JP2020070429A - Oxygen plasma treated resin film, gas barrier vapor deposition film and gas barrier laminate using the gas barrier vapor deposition film, gas barrier packaging material, gas barrier package, gas barrier packaging bag and manufacturing method of these - Google Patents

Abstract

To provide an oxygen plasma treated resin film capable of having an inorganic vapor deposition layer with excellent waterproof adhesion against a resin film as well as excellent in gas barrier properties, a gas barrier vapor deposition film produced by laminating an inorganic vapor deposition layer onto the oxygen plasma treated resin film, a laminate using the gas barrier vapor deposition film, a packaging material, a package and a manufacturing method of these.SOLUTION: An oxygen plasma treated resin film has an oxygen plasma treated surface for forming an inorganic vapor deposition layer, on one side thereof. In the oxygen plasma treated resin film, the oxygen plasma treated surface is a surface formed by: making a resin film continuously pass through a space in which plasma electrodes and a magnet are facing with each other in a substantially constant distance under atmospheric pressure of 1-9 Pa, and oxygen plasma is held by the magnet in a substantially homogeneous density; and substantially vertically colliding the oxygen plasma on one side of the resin film by bias voltage between the plasma electrodes.SELECTED DRAWING: Figure 1

Description

  INDUSTRIAL APPLICABILITY The present invention is suitable for use as a packaging material for foods, pharmaceuticals, etc., or as a sealing material for industrial materials such as displays, an oxygen plasma-treated resin film, which has excellent barrier properties against oxygen and water vapor, and a plastic substrate and aluminum oxide. The present invention relates to a gas-barrier vapor-deposited film having improved water-proof adhesion performance with a vapor-deposited film, a gas-barrier laminate, a gas-barrier packaging material, a gas-barrier packaging bag, and a method for producing them.

  In the field of packaging materials for foods, pharmaceuticals, etc., and encapsulating materials for industrial materials such as displays, in order to prevent alteration of the contents and maintain the functions and properties, it is not affected by temperature, humidity, etc. A gas barrier film capable of stably exhibiting a high gas barrier property is demanded, and a gas barrier vapor deposition film in which a gas barrier layer composed of a thin film of a vapor deposition film of silicon oxide, aluminum oxide, etc. and a gas barrier coating film layer are also developed has been developed. ing.

  However, the resin base material of a laminated film having a vapor-deposited film which is easily affected by temperature, humidity, etc. is likely to undergo dimensional change, and therefore, it is possible to cope with expansion and contraction due to dimensional change of the resin base material. However, it is difficult to follow a vapor deposition film such as a vapor deposition film of silicon oxide or a vapor deposition film of aluminum oxide provided thereon.

Therefore, in an environment in which water is present between the resin substrate and the vapor-deposited film such as the silicon oxide vapor-deposited film or the aluminum oxide vapor-deposited film, delamination often occurs, and further cracks, pinholes, etc. Occur.
As a result, there is a problem that the original gas barrier performance is significantly damaged and it is extremely difficult to maintain the gas barrier performance.

  In the case of forming a vapor deposition film of an inorganic oxide such as aluminum oxide on a resin substrate by the method using the above vapor deposition film, in order to obtain high water resistance adhesion between the resin substrate and the vapor deposition film formed. Although a gas barrier film having a structure in which an undercoat layer is provided as an adhesive layer on the surface of a resin film is implemented, the cost is increased because the number of steps is increased as a manufacturing method. (Patent Document 1)

  Therefore, there is a technique for improving the water-resistant adhesion by pretreating the surface of the resin base material using a reactive ion etching (RIE) method in which an electrode for generating plasma is on the resin base material side to generate plasma. It is implemented (Patent Document 2).

The plasma RIE method simultaneously obtains two effects, that is, a chemical effect such as having a functional group on the surface of the base material and a physical effect of ion-etching the surface to remove impurities and smooth the surface. It exhibits water-resistant adhesion.
However, in the RIE method, since a functional group is provided on the resin substrate, the water resistance that causes hydrolysis at the interface is still insufficient. Further, in order to obtain sufficient water resistant adhesion by the RIE method, an Ed value (= plasma density × processing time) of a certain value or more is required.

In order to obtain an Ed value above a certain value by the same method, a method of increasing the plasma density and a method of lengthening the processing time can be considered. However, in order to increase the plasma density, a high output power source is required, There is a problem that the resin base material is greatly damaged, and when the processing time is lengthened, a decrease in productivity becomes a problem (see Patent Documents 3 and 4).

  Therefore, it solves the problem in forming the vapor deposition film of the inorganic oxide on the surface of the resin substrate to be transported as described above, and the water-resistant adhesion between the resin substrate and the vapor deposition film is good, and the gas barrier property is excellent. Laminated films are desired.

JP, 2000-43182, A JP, 2005-335109, A Japanese Patent No. 4461737 Japanese Patent No. 4135496

  The present invention has been made in view of the above problems and findings, and its purpose is to have an inorganic vapor deposition layer having good water-resistant adhesion with a resin film and excellent gas barrier properties. Oxygen plasma treated resin film, and a gas barrier vapor deposition film produced by laminating an inorganic vapor deposition layer on the oxygen plasma treated resin film, and further a laminate, a packaging material, a package using the gas barrier vapor deposition film, and Is to provide a method for manufacturing them.

As a result of earnestly studying to achieve the above problems,
It has been found that an oxygen plasma-treated resin film having a specific oxygen plasma-treated surface for forming an inorganic vapor-deposited layer on one side solves the above problems.

That is, the present invention is characterized by the following points.
1. An oxygen plasma treatment resin film having an oxygen plasma treatment surface on one side for forming an inorganic vapor deposition layer,
The oxygen plasma-treated surface has a resin film continuously in a space where the plasma electrode and the magnet face each other at a substantially constant distance under an atmospheric pressure of 1 to 9 Pa, and the oxygen plasma is held by the magnet at a substantially uniform density. An oxygen plasma-treated resin film, which is a surface formed by causing the oxygen plasma to collide with one surface of the resin film substantially perpendicularly by a bias voltage between the plasma electrodes.
2. The plasma forming gas for forming the oxygen plasma is a mixed gas containing oxygen and argon in a volume ratio of oxygen / argon of not less than 1/1 and not more than 3/1. The oxygen plasma-treated resin film as described in 1 above.
3. 3. The oxygen plasma treated resin film as described in 1 or 2 above, wherein the resin film is a polyethylene terephthalate film.
4. 3. The oxygen plasma-treated resin film as described in 1 or 2 above, wherein the resin film is a biomass-derived polyester film.
5. 3. The oxygen plasma treated resin film as described in 1 or 2 above, wherein the resin film is a recycled polyethylene terephthalate film.
6. The oxygen plasma treated resin film according to any one of 1 to 5 above, wherein an inorganic vapor deposition layer is laminated adjacent to the oxygen plasma treated surface, and an interface between the inorganic vapor deposition layer and the oxygen plasma treated surface. The vapor-deposited film having gas barrier properties, which has an adhesive strength of 1.5 N / 15 mm or more and 4 N / 15 mm or less when immersed in water, as measured by the 180-degree peeling method.
7. 7. The gas barrier vapor deposition film as described in 6 above, wherein the formation of the oxygen plasma treated surface and the formation of the inorganic vapor deposition layer are continuously performed in-line.
8. 8. The gas barrier vapor deposition film as described in 6 or 7 above, wherein the inorganic vapor deposition layer is an aluminum oxide vapor deposition layer.
9. The gas barrier property according to the above 8, wherein the vapor deposition layer of aluminum oxide has a molar ratio of oxygen atoms / aluminum atoms of 1.2 or more and 5 or less as determined by X-ray photoelectron spectroscopy (XPS). Evaporated film.
10. A gas barrier vapor deposition film comprising an inorganic vapor deposition layer and an organic protective layer adjacently laminated on the inorganic vapor deposition layer, wherein the organic protective layer comprises a gas barrier coating layer and / or a primer layer. The gas barrier vapor deposition film according to any one of 1 to 9.
11. 11. The gas barrier property according to the above 10, wherein the gas barrier coating layer is formed by applying a gas barrier resin composition containing at least a metal alkoxide and a hydroxyl group-containing water-soluble resin. Evaporated film.
12. The surface of the gas barrier coating layer is characterized in that the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) is 1.20 or more and 1.60 or less. The vapor-deposited gas barrier film as described in 11 above.
13. The above-mentioned 10 or 10, wherein the primer layer is formed by applying a primer liquid containing at least one kind or two or more kinds selected from the group consisting of polyester, polyurethane and polyester urethane. 11. A gas barrier vapor-deposited film according to item 11.
14. 14. The gas barrier vapor deposition film as described in 13 above, wherein the primer liquid further contains inorganic fine particles and / or a metal alkoxide.
15. 15. The gas barrier vapor deposition film as described in 11 or 14, wherein the metal alkoxide is a tetrafunctional silicon compound.
16. A gas barrier laminate having a layer comprising the gas barrier vapor deposition film according to any one of 6 to 15 and a sealant layer.
17. The gas barrier laminate according to 16 above, which has an oxygen permeability of 0.80 cc / m ² · atm · day or less after a bending test according to ASTM F392 under the following test conditions.
<Test conditions>
Stroke: 80mm
Bending operation: 400 ° / 80mm
Bending speed: 40 cpm
Number of bends: 10 times 18. A gas barrier packaging material produced from the gas barrier laminate according to the above 16.
19. A gas barrier packaging body, which is produced from the gas barrier packaging material described in 18 above.
20. A gas-barrier packaging bag for wettable contents, characterized by being made from the gas-barrier packaging material according to the above 18.
21. An oxygen plasma treatment surface for forming an inorganic vapor deposition layer, a method for producing an oxygen plasma treatment resin film having one surface,
Under an atmospheric pressure of 1 to 9 Pa, the plasma electrode and the magnet are opposed to each other at a substantially constant distance, and the resin film is continuously passed through a space where the oxygen plasma is held by the magnet at a substantially uniform density.
A method for producing an oxygen plasma-treated resin film, characterized in that the oxygen plasma-treated surface is formed on one surface of the resin film by causing the oxygen plasma to impinge substantially vertically by a bias voltage between plasma electrodes.
22. The plasma forming gas for forming the oxygen plasma is a mixed gas containing oxygen and argon in a volume ratio of oxygen / argon of not less than 1/1 and not more than 3/1. 21. The method for producing an oxygen plasma-treated resin film as described in 21 above.
23. 23. The method for producing an oxygen plasma-treated resin film as described in 21 or 22 above, wherein the resin film is a polyethylene terephthalate film.
24. 23. The method for producing an oxygen plasma-treated resin film as described in 21 or 22 above, wherein the resin film is a biomass-derived polyester film.
25. 23. The method for producing an oxygen plasma-treated resin film as described in 21 or 22 above, wherein the resin film is a recycled polyethylene terephthalate film.
26. A gas barrier in which an inorganic vapor-deposition layer is adjacently laminated on the oxygen plasma-treated surface of the oxygen plasma-treated resin film produced by the method for producing an oxygen plasma-treated resin film according to any one of 21 to 25 above. A method for producing a vapor-deposited film,
The adhesive strength of the interface between the inorganic vapor-deposited layer and the oxygen plasma treated surface when immersed in water, measured by a 180 degree peeling method, is 1.5 N / 15 mm or more and 4 N / 15 mm or less, Gas barrier vapor deposition film manufacturing method.
27. 27. The method for producing a gas barrier vapor deposition film as described in 26 above, wherein the formation of the oxygen plasma treated surface and the formation of the inorganic vapor deposition layer are continuously performed in-line.
28. 28. The method for producing a gas barrier vapor deposition film as described in 26 or 27 above, wherein the inorganic vapor deposition layer is an aluminum oxide vapor deposition layer.
29. 29. The gas barrier property according to 28 above, wherein the vapor deposition layer of aluminum oxide has a molar ratio of oxygen atoms / aluminum atoms of 1.2 or more and 5 or less as determined by X-ray photoelectron spectroscopy (XPS). Manufacturing method of vapor-deposited film.
30. A method for producing a vapor barrier vapor deposition film, further comprising an organic protective layer adjacently laminated on the inorganic vapor deposition layer,
30. The method for producing a gas barrier vapor deposition film as described in any one of 26 to 29 above, wherein the organic protective layer comprises a gas barrier coating layer and / or a primer layer. 31. 31. Production of a gas barrier vapor deposition film as described in 30 above, wherein the gas barrier coating layer is formed by applying a gas barrier resin composition containing at least a metal alkoxide and a hydroxyl group-containing water-soluble resin. Method.
31. 30. The above-mentioned 30 or 31, wherein the primer layer is formed by applying a primer liquid containing at least one kind or two kinds or more selected from the group consisting of polyester, polyurethane and polyester urethane. , A method for producing a vapor-deposited film having gas barrier properties.
33. 33. The method for producing a gas barrier vapor deposition film as described in 32 above, wherein the primer liquid further contains inorganic fine particles and / or a metal alkoxide.
34. The said metal alkoxide is a silane coupling agent, The manufacturing method of the gas barrier vapor deposition film of any one of said 31-33 characterized by the above-mentioned.
35. 35. A method for producing a gas barrier laminate, comprising laminating a sealant layer on a layer formed of the gas barrier vapor deposition film produced by the method for producing a gas barrier vapor deposition film according to any one of 26 to 34 above. .
36. 36. A method for producing a gas barrier packaging material, which comprises producing a gas barrier packaging material from the gas barrier laminate produced by the method for producing a gas barrier laminate described in 35 above.
37. 37. A method for producing a gas barrier packaging, which comprises producing a gas barrier packaging from the gas barrier packaging produced by the method for producing a gas barrier packaging according to 36 above.
38. A gas barrier packaging material for wettable contents, characterized in that a gas barrier packaging material for wettable contents is produced from the gas barrier packaging material produced by the method for producing gas barrier packaging material according to the above 36. Body manufacturing method.

  The oxygen plasma-treated resin film of the present invention is excellent in water-resistant adhesion because it can improve the water-resistant adhesiveness between the resin film and the inorganic vapor-deposited layer when the inorganic plasma-deposited layer is laminated on the oxygen plasma-treated surface. It is possible to obtain a vapor-deposited film having a gas barrier property, and further, a laminate, a packaging material, a package and a packaging bag, each having a water-resistant adhesive property, using the vapor deposition film having a gas barrier property.

It is sectional drawing which shows an example of the gas barrier vapor deposition film of this invention. It is sectional drawing which shows an example of another aspect of the gas barrier vapor deposition film of this invention. It is sectional drawing which shows an example of the gas barrier laminated body of this invention. It is a top view which shows an example of the apparatus which forms the oxygen plasma process surface in this invention. It is a top view which shows an example of another aspect of the apparatus which forms the oxygen plasma process surface in this invention. It is a top view which shows an example of the apparatus which forms the inorganic vapor deposition layer in this invention.

Hereinafter, a barrier film having improved water-resistant adhesion according to an embodiment of the present invention will be described in detail with reference to the drawings. It should be noted that this embodiment is merely an example and does not limit the present invention.
Hereinafter, the present invention will be described with reference to the drawings. However, the present invention is not limited to these concretely exemplified forms and various concretely described structures.
In each drawing, the size and ratio of members may be changed or exaggerated for easy understanding. In addition, for the sake of easy viewing, a part unnecessary for explanation or a repeated code may be omitted.

<Oxygen plasma treated resin film>
The oxygen plasma treated resin film of the present invention is a resin film having an oxygen plasma treated surface formed by a specific oxygen plasma treatment on one surface.
The oxygen plasma-treated surface is capable of exhibiting an excellent adhesive force with the inorganic vapor deposition layer even after water immersion.

  The oxygen plasma-treated resin film of the present invention may have a corona-treated surface and / or a primer layer on one side opposite to the oxygen plasma-treated surface. Thereby, when another layer is laminated on this surface, excellent adhesion can be obtained.

[Resin film]
The resin contained in the resin film is not particularly limited, and a known resin can be used to prepare a film or sheet.

  For example, polyester resins such as polyethylene terephthalate (hereinafter also referred to as PET), polybutylene terephthalate (hereinafter also referred to as PBT), polyethylene naphthalate (hereinafter also referred to as PEN), polyethylene furanoate; polyamide resin 6, polyamide resin 6, A polyamide resin such as polyamide resin 66, polyamide resin 610, polyamide resin 612, polyamide resin 11 or polyamide resin 12; or a film or sheet made of a polyolefin resin such as an α-olefin polymer such as polyethylene or polypropylene. You can

Among the above, a polyester resin is preferable, and among the polyester resins,
A polyethylene terephthalate resin is more preferable.
As the polyester-based resin, biomass-derived polyester-based resin or recycled polyester-based resin may be used, and particularly biomass-derived polyethylene terephthalate-based resin or recycled polyethylene terephthalate-based resin is preferably used.

  The thickness of the resin film is not particularly limited as long as it can withstand the oxygen plasma treatment and the lamination of the inorganic vapor deposition layer, and from the viewpoint of flexibility and shape retention, it is 5 μm or more and 400 μm or less. It is preferably 5 μm or more and 200 μm or less, more preferably 5 μm or more and 100 μm or less, particularly preferably 5 μm or more and 25 μm or less. When the thickness of the resin film is within the above range, the resin film is easy to bend and does not break during transportation, and it is easy to handle in an apparatus for elementary plasma treatment or lamination of inorganic vapor deposition layers.

The breaking strength of the resin film is preferably 5 kg / mm ² or more and 40 kg / mm ² or less in the MD direction, and 5 kg / mm ² or more and 35 kg / mm ² or less in the TD direction.
The breaking elongation of the resin film is preferably 50% or more and 350% or less in the MD direction, and 50% or more and 300% or less in the TD direction.

  The shrinkage rate of the resin film when left for 30 minutes in a temperature environment of 150 ° C. is preferably 0.1% or more and 5% or less.

  The resin film may contain various additives in the manufacturing process or after the manufacturing, as long as the characteristics are not impaired. As an additive, for example, a plasticizer, a UV stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a thread friction reducing agent, a release agent, an antioxidant, an ion. An exchange agent, a coloring pigment, etc. are mentioned. The content of the additive in the resin film is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 20% by mass or less.

The resin film can be formed by using the above resin and forming it into a film by, for example, a T-die method.
For example, after the resin is dried, the resin composition is melted by supplying it to a melt extruder heated to a temperature of Tm to Tm + 70 ° C., which is equal to or higher than the melting point temperature (Tm) of the resin to melt the resin composition. A film can be formed by extruding a sheet from a die and rapidly 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 or the like can be used according to the purpose.
The resin film thus obtained is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the resin film extruded on the cooling drum as described above is subsequently heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film.

This stretching is preferably performed by utilizing the peripheral speed difference between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C or higher and 100 ° C or lower. The longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, though it depends on the required characteristics of the film application. If the draw ratio is less than 2.5 times, the unevenness in the thickness of the resin film tends to be large, and it tends to be difficult to obtain a good film.
The longitudinally stretched resin film is successively subjected to the treatment steps of transverse stretching, heat setting and heat relaxation to obtain a biaxially stretched film. The transverse stretching is usually performed in 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, though it depends on the properties required for this application. If it is less than 2.5 times, it is difficult to obtain a good film because the thickness unevenness of the resin film becomes large, and if it exceeds 5.0 times, breakage easily occurs during film formation.

  After transverse stretching, heat setting treatment is subsequently carried out, but the preferable temperature range for heat setting is a glass transition temperature (Tg) of the resin + 70 ° C or higher and a melting point temperature (Tm) of -10 ° C or lower. The heat setting time is preferably 1 second or more and 60 seconds or less. Further, for applications requiring a low heat shrinkage, heat relaxation treatment may be carried out as necessary.

(Polyethylene terephthalate resin)
The polyethylene terephthalate-based resin is pure polyethylene terephthalate, or a resin containing polyethylene terephthalate as a main component, and may contain a resin other than polyethylene terephthalate, and may be a raw material of polyethylene terephthalate and a polyester raw material other than polyethylene terephthalate. It may contain a copolymer.

Examples of the dicarboxylic acid unit of the copolymer include terephthalic acid and, for example, isophthalic acid, and the derivatives thereof include lower alkyl esters of those dicarboxylic acids, specifically, methyl ester, ethyl ester and propyl. Examples thereof include esters and butyl esters.
Examples of the diol unit of the copolymer include ethylene glycol and 1,4-butanediol.

(Polybutylene terephthalate resin)
The polybutylene terephthalate resin is pure polybutylene terephthalate (PBT) or a resin containing PBT as a main component. The content of PBT is preferably 60% by mass or more, more preferably 70% by mass or more, more preferably 75% by mass or more, and particularly preferably 80% by mass or more. If it is less than 60% by mass, the mechanical properties as PBT tend to be insufficient.

  The PBT-based resin may include a polyester resin 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, naphthalenedicarboxylic acid, biphenyldicarboxylic 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 -Pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, polyethylene glycol, polytetramethylene glycol, polycarbonate diol and other diols Min can be mentioned copolymerized PBT resin.

Since PBT has a high heat distortion temperature, excellent mechanical strength and electrical characteristics, and good moldability, it can be used as a packaging bag for storing contents such as foods, so that it can be used for retort treatment. Can be suppressed and the strength thereof can be prevented from being lowered, and the packaging bag can be provided with puncture resistance as in the case of containing a nylon film. Furthermore, it has excellent impact strength, pinhole resistance, and drawability.
However, since PBT is easily hydrolyzed in a high temperature and high humidity environment, it tends to cause a reduction in adhesion strength and barrier properties after retort treatment, but it has a characteristic that it is less likely to absorb water than nylon.

Therefore, even when the layer containing PBT is disposed on the outer surface of the packaging material, it is possible to suppress a decrease in the laminating strength between the packaging materials of the packaging bag.
By having such properties, the PBT-containing film can be preferably replaced by a conventional PET film-nylon film laminated packaging material for a retort packaging bag.

And the resin film using the film containing PBT can be classified into two modes depending on its composition.
The layer structure of the film according to the first aspect is produced by forming a resin into multiple layers by a casting method, and includes a multilayer structure portion including a plurality of unit layers.
The film according to the second aspect is composed of a single layer containing polyester having PBT as a main repeating unit.

In the first aspect, each of the plurality of unit layers preferably contains PBT as a main component.
For example, the PBT content in each of the plurality of unit layers is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 75% by mass or more, and particularly preferably 80% by mass or more.
In the plurality of unit layers, the (n + 1) th unit layer is directly laminated on the nth unit layer. That is, no adhesive layer or adhesive layer is interposed between the plurality of unit layers. Such a PBT-containing film is composed of a multi-layer structure part containing at least 10 layers or more, preferably 60 layers or more, more preferably 250 layers or more, still more preferably 1000 layers or more.
Further, the film containing PBT may be a copolymer of PBT. As for the dicarboxylic acid component, terephthalic acid is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, and most preferably 100 mol%.
The glycol component is preferably 90 mol% or more of 4-butanediol, more preferably 95 mol% or more, still more preferably 97 mol% or more.

In the second embodiment, the polyester having PBT as a main repeating unit is, for example, 1,4-butanediol as a glycol component, or an ester-forming derivative thereof, and terephthalic acid as a dibasic acid component, or an ester thereof. It includes a homo- or copolymer-type polyester obtained by condensing the forming derivative as a main component.
70 mass% or more is preferable, as for the content rate of PBT which concerns on a 2nd structure, 80 mass% or more is more preferable, and its 90 mass% or more is still more preferable.
The PBT-containing film according to the second aspect may include a polyester resin other than PBT in an amount of 30% by mass or less. By including the polyester resin, PBT crystallization can be suppressed and the stretching processability of the polybutylene terephthalate film can be improved.

  As the polyester resin blended with PBT, a polyester having ethylene terephthalate as a main repeating unit can be used. For example, a homotype having ethylene glycol as a glycol component and terephthalic acid as a dibasic acid component as a main component can be preferably used.

  The film containing PBT according to the second aspect can be produced by the tubular method or the tenter method. By the tubular method or the tenter method, the unstretched raw fabric may be simultaneously stretched in the machine direction and the transverse direction, or may be sequentially stretched in the machine direction and the transverse direction. Among them, the tubular method can obtain a stretched film having a good physical property balance in the circumferential direction, and is particularly preferably adopted.

(Polyester resin derived from biomass)
Biomass-derived polyester resin is a resin containing as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, where the diol unit is a biomass-derived ethylene glycol unit and the dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid unit. The polyester structural part of is contained in the resin in an amount of 50 to 95% by mass, preferably 50 to 90% by mass.

  Here, the biomass-derived polyester resin may be a mixture of a polyester synthesized using only biomass-derived ethylene glycol as the diol and a polyester synthesized using only fossil fuel-derived ethylene glycol as the diol. The diol may be a copolymer synthesized by mixing a biomass-derived ethylene glycol and a fossil fuel-derived ethylene glycol.

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 the same as conventional fossil-fuel-derived polyester films and mechanical films. Physical properties such as physical properties are comparable. Therefore, the resin film of the present invention and an oxygen plasma-treated resin film using the same, a gas barrier vapor deposition film, a gas gas barrier laminate, a gas gas barrier packaging material, a gas gas barrier packaging body, a layer made of a carbon neutral material Therefore, the amount of fossil fuel used can be significantly reduced, and the environmental load can be reduced, as compared to the case where the conventional raw material is obtained from only fossil fuel.
The biomass-derived ethylene glycol is derived from ethanol (biomass ethanol) produced from biomass such as sugar cane and corn.

  For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method and a method of producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.

As the dicarboxylic acid unit of polyester, a dicarboxylic acid derived from fossil fuel is used. As the dicarboxylic acid, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, and derivatives thereof can be used.
Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl ester of aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl ester. Esters and the like can be mentioned. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid.

  Examples of the non-biomass-derived polyester that may be contained in the resin composition forming the biomass-derived polyester film in a proportion of 5 to 45 mass% include fossil fuel-derived polyesters, fossil fuel-derived polyester recycled polyesters, Examples include recycled polyester of biomass-derived polyester products.

In the biomass-derived polyester resin, the content of biomass-derived carbon measured by radioactive carbon ( ¹⁴ C) is preferably 10 to 19% based on the total carbon in the polyester. Carbon dioxide in the atmosphere contains ¹⁴ C at a constant rate (105.5 pMC), so the plant that grows by incorporating carbon dioxide in the atmosphere, such as corn, also has a ¹⁴ C content of about 105.5 pMC. Is known to be. It is also known that fossil fuel contains almost no ¹⁴ C.
Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of ¹⁴ C contained in all carbon atoms in the polyester.
In the present invention, when the content of ¹⁴ C in the polyester was P ¹⁴ C, the content of P _{bio Bio} carbon from biomass, it is defined as follows.
P _bio (%) = P ¹⁴ C / 105.5 × 100

Taking polyethylene terephthalate as an example, since polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1, only polyethylene glycol derived from biomass is available. When the above is used, the biomass-derived carbon content P _bio in the polyester is 20%. In the present invention, P _bio of the resin film is preferably 10 to 19%. If it is less than 10%, the effect as a carbon offset material becomes poor. On the other hand, as described above, P _bio is preferably as close to 20% as possible, but from the viewpoint of problems in the manufacturing process of the film and physical properties, it is preferable that the resin contains the recycled polyester and additives as described above. The actual upper limit is about 18%.

(Recycled polyester resin)
Recycled polyester is a polyester resin manufactured by mechanical recycling using a polyester resin product as a raw material.

  Among the recycled polyester resins, recycled PET resins are preferable.

  Here, mechanical recycling generally means that resin products such as collected PET bottles are crushed and washed with an alkali to remove dirt and foreign substances on the surface of the resin product, and then dried for a certain period of time under high temperature and reduced pressure to remove the resin. This is a method in which the contaminants remaining inside are diffused to be decontaminated, stains are removed, and the raw material resin is returned again.

  Hereinafter, in this specification, for example, a polyester resin or a PET resin obtained by recycling is referred to as a recycled polyester resin or a recycled PET resin, whereas a polyester resin or a PET resin that is not a recycled product is used. The resin is described as a virgin polyester resin or a virgin PET resin.

Specific examples of the recycled polyester resin include a recycled PET resin obtained by recycling PET bottles by mechanical recycling. In this recycled PET resin, the diol unit is derived from ethylene glycol and the dicarboxylic acid unit is terephthalic acid. As a seed, and may further include isophthalic acid.
Among 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% or less, based on the total dicarboxylic acid components constituting PET. % Or more and 2.5 mol% or less is more preferable.
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 be lowered and the heat resistance may be insufficient.

  The PET may be biomass PET in addition to ordinary PET derived from fossil fuel. "Biomass PET" is one that contains ethylene glycol derived from biomass as a diol component and dicarboxylic acid derived from fossil fuel as a dicarboxylic acid component. This biomass PET may be formed of only PET having a biomass-derived ethylene glycol as a diol component and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid component, or a biomass-derived ethylene glycol and a fossil fuel-derived diol as a 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 can be obtained by a conventionally known method of polycondensing the above-mentioned diol component and dicarboxylic acid component.
Specifically, a general method of melt polymerization in which a polycondensation reaction is performed under reduced pressure after an esterification reaction and / or a transesterification reaction between the above-mentioned diol component and dicarboxylic acid component, or an organic solvent Can be produced by a known solution heating dehydration condensation method using

The amount of the diol component used for producing the PET is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but in general, esterification and / or transesterification reaction and / or polycondensation are conducted. Since there is distillation during the reaction, it is used in excess of 0.1 mol% or more and 20 mol% or less.
The polycondensation reaction is preferably performed 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 may be added at the time of charging the raw materials or at the start of depressurization.

PET obtained by recycling PET bottles and the like may be subjected to solid-state polymerization as necessary in order to further increase the degree of polymerization and to remove oligomers such as cyclic trimers.
Specifically, in the solid phase polymerization, after PET is made into chips and dried, PET is pre-crystallized by heating at a temperature of 100 ° C. or higher and 180 ° C. or lower for about 1 to 8 hours, and then 190 It is carried out by heating at a temperature of not lower than 230C and not higher than 230C for 1 hour to several tens of hours under an inert gas atmosphere or under reduced pressure.

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

  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.

  As the virgin PET, the diol component as described above may be ethylene glycol, the dicarboxylic acid component may be PET containing terephthalic acid and isophthalic acid, and the dicarboxylic acid component may be PET containing no isophthalic acid. Good. Moreover, the resin base material layer may contain polyester other than PET. For example, as the dicarboxylic acid component, an aliphatic dicarboxylic acid or the like may be contained in addition to the aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid, which usually have 2 or more and 40 or less carbon atoms. Examples include chain or alicyclic dicarboxylic acids. Examples of the derivative of the aliphatic dicarboxylic acid include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the above aliphatic dicarboxylic acid, and cyclic acid anhydrides of the above aliphatic dicarboxylic acid such as succinic anhydride. . Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable as the aliphatic dicarboxylic acid, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, the methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

The resin base material made of such PET may be a single layer or a multilayer.
When the above-mentioned recycled PET is used as the resin base material, the resin base material may be provided with the outermost three layers of the upper layer, the middle layer and the lower layer close to the sealant layer.
In this case, it is preferable that the middle layer is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the upper layer and the lower layer are layers composed only of virgin PET.
As described above, by using only virgin PET for the upper layer and the lower layer, it is possible to prevent the recycled PET from being exposed from the front surface or the back surface of the resin base material layer. Therefore, the hygiene of the laminate can be ensured.

  Further, the resin base material layer may be a resin base material layer having two layers of an intermediate layer and a lower layer without providing the above-mentioned upper layer. Further, the resin base material layer may be a resin base material layer including two layers, an upper layer and an intermediate layer, without providing a lower layer. Also in these cases, it is preferable that the middle layer is a layer composed only of recycled PET or a mixed layer of recycled PET and virgin PET, and the upper layer and the lower layer are layers composed only of virgin PET.

  When one layer is formed by mixing recycled PET and virgin PET, there are a method of supplying them separately to a molding machine and a method of supplying them after mixing them by dry blending. Among them, the method of mixing by dry blending is preferable from the viewpoint of easy operation.

  The virgin PET may be fossil fuel polyethylene terephthalate (hereinafter also referred to as fossil fuel PET) or biomass PET. Here, the “fossil fuel PET” is one in which a diol derived from fossil fuel is a diol component and a dicarboxylic acid derived from fossil fuel is a dicarboxylic acid component. The recycled PET may be obtained by recycling a PET resin product formed by using fossil fuel PET or may be obtained by recycling a PET resin product formed by using biomass PET. It may be.

[Oxygen plasma treatment]
In the present invention, the oxygen plasma treated surface, which is one surface of the oxygen plasma treated resin film, is a surface for forming the inorganic vapor deposition layer.

By the oxygen plasma treatment, the surface of the resin film changes its fine surface shape and chemical properties such as chemical bonding state and functional group species, that is, the physical properties of the resin film are physically or chemically modified. After the quality treatment, the adhesiveness between the resin film and the inorganic vapor-deposited layer becomes high, and the water-resistant adhesiveness and the like can be improved.
However, there is no way to analyze the detailed chemical composition of the oxygen plasma treated surface.

The oxygen plasma treatment is preferably performed under an atmospheric pressure of 1 to 9 Pa. By performing the oxygen plasma treatment at the atmospheric pressure within the above range, the oxygen plasma treated surface can be stably formed on the resin film.
Further, in order to perform the oxygen plasma treatment for improving the adhesiveness with the inorganic vapor deposition layer, the resin film is placed on the space where the oxygen plasma is held between the magnet and the plasma electrode, which are installed facing each other at a substantially constant distance. Is preferably passed continuously.

Here, it is preferable that the plasma is held at a substantially equal density by a magnet, and that the oxygen plasma strikes one surface of the resin film substantially perpendicularly.
Further, in order to make the oxygen plasma collide with one surface of the resin film substantially perpendicularly, the direction of the bias voltage between the pair of plasma electrodes is preferably substantially perpendicular to the resin film.
In the present invention, oxygen plasma treatment is performed only on one surface of the resin film 1.

<Oxygen plasma processing device>
FIG. 4 is a plan view schematically showing the configuration of a roller-type continuous plasma processing apparatus 10, which is an example of a plasma processing apparatus suitable for oxygen plasma processing in the present invention.

  This facilitates formation of plasma P consisting of oxygen plasma, and enables stable discharge and oxygen plasma treatment for a long time, resulting in damage to the resin film 1 (electrical charge-up). Generation, etching, coloring) and stress generated on the oxygen plasma treated surface 2 can be reduced, and the effect of implanting ions or oxygen plasma into the resin film 1 can be adjusted to obtain an oxygen plasma treated surface with good adhesion. 2 can be formed. Also, the oxygen plasma treatment rate can be improved.

  As shown in FIG. 4, the roller type continuous plasma processing apparatus 10 has partition walls 35a and 35b in the decompression chamber 12, and divides the decompression chamber 12 into a resin film transfer chamber 12A and a plasma processing chamber 12B. ..

The resin film 1 moves from the unwinding roll 13 in the resin film transport chamber 12A to the plasma processing chamber 12B via the guide roller 14a, the rectangular hole between the partition wall 35a and the electrode roller 20, and the like. Then, it is wound around the surface of the electrode roller 20, one side is subjected to oxygen plasma treatment, and is conveyed to the outside of the roller type continuous plasma treatment apparatus 10 via the guide roller 14b.
The oxygen plasma-treated film 4 obtained by finishing the oxygen plasma treatment may be once taken up and taken out, and even if the inorganic vapor-deposited layer 3 is formed continuously in-line without exposing to the atmosphere. Good.
Here, although not shown in the drawing, a tension pickup roller may be further provided to convey the sheet while adjusting the tension, if necessary.

The roller type continuous plasma processing apparatus 10 includes a plasma supplying means and a magnetic forming means as plasma processing means.
The plasma supply means includes a plasma forming gas supply device 18, a plasma forming gas supply nozzle 23 (hereinafter, also referred to as supply nozzle 23) connected thereto, an electrode roller 20 which is a plasma electrode, and an electrode 22, The magnetic forming means includes a magnet 21.

The electrodes 22a to 22c, the supply nozzles 23a to 23c, and the magnet 21 are arranged along the surface near the outer periphery of the electrode roller 20 so as to cover a part of the electrode roller 20, and the electrode roller 20 and the electrodes 22a to 22c. , The supply nozzles 23a to 23c and the magnet 21 are arranged so as to form a gap.
When the resin film 1 is wound around the surface of the electrode roller 20, the distance between the electrode roller 20 which is one of the electrodes and the resin film 1 is fixed to substantially zero, and the distance between the magnet 21 and the electrode roller 20 is fixed. It is kept at a substantially constant distance.

Further, the magnet 21, the electrodes 22a to 22c, and the supply nozzles 23a to 23c are on the side of the oxygen plasma treated surface 2 of the resin film 1, and the arrangement is such that only one side of the resin film 1 can be treated with oxygen plasma.
Then, the supply nozzles 23a to 23c are opened in the space of the gap to supply the plasma forming gas, and a voltage is applied between the electrode roller 20 and the electrode 22 to generate the plasma P.
The plasma P is held in the space at a high density by the magnet 21, and the oxygen plasma is implanted substantially perpendicular to the resin film 1 by the bias voltage between the electrode roller 20 and the electrodes 22a to 22c ( Oxygen plasma collides with one surface of the resin film 1), and the oxygen plasma-treated surface 2 having improved adhesion to the inorganic vapor deposition layer 3 is efficiently formed on one surface of the resin film 1.
Then, by keeping the distance between the magnet 21 and the electrode roller 20 constant, the magnetic field in the vicinity of the film is kept uniform, whereby the ionized oxygen (oxygen plasma) has almost the same kinetic energy and the surface of the resin film 1 is kept. In this case, the plasma treatment degree in the width direction of the resin film 1 is made uniform.

The transport speed of the resin film 1 is not particularly limited, but in the present invention, it is possible to perform a high-speed film forming process, and from the viewpoint of production efficiency, at least 200 m / min or more is preferable, and 480 m / min or more. , 1000 m / min or less is more preferable.
The electric power for generating oxygen plasma is preferably 50 W · sec / m ² or more and 4000 W · sec / m ² or less. If it is less than 50 W · sec / m ² , the effect of oxygen plasma treatment is difficult to be exhibited, and if it is more than 4000 W · sec / m ² , the resin film 1 is deteriorated due to oxygen plasma such as consumption of the resin film 1, discoloration of coloring, and baking. Tends to occur.

(Resin film transfer chamber 12A and plasma processing chamber 12B)
Although not shown, the decompression chamber 12 is connected to a vacuum pump via a pressure adjusting valve, and the entire resin film transfer chamber 12A and the plasma processing chamber 12B can be decompressed. It is possible to have an exhaust chamber inside each chamber, and it is possible to control the atmospheric pressure during plasma processing and to control the invasion of the plasma P into the resin film transfer chamber 12A.
As the vacuum pump, a dry pump, a turbo molecular pump, a cryopump, etc. can be used, and it is possible to arbitrarily set a reduced pressure by adjusting the exhaust capacity and the opening degree of the pressure adjusting valve. The pressure can be reduced to 10 ^-5 Pa.

The electrode roller 20 is provided in the plasma processing chamber 12B so that a part of the electrode roller 20 is exposed to the resin film transport chamber 12A.
The resin film transfer chamber 12A is partitioned by the partition wall 35a (zone seal) from the plasma processing chamber 12B in which the electrodes are present, and has a different pressure. By making the resin film transfer chamber 12A and the plasma processing chamber 12B different in pressure, the plasma P of the plasma processing chamber 12B leaks to the resin film transfer chamber 12A, and the plasma discharge state of the plasma processing chamber 12B becomes unstable. Stable film formation and substrate transfer without causing control failure due to damage to the members of the resin film transfer chamber 12A or electrical damage to the electric circuit for controlling the resin film transfer mechanism. Is possible.

(Electrode roller 20)
By winding the resin film 1 by using the electrode roller 20 as one of the plasma electrodes, it becomes easy to prevent the resin film 1 from shrinking and being damaged by heat during the oxygen plasma treatment. It becomes easy to make the oxygen plasma uniformly collide with the film 1 in a wide range substantially vertically.

The electrode roller 20 preferably has a surface temperature adjusting means. Specifically, it is preferable that a pipe for circulating a temperature control medium such as a refrigerant or a heat medium for temperature control is installed inside the electrode roller 20, and the surface temperature of the electrode roller 20 is from −20 ° C. It is more preferable that the temperature can be adjusted to a constant temperature between 100 ° C.
The roller main body of the electrode roller 20, the rotating shaft, the bearing, and the roller support are made of a metal conductive material, and both ends of the cylindrical outer peripheral surface of the electrode roller 20 around which the resin film 1 is wound and the rotating shaft. It is preferable to provide an electrically insulating portion around the periphery.

The electrode roller 20 is preferably formed of a material containing at least one selected from the group consisting of stainless steel, iron, copper, and chromium. The surface of the electrode roller 20 may be subjected to a hard chrome hard coat treatment or the like to prevent scratches. Since these materials are easy to process and have good thermal conductivity, the temperature controllability of the surface temperature of the electrode roller 20 can be made excellent.

Further, the electrode roller 20 may be electrically installed at the ground level. When the electrode roller 20 is installed at the earth level, the charged charges accumulated on the surface of the resin film 1 are released to the earth level, and as a result, the stable oxygen plasma treated surface 2 can be formed.
Alternatively, the electrode roller 20 may be installed at an electrically floating level, that is, at an insulation potential. By setting the potential of the electrode roller 20 to the floating level, it is possible to prevent power leakage, increase the input power of the oxygen plasma treatment, and increase the utilization efficiency for the oxygen plasma treatment.
When the electrode roller 20 is at an electrically floating level, it is possible to install a mechanism for applying a DC potential to the electrode roller 20 to strengthen or weaken the implantation effect of oxygen plasma on the resin film 1. In order to enhance the oxygen plasma implantation effect, it is preferable to give a negative potential to the resin film 1, and to weaken the oxygen plasma implantation effect, it is preferable to give the resin film 1 a positive plus potential.

  By such adjustment, the effect of implanting oxygen plasma into the resin film 1 can be adjusted, and the damage caused by implanting oxygen plasma into the resin film 1 can be reduced.

(Magnet 21)
The magnet 21 is kept at a substantially constant distance from the electrode roller 20 in order to uniformly and densely retain the plasma P in the space on one side of the resin film 1.

The magnetic flux density at one surface position of the resin film 1 by the magnet 21 is preferably 10 gauss or more and 10000 gauss or less. When the magnetic flux density is 10 gauss or more, it becomes possible to sufficiently enhance the reactivity of plasma, and it is possible to form a favorable oxygen plasma treated surface 2 at high speed. In addition, an expensive magnet or magnetic field generating mechanism is required to increase the magnetic flux density to higher than 10,000 gauss.
It is preferable that the magnet 21, which is a magnetism forming means, is installed on a base plate in a magnet case having an insulating spacer.

Further, since the ions and thermoelectrons formed during the oxygen plasma treatment move according to the arrangement structure of the magnet 21, even when the oxygen plasma treatment is performed on the resin film 1 having a large area of 1 m ² or more, for example, the electrons By uniformly diffusing the ions and ions and the decomposed product of the resin film 1, uniform and stable oxygen plasma treatment becomes possible.
Furthermore, since the localized distribution of thermoelectrons and ions in the vicinity of the electrode portion and the magnet 21 does not occur, the heat resistance requirement for the constituent members is reduced, the constituent members can be manufactured at low cost, and thermal deformation is possible. It is possible to suppress the occurrence of defects such as perforation and cracking of the structure.

(Electrode 22)
The electrode 22 can generate a desired plasma P in the vicinity of the outer periphery of the electrode roller 20 at a desired density, and a bias voltage for making the plasma P a positive potential can be applied between the electrode 22 and the electrode roller 20, It is connected to a power source 32 through a power supply wiring 31.
The electrode 22 is electrically conductive for supplying electric power, has excellent plasma resistance, has heat resistance, has high cooling efficiency with cooling water (high thermal conductivity), is a nonmagnetic material, and has excellent workability. It is preferable to use a material and manufacture the same. Specifically, aluminum, copper, and stainless steel are preferably used.

Further, it is preferable that a temperature control medium pipe for cooling the electrode 22 and the adjacent magnet 21 is provided inside the electrode 22.
The electrode 22 is preferably attached to an insulating shield plate installed in a magnet case containing the magnet 21. The insulating shield plate is preferably made of a material that is insulative, has excellent plasma resistance, has heat resistance, and has excellent workability. Specifically, fluorine resin and polyimide resin are preferably used.

  Further, since the electrode 22 is electrically insulated from the magnet case in which the magnet 21 is provided, it can be electrically set to a floating level.

(Supply of plasma forming gas)
The supply nozzle 23 is connected to the plasma forming gas supply device 18, and the supplied plasma forming gas measures a gas flow rate from a gas storage section (not shown) through a flow rate controller (not shown). It is preferable to be supplied while it is being supplied.
Although the number of the supply nozzles 23 is one at each location in the drawing, they may be individually provided for each type of plasma forming gas to be supplied.
The plasma forming gas to be supplied is preferably a mixed gas containing oxygen / argon in a volume ratio of 1/1 or more and 3/1 or less.
As the plasma forming gas, this mixed gas may be supplied from one supply nozzle 23, or each of oxygen and argon may be supplied from different supply nozzles 23.
(Electrode and plasma forming gas supply nozzle)
FIG. 5 is a plan view schematically showing a configuration of a roller-type continuous plasma processing apparatus 10, which is an example of another aspect of a plasma processing apparatus suitable for oxygen plasma processing in the present invention.
The roller type continuous plasma processing apparatus 10 includes a plasma supplying means and a magnetic forming means as plasma processing means.
The plasma supply means includes a plasma forming gas supply device 18, an electrode / plasma forming gas supply nozzle 26 and an electrode roller 20 connected to the plasma forming gas supply device 18, and the magnetic forming means includes a magnet 21.
The electrode / plasma forming gas supply nozzle 26 is a combination of the electrode 22 and the plasma forming gas supply nozzle 23 described above, and fulfills the respective functions.
The electrode / plasma forming gas supply nozzle 26 is a component that also serves as an electrode for applying an arbitrary voltage between the electrode roller 20 and the plasma forming gas supply means, and is a bias voltage for making the plasma P a positive potential. Is connected to the power source 32 through the power supply wiring 31 so that the voltage can be applied.
The electrode portion of the electrode / plasma forming gas supply nozzle 26 is electrically conductive for supplying electric power, has excellent plasma resistance, has heat resistance, has high cooling efficiency with cooling water (high thermal conductivity), and is non-conductive. It is preferable to use a magnetic material that is excellent in workability. Specifically, aluminum, copper, and stainless steel are preferably used.

The electrode / plasma forming gas supply nozzles 26a to 26c and the magnet 21 are arranged along the surface near the outer periphery of the electrode roller 20 so as to cover a part of the electrode roller 20, and the electrode roller 20 and the electrode / plasma. A space is formed between the forming gas supply nozzles 26a to 26c and the magnet 21.
The distance between the electrode roller 20 and the magnet 21 is maintained at a substantially constant distance.

Further, the magnet 21 and the electrode / plasma forming gas supply nozzles 26a to 26c are located on the side of the oxygen plasma treated surface of the resin film 1 so that only one side of the resin film 1 can be treated with oxygen plasma.
Then, electrodes and plasma forming gas supply nozzles 26a to 26c are opened in the space of the void,
The plasma forming gas is supplied, and the electrode / plasma forming gas supply nozzles 26a to 26c facing the electrode roller 20 are applied to generate the plasma P.
The plasma P is uniformly held in the space with a high density by the magnet 21, and is substantially perpendicular to the resin film 1 between the electrode roller 20 and the electrode / plasma forming gas supply nozzles 26a to 26c facing each other. Due to the generated bias voltage, oxygen plasma is implanted in a direction substantially perpendicular to the resin film 1, and the oxygen plasma treated surface 2 having improved adhesion to the inorganic vapor deposition layer 3 on one surface of the resin film 1 efficiently. It is formed.
In this embodiment as well, the plasma forming gas supply nozzle 22 may be separately installed and the plasma forming gas may be supplied from the electrode / plasma forming gas supply nozzle 26 and the plasma forming gas supply nozzle 22.
The supplied plasma-forming gas is preferably supplied from a gas reservoir (not shown) while measuring the flow rate via a flow rate controller (not shown).

<Gas barrier vapor deposition film>
As shown in FIG. 1, the barrier vapor deposition film 7 of the present invention has a structure in which an inorganic vapor deposition layer 3 is laminated adjacent to the oxygen plasma treatment surface 2 of the oxygen plasma treatment resin film 4 of the present invention. ..
As shown in FIG. 2, the barrier vapor deposition film 7 of the present invention further comprises an organic protective layer 5 composed of a gas barrier coating layer and / or a primer layer adjacent to the inorganic vapor deposition layer 3 as necessary. It may have a laminated structure.

In the gas barrier vapor deposition film of the present invention, since the oxygen plasma treatment surface is formed by the above specific oxygen plasma treatment, the interface between the inorganic vapor deposition layer and the oxygen plasma treatment surface is excellent in adhesive strength during water immersion. It also has water resistance and adhesion.
The adhesive strength during water immersion according to the present invention is the interlayer lamination strength during water immersion at the interface between the inorganic vapor-deposited layer and the oxygen plasma-treated surface of the resin film, which indicates water-resistant adhesion, and the barrier property of the present invention. The vapor-deposited film has excellent water resistance adhesion.
The adhesive strength at the time of immersion is preferably 1.5 N / 15 mm or more and 4 N / 15 mm or less.

(Measurement method of adhesive strength during flooding)
For the test piece for measuring the adhesive strength during water immersion, in order to facilitate the measurement, a cover film is attached to the organic protective layer of the vapor-deposited barrier film on which the gas barrier coating layer side is laminated with an adhesive. It is preferable to use the attached one. By grasping and peeling off the cover film portion, it is possible to easily measure the adhesive strength at the interface between the inorganic vapor deposition layer and the oxygen plasma treated surface.

The cover film is preferably a film such as an adhesive layer / CPP. The cover film is adhered to the gas barrier coating layer of the barrier vapor deposition film via the adhesive layer to produce a laminate having the following layer structure. After the laminated body is manufactured, it is subjected to an aging treatment for 48 hours and cut into a strip having a width of 15 mm to obtain a test piece.
Resin film / oxygen plasma treated surface / inorganic vapor deposition layer / organic protective layer // adhesive layer / CPP

According to JIS K6854-2, this test piece was subjected to a 180-degree peeling method using a tensile tester after water was dropped onto a peeling surface with a dropper in a state where the adhesive layer was peeled off in advance. To measure the adhesive strength.
In the vapor-deposited film having the inorganic vapor-deposited layer, the interface where peeling is likely to occur due to the lowest adhesive strength, and particularly peeling due to water immersion is the interface between the inorganic vapor-deposited layer and the resin film (oxygen plasma treated surface).

  Therefore, at the time of measuring the adhesive strength, peeling proceeds from the peeling interface of the adhesive layer at the start of peeling, but if the adhesive layer is firmly adhered, the peeled surface has the weakest adhesion strength with the inorganic vapor deposition layer and oxygen. It propagates to the interface with the plasma-treated surface, and the adhesive strength at the interface can be measured.

[Inorganic deposition layer]
The composition of the inorganic vapor deposition layer in the present invention is not particularly limited, since it is used as a gas barrier inorganic vapor deposition film, specifically, metal such as silicon, aluminum, magnesium, titanium, tin, indium, zinc, zirconium, Alternatively, these oxides, nitrides, carbides, and mixtures thereof may be mentioned.
Among the above, the inorganic vapor deposition layer is preferably a metal vapor deposition layer or a metal oxide vapor deposition layer.

When the inorganic vapor deposition layer is a metal vapor deposition layer, it is more preferably an aluminum vapor deposition layer.
When the inorganic vapor deposition layer is a metal oxide vapor deposition layer, it is more preferably an aluminum oxide vapor deposition layer.
Further, the molar ratio of oxygen atom / aluminum atom of the vapor-deposited aluminum oxide layer by X-ray photoelectron spectroscopy (XPS) is preferably 1.2 or more and 5 or less.
When the aluminum oxide vapor deposition layer has a high degree of oxidation with a molar ratio in the above range, the transparency, water resistance adhesion and gas barrier property of the aluminum oxide vapor deposition layer are enhanced.

The thickness of the inorganic vapor deposition layer is preferably 3 to 50 nm. If the thickness of the inorganic vapor deposition layer is 3 nm or more, the barrier property can be maintained.
If productivity is important, 3 nm or more and less than 12 nm is preferable, and if high barrier property, mechanical / thermal / humidity durability, or retort suitability is required, 12 nm or more, 50 nm or more. The following are preferred.

The formation of the inorganic vapor-deposited layer is performed in-line continuously with the formation of the oxygen plasma-treated surface, but after the formation of the oxygen plasma-treated surface, it is once taken out into the atmosphere and discontinuously performed offline. Good.
The inorganic vapor-deposited layer of the gas barrier vapor-deposited film of the present invention exhibits sufficient water-resistant adhesion even when it is performed off-line. However, when it is performed in-line, further excellent water-resistant adhesion can be exhibited.

<Continuous inorganic vapor deposition layer forming device>
As the inorganic vapor deposition layer forming apparatus, there are known physical vapor deposition apparatuses such as a resistance heating vacuum film forming apparatus, a sputtering apparatus, an ion plating film forming apparatus, an ion beam assisted film forming apparatus, and a cluster ion beam film forming apparatus, and plasma CVD. A chemical vapor deposition device such as a film forming device, a plasma polymerization film forming device, a thermal CVD film forming device, or a catalytic reaction type CVD film forming device can be used.
For example, in the continuous inorganic vapor deposition layer forming apparatus shown in FIG. 6, the vapor deposition layer forming chamber 12D is provided with an inorganic vapor deposition layer forming apparatus including a vapor deposition roller 24 and a vapor deposition layer forming means 25. By this inorganic vapor deposition layer forming apparatus, the inorganic vapor deposition layer 3 is formed on the oxygen plasma treated surface 2 of the oxygen plasma treated film 4.

Here, when a vacuum film forming apparatus is used as the vapor deposition layer forming means 25, a metal material is filled in the crucible and heated to a high temperature to generate metal vapor as an evaporation source of the vapor deposition layer forming means.
When forming the metal vapor deposition layer, an inert gas can be supplied from the gas supply means to form the metal vapor deposition layer on the oxygen plasma treated surface 2, and when the metal oxide vapor deposition layer is formed. A metal oxide vapor deposition layer can be formed on the oxygen plasma treated surface 2 by supplying a gas containing oxygen from the gas supply means.
For example, an aluminum wire is used as a metal material, aluminum metal vapor is generated by a heating means by resistance heating, and the aluminum oxide vapor deposition layer is formed by stacking on an oxygen plasma treated surface while being oxidized by an oxygen / argon mixed gas. You can

As the evaporation source, a sputter evaporation source, an arc evaporation source, or a plasma CVD film forming mechanism such as a plasma generating electrode or a raw material gas supply means can be adopted.
The number of inorganic vapor deposition layer forming devices provided in the vapor deposition layer forming chamber 12D may be one, or two or more inorganic vapor deposition layer forming devices of the same type or different types may be provided.

When the thick inorganic vapor-deposited layer 3 is formed by one inorganic vapor-deposited layer forming apparatus, the inorganic vapor-deposited layer 3 becomes brittle due to stress, and cracks are generated to significantly reduce the gas barrier property, or during transportation or winding. At times, the inorganic vapor deposition layer 3 is likely to peel off. Therefore, in order to obtain the thick inorganic vapor deposition layer 3, it is preferable to provide a plurality of inorganic vapor deposition layer forming devices and stack the inorganic vapor deposition layers having the same composition a plurality of times.
Further, the inorganic vapor deposition layers 3 having different compositions may be formed by using a plurality of inorganic vapor deposition layer forming devices. In that case, not only the gas barrier property but also a multilayer film having various functions can be obtained. ..

The vapor deposition roller 24 is preferably made of a material containing at least one of stainless steel, iron, copper, and chromium.
Further, the surface of the vapor deposition roller 24 may be subjected to a hard chrome hard coat treatment or the like to prevent scratches. Since these materials are easy to process and the vapor deposition roller 24 itself has good thermal conductivity, the temperature controllability at the time of temperature control is excellent.
The more flat the surface of the vapor deposition roller 24, the more preferable.

The vapor deposition roller 24 should be set at a constant temperature between -20 ° C and 200 ° C by using a cooling medium and / or a heat source medium or a heater in view of heat resistance of related mechanical parts and versatility. It is preferable to have a temperature control mechanism capable of
Since the vapor deposition roller 24 has a temperature adjusting mechanism, it is possible to suppress the fluctuation of the temperature of the oxygen plasma-treated resin film 1 due to the heat generated when the inorganic vapor deposition layer is formed.
Specifically, an ethylene glycol aqueous solution is used as a cooling medium (refrigerant), and silicon oil is used as a heat source medium (heating medium) to adjust the temperature by circulating in the vapor deposition roller 24 or a position facing the vapor deposition roller 24. It is possible to heat by installing a heater in.

Next, the operation of the continuous inorganic vapor deposition layer forming apparatus will be described.
The oxygen plasma treated resin film 4 is wound around the vapor deposition roll 24 in the vapor deposition layer forming chamber 12D from the barrier laminate film transport chamber 12C via the guide roller 14c, and guided to the barrier laminate film transport chamber 12C. Via the roller 14d, the oxygen plasma treated surface 2 is guided to the take-up roller 15 so that the surface 2 becomes the front side.
Then, the inside of the barrier laminate film transport chamber 12C and the vapor deposition layer forming chamber 12D is depressurized by a vacuum pump.
After the pressure is reduced to a predetermined pressure, the formation of the inorganic vapor deposition layer 3 by the vapor deposition layer forming means 25 is started.

[Organic protective layer]
An organic protective layer can be laminated adjacent to the surface of the inorganic vapor deposition layer of the gas barrier vapor deposition film of the present invention. As the organic protective layer, a gas barrier coating layer and / or a primer layer can be applied.
When both the gas barrier coating layer and the primer layer are laminated, whichever layer may be adjacently laminated on the surface of the inorganic vapor deposition layer, but the gas barrier coating layer is formed on the surface of the inorganic vapor deposition layer. Is preferably laminated adjacent to.

  The organic protective layer protects the inorganic vapor deposition layer mechanically and chemically and improves the gas barrier property and retort resistance of the gas barrier vapor deposition film, and is preferably formed by coating.

(Gas barrier coating layer)
The gas barrier coating layer improves the gas barrier property and the retort resistance of the gas barrier vapor deposition film.

  The gas barrier coating layer is preferably formed by coating and solidifying a gas barrier resin composition (barrier coating agent) containing at least a metal alkoxide and a hydroxyl group-containing water-soluble resin.

The gas barrier resin composition may further contain a silane coupling agent, a sol-gel method catalyst, etc., if necessary.
The composition of the gas barrier resin composition is, for example, preferably 100 to 500 parts by mass of the hydroxyl group-containing water-soluble resin with respect to 100 parts by mass of the metal alkoxide.
Furthermore, when the silane coupling agent is contained, it is preferably contained within the range of 1 to 20 parts by weight. When the amount is more than the above range, the rigidity and brittleness of the gas barrier coating layer become too large, which is not preferable.
The film thickness of the gas barrier coating layer after drying is preferably 100 to 500 nm. Within this range, the gas barrier coating layer is unlikely to crack, and the surface of the inorganic vapor deposition layer can be sufficiently coated and protected.

The metal alkoxide is represented by the general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, and different R ¹ and R ² are in one molecule). , 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 a valence of M). One kind or two or more kinds of metal alkoxides may be a mixture of two or more kinds.
Examples of the metal atom represented by M of the metal alkoxide include silicon, zirconium, titanium, aluminum, and the like. For example, it is preferable to use an alkoxysilane in which M is Si.

The above-mentioned alkoxysilane is, for example, one represented by the general formula Si (OR ^a ) ₄ (wherein R ^a represents a lower alkyl group). In the above, as R ^a , a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or the like is used.
Specific examples of the above-mentioned alkoxysilane include, for example, tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si. (OC ₄ H ₉ ) ₄ and others can be used. The above alkoxides may be used in combination of two or more kinds.

As the silane coupling agent, those having a reactive group such as a vinyl group, an epoxy group, a methacryl group and an amino group can be used. Particularly preferred are organoalkoxysilanes having an epoxy group, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxy. Propyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The silane coupling agents as described above may be used alone or in combination of two or more.

  As the water-soluble polymer, it is preferable to use a polyvinyl alcohol resin or an ethylene / vinyl alcohol copolymer, either alone or in combination. In the present invention, it is preferable to use a polyvinyl alcohol resin.

As the polyvinyl alcohol resin, those obtained by saponifying polyvinyl acetate can be generally used. As the polyvinyl alcohol-based resin, a partially saponified polyvinyl alcohol-based resin in which several tens% of acetic acid groups remain, or a completely saponified polyvinyl alcohol in which acetic acid groups do not remain, modified polyvinyl alcohol in which OH groups are modified It may be a resin.
The polymerization degree of the polyvinyl alcohol-based resin may be any as long as it is within the range (about 100 to 5000) used in the conventional sol-gel method.
Further, the film hardness of the barrier coating layer is preferably high, and for that purpose, it is preferable to use a polyvinyl alcohol-based resin having a saponification degree of 70% or more, which is likely to have a high crystallinity.
As such a polyvinyl alcohol-based resin, RS-110 (saponification degree = 99%, polymerization degree = 1,000), which is an RS resin manufactured by Kuraray Co., Ltd., and “Gothenol” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. NM-14 (saponification degree = 99%, polymerization degree = 1,400) ”and the like.

As the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used.
For example, the partial saponification product in which several tens mol% of acetic acid groups remain, to the complete saponification product in which only several mol% of acetic acid groups remain or no acetic acid groups remain, are not particularly limited.
The degree of saponification of the ethylene / vinyl alcohol copolymer is preferably 80 mol% or more and 100% or less, more preferably 90 mol% or more and 100 mol% or less, still more preferably 95 mol% or more and 100 mol% or less.

  As the sol-gel method catalyst, an acid or amine compound is suitable.

As the acid, for example, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid can be used.
The content of the acid is preferably 0.001 to 0.05 mol% and more preferably 0.01 to 0.03 mol% with respect to the total molar amount of the alkoxy groups of the metal alkoxide. If it is less than 0.001% mol, the catalytic effect is too small, and if it is more than 0.05 mol%, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

As the amine compound, a tertiary amine which is substantially insoluble in water and soluble in an organic solvent is suitable. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. Particularly, N, N-dimethylbenzylamine is preferable.
The content of the amine compound is, for example, preferably 0.01 to 1.0 part by mass, particularly preferably 0.03 to 0.3 part by mass, per 100 parts by mass of the metal alkoxide. If it is less than 0.01 part by mass, the catalytic effect is too small, and if it is more than 1.0 part by mass, the catalytic effect is too strong and the reaction rate becomes too fast, which tends to cause non-uniformity.

As the solvent, it is preferable to use water or an alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropanol, n-butanol, or the like.

In the present invention, the gas barrier coating layer can be formed by the following method.
First, a gas barrier resin composition is prepared by adding a metal alkoxide, a hydroxyl group-containing water-soluble resin, and, if necessary, a silane coupling agent, a sol-gel method catalyst and the like to a solvent and mixing them.
Then, the above gas barrier resin composition is applied onto the inorganic vapor-deposited layer by a conventional method and dried. By this drying step, the polycondensation reaction in the gas barrier resin composition further progresses and a coating film is formed.

The coating film may be formed by forming one layer by performing the above application and drying once, or by forming two or more layers by performing the above application and drying multiple times.
Then, heat treatment is performed for 3 seconds to 10 minutes at a temperature of 20 to 200 ° C. and lower than the melting point of the resin film, preferably 50 to 180 ° C. As a result, the polycondensation polycondensation reaction of the gas barrier resin composition further proceeds, and the gas barrier coating layer is formed.

On the surface of the gas barrier coating layer, good barrier properties are exhibited by adjusting the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) to 1.20 or more. be able to.
By adjusting the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) on the surface of the gas barrier coating layer to 1.60 or less, the oxygen transmission rate after the bending test. Can be suppressed.

(Primer layer)
The primer layer improves the gas barrier property of the vapor deposition film having gas barrier properties and the adhesive property with other resin layers.
It is preferable that the primer layer is formed by applying and solidifying a primer liquid containing at least a urethane resin. And, if necessary, it is preferable to further contain a silane coupling agent and silica fine particles.

  The film thickness of the primer layer after drying is preferably 0.01 to 30 μm, more preferably 0.1 to 10 μm.

When the primer layer contains the urethane resin, the primer layer has appropriate elasticity or flexibility, and the influence of the pressure during printing or lamination on the inorganic vapor deposition layer can be reduced, and the deterioration of the gas barrier property can be suppressed.
As the urethane resin, both conventionally known polyester urethane resin and polyether urethane resin can be used. As such a urethane resin, a reaction product of polyol such as polyester polyol or polyether polyol and polyisocyanate can be used.

  Examples of the above-mentioned polyester polyols include polyester polyols obtained by reacting a low molecular weight polyol with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolacton; Examples thereof include polyester polyols obtained by copolymerization. These polyester polyols can be used alone or in combination of two or more kinds.

As the low molecular weight polyol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol having a molecular weight of about 50 to 300 is used. Some aliphatic polyols; polyols having an alicyclic structure such as cyclohexanedimethanol; and polyols having an aromatic structure such as bisphenol A and bisphenol F. Examples of the polycarboxylic acid that can be used for producing the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and the like. Aromatic polycarboxylic acids; anhydrides or esterified products thereof, and the like. Further, as the polyester polyol, a polyester polyurethane polyol having a urethane bond in the molecular structure, which is obtained by modifying the above polyester polyol with polyisocyanate, can also be used. These polyester polyols can be used alone or in combination of two or more kinds.

  Examples of the above-mentioned polyether polyol include those obtained by addition-polymerizing alkylene oxide with one or more compounds having two or more active hydrogen atoms as an initiator. Examples of the compound having two or more active hydrogen atoms include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, and diester. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, water and hexanetriol. Examples of the alkylene oxide include propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like. Further, as the polyether polyol, it is also possible to use a polyether polyurethane polyol having a urethane bond in the molecular structure, which is obtained by modifying the above polyether polyol with polyisocyanate. These polyether polyols can be used alone or in combination of two or more kinds.

  Examples of the polyisocyanate include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate. Aromatic polyisocyanates such as crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate and naphthalene diisocyanate; and aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate. Among these, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and crude diphenylmethane diisocyanate are preferable. In addition, these polyisocyanates can be used alone or in combination of two or more kinds.

  As the silane coupling agent, a conventionally known silane coupling agent can be used, and for example, the same silane coupling agent as that used in the above gas barrier resin composition is preferably used. By including the silane coupling agent in the primer layer, interlayer adhesion with the gas barrier coating layer can be improved.

As the silica fine particles, conventionally known silica can be used.
In particular, when the urethane resin is polyether polyurethane, the primer layer containing silica fine particles can suppress blocking during winding in the process of producing the gas barrier vapor deposition film.

  Examples of means for forming the primer layer by coating include roll coating such as a gravure roll coater, spray coating, spin coating, dipping, a brush, a bar code and an applicator. The primer layer may be formed by coating once or multiple times.

<Gas barrier laminate>
The gas barrier laminate of the present invention is a laminate having a layer composed of the gas barrier vapor deposition film of the present invention and a sealant layer, the gas barrier vapor deposition film of the present invention, a heat-sealable sealant layer, an adhesive. It is produced by laminating with or without intervening.

  The sealant layer may be laminated on either side of the gas barrier vapor deposition film, but as shown in FIG. 3, the sealant layer 6 is the gas barrier vapor deposition film 7 on the inorganic vapor deposition layer 3 side or the gas barrier property. It is preferably laminated on the outermost surface of the gas barrier laminate 7 on the coating layer 5 side.

  The gas barrier laminate of the present invention further has, if necessary, a function to be imparted when used in a packaging material, for example, a light-shielding layer for imparting light-shielding properties, a decorative layer, and a printing layer for imparting printing. , A pattern layer, a laser printing layer, and various functional layers such as a deodorant layer that decomposes or adsorbs odor can be included as a layer structure.

[Sealant layer]
The sealant layer is a layer containing one or more heat-sealable resins and is a layer that can be adhered by heating. Dry lamination using a resin film or extrusion lamination including coextrusion, or resin coating. It is a layer formed of a film or the like.

  As the resin contained in the sealant layer, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, polymethylpentene, polystyrene, ethylene-vinyl acetate copolymer , Α-olefin copolymers, ionomer resins, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, resins such as elastomers, and the like. It is possible to use a resin mixed with or a film of these resins.

The sealant layer may be a single layer or a multilayer structure of two or more layers. In the case of a multi-layered structure, the composition of each layer may be the same or different, and a layer consisting only of the heat-sealable resin or a layer not containing the heat-sealable resin may be included.
Furthermore, a functional layer having various functions and an adhesive layer can be included. However, the layer forming the outermost surface of one side of the gas barrier laminate preferably contains a resin having excellent heat-sealing properties.

  Further, in the sealant layer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antiblocking agent, a flame retardant, a crosslinking agent, a colorant, a pigment, a lubricant, a filler, a reinforcing agent, a modifier. One or more kinds of various inorganic or organic additives such as resin for use can be appropriately contained. The content thereof can be arbitrarily set from an extremely small amount to several tens of% depending on its purpose.

<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.
The gas barrier laminate of the present invention can be further laminated with a functional film depending on the application to produce a gas barrier packaging material.
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, paper can be laminated as long as it is a packaging material for liquid paper containers.

<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, a heat-sealing process in which a sealant layer of a gas barrier packaging material composed of a multilayer film is heat-sealed to produce a gas barrier package in the form of pillow packaging bag, three-sided seal, four-sided seal, gusset type, or the like. In addition, if the packaging material is made of a laminated body in which papers are laminated, a Goebeltop type liquid paper container packaging body for alcohol, juice or the like can be produced.

<Gas barrier packaging bag for wet contents>
Since the packaging material of the present invention has excellent water-resistant adhesion, it can be suitably used as a gas barrier packaging bag for wet contents such as alcoholic beverages, sweets, jellies and liquid beverages.

  The raw materials used in the examples are as follows.

PET film 1: A petroleum-derived polyethylene terephthalate film having a thickness of 12 μm.
Polyvinyl alcohol A: Polyvinyl alcohol having a degree of polymerization of 2400 and a saponification degree of 99% or more.
Polyurethane A: Polyester urethane resin (manufactured by Dainichiseika Kogyo Co., Ltd.)
Sealant film 1: 70 μm thick unstretched polypropylene film (manufactured by Toray Industries, Inc.) Dry lamination adhesive 1: Two-component curable polyurethane adhesive (manufactured by Rock Paint Co., Ltd.)

[Example 1]
The oxygen plasma treatment surface and the inorganic vapor deposition layer are formed by connecting the roller type continuous oxygen plasma treatment apparatus 10 shown in FIG. 5 and the roller type continuous vapor deposition layer forming apparatus 11 shown in FIG. Without touching, it was performed continuously in-line.

<Formation of oxygen plasma treated surface>
The roller type continuous oxygen plasma processing apparatus 10 shown in FIG. 5 was used for forming the oxygen plasma processing surface.
First, as the resin film 1, a roll wound with the PET film 1 is prepared and set on the unwinding roller 13 of the resin film transport chamber 12A, and the electrode is passed through the guide roller 14a in the plasma processing chamber 12B. It was wound around the surface of the roller 20 and pulled out to the roller type continuous oxygen plasma processing apparatus 10 via the guide roller 14b.

  Next, the surface of the PET film 1 on which the oxygen plasma-treated surface 2 is formed is subjected to oxygen plasma treatment under the following conditions to form the oxygen plasma-treated surface 2 to produce an oxygen plasma-treated resin film 4. , Roller type continuous oxygen plasma processing apparatus 10.

(Oxygen plasma pretreatment conditions)
・ Plasma intensity: 200W ・ sec / m ²
・ Plasma forming gas ratio: oxygen / argon = 2/1
・ Voltage applied between the electrode roller and the electrode that also serves as the plasma forming gas supply nozzle: 340 V
・ Degree of vacuum in plasma processing chamber: 3.8 Pa

<Formation of inorganic vapor deposition layer>
The oxygen plasma-treated resin film drawn out from the roller-type continuous oxygen plasma processing apparatus 10 is drawn into the roller-type continuous vapor deposition layer forming apparatus 11, and is guided from the barrier laminated film transport chamber 12C to the vapor deposition layer forming chamber 12D. It wound around the surface of the vapor deposition roller 24 via 14c, and was wound around the winding roller 15 in the barrier laminate film transport chamber 12C via the guide roller 14d.

  Then, on the oxygen plasma-treated surface, metal aluminum was evaporated using a reactive resistance heating method as a heating means of the vacuum deposition method under the following conditions, and was oxidized by the supplied oxygen gas to have a thickness of 12 nm. An inorganic vapor deposition layer composed of an aluminum oxide vapor deposition film was formed to prepare a vapor barrier film having a gas barrier property.

(Formation conditions of aluminum oxide vapor deposition layer)
・ Degree of vacuum: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min

<Formation of gas barrier coating layer>
395 g of water, 105 g of isopropyl alcohol and 9.3 g of 0.5N hydrochloric acid were mixed, and 127 g of tetraethoxysilane as a metal alkoxide was mixed with the solution adjusted to pH 2.2 while cooling to 10 ° C. to form solution A. Prepared.
As a water-soluble polymer, a solution B was prepared by mixing 14.7 g of polyvinyl alcohol having a saponification number of 99% or more and a polymerization degree of 2400, 324 g of water, and 17 g of isopropyl alcohol.
A solution obtained by mixing the liquid A and the liquid B in a mass ratio of 6.5: 3.5 was used as a resin composition and a barrier coating agent for the barrier coating layer.
Then, the barrier coating agent prepared above was coated on the vapor-deposited aluminum oxide film of the PET film by spin coating.
Then, heat treatment was performed in an oven at 180 ° C. for 60 seconds to form a barrier coating layer having a thickness of about 400 nm on the aluminum oxide vapor deposition film to obtain a barrier vapor deposition film.

[Example 2]

An oxygen plasma-treated resin film was produced in the same manner as in Example 1, and then an inorganic vapor deposition layer made of a 12 nm-thick aluminum oxide vapor deposition film was formed to produce a gas barrier vapor deposition film.

<Formation of primer layer>
A primer layer was formed as an organic protective layer adjacent to the aluminum oxide vapor deposition film of the gas barrier vapor deposition film obtained above as described below.
First, polyurethane A (150 g) was mixed with a curing agent (5 g) to prepare primer liquid 1.
Next, the primer liquid 1 prepared above was coated on the aluminum oxide vapor deposition film of the gas barrier vapor deposition film formed above by a spin coating method.
Then, by performing a heat treatment at 100 ° C. for 30 seconds in an oven, a primer layer having a thickness of about 300 nm was formed adjacently on the aluminum oxide vapor deposition film to prepare a gas barrier vapor deposition film having the primer layer. ..

<Production of gas barrier laminate>
A gas barrier laminate was prepared in the same manner as in Example 1.

[Example 3]
A gas barrier vapor deposition film was produced in the same manner as in Example 1 except that the liquid A and the liquid B forming the gas barrier coating layer were mixed at a mass ratio of 6: 4.

[Example 4]
A gas barrier vapor deposition film was produced in the same manner as in Example 1 except that the liquid A and the liquid B forming the gas barrier coating layer were mixed at a mass ratio of 7: 3.

[Example 5]
A gas barrier vapor deposition film was produced in the same manner as in Example 1 except that the liquid A and the liquid B forming the gas barrier coating layer were mixed at a mass ratio of 2: 8.

[Example 6]
A gas barrier vapor deposition film was produced in the same manner as in Example 1 except that the liquid A and the liquid B forming the gas barrier coating layer were mixed at a mass ratio of 8: 2.

[Example 7]
A gas barrier vapor deposition film was produced in the same manner as in Example 3 except that the thickness of the inorganic vapor deposition layer was changed to 8 nm.

[Example 8]
A gas barrier vapor deposition film was produced in the same manner as in Example 2 except that the thickness of the inorganic vapor deposition layer was changed to 8 nm.

[Comparative Example 1]
A gas barrier coating layer formed from the gas barrier resin composition 1 was operated in the same manner as in Example 1 except that the oxygen plasma-treated surface of the PET film 1 was plasma-treated under the following conditions using the direct plasma method. A vapor barrier film having a gas barrier property was prepared. Then, the same operation as in Example 1 was carried out to produce a gas barrier laminate. The direct plasma method means a method in which a bias voltage is not applied to the plastic base material.

(Oxygen plasma treatment conditions)
・ DC plasma intensity: 150W ・ sec / m ²
・ Plasma forming gas ratio: oxygen / argon = 2/1
・ Magnetic forming means: None ・ Voltage applied between electrode roller and plasma forming gas supply nozzle that also serves as an electrode: None ・ Degree of vacuum in plasma processing chamber: 4.0 Pa

(Formation conditions of aluminum oxide vapor deposition layer)
・ Degree of vacuum: 8.1 × 10 ^-2 Pa
・ Transport speed: 400m / min

[Comparative example 2]
A primer formed from primer solution 1 was operated in the same manner as in Comparative example 1 except that the gas barrier coating layer formed from the gas barrier resin composition 1 of Comparative Example 1 was changed to a primer layer formed from the primer solution 1. A gas barrier vapor deposition film having layers was prepared. Then, the same operation as in Example 1 was carried out to produce a gas barrier laminate.

<Summary of evaluation results>
The measurement results are shown in Table 1.
As shown in Examples 1 to 8, the gas barrier vapor deposition layer film of the present invention was excellent in water-proof adhesion strength. The ratio of silicon atoms to carbon atoms (Si
The vapor-deposited gas barrier film having a / C) ratio of 1.20 or more showed good barrier properties. In the gas barrier vapor deposition film in which the ratio of silicon atoms to carbon atoms (Si / C) on the surface of the gas barrier coating layer was 1.60 or less, deterioration of oxygen permeability was suppressed even after the bending test.

<Measurement method of evaluation items>
Using the gas barrier vapor deposition film produced in each of the above Examples and Comparative Examples as a sample for measurement, elemental analysis of the gas barrier coating layer surface, oxygen permeability, water vapor permeability, and water-resistant adhesion strength, using the following method. It was measured.

[Elemental analysis of gas barrier coating layer surface]
By X-ray photoelectron spectroscopy (XPS), the ratio of Si element and C element present on the surface of the gas barrier coating layer was measured by narrow scan analysis under the following measurement conditions. The measurement results are shown in Table 2.
[Measurement condition]
Equipment used: "ESCA-3400" (manufactured by Kratos) (Shimadzu Corporation)
[1] Spectrum collection conditions Incident X-ray: MgKα (monochromatic X-ray, hν = 1486.6 eV)
X-ray output: 150W (10kV ・ 15mA)
Measurement area: 6mmφ
Photoelectron capture angle: 90 degrees [2] Ion sputtering conditions Ion species: Ar +
Accelerating voltage: 0.2 (kV)
Emission current: 20 (mA)
etch range: 10 mmφ
Ion sputtering time (*): 30 seconds + 30 seconds + 60 seconds (total 120s), and collect spectra.

[Oxygen permeability]
A gas barrier vapor deposition film with an organic protective layer was used as a test piece.
Using the oxygen permeability measuring device (Modern Control (MOCON) [model name: OX-TRAN 2/21]), the above-mentioned test sample was prepared so that the sensor side would be the organic protective layer surface of the gas barrier vapor deposition film. And set to 23 ° C. It was measured in accordance with JIS K 7126 method under the measurement conditions in a 90% RH atmosphere.

[Oxygen permeability after bending test]
On the organic protective layer side of the gas barrier vapor deposition films produced in Examples and Comparative Examples, a two-component curing type polyurethane adhesive was applied, and a 70 μm-thick unstretched polypropylene film (CPP) was laminated and dried. A laminate having the following layer structure was obtained.
(PET film / inorganic vapor deposition layer / organic protective layer / adhesive layer / CPP)
This was made into a cylinder, and a Gelbo flex test according to ASTM F392 was performed. As a measuring device for the Gelbo flex test, a Gelbo flex tester manufactured by Tester Sangyo Co., Ltd. (model number: BE-1005) was used, The measurement conditions were as follows: stroke: 80 mm, bending operation: 400 ° / 80 mm, bending speed: 40 cpm, 10 times bending.
Then, a part of the film was cut out to obtain a test sample, and the oxygen transmission rate was measured.
Using the oxygen permeability measuring device (Modern Control (MOCON) [model name: OX-TRAN 2/21]), the above-mentioned test sample was prepared so that the sensor side would be the organic protective layer surface of the gas barrier vapor deposition film. And set to 23 ° C. It was measured in accordance with JIS K 7126 method under the measurement conditions in a 90% RH atmosphere.

[Water vapor permeability]
A gas barrier vapor deposition film with an organic protective layer was used as a test piece.
Using the water vapor permeability measuring device (measuring machine [model name, PERMATRAN 3/33] manufactured by MOCON) so that the sensor side is the organic protective layer surface of the gas barrier vapor deposition film, for the above test The sample was set and measured according to JIS K 7129 under measurement conditions of 40 ° C. and 100% RH atmosphere.

[Adhesive strength when flooded]
A two-component curable polyurethane adhesive was applied to the organic protective layer side of a 70 μm thick unstretched polypropylene film (CPP) and a gas barrier vapor deposition film and dried to obtain a laminate having the following layer structure.
(PET film / inorganic vapor deposition layer / organic protective layer / adhesive layer / CPP)
Then, the laminate was subjected to an aging treatment for 48 hours and then cut into a strip having a width of 15 mm to obtain a test piece.
Regarding the obtained test piece film, using a tensile tester ([Model name: Tensilon universal material testing machine] manufactured by Orientec Co., Ltd.), in accordance with JIS K6854-2, a standard such as 23 ° C. 50% RH The adhesion strength was measured under a normal temperature and normal humidity environment.
At the time of measurement, the CPP film side and the gas barrier vapor deposition film side are respectively held by the grips of the measuring instrument, and water is dropped on the peeling interface using a dropper, and the CPP film and the gas barrier vapor deposition film are still laminated. The parts were pulled in directions opposite to each other (180 ° peeling) at a speed of 50 mm / min in a direction orthogonal to the plane direction of the part, and the average value of the tensile stress in the stable region was measured.

  Peeling is in front of the stable region, the water-proof adhesion strength in the test piece is the weakest, and has propagated between the inorganic plasma-deposited layer / oxidized plasma-treated surface of the PET film. The water-proof adhesion strength between the surface of the vapor-deposited film having a gas barrier property treated with oxidative plasma and the inorganic vapor-deposited layer was used.

1 resin film,
2 Oxygen plasma treated surface 3 Inorganic vapor deposition layer 4 Oxygen plasma treated resin film 5 Organic protective layer (barrier coating layer and / or primer layer)
6 Sealant Layer 7 Vapor Deposition Film P Plasma 10 Roller-type Continuous Oxygen Plasma Processing Device 11 Roller-type Continuous Vapor Deposition Layer Forming Device 12 Decompression Chamber 12A Resin Film Transfer Chamber 12B Plasma Processing Chamber 12C Barrier Laminated Film Transfer Chamber 12D Deposition Layer Formation Room 13 Unwinding Roller 14a to d Guide Roller 15 Winding Roller 18 Plasma Forming Gas Supply Device 20 Electrode Roller 21 Magnets 22a to c Electrodes 23a to c Plasma Forming Gas Supply Nozzle 24 Deposition Roller 25 Deposition Layer Forming Means 26a to c Electrode and Plasma Forming gas supply nozzle 31 Power supply wiring 32 Power supplies 35a to 35d Partition wall

Claims (38)

An oxygen plasma treatment resin film having an oxygen plasma treatment surface on one side for forming an inorganic vapor deposition layer,
The oxygen plasma-treated surface has a resin film continuously in a space where the plasma electrode and the magnet face each other at a substantially constant distance under an atmospheric pressure of 1 to 9 Pa, and the oxygen plasma is held by the magnet at a substantially uniform density. An oxygen plasma-treated resin film, which is a surface formed by causing the oxygen plasma to collide with one surface of the resin film substantially perpendicularly by a bias voltage between the plasma electrodes. The plasma forming gas for forming the oxygen plasma is a mixed gas containing oxygen and argon in a volume ratio of oxygen / argon of not less than 1/1 and not more than 3/1. To do
The oxygen plasma-treated resin film according to claim 1.   The oxygen plasma-treated resin film according to claim 1 or 2, wherein the resin film is a polyethylene terephthalate film. Wherein the resin film is a biomass-derived polyester film,
The oxygen plasma-treated resin film according to claim 1. Wherein the resin film is a recycled polyethylene terephthalate film,
The oxygen plasma-treated resin film according to claim 1. Inorganic vapor deposition layer is laminated | stacked adjacently on the said oxygen plasma processing surface of the oxygen plasma processing resin film in any one of Claims 1-5,
The adhesive strength of the interface between the inorganic vapor-deposited layer and the surface treated with oxygen plasma when measured by a 180-degree peeling method when immersed in water is 1.5 N / 15 mm or more and 4 N / 15 mm or less,
Gas barrier vapor deposition film. The formation of the oxygen plasma treated surface, and the formation of the inorganic vapor deposition layer, in-line, characterized in that it is performed continuously,
The vapor-deposited gas barrier film according to claim 6. The inorganic vapor deposition layer is an aluminum oxide vapor deposition layer,
The vapor-deposited gas barrier film according to claim 6 or 7. A molar ratio of oxygen atom / aluminum atom of the vapor-deposited aluminum oxide layer by X-ray photoelectron spectroscopy (XPS) is 1.2 or more and 5 or less,
The gas barrier vapor deposition film according to claim 8. On the inorganic vapor deposition layer, a gas barrier vapor deposition film further laminated organic protective layer adjacently,
The organic protective layer comprises a gas barrier coating layer and / or a primer layer,
The gas barrier vapor deposition film according to any one of claims 6 to 9.   11. The gas barrier according to claim 10, wherein the gas barrier coating layer is formed by applying a gas barrier resin composition containing at least a metal alkoxide and a hydroxyl group-containing water-soluble resin. Vapor deposition film. The surface of the gas barrier coating layer is characterized in that the ratio of silicon atoms to carbon atoms (Si / C) measured by X-ray photoelectron spectroscopy (XPS) is 1.20 or more and 1.60 or less. ,
The gas barrier vapor deposition film according to claim 11. The primer layer is formed by applying a primer liquid containing at least one or two or more selected from the group consisting of polyester, polyurethane, and polyester urethane.
The vapor-deposited gas barrier film according to claim 10. The primer liquid further contains inorganic fine particles and / or a metal alkoxide.
The gas barrier vapor deposition film according to claim 13. The metal alkoxide is a tetrafunctional silicon-based compound,
The gas barrier vapor deposition film according to claim 11 or 14.   A gas barrier laminate comprising a layer comprising the gas barrier vapor deposition film according to any one of claims 6 to 15 and a sealant layer. The gas barrier laminate according to claim 16, which has an oxygen permeability of 0.80 cc / m ² · atm · day or less after a bending test according to ASTM F392 under the following test conditions.
<Test conditions>
Stroke: 80mm
Bending operation: 400 ° / 80mm
Bending speed: 40 cpm
Number of bends: 10 times   A gas barrier packaging material produced from the gas barrier laminate according to claim 16.   A gas barrier packaging material, which is produced from the gas barrier packaging material according to claim 18.   A gas barrier packaging bag for wettable contents, characterized in that it is made from the gas barrier packaging material according to claim 18. An oxygen plasma treatment surface for forming an inorganic vapor deposition layer, a method for producing an oxygen plasma treatment resin film having one surface,
Under an atmospheric pressure of 1 to 9 Pa, the plasma electrode and the magnet are opposed to each other at a substantially constant distance, and the resin film is continuously passed through a space where the oxygen plasma is held by the magnet at a substantially uniform density.
A method for producing an oxygen plasma-treated resin film, characterized in that the oxygen plasma-treated surface is formed on one surface of the resin film by causing the oxygen plasma to impinge substantially vertically by a bias voltage between plasma electrodes. The plasma forming gas for forming the oxygen plasma is a mixed gas containing oxygen and argon in a volume ratio of oxygen / argon of not less than 1/1 and not more than 3/1. To do
The method for producing an oxygen plasma-treated resin film according to claim 21.   The method for producing an oxygen plasma-treated resin film according to claim 21 or 22, wherein the resin film is a polyethylene terephthalate film. Wherein the resin film is a biomass-derived polyester film,
The method for producing an oxygen plasma-treated resin film according to claim 21 or 22. Wherein the resin film is a recycled polyethylene terephthalate film,
The method for producing an oxygen plasma-treated resin film according to claim 21 or 22. An inorganic vapor deposition layer is laminated adjacently on the oxygen plasma-treated surface of the oxygen plasma-treated resin film produced by the method for producing an oxygen plasma-treated resin film according to any one of claims 21 to 25, A method for producing a gas barrier vapor deposition film,
The adhesive strength of the interface between the inorganic vapor-deposited layer and the oxygen plasma treated surface when immersed in water, measured by a 180 degree peeling method, is 1.5 N / 15 mm or more and 4 N / 15 mm or less, Gas barrier vapor deposition film manufacturing method. The formation of the oxygen plasma treated surface, and the formation of the inorganic vapor deposition layer, in-line, characterized by performing continuously.
The method for producing a gas barrier vapor deposition film according to claim 26. The inorganic vapor deposition layer is an aluminum oxide vapor deposition layer,
The method for producing a vapor-deposited gas barrier film according to claim 26 or 27. A molar ratio of oxygen atom / aluminum atom of the vapor-deposited aluminum oxide layer by X-ray photoelectron spectroscopy (XPS) is 1.2 or more and 5 or less,
The method for producing a gas barrier vapor deposition film according to claim 28. A method for producing a vapor barrier vapor deposition film, further comprising an organic protective layer adjacently laminated on the inorganic vapor deposition layer,
The organic protective layer comprises a gas barrier coating layer and / or a primer layer,
The method for producing a vapor-deposited gas barrier film according to any one of claims 26 to 29. The gas barrier coating layer is formed by applying at least a gas barrier resin composition containing a metal alkoxide and a hydroxyl group-containing water-soluble resin,
The method for producing a gas barrier vapor deposition film according to claim 30. The primer layer is formed by applying a primer liquid containing at least one kind or two or more kinds selected from the group consisting of polyester, polyurethane and polyester urethane.
The method for producing a vapor-deposited gas barrier film according to claim 30 or 31. The primer liquid further contains inorganic fine particles and / or a metal alkoxide.
The method for producing a gas barrier vapor deposition film according to claim 32. Wherein the metal alkoxide is a silane coupling agent,
The method for producing a gas barrier vapor deposition film according to any one of claims 31 to 33.   The manufacture of a gas barrier laminate, comprising laminating a sealant layer on a layer composed of the gas barrier vapor deposition film produced by the method for producing a gas barrier vapor deposition film according to any one of claims 26 to 34. Method.   A method for producing a gas barrier packaging material, comprising producing a gas barrier packaging material from the gas barrier laminate produced by the method for producing a gas barrier laminate according to claim 35.   A method for producing a gas barrier packaging body, comprising producing a gas barrier packaging body from the gas barrier packaging material produced by the method for producing a gas barrier packaging material according to claim 36.   A gas barrier property for a wettable content, characterized by producing a gas barrier property package for a wettable content from the gas barrier property packaging material produced by the method for producing a gas barrier property packaging material according to claim 36. A method for manufacturing a package.