JP5351204B2 - Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a gas barrier film capable of improving interlayer adhesion while preventing a functional group located on a surface of a base material from amidating and nitriding and without depending on oxygen binding, and the gas barrier film obtained by the manufacturing method. <P>SOLUTION: The manufacturing method includes: a plasma treatment step of plasma-treating in advance a surface of a plastic film to be a base material with introduction of an inert gas under environments of an atmospheric pressure of 1&times;10<SP POS="POST">-1</SP>to 1&times;10<SP POS="POST">-3</SP>Torr; and a step of laminating, after the plasma-treatment step, a first polymer resin layer containing scaly silica including a silanol group on its surface added into a base resin, a gas barrier layer, and a second polymer resin layer containing scaly silica including a silanol group added into a base resin in the order named. The gas barrier film obtained by the method is also disclosed. <P>COPYRIGHT: (C)2013,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a gas barrier film having a hot water resistance and a gas barrier film having a hot water resistance obtained by the production method, and specifically, it is possible to suppress and prevent the occurrence of delamination, The present invention relates to a method for producing a gas barrier film having a high barrier property with a higher barrier property than conventional and having a hot water resistance, and a gas barrier film having a hot water resistance obtained by the production method.

  Conventionally, a plastic film imparted with a gas barrier property (hereinafter also simply referred to as a “gas barrier film”) for protecting a substance that dislikes oxygen and moisture has been widely used in various scenes. For example, it is used as a packaging material for food or as a packaging material for electronic component materials. In such use, the packaging material is strongly required to have the property of suppressing or preventing the alteration of the contents. In particular, there has recently been a need for a packaging material that can easily protect articles that are so delicate that they are easily altered by oxygen, water vapor, and the like and that require careful handling from oxygen and water vapor.

  Conventionally, plastic films made of polyvinylidene chloride, polyacrylonitrile, or the like have been used as films having gas barrier properties, but these films are no longer used because they discharge environmental harmful substances upon disposal. From the viewpoint of environmental problems, it seems that it is preferable to use a plastic film made of polyvinyl alcohol. However, this film has a high gas barrier humidity dependency, that is, a gas barrier property, particularly water vapor, under high humidity. Since the barrier property is remarkably and easily deteriorated, it cannot be used in a scene that requires a high gas barrier property.

  Therefore, a film in which an inorganic substance such as silicon oxide or aluminum oxide is provided on the surface of a plastic film by physical vapor deposition or chemical vapor deposition is used as a packaging material as a gas barrier film. However, these gas barrier films have durability against bending. In other words, cracks are easily generated in the vapor deposition layer during bending, so that there is a problem that the barrier property is easily lowered. In addition, since the interlayer adhesion between the plastic film and the inorganic material deposited on the surface is small, if the film is repeatedly bent, the inorganic material cannot follow the flexibility of the film. Since there was a loss of sex, there was a problem in practical use.

  Therefore, various proposals have been made to deal with such problems. For example, in Patent Document 1, a surface of a polyester film used as a substrate is subjected to plasma treatment, and then an invention relating to a laminate having a polymer layer containing Si in a structural unit and formed by a plasma polymerization method on the surface. Is disclosed.

Patent registration No. 3427398

  If it is a laminated body described in Patent Document 1, it is possible to obtain a ceramic film having excellent adhesion and flexibility between a polyester film as a base film and a polymer layer laminated on the surface. Is possible.

  However, if the invention described in Patent Document 1 is examined in detail, this invention is mainly intended to control the degree of oxidation in plasma polymerization. Although the adhesion between the polyester film and the polymer layer is improved by the formation of oxidative bonds, the oxidative bonds are formed after lamination because the oxidative bonds are formed on the laminated surface, that is, the surface subjected to plasma treatment. However, since the interlaminar adhesion force is lost due to being easily cut, a laminated body in which it is difficult to maintain high barrier properties is a problem.

  The present invention has been made in view of such problems, and the object thereof is to prevent adhesion of functional groups located on the surface of the substrate to amidation or nitridation, and without relying on oxygen bonding. It is providing the gas barrier film by the manufacturing method of the gas barrier film which made it possible to improve, and the manufacturing method which concerns.

In order to solve the above-mentioned problem, the invention according to claim 1 of the present invention provides at least an air pressure of 1 × 10 ⁻¹ to 1 × 10 ⁻ under the introduction of an inert gas to the surface of a plastic film serving as a base material. ^A plasma treatment step in which plasma treatment is performed in advance in an environment of ³ Torr; and a first polymer resin obtained by adding scaly silica having a silanol group to the base material on the surface of the substrate subjected to the plasma treatment. A gas barrier layer laminating step in which a gas barrier layer having a gas barrier property is laminated on the surface after the first polymer resin laminating step is performed, and the first polymer resin laminating step is performed; After the gas barrier layer laminating step, a second polymer resin in which a scaly silica having a silanol group is added to the main agent is laminated on the surface of the gas barrier layer. A molecular resin laminating step, wherein the plasma treatment is a glow discharge plasma treatment, and the substrate surface on which the glow discharge plasma treatment step has been applied has the same structure as the fourth periodic group in the periodic table. It is characterized by adhering any metal belonging to Group 12 or an alloy of metals within the range.

Invention of Claim 2 of this invention is a manufacturing method of the gas barrier film which has the hot-water resistance described in Claim 1, Comprising: The 1st or 2nd polymer which added the scaly silica which has the said silanol group In the cross-sectional view of the resin layer, the lamellar silica having the silanol group is dispersed in layers so as to be staggered in the horizontal direction and in the thickness direction of the cross-sectional view, thereby exhibiting a maze effect. It is characterized by this.

Invention of Claim 3 of this invention is a manufacturing method of the gas barrier film which has the hot water resistance of Claim 1 or Claim 2, Comprising: The scaly silica which has the said silanol group is said 1st or It is characterized by being in the range of 0.01 wt% or more and 1 wt% or less with respect to the concentration of the main component solid content of the second polymer resin layer.

  Invention of Claim 4 of this invention is a manufacturing method of the gas barrier film of any one of Claim 1 thru | or 3, Comprising: Said 1st polymer resin or said 2nd polymer resin Either one or both of them is based on a silane coupling agent or a polymer resin mainly composed of a silane coupling agent.

  Invention of Claim 5 of this invention is a manufacturing method of the gas barrier film which has the hot-water resistance of any one of Claim 1 thru | or 4, Comprising: The substance which comprises the said gas barrier layer is Any one of the group consisting of silicon, titanium, tin, zinc, aluminum, indium, magnesium, or any of oxides, nitrides, or compounds thereof, or plural or oxides thereof in the group, It is a nitride or a compound, and the gas barrier layer is laminated by a vacuum deposition method.

  Invention of Claim 6 of this invention is a manufacturing method of the gas barrier film which has the hot water resistance of any one of Claim 1 thru | or 5, Comprising: The oxidation by which the said gas barrier layer is shown by SiOx It is silicon, and x is 1.0 ≦ x ≦ 2.0.

  The invention relating to the gas barrier film according to claim 7 of the present invention is characterized by being manufactured by the method for manufacturing a gas barrier film according to any one of claims 1 to 6.

  The invention relating to the solar battery backsheet according to claim 8 of the present invention is characterized by using the gas barrier film according to claim 7.

  As described above, conventionally, even if it is easy to improve the oxygen gas barrier property, the water vapor barrier property is improved at the same time, or even if it is easy to improve the water vapor gas barrier property, the oxygen gas barrier property is simultaneously improved. It was difficult to improve, if it is a method for producing a gas barrier film having hot water resistance according to the present invention, it becomes possible to improve the water vapor gas barrier property simultaneously with the oxygen gas barrier property, For example, a material having hot water resistance suitable as a packaging material for electronic members required to have a high level of oxygen gas barrier property and water vapor gas barrier property can be obtained. In the manufacturing method according to the present invention, the surface of the plastic film is simply and purely physically roughened by applying a so-called GD plasma treatment to the surface of the plastic film as a base material while introducing an inert gas. This is because a so-called anchor coat layer is laminated on the surface, or a gas barrier substance is laminated directly, thereby strengthening the connection with the base film, that is, in this portion, hydrolysis is caused. As a result, it is possible to suppress a decrease in adhesion due to the occurrence, and delamination associated therewith, and as a result, a gas barrier film having a hot water resistance capable of maintaining gas barrier properties at a high level can be obtained. Further, by applying a GD plasma treatment with an inert gas introduced to the surface of the base material, a state in which the substances laminated on the surface are densely aggregated is induced, and the layers are so laminated. The property can be made to be a high level having more resistance to hot water.

  And in this invention, since the scaly silica which has a silanol group is added with respect to the main ingredient to the 1st polymer resin layer and / or the 2nd polymer resin layer, the scaly silica is in these polymer resin layers. As a result, the scaly silica becomes like a barricade, and molecules such as oxygen and water vapor penetrate directly into the inside, in other words, molecules such as oxygen and water vapor are outside these polymer resin layers. As the scale-like silica spreads in the coating layer, it is necessary to bypass the scale-like silica when passing through these polymer resin layers. Therefore, it takes time for the gas to enter, and as a result, it becomes possible to obtain a gas barrier film that makes it possible to obtain a higher gas barrier property.

  Embodiments of the present invention will be described below. The embodiment shown here is merely an example, and is not necessarily limited to this embodiment.

(Embodiment 1)
A method for producing a gas barrier film having hot water resistance according to the present invention will be described as a first embodiment.

In the method for producing a gas barrier film having hot water resistance according to the present embodiment, at least air pressure 1 × 10 ⁻¹ to 1 × 10 ^{−3 with} an inert gas introduced into the surface of a plastic film serving as a substrate. A plasma treatment step in which plasma treatment is performed in an environment called Torr, and a first polymer resin in which scaly silica having a silanol group is added to the base material are laminated on the surface of the base material subjected to the plasma treatment. A gas barrier layer laminating step in which a gas barrier layer having a gas barrier property is laminated on the surface thereof after performing the first polymer resin laminating step, After the gas barrier layer laminating step, a second polymer resin obtained by adding scaly silica having a silanol group to the main agent is laminated on the surface of the gas barrier layer. A second polymer resin laminating step, wherein the plasma treatment is a glow discharge plasma treatment, and the substrate surface on which the glow discharge plasma treatment step has been applied has a fourth period fourth in the periodic table. Any metal belonging to Group 12 to Group 12, or an alloy of metals within the range is attached.

Hereinafter, description will be made sequentially.
First, plasma treatment is performed on the surface of a plastic film as a base material while introducing an inert gas. In this embodiment, the atmospheric pressure is 1 × 10 ⁻¹ to 1 × 10 ⁻³ Torr in the present embodiment. Suppose that That is, the plasma treatment in the present embodiment is a GD plasma treatment with an inert gas introduced. Further, the plasma treatment in the present embodiment is a glow discharge plasma treatment, and any one of the fourth to fourth groups in the periodic table on the surface of the base material on which the glow discharge plasma treatment step has been further performed. Or an alloy of metals within the above range adheres to each other. (Hereinafter, the plasma treatment in the present invention is also referred to as “GD plasma treatment”.)

More specifically, the inert gas is preferably argon gas or argon gas mixed with oxygen, and argon gas is used here. The atmospheric pressure is preferably 1 × 10 ⁻¹ to 1 × 10 ⁻³ Torr as described above. This is because plasma discharge occurs when the GD plasma treatment is performed in the presence of argon gas within this range, and the desired effect described later can be reliably obtained. In order to obtain the effect of the GD plasma treatment more reliably, the atmospheric pressure range may be 2 × 10 ⁻² Torr or more and 7 × 10 ⁻² Torr or less. In this embodiment, it is assumed that 5 × 10 ⁻² Torr.

  The state of the GD plasma-treated surface of the base film after the GD plasma treatment according to the present embodiment is determined based on the result of photoelectron spectroscopy (XPS) analysis in which the carbonyl group of the surface functional group is nitrided or It is necessary not to be in an oxidized state. In addition, the surface roughness Ra of any 10 points (excluding protrusions such as fillers) extracted within 1 μm square by atomic force microscope observation is 0.6 nm ± 0.2 nm, and the 10-point average height The thickness Rz satisfies the condition that Rz ≧ 6 nm and the result of contact angle measurement with pure water is 50 ° ± 5 °. This is the same condition in each GD plasma processing in all embodiments described later, that is, in the GD plasma processing in the present invention. The GD plasma processing will be described in detail later.

  The plastic film to be a base material to be subjected to the GD plasma treatment is not particularly limited in the present embodiment, and may be any material that is conventionally used as a base film for a gas barrier film. Polyethylene terephthalate (PET) film, nylon film, unstretched polypropylene (CPP) film, linear low density polyethylene (LLPDE) film, polyethylene naphthalate (PEN) film, cyclic polyolefin (COP) film, polycarbonate (PC) film , Polyethersulfone (PES) film, etc.

  The thickness of the film to be used is not particularly limited, but in the present embodiment, a thickness that does not break even when GD plasma treatment is applied is necessary, and finally a gas barrier film having high barrier properties is obtained. Of course, if a certain degree of flexibility is required, it is necessary to make the thickness not more than a level that can ensure such flexibility, as a matter of course. If this point is considered more specifically, it can be said that the thickness of the film is preferably 5 μm or more and 200 μm or less. It is because it is highly likely to break without being able to withstand the above treatment, and when it is 200 μm or more, the flexibility of the actually obtained film becomes poor, and as a result, it becomes unsuitable as a packaging material. Because. In this embodiment, it is assumed that the PET film has a thickness of 12 μm, but it is not necessarily limited thereto.

  The plastic film to be a base material to be subjected to the GD plasma treatment is not particularly limited in the present embodiment, and may be any material that is conventionally used as a base film for a gas barrier film. Polyethylene terephthalate (PET) film, nylon film, unstretched polypropylene (CPP) film, linear low density polyethylene (LLPDE) film, polyethylene naphthalate (PEN) film, cyclic polyolefin (COP) film, polycarbonate (PC) film , Polyethersulfone (PES) film, etc.

  The thickness of the film to be used is not particularly limited, but in the present embodiment, a thickness that does not break even when GD plasma treatment is applied is necessary, and finally a gas barrier film having high barrier properties is obtained. Of course, if a certain degree of flexibility is required, it is necessary to make the thickness not more than a level that can ensure such flexibility, as a matter of course. If this point is considered more specifically, it can be said that the thickness of the film is preferably 5 μm or more and 200 μm or less. It is because it is highly likely to break without being able to withstand the above treatment, and when it is 200 μm or more, the flexibility of the actually obtained film becomes poor, and as a result, it becomes unsuitable as a packaging material. Because. In this embodiment, it is assumed that the PET film has a thickness of 12 μm, but it is not necessarily limited thereto.

  Further, the material of the plastic film used in the present embodiment is not particularly limited, but this film is not subjected to any pretreatment such as corona treatment or easy adhesion coating on its surface, and is a so-called plain. A film of the type is desirable. That is, even if GD plasma processing is performed on a surface that has been subjected to processing such as corona processing or easy adhesion coating, it is highly likely that a harmful surface condition will appear in this embodiment. . This point will be described in detail again.

  When the plasma processing step for performing the GD plasma treatment using the argon gas on the PET film surface is completed in this manner, the first polymer resin as the first layer is laminated on the surface subjected to the GD plasma treatment. The first polymer resin laminating step is executed.

The reason for providing this first layer is as follows.
In a conventional gas barrier film, a layer made of a metal or metal oxide is directly laminated on the surface of the base film. When the obtained layer is actually used, it is necessary to perform further processing after the lamination. Since the interlayer adhesion between the material film and the metal layer is not sufficient, it peels off, and as a result, a suitable gas barrier film cannot be produced, and the gas barrier property is lowered during use.

  However, by providing this first layer, the unevenness on the laminated surface is first relaxed, that is, the laminated surface becomes substantially smooth, so that the adhesion between the laminates is improved, that is, the interlayer adhesion is secured. In addition, when a gas barrier layer described later is laminated, it is possible to make the gas barrier layer dense. Furthermore, the first layer functions like a so-called adhesive, and it is possible to prevent the base film and the gas barrier layer from being easily peeled off. Therefore, in order to achieve such an object, the first layer is provided in this embodiment mode. Furthermore, if the first layer itself has a gas barrier property, it is possible to further contribute to the improvement of the gas barrier property as a whole.

  The first polymer resin as a material suitable for such purposes will be described.

  Although it does not specifically limit as this 1st polymer resin, A silane coupling agent is the most suitable. More preferable are epoxy silane coupling agents, amino silane coupling agents, methacrylic silane coupling agents, and ureido silane coupling agents. In this embodiment, epoxy silanes are used. A coupling agent is used as the first polymer resin.

The reason for providing this first layer is as follows.
In a conventional gas barrier film, a layer made of a metal or metal oxide is directly laminated on the surface of the base film. When the obtained layer is actually used, it is necessary to perform further processing after the lamination. Since the interlayer adhesion between the material film and the metal layer is not sufficient, it peels off, and as a result, a suitable gas barrier film cannot be produced, and the gas barrier property is lowered during use.

  However, by providing this first layer, the unevenness on the laminated surface is first relaxed, that is, the laminated surface becomes substantially smooth, so that the adhesion between the laminates is improved, that is, the interlayer adhesion is secured. In addition, when a gas barrier layer described later is laminated, it is possible to make the gas barrier layer dense. Furthermore, the first layer functions like a so-called adhesive, and it is possible to prevent the base film and the gas barrier layer from being easily peeled off. Therefore, in order to achieve such an object, the first layer is provided in this embodiment mode. Furthermore, if the first layer itself has a gas barrier property, it is possible to further contribute to the improvement of the gas barrier property as a whole.

  And as a material suitable for such purpose, it can be said that a silane coupling agent or a polymer resin mainly containing a silane coupling agent is suitable. In the present embodiment, an epoxy-based resin is used as the first polymer resin. A silane coupling agent is used, and in the following embodiment, description will be continued assuming that this is used.

  The technique for laminating the first polymer resin may be a conventionally known technique, but in this embodiment, the coating method is used, and the thickness of the lamination is 0.2 μm. Incidentally, the thickness of the layer is preferably 0.03 μm or more and 2 μm or less, but if it is 0.03 μm or less, the above-mentioned effect is difficult to be obtained, and if it is 2 μm or more, the gas barrier obtained by the present embodiment. This is because the thickness of the entire film increases and the film becomes inflexible. Further, holograms are generated, cracks are generated, and the drying process takes time during actual production. This is because it is not suitable as a packaging material for reasons such as difficulty in cost control.

  In the present embodiment, the first polymer resin layer containing the scaly silica is formed by adding the scaly silica to the first polymer resin. This scaly silica is SiO. The average size is 1 μm to 100 μm. Further, the scaly silica preferably has a silanol group. This is because by using scaly silica having a silanol group, the crosslinking density can be improved by hydrogen bonding, and as a result, the denseness of the coating film and the adhesion to the deposited film can be improved.

 And the shape is scaly, that is, it has a very thin scaly shape with almost no thickness. And most of all, the silica itself has gas barrier properties, and the silica is in the form of scaly and is dispersed and present inside the first polymer resin layer originally formed of a resin having gas barrier properties. In addition, the gas barrier property of the gas barrier film according to the present embodiment is supplemented by the scaly silica, so that it is possible to obtain a higher gas barrier property. In addition, when the first polymer resin layer is based on a modified polyvinyl alcohol resin, a layer having a high gas barrier property can be easily formed by simply adding a predetermined amount of scaly silica thereto. become.

  Such scaly silica may be obtained by various known methods, and detailed description thereof is omitted here. For example, silica is deposited on the surface of a polyethylene terephthalate film by a generally known method. The silica vapor deposition film obtained can be obtained by performing ultrasonic crushing using an ultrasonic water tank.

  And in this Embodiment, it obtains by adding the suitable amount of 0.01 to 1 weight% of the scaly silica which has a silanol group with respect to the main ingredient in the 1st polymer resin layer mentioned above. The coating composition is laminated on the surface of the base film. However, for example, when the content is 0.01% by weight or less, the effect of adding scaly silica does not occur because the silica arrangement becomes porous. In addition, if added in an amount of 1% by weight or more, the scale-like silica is excessively increased, the flexibility and transparency of the first polymer resin layer is lost, and the adhesive strength is reduced. Is preferred.

  When the first polymer resin layer to which the flaky silica has been added as described above is formed, the flaky silica having the silanol group in the cross-sectional view of the first polymer resin layer is in a substantially horizontal direction and in the cross-sectional view vertically. If it has a structure in which it is dispersed in the main agent so as to be stacked in layers so as to be staggered in the direction, the gas barrier property of the first polymer resin layer and thus the overall gas barrier property can be greatly improved. Can be expensive.

  In other words, if the scaly silica is developed as if it is regularly arranged in the first polymer resin layer, molecules such as oxygen and water vapor entering from the outside of the first polymer resin layer are temporarily scaly. If the silica is aligned, it will penetrate the first polymer resin layer very easily and in a short period of time if it goes straight on a straight line as it occurs in the gap between the scaly silicas. However, as described above, the scaly silica is randomly expanded in the first polymer resin layer, but the layers of the scaly silica become like a barricade, and molecules such as oxygen and water vapor go straight ahead. Intruding into the inside, in other words, when molecules such as oxygen and water vapor try to penetrate from the outside of the first polymer resin layer toward the base film side, when passing through the first polymer resin layer Is scaly silica It is necessary to make a detour, that is, when an invading molecule hits the scaly silica, it bypasses it along the scaly silica, and when it reaches the end of the scaly silica, it will invade again from there. However, since scaly silica exists again at the tip, there will be a large number of processes for detouring this, so oxygen takes time to invade water vapor, resulting in gas barrier properties. It becomes possible to obtain.

  Therefore, the gas barrier layer in the present embodiment can further improve the gas barrier property by including the first polymer resin layer containing scaly silica in this way.

  In the following description, it is assumed that the first polymer resin layer contains scaly silica.

  Thus, if it is a gas barrier film by this Embodiment, by apply | coating a coating agent, without increasing the film thickness of an inorganic oxide vapor deposition film, a different kind of gas barrier layer from an inorganic oxide vapor deposition film is laminated | stacked. Thus, the gas barrier property can be improved, and since the gas barrier layer in the present embodiment is derived from a silane compound, the obtained gas barrier film is excellent in crack resistance and has flexibility of the coating film. Can be made

  When the first polymer resin of the first polymer resin is laminated on the surface of the PET film in this way and cured, a gas barrier layer laminating step is next performed in which a gas barrier layer having gas barrier properties is laminated on the surface.

  As a gas barrier substance constituting the gas barrier layer in the present embodiment, for example, one of a group consisting of silicon, titanium, tin, zinc, aluminum, indium, and magnesium, or an oxide, nitride, or compound thereof Or a plurality of oxides, nitrides, or compounds thereof in the group. More specifically, for example, silicon may be used, silicon oxide or silicon nitride may be used, and a silicon compound may be used. Further, it may be an oxide or nitride of an alloy of tin and indium. That is, a gas barrier layer made of a material made of these group of metals may be used.

  Alternatively, the gas barrier layer may be made of silicon oxide represented by SiOx, and x may satisfy 1.0 ≦ x ≦ 2.0.

  As will be described later, the SiOx layer is basically transparent, and the high barrier obtained by the present embodiment can be obtained by using all the materials used for the high barrier film according to the present embodiment that are basically transparent. The entire protective film becomes transparent, and if such a high-barrier film is used as a packaging material, the contents can be easily seen, so the contents are not only protected from gas but also the state of the contents is also visible. It can be said that the use of SiOx is advantageous in this respect.

  When laminating SiOx, the laminating method may be a conventionally known one. In this embodiment mode, the vacuum deposition method is used. However, the method is not necessarily limited to this, and a so-called physical vapor deposition method, chemical vapor deposition method, or other known methods may be used.

  The thickness of the gas barrier layer is preferably 70 to 1000 mm. This is because if the gas barrier layer is 70 mm or less, the gas barrier layer itself has insufficient gas barrier properties, and if it is 1000 mm or more, the flexibility of the entire gas barrier film is poor. . In the present embodiment, this thickness is 120 mm.

  As described above, the method for manufacturing a gas barrier film having hot water resistance according to the present embodiment first performs a plasma processing step of performing GD plasma processing, and then executes a first polymer resin lamination step on the surface thereof. Next, a gas barrier layer stacking step is performed. Here, the GD plasma processing in this embodiment will be further described.

As described above, in the method for manufacturing a gas barrier film having hot water resistance according to the present embodiment, a GD plasma treatment is performed on a PET film having a film thickness of 12 μm while introducing argon gas. The atmospheric pressure at this time is 5 × 10 ⁻² Torr.

  By performing GD plasma treatment on the surface of the PET film, which is the base film, for example, the surface of the PET film that was “smooth” at first will be in a state of “slowly” after GD plasma treatment. . In the present embodiment, even if this GD plasma treatment is performed, the carbonyl group of the surface functional group present on the surface of the PET film is not oxidized or nitrided.

This is further described as follows.
Even if any lamination is performed on the surface of the PET film whose surface is untreated (plain), the laminate is not fixed on the surface of the PET film having a “smooth” surface, and a phenomenon called “repel” occurs. Lamination with a desired level of adhesion cannot be performed.

  Therefore, if the conventional plasma treatment is performed on the surface of the PET film having a smooth surface, the surface will appear to have been rolled up to some extent, and the laminate will be bonded to the raised portion to improve adhesion. Conceivable. However, at this time, if the portion that has been raised is closely observed, it can be seen that the carbonyl group, which is a surface functional group, is present in an oxidized or nitrided state by performing normal plasma treatment. When any laminate is laminated on the oxidized (nitrided) carbonyl group, the oxidized (nitrided) carbonyl group and the laminate first form an oxygen (nitrogen) bond. It looks like it ’s improved. However, when the laminated body obtained in this way passes a certain period of time, the oxygen (nitrogen) bond portion is easily cut, for example, by hydrolysis. This is caused by a reaction between moisture in the atmosphere and an oxygen (nitrogen) bonding portion. The fact that this oxygen (nitrogen) bond is broken means that delamination easily occurs, that is, the phenomenon that the function imparted by the laminate is weakened or disappears due to delamination. Will occur.

  In other words, the laminated body obtained by performing the lamination after performing the conventional plasma treatment is exposed to the moisture in the atmosphere immediately after it is completed as a laminated body, and the oxygen (nitrogen) bond in the laminated part is caused by the moisture. Hydrolysis occurs in the portion, and therefore, the bonded portion is cut, resulting in delamination, resulting in the loss of the gas barrier property intended in the present invention.

  However, in the present invention, the occurrence of the above phenomenon is avoided because the GD plasma treatment is first performed and the argon gas is used as the introduced gas.

  First, by using argon gas as the introduced gas, the carbonyl group, which is the surface functional group of the PET film, is not oxidized or nitrided during the plasma treatment. In other words, the PET film surface is in a state of “slow up” in a state where the PET film surface is not oxidized or nitrided. It is not bonded by (nitrogen) bonding, but directly bonded to the surface of the PET film that has been physically raised. Therefore, when this is exposed to moisture in the atmosphere, hydrolysis does not occur at the bonding portion, and as a result, delamination does not occur. Therefore, the interlayer adhesion after lamination can be maintained as it is, that is, the function can be maintained.

  In addition, by using GD plasma treatment, the moisture and nitrogen contained in the atmosphere are prevented from inadvertently reacting with the carbonyl group, which is a surface functional group, during plasma treatment. It will be possible.

  Although the same effect can be expected by introducing an inert gas other than argon gas, detailed description thereof is omitted here.

  In addition, it may be difficult to use only argon as the introduced gas in the vacuum chamber when GD plasma processing is actually performed, and oxygen may inevitably be mixed. However, the mixing ratio of oxygen may be 10% or less with respect to the total amount of argon gas. For example, when GD plasma treatment is performed in a vacuum chamber, it is assumed that water vapor in the vacuum chamber is activated and binds to a functional group on the surface of the PET film. It is conceivable that there will be cases where they are combined.

  Accordingly, as a result of intensive studies and examinations by the inventors, it has been found that if the proportion of oxygen is 10% or less of the total amount of the inert gas, the effects of the present embodiment can be sufficiently achieved. In the embodiment, it is assumed that a part of oxygen may be mixed in the inert gas at that level.

  Further, by performing GD plasma treatment, the laminate has a denser structure, and as a result, the gas barrier property can be further improved. This point will be briefly described.

  Normally, when a gas barrier material such as SiOx is to be deposited on a PET film having an untreated surface, the portions where SiOx is deposited first are scattered on the surface of the PET film. That is, the SiOx molecules are not suddenly densely deposited on the PET film surface, but are first deposited in a state where SiOx is scattered in the form of dots on the PET film surface. When SiOx is further evaporated in this state, the SiOx molecules do not enter the gap between the SiOx already deposited on the PET film surface, but try to further deposit on the SiOx molecules on the PET film surface. And in fact it is vapor deposited like that. That is, the SiOx molecules present as dots on the surface of the PET film are used as nuclei, and SiOx is deposited one after another in such a state that the nuclei grow.

  Eventually, SiOx molecules grown from adjacent nuclei are bonded to each other, and a film of SiOx molecules on one surface, that is, a gas barrier layer of SiOx is finally formed.

  When the gas barrier layer that has reached this state is observed in a substantially side view, the distance from the PET film surface to the gas barrier layer by SiOx that has reached a dense state is approximately 3 nm to 5 nm, and further, the gas barrier layer is, for example, 10 nm on the surface. It is in a laminated state.

  That is, in the gap of 3 nm to 5 nm existing between the dense gas barrier layer and the PET film surface, there is a non-dense and sparse SiOx layer. In this case, since there are a large number of voids in which no gas barrier substance is present, the presence of this portion is a major factor for reducing the gas barrier property.

  Therefore, in order to eliminate this unnecessary void as much as possible, when plasma treatment using oxygen or nitrogen as an introduction gas is performed, countless fine irregularities appearing on the surface of the PET film are generated. On the other hand, when SiOx is vapor-deposited, first, SiOx molecules enter the recesses, and then SiOx molecules further deposit with the SiOx molecules entering the recesses as nuclei.

  At this time, when the SiOx molecules enter the recesses, the recesses are filled with the SiOx molecules, but as described above, this is the same substance as the evaporated material, rather than directly depositing SiOx on the PET film surface. This is because SiOx is further deposited on SiOx, and in this case, the state in which SiOx is later deposited around the first SiOx existing in the recess, that is, as if the recess is filled with SiOx is observed. And it is actually buried like that.

  When the deposition is further continued, the SiOx growing as described above are combined with each other, and thereafter the deposition of SiOx in a dense state is continued.

  In this case, the above-described gap portion of about 3 nm to 5 nm is in a state as if it was replaced by the uneven protrusions generated by the plasma treatment. In other words, it can be said that useless voids that impede gas barrier properties are unlikely to occur in this case, which in turn contributes to improvement of gas barrier properties.

  Further, since the layer having a smooth surface can be laminated in this way, the surface of the film obtained by the manufacturing method in the present embodiment can be made very smooth. This is because the surface of the first PET film itself was in a state of being overwhelmed by the GD plasma treatment, but by laminating the surface, the surface of the layer became smooth, and thus the surface was smooth. In addition, since the smoothness is maintained even if the lamination is repeated further, it is easy to make the surface of the finally obtained laminate very smooth by applying a plasma treatment to the substrate surface in advance. It becomes possible.

  If a smooth and dense lamination can be realized, the lamination on the surface inevitably becomes a smooth and dense lamination.

  Here, the case where silicon is vapor-deposited has been described, but the same applies to a resin such as a silane coupling agent. That is, the silane coupling agent was directly applied to the surface of the PET film that had not been subjected to any treatment, and the silane coupling agent was repelled on the surface of the PET film, and sufficient adhesion was secured. Although it is difficult to stack in a state, by performing plasma treatment in advance, the silane coupling agent enters the recess as described above, and the silane coupling agent is further repelled based on that. Instead, they are stacked one after another, and eventually, a state in which the silane coupling agent is stacked in a dense state appears.

  However, as described above, when oxygen or nitrogen is used as the introduction gas, for example, a carbonyl group present on the surface is replaced with oxygen or nitrogen on the surface of the PET film after the plasma treatment, which has been in a flared state. This causes a phenomenon that oxygen and nitrogen are combined with silicon to be deposited. For example, if this is exposed to water vapor with this bond, the water vapor will attack the bonded portion and cut it, causing phenomena such as delamination and degradation of gas barrier properties. is there. Details of this are as described above. Therefore, in the present embodiment, an inert gas, particularly argon gas is preferably used in order to prevent such unnecessary bonding. In the present embodiment, the GD plasma treatment is not merely a plasma treatment, but oxygen or nitrogen existing in the atmosphere reacts with the surface of the PET film during the plasma treatment unless it is in a substantially vacuum state. This is because the above-described useless oxygen bond or the like is generated.

In order to produce the mechanism as described above, the gas barrier film manufacturing method according to the present embodiment performs GD plasma processing using an inert gas as an introduction gas. The atmospheric pressure is set to 1 × 10 ⁻¹ to 1 × 10 ⁻³ Torr in order to obtain a vacuum state in which unnecessary oxygen bonds are not generated.

  Further, in this embodiment, the plasma processing is GD plasma processing. This point will be explained.

  The GD plasma treatment is a plasma treatment using glow discharge, and the greatest feature of the GD plasma treatment is a target used as a cathode.

  In the first place, the GD plasma treatment is a plasma treatment using low-pressure gas glow discharge, and only the submicron layer below the substrate surface changes on the surface of the substrate surface treated by this plasma treatment. It has the characteristic of hardly affecting its properties.

  For example, when a GD plasma process performed by applying a voltage in an argon atmosphere is performed on the substrate surface, argon plasma is first generated, and then foreign substances attached to the substrate surface are removed by the argon ions. That is, the substrate surface is cleaned.

  Next, ions in the plasma collide with the target and desorb atoms on the target surface. As a result, various kinds of scientific species such as electrons, ions, radicals, or excited electrons are generated by the target. Has a long lifetime and accumulates at high concentrations in the gas phase. And when this radical arrives at the base material surface and adheres there, it will be in the state that the base material surface was plasma-treated.

  In this state, as described above, only the submicron layer portion below the surface of the base material reacts, so that the GD plasma processing hardly affects the properties of the base material itself.

  As a target used for the GD plasma treatment in the present embodiment, any metal belonging to Group 4 to Group 12 in the periodic table in the periodic table, or an alloy of metals in the range is used, so that glow By subjecting the substrate film surface to plasma treatment using electric discharge, the metal or alloy adheres to the substrate surface, and a thin film layer is formed.

  Taking iron contained in this range of metal as an example, it is known that iron has a strong redox power, but it is therefore highly reactive with silica. And by adhering to the surface of the base material, when a layer having a gas barrier property, which is further laminated on the surface, specifically, a layer made of silica is laminated, the adhesion to the base material is remarkably preferable. It can be done.

This point will be further described.
First, iron is laminated on the surface of the base material. However, as described above, since there is no foreign matter or the like on the surface of the base material, iron adheres in a dense state, that is, is laminated. Next, silica is sequentially laminated on the substrate surface and iron on the surface, and a strong bond is formed by iron and silica. In that situation, the silica continues to be laminated, but since the bond formed by iron and silica is strong, it can be said that the adhesion between iron and silica is good, that is, the base material and the deposited layer (silica layer) It can be said that the adhesion of is very strong. In this process, due to the influence of the strong bond between iron and silica formed earlier, the silica layer continues to be laminated for a while in the form of more agglomerated silica, so that the resulting silica layer is a dense deposited film As a result, the barrier property is improved. As silica is continuously deposited on the iron surface, the iron eventually expands into the silica layer, and finally, a layer in which iron is scattered in the silica layer is formed on the substrate surface. It will be laminated. That is, it is not simply a laminate of base material / iron layer / silica layer, but a layer in which iron and silica are mixed is laminated on the surface of the base material. As a result, the gas barrier layer can be improved in barrier properties as compared with the case of a layer made of silica alone. Moreover, the interlayer adhesion between the substrate and the vapor deposition layer is further improved. Furthermore, it becomes a layer strong against the cohesive stress, and as a result, the wettability can be improved.

  In addition, similar effects can be expected by using a substance within the above range, and the stress inherent to the base material can be further enhanced, and it can be tough against cohesive failure. This also has the effect.

  In this embodiment, iron (SUS304) is used as a target in order to obtain the above-described effect. However, even if it is a substance other than that, it depends on a metal belonging to the above-mentioned periodic table range, or between metals in the range. An alloy may be used as a target.

  As mentioned above, if it is the manufacturing method of the gas barrier film which has the hot water resistance which concerns on this Embodiment, the gas barrier film which has the structure of a base film / 1st polymer resin layer / gas barrier layer will have Can be obtained.

  For example, a polymer resin film such as a PET film is used as a base material, and the surface is made to a certain extent by GD plasma treatment using an inert gas as an introduction gas. By laminating with a ring agent and laminating a gas barrier layer made of a gas barrier substance such as silicon on the surface, a laminate having a dense gas barrier layer is formed, and a silane coupling agent is placed between the PET film and the gas barrier layer. By laminating so as to be positioned, the interlayer adhesion is further strengthened, and since each layer is in a densely laminated state, the gas barrier property is further improved, especially for water vapor and the like. It is possible to obtain a gas barrier film having a very good hot water resistance.

  When the above is completed, that is, when the lamination of the gas barrier layer is finished, a second polymer resin laminating step of laminating the second polymer resin on the surface of the gas barrier layer is executed.

  With respect to the second polymer resin, for example, if it is a substance having a gas barrier property, it is possible to further supplement the gas barrier property obtained by the gas barrier layer by laminating it on the surface of the gas barrier layer, that is, more heat. It is conceivable that high barrier properties having water resistance can be obtained, and it is expected to play a role as a top coat layer for protecting the gas barrier layer itself.

  By laminating the second polymer resin on the surface of the base material that has been subjected to plasma treatment, the gas barrier property can be supplemented in the present embodiment. That is, when only the gas barrier layer in this embodiment is provided, if the film thickness is increased in order to improve the gas barrier property, problems such as lack of flexibility and easy cracking occur. It is possible to avoid the occurrence of cracks that would occur if the thickness of the gas barrier layer is increased by providing molecular resin on the surface of the substrate after plasma treatment in advance, that is, with the thickness of the gas barrier layer remaining unchanged. As a result, the gas barrier property can be improved while ensuring flexibility.

  The second polymer resin is preferably a layer having thermosetting properties, and further a curing reaction being accelerated by epoxy ring-opening polymerization and condensation reaction with a curing catalyst. In addition to the usual condensation, this property improves the reaction rate by causing an addition reaction between a silanol group and an epoxy group, and also deposits an oxide oxide inorganic oxide in the ring opening reaction of the epoxy group. This is because coordination to the dangling bond (oxygen defect) of the film occurs, and as a result, the gas barrier property of the gas barrier layer can be complemented.

  Further, the second polymer resin and the layer using the second polymer resin in the present embodiment will be described.

  Regarding this second polymer resin, for example, if it is a substance having a gas barrier property, it is possible to further supplement the gas barrier property obtained by the gas barrier layer by laminating it on the surface of the gas barrier layer, that is, a higher barrier. It can be considered that it can be obtained, and is expected to play a role as a top coat layer for protecting the gas barrier layer itself.

  Further, the second polymer resin is more preferably a polymer resin having a gas barrier property like the first polymer resin described above, and for example, an epoxy silane coupling agent is preferable. . If the same epoxy-based silane coupling agent as the first polymer resin is used as the second polymer resin, the same substance can be used in the manufacturing process to facilitate the work. In order to stabilize the physical properties of the obtained high barrier film, it can be said that it is preferable that the number of constituent materials is as small as possible. Therefore, in this embodiment, the epoxy silane that is the same material as the first layer is used. A coupling agent is used. And by laminating this second polymer resin layer, the gas barrier property can be further improved.

  The thickness of the second polymer resin layer is preferably 0.03 μm or more and 2 μm or less, but if this is 0.03 μm or less, the purpose of improving the gas barrier property cannot be achieved. This is because the flexibility of the film becomes poor. In the present embodiment, this thickness is 0.3 μm.

  The second polymer resin layer is also described in the first embodiment in order to accelerate the curing of the silane coupling agent, as described in the section relating to the first polymer resin layer. It is conceivable to add a curing catalyst similar to the above. The details are the same as described above, and the description thereof is omitted here.

  The second polymer resin is not particularly limited, but is most preferably a silane coupling agent. More preferable are epoxy silane coupling agents, amino silane coupling agents, methacrylic silane coupling agents, and ureido silane coupling agents. In this embodiment, epoxy silanes are used. A coupling agent is used as the second polymer resin.

  In the second embodiment, the second polymer resin is made to contain the scaly silica described above to obtain the second polymer resin layer. Since the scaly silica to be used and the effects obtained as a result are the same as those described above, further detailed description is omitted.

  According to the method for producing a gas barrier film according to the present embodiment thus performed, a gas barrier film having a configuration of base film / first polymer resin layer / gas barrier layer / second polymer resin is obtained. I can do it.

  In addition, when the gas barrier layer is laminated by directly laminating a substance having a gas barrier property on the surface of the base film subjected to GD plasma treatment using an inert gas as an introduction gas, the above plasma treatment Since there is no problem in terms of adhesion in the present embodiment, detailed description thereof is omitted here.

  According to the method for producing a gas barrier film having hot water resistance according to the present embodiment executed in this way, the structure of base film / first polymer resin layer / gas barrier layer / second polymer resin is used. A gas barrier film having hot water resistance can be obtained.

  In the present embodiment, the production method of the gas barrier film having the structure of the base film / first polymer resin layer / gas barrier layer / second term molecular resin layer has been described. However, the order of the lamination is assumed to be random. It is also possible to do. This will be briefly described below.

The tree for randomly laminating is as follows.
First, a plasma treatment process is first performed in which a glow discharge plasma treatment is performed in advance in an environment where the atmospheric pressure is 1 × 10 ⁻¹ to 1 × 10 ⁻³ Torr with introduction of an inert gas on the surface of a plastic film as a base After running on
(A) a gas barrier layer stacking step in which layers having gas barrier properties are stacked;
(B) a first polymer resin lamination step in which the first polymer resin is laminated;
(C) a second polymer resin lamination step in which the second polymer resin is laminated;
Each of these steps is performed according to the following conditions.
It is assumed that the first polymer resin and the second polymer resin used here contain the above-mentioned scaly silica. The description of using scaly silica is as described above, and detailed description thereof is omitted here.

(Condition 1) (A) must be executed once.
(Condition 2) The same process is not repeated.
(Condition 3) Either (B) or (C) may not be executed.
(Condition 4) Every time the process of any one of (A) to (C) is executed once, it is assumed that the process is executed once, and the process is executed twice or more in total.

Further explanation will be continued.
The method for producing a gas barrier film having hot water resistance according to the present embodiment basically includes a gas barrier layer, a first polymer resin layer, and a second polymer resin layer on the surface of a base film subjected to GD plasma treatment. That is, each process for stacking is executed. A plurality of these layers may be regularly stacked or randomly stacked.

For example, base film / first polymer resin layer / gas barrier layer / first polymer resin layer / gas barrier layer / second polymer resin layer ...
Also possible is a base film / gas barrier layer / first polymer resin layer / gas barrier layer / second polymer resin layer ...
The form is also conceivable.

  And since it aims at obtaining the gas barrier film which has a hot water resistance in this invention, naturally (A) must be performed once, ie, the gas barrier film which has the hot water resistance finally obtained. When the above structure is observed, it can be said that at least one layer cannot be formed into a gas barrier film unless a gas barrier layer is present, which is self-evident.

  Then, the gas barrier layer, the first polymer resin layer, and the second polymer resin layer may be laminated in the method for producing a gas barrier film having hot water resistance according to the present embodiment. .

For example, if you want to ensure gas barrier properties at the expense of some flexibility,
It can be considered that the unit of “first polymer resin layer / gas barrier layer / second polymer resin layer” is repeatedly laminated on the gas barrier layer side of “base film / gas barrier layer”. In this case, it is obvious that the first polymer resin layer and the second polymer resin layer are different resins.

  If it is not desired to have regularity in the layering, the surface of the “base film / gas barrier layer” includes a first polymer resin layer, a second polymer resin layer, and a separate gas barrier layer. You just have to stack them.

  Furthermore, in the above-mentioned case, it is naturally possible to use “base film / first polymer resin layer / gas barrier layer” instead of “base film / gas barrier layer”, or “base film / second polymer”. A resin layer / gas barrier layer ”is also conceivable.

However, in consideration of the balance between the properties of flexibility and gas barrier properties, it is not realistic to laminate infinitely. In the present embodiment, the base film / first polymer resin layer is finally used. The structure of / gas barrier layer / first polymer resin layer / gas barrier layer is obtained.

  Moreover, it can be said that it is practical that the thickness of the gas barrier film having the hot water resistance obtained by the present embodiment is designed to be within 12 μm to 20 μm, more preferably within 12 μm to 15 μm.

  In addition, since the specific lamination | stacking method of each layer is the same as that of the case in each embodiment demonstrated so far, the detailed description is abbreviate | omitted.

  In addition, when the gas barrier layer is laminated by directly laminating a substance having a gas barrier property on the surface of the base film subjected to GD plasma treatment using an inert gas as an introduction gas, the above plasma treatment Since there is no problem in terms of adhesion in the present embodiment, detailed description thereof is omitted here.

  Anyway, as described above, by the method for manufacturing a gas barrier film having a hot water resistance according to the present embodiment, a gas barrier film having a hot water resistance comprising a plurality of layers including at least one gas barrier layer. Can be obtained.

  Further, various embodiments according to the invention of the present application have been described above. Among them, in order to improve the adhesion when something is further laminated on the surface of the first polymer resin layer. By performing the same plasma treatment process as described above on the surface of the first polymer resin layer after performing the first polymer resin layer laminating process, the adhesion of the first polymer resin layer is improved. It is conceivable to improve the interlayer adhesion, