of obtaining a depth distribution that can be approximated to the concentration distribution of elemental bonded Al ₂ O ₄ H.

Using Cs, perform etching from the outermost surface of the barrier coating layer, and analyze the elemental bonds at the interface between the barrier coating layer, the aluminum oxide vapor deposited film, and the film base material such as polyester film, and the element bonds in the vapor deposited film. Graph 1 of the measured elements and elemental bonds was obtained. In the graph, first, the position where the strength of SiO2 (mass number 59.96), which is a constituent element of the barrier coating layer, is half of that of the barrier coating layer is defined as the interface between the barrier coating layer and the aluminum oxide vapor deposited film, and then , oxidize the half of the layer of C6 (mass number 72.00), which is the constituent material of the plastic base material, as the interface between the film base material and the aluminum oxide vapor deposited film, from the first interface to the second interface. It was made into an aluminum vapor-deposited film.
Next, the peak in the graph representing the measured elemental bond Al ₂ O ₄ H (mass number 118.93) is determined, and the transition region from the peak to the interface can be determined.
However, when the barrier coating layer is composed of a material having the same mass number as Al ₂ O ₄ H (mass number 118.93), it is necessary to separate the waveform of 118.93.
In this case, at the interface between the barrier coating layer and the aluminum oxide layer, reactant AlSiO ₄ and hydroxide Al ₂ O ₄ H are generated at the interface between the barrier coating layer and the aluminum oxide layer. Separate ₂ O ₄ H. This can be handled appropriately depending on the material of the barrier coating layer.

An example of the waveform separation method is shown below.
A profile with a mass number of 118.93 obtained by TOF-SIMS is subjected to nonlinear curve fitting using a Gaussian function, and overlapping peaks are separated using a least squares method Levenberg Marquardt algorithm.
By performing the above operations, the metamorphosis rate of the transition region of the aluminum oxide vapor deposited film was determined as (transition region thickness from the peak of Al ₂ O ₄ H to the interface/aluminum oxide vapor deposition film thickness)×100 (%).

(Oxygen permeability)
Barrier film/adhesive/nylon film 15μm/adhesive prepared for measurement using an oxygen permeability measuring device (manufactured by Modern Control (MOCON) [model name: OX-TRAN 2/21]) /CPP70μm packaging material, set the above test sample so that the oxygen supply side is the base material layer surface of the barrier film, and measured in accordance with JIS K7126 B method under measurement conditions of 23 ° C. and 90% RH atmosphere. did.
As a measurement sample,
1) Composite laminated film before retort processing 2) High retort processing conditions: 135°C, 40 minutes processed packaging material on one side of the bag of packaging material 3) Semi-retort processing conditions: 121°C, 40 minutes A packaging material with one side of the bag was used, which was made into a bag after the treatment.

(water vapor permeability)
Using a water vapor permeability measuring device (a measuring device manufactured by MOCON [Model name: PERMATRAN 3/33]), measure the above test sample so that the sensor side is the base material layer surface of the barrier film. The measurement was carried out in accordance with JIS K7126 B method under the measurement conditions of 40° C. and 100% RH atmosphere.
As a measurement sample,
1) Packaging material before retort processing 2) High retort processing conditions: 135°C, 40 minutes processing of packaging material on one side of the bag 3) Semi-retort processing conditions: 121°C, 40 minutes The packaging material used was one side of the bag, which had been made into a treated bag.

(Normal peel strength after retort treatment)
A two-component curable polyurethane adhesive was applied to the barrier coating layer side of the barrier film and dried, and a 70-μm thick unstretched polypropylene film was coated with a two-component polyurethane adhesive and stretched to a 15-μm thickness. A packaging material was produced by dry laminating the nylon film and the bonded film.
100 mL of water was poured into a four-sided pouch made into a B5 size using the above packaging material, and a hydrothermal retort treatment (high retort treatment) was performed at 135° C. for 40 minutes.
After the retort treatment, samples were prepared by cutting the four-sided pouch into strips with a width of 15 mm from which water was removed.
This sample was tested for peeling between the base material layer of the barrier film and the aluminum oxide vapor deposited film using a tensile testing machine (manufactured by Orientech Co., Ltd. [Model name: Tensilon universal material testing machine]) in accordance with JIS K6854-2. The strength was measured.
In addition, regarding Example 4, a hydrothermal retort treatment (semi-retort treatment) was performed at 121° C. for 40 minutes.
As shown in FIG. 7, the measurement first consists of a base material layer (PET film or PBT film) 52, an inorganic oxide vapor deposited layer (aluminum oxide vapor deposited film) 53, a barrier coat layer 54, and an intermediate layer (stretched nylon film). A rectangular test piece 60 was prepared in which the heat seal layer (unstretched polypropylene film) 55 and the heat seal layer (unstretched polypropylene film) 56 (hereinafter also referred to as the inorganic oxide vapor deposited layer 53 side) were separated by 15 mm in the long side direction. Thereafter, as shown in FIG. 8, the parts of the base layer 52 and the inorganic oxide vapor deposited layer 53 that had already been peeled off were gripped with grips 61 and 62 of the measuring instrument, respectively.
Further, the grips 61 and 62 are moved in opposite directions (180° peeling: T-shaped Peeling method), the sample was pulled at a speed of 50 mm/min, and the average value of the tensile stress in the stable region (see FIG. 9) was measured. The distance S between the grips 61 and 62 at the time of starting the pulling was 30 mm, and the distance S between the grips 61 and 62 at the time of ending the pulling was 60 mm. FIG. 9 is a diagram showing changes in tensile stress with respect to the distance S between the grips 61 and 62.
As shown in FIG. 9, the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than the first region. The average value of the tensile stress in the stable region was measured, and the value was taken as the peel strength between the base material layer of the barrier film and the aluminum oxide vapor deposited film.

(Water peel strength after retort treatment)
The wet peel strength was measured by the same method as the normal peel strength, except for the points described below.
In measuring the water peel strength, the base material layer and the inorganic oxide vapor deposited layer (aluminum oxide vapor deposited film) side of the test piece were peeled off by 15 mm, and then the adhesive interface between the base material layer and the aluminum oxide vapor deposited film side was peeled off. The peel strength was measured.
In addition, when measuring the peel strength with water, when measuring the peel strength, the part where the base material layer and the aluminum oxide vapor deposited film side maintain bonding when viewed along the longitudinal direction of the test piece. The measurement was performed while water was dropped with a dropper at the boundary between the base material layer and the part where the aluminum oxide vapor-deposited film side was peeled off.

(Color)
L*a*b* table of one sample for measurement (base material layer/aluminum oxide vapor deposited film/barrier coat layer) using a spectrophotometer (manufactured by Konica Minolta Co., Ltd. [model name: CM-700d)] The L* value, a* value, and b* value in the color system were measured.

<Evaluation results>
The measurement results for each example are shown in Table 3, and while the examples of the present application maintain sufficient gas barrier properties and peel strength even after high-retort treatment, those of the comparative examples maintain sufficient gas barrier properties and peel strength. In this case, plasma discharge was not stable and oxygen plasma pretreatment could not be performed.

<<Experiment 3>>
[Example 1]
<Formation of aluminum oxide vapor deposited film>
First, a roll of petroleum-derived polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 12 μm as a plastic base material was prepared.
Next, on the side of the PET film on which the vapor deposition film is to be provided, a continuous vapor deposition film forming apparatus in which a pretreatment section in which an oxygen plasma pretreatment device is arranged and a film formation section are separated is used. Plasma is introduced from a plasma supply nozzle, subjected to oxygen plasma pretreatment at a conveyance speed of 400 m/min, and then continuously conveyed to the oxygen plasma treatment surface in the film forming section under the following conditions. A 12 nm thick aluminum oxide vapor deposited film was formed on the PET film using a resistance heating method.

(Oxygen plasma pretreatment conditions)
・Plasma intensity: 150W・sec/m ²
・Plasma forming gas ratio: oxygen/argon = 2/1
・Voltage applied between pretreatment drum and plasma supply nozzle: 340V
・Pre-treatment section pressure: 3.8 Pa

(Aluminum oxide film forming conditions)
・Pressure: 8.1×10-2Pa
・Transportation speed: 400m/min
・Oxygen gas supply amount: 8000sccm

<Formation of barrier coating layer>
A mixture of 307 g of water, 147 g of isopropyl alcohol, and 7.3 g of 0.5N hydrochloric acid was added to a solution adjusted to pH 2.2, and 175 g of tetraethoxysilane was added as a metal alkoxide, and 3-glycidoxypropyltrimethoxysilane was added as a silane coupling agent. Solution A was prepared by mixing 8.7 g while cooling to 10°C.
A solution B was prepared by mixing 14.7 g of polyvinyl alcohol with a polymerization degree of 2400 with a saponification value of 99% or higher, 324 g of water, and 17 g of isopropyl alcohol as a water-soluble polymer.
A solution obtained by mixing liquid A and liquid B at a weight ratio of 6.5:3.5 was used as a barrier coat composition.
The barrier coating composition prepared above was coated on the aluminum oxide vapor-deposited film of the above PET film by a spin coating method.
Thereafter, heat treatment was performed in an oven at 180° C. for 60 seconds to form a barrier coating layer with a thickness of about 400 nm on the aluminum oxide vapor deposited film, thereby obtaining a barrier film.

[Example 2]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the oxygen gas supply amount was changed to 10,000 sccm.

[Example 3]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the plasma pretreatment conditions were not performed.

[Example 4]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1, except that a biomass-derived PET film with a thickness of 12 μm was used as the plastic base material and the plasma pretreatment conditions were changed to 250 W·sec/m 2 .

[Comparative example 1]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the ratio of oxygen gas/Ar gas was changed to 5/1.

[Reference example 1]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the oxygen plasma pretreatment conditions were changed to 1000 W·sec/m 2 .

[Reference example 2]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the oxygen gas supply amount was changed to 20,000 sccm.

[Reference example 3]
A gas barrier vapor-deposited film was obtained in the same manner as in Example 1 except that the oxygen gas supply amount was changed to 6000 sccm.

The measurement results are shown in Table 5. As shown in each example, the gas barrier vapor-deposited film of the present invention exhibited good oxygen permeability and water vapor permeability, as well as good water peel strength and printability.
In the comparative example, plasma discharge was not stable and oxygen plasma pretreatment was not possible.

(Measurement method of evaluation items)
Gas-barrier vapor-deposited films produced under the conditions shown in the above Examples or Comparative Examples were used as samples for measurement, and oxygen permeability, water vapor permeability, water peel strength, printability, etc. were measured.

(Oxygen permeability)
Using an oxygen permeability measuring device (OX-TRAN2/21, manufactured by MOCON), set the barrier resin film with a barrier coating layer so that the resin base side is on the oxygen supply side, and measure according to JIS K 7126 B method. Accordingly, the oxygen permeability was measured at 23° C. and in a 90% RH atmosphere.

(water vapor permeability)
Using a water vapor permeability measuring device (manufactured by MOCON, PERMATRAN 3/33), set the barrier resin film with a barrier coating layer so that the resin base layer side faces the sensor side, and measure according to JIS K 7126 B method. The water vapor permeability was measured at 40° C. in a 100% RH atmosphere.

(Total light transmittance)
Using an optical measurement device (manufactured by Suga Test Instruments Co., Ltd. [model name: haze meter)], set the barrier resin film with a barrier coating layer so that the base film side faces the light source side, and measure according to JIS K7136. did.
(Haze)
Using an optical measurement device (manufactured by Suga Test Instruments Co., Ltd. [model name: haze meter)], set the barrier resin film with a barrier coating layer so that the base film side faces the light source side, and measure according to JIS K7136. did.

(Water peel strength)
A two-component curable polyurethane adhesive was applied to the barrier coating layer side of the barrier film and dried, and a 70-μm thick unstretched polypropylene film was coated with a two-component polyurethane adhesive and stretched to a 15-μm thickness. A packaging material was produced by dry laminating the nylon film and the bonded film.
As shown in FIG. 7, the measurement first consists of a base material layer (PET film or PBT film) 52, an inorganic oxide vapor deposited layer (aluminum oxide vapor deposited film) 53, a barrier coat layer 54, and an intermediate layer (stretched nylon film). A rectangular test piece 60 was prepared in which the heat seal layer (unstretched polypropylene film) 55 and the heat seal layer (unstretched polypropylene film) 56 (hereinafter also referred to as the inorganic oxide vapor deposited layer 53 side) were separated by 15 mm in the long side direction.
Next, when looking along the longitudinal direction of the test piece, the part where the base material layer and the aluminum oxide vapor-deposited film side maintain bonding, and the part where the base material layer and the aluminum oxide vapor-deposited film side are peeled off. I used a dropper to drop water on the boundary between the two parts.
Thereafter, as shown in FIG. 8, the parts of the base layer 52 and the inorganic oxide vapor deposited layer 53 that had already been peeled off were gripped with grips 61 and 62 of the measuring instrument, respectively.
Further, the grips 61 and 62 are moved in opposite directions (180° peeling: T-shaped Peeling method), the sample was pulled at a speed of 50 mm/min, and the average value of the tensile stress in the stable region (see FIG. 9) was measured. The distance S between the grips 61 and 62 at the time of starting the pulling was 30 mm, and the distance S between the grips 61 and 62 at the time of ending the pulling was 60 mm.
FIG. 9 is a diagram showing changes in tensile stress with respect to the distance S between the grips 61 and 62. As shown in FIG. 9, the change in tensile stress with respect to the interval S passes through the first region and enters the second region (stable region) where the rate of change is smaller than the first region. The average value of the tensile stress in the stable region was measured, and the value was taken as the peel strength between the base material layer of the barrier film and the aluminum oxide vapor deposited film.

1 Gas barrier vapor deposited film 2 Polyethylene terephthalate film 3 Inorganic oxide vapor deposited film layer 4 Barrier coating layer 5 Gas barrier laminate 6 Sealant layer S Plastic base material P Plasma 10 Roller type continuous vapor deposition film forming device 12 Vapor deposited film forming device , reduced pressure chamber 12A, deposition target substrate transfer chamber 12B, plasma pretreatment chamber 12C, vapor deposition film formation chamber 14 a to d, guide roll 15, take-up roller 18, source gas volatilization supply device 20, pretreatment roller 21, magnet 22, plasma supply nozzle 23, film formation Roller 24 Vapor deposited film forming means 31 Power supply wiring 32 Power supply 35a to 35c Partition wall 52 Base layer 53 Inorganic oxide vapor deposition layer 54 Barrier coat layer 55 Intermediate layer 56 Heat seal layer 60 Test pieces 61, 62 Grip

Claims (27)

A gas barrier vapor-deposited film comprising a base layer made of a resin film, an inorganic oxide vapor-deposited film layer, and a barrier coating layer,
The inorganic oxide vapor deposited film layer contains aluminum oxide as a main component and is laminated adjacent to the base material layer,
The barrier coating layer is laminated adjacently on the surface of the inorganic oxide vapor-deposited film layer opposite to the base layer, and is made of a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin. was formed,
The moisture content of the laminated portion consisting only of the base layer, the inorganic oxide vapor-deposited film layer, and the barrier coating layer is 0.33% by mass or more and 0.45% by mass or less,
Gas barrier vapor deposited film. A transition region is formed in the inorganic oxide vapor-deposited film layer, which defines the adhesion strength between the surface of the base layer and the inorganic oxide vapor-deposited film layer,
The transition region contains elemental bonds Al ₂ O ₄ H that are metamorphosed into aluminum hydroxide, detected by etching using time-of-flight secondary ion mass spectrometry (TOF-SIMS),
The modified inorganic oxide vapor deposited film layer defined by etching the barrier coating layer and the inorganic oxide vapor deposited film layer using TOF-SIMS. The metamorphism rate of the transition region defined by the ratio of the transition region is 5% or more and 60% or less,
The gas barrier vapor-deposited film according to claim 1. In the inorganic oxide vapor-deposited film layer, elemental bonding structures represented by Al ₃ are distributed,
The intensity ratio Al ₃ /Al of the maximum Al ₃ concentration element bonding structure portion in the inorganic oxide vapor deposited film layer when the gas barrier vapor deposited film is analyzed by time-of-flight secondary ion mass spectrometry (TOF-SIMS) The gas barrier vapor-deposited film according to claim 1 or 2, wherein ₂ O ₃ ×100 is 1 or more and 20 or less. The maximum Al ₃ concentration elemental bonding structure portion is 4% or more and 45% or less of the film thickness of the inorganic oxide vapor-deposited film layer from the surface opposite to the resin base material of the inorganic oxide vapor-deposited film layer. The gas barrier vapor-deposited film according to claim 3, which is present at a depth position. The gas barrier vapor-deposited film according to any one of claims 1 to 4, wherein the surface of the base layer is an oxygen plasma-treated surface. The gas barrier vapor-deposited film according to claim 5, wherein the inorganic oxide vapor-deposited film layer is laminated in-line on the oxygen plasma-treated surface. A mass ratio of hydroxyl group-containing water-soluble resin/metal alkoxide in the resin composition is 5/95 or more and 20/80 or less,
The gas barrier vapor-deposited film according to any one of claims 1 to 6. The gas barrier vapor-deposited film according to claim 1, wherein the barrier coating layer has a thickness of 150 nm or more and 800 nm or less. The gas barrier according to any one of claims 1 to 8, wherein the base material layer is a polyethylene terephthalate film produced by performing a polyethylene terephthalate synthesis step and a film forming step in-line. vapor-deposited film. The gas barrier vapor-deposited film according to any one of claims 1 to 8, wherein the base layer is a polyethylene terephthalate film. The gas barrier vapor-deposited film according to any one of claims 1 to 8, wherein the base layer comprises a recycled polyethylene terephthalate film. The gas barrier vapor-deposited film according to any one of claims 1 to 8, wherein the base layer is a polybutylene terephthalate film. The gas barrier vapor-deposited film according to any one of claims 1 to 8, wherein the base material layer is a biomass-derived polyester film. The gas barrier vapor-deposited film according to claim 1, wherein the base layer is a high stiffness PET film. Any one of claims 1 to 14, wherein the barrier coating layer is formed from a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin having a degree of saponification of 90% or more and 100% or less. Gas barrier vapor-deposited film according to item 1. A gas barrier laminate comprising the gas barrier vapor-deposited film according to any one of claims 1 to 15 and a sealant layer. A gas barrier packaging material produced from the gas barrier laminate according to claim 16. A gas barrier packaging body made from the gas barrier packaging material according to claim 17. The gas barrier packaging body according to claim 18, which is used for retort sterilization packaging. A manufacturing method for manufacturing a gas barrier vapor-deposited film, comprising:
An inorganic oxide vapor-deposited film layer containing aluminum oxide as a main component is laminated on the surface of a base material layer made of a resin film by physical vapor deposition,
Next, a resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin is applied adjacent to the inorganic oxide vapor-deposited film layer and dried to form a barrier coating layer,
Producing the gas barrier vapor-deposited film, in which the moisture content of the laminated portion consisting only of the base layer, the inorganic oxide vapor-deposited film layer , and the barrier coating layer is 0.33% by mass or more and 0.45% by mass or less. characterized by
A method for producing a gas barrier vapor-deposited film. 21. The method for producing a gas barrier vapor-deposited film according to claim 20, wherein the base layer has a moisture content of 0.22% by mass or more and 0.33% by mass or less. A method for producing a gas barrier laminate, comprising laminating a sealant layer on the surface of the gas barrier vapor-deposited film according to any one of claims 1 to 15 by a dry lamination method or an extrusion lamination method. A method for quality control of a gas barrier vapor deposited film in a method for producing a gas barrier vapor deposited film, the method comprising:
A resin composition containing a base material layer made of a resin film, an inorganic oxide vapor-deposited film layer, a metal alkoxide, and a water-soluble resin containing a hydroxyl group is applied, and the moisture content of the laminated part made only of the dried barrier coating layer is measured. When the water content is less than 0.33% by mass or greater than 0.45% by mass, at least one or more selected from the group consisting of heat treatment, humidification treatment, and constant temperature treatment at room temperature is applied. A quality control method for a gas barrier vapor-deposited film, the method comprising controlling the moisture content to 0.33% by mass or more and 0.45% by mass or less by performing a treatment. 24. The quality control method for a gas barrier vapor-deposited film according to claim 23, wherein the heat treatment is performed in an environment of 30°C or higher and 120°C or lower. 25. The quality control method for a gas barrier deposited film according to claim 23 or 24, wherein the humidification treatment is performed in an environment with a relative humidity of 30% RH or more and 100% RH or less. The method for quality control of a gas barrier vapor-deposited film according to any one of claims 23 to 25, characterized in that the constant temperature treatment at room temperature is performed in an environment of 5° C. or higher and lower than 30° C. A method for quality control of a gas barrier laminate in a method for producing a gas barrier laminate, comprising:
The method is characterized in that the quality control of the gas barrier vapor deposited film is carried out by the quality control method of the gas barrier vapor deposited film according to any one of claims 23 to 26.
Quality control method for gas barrier laminates.

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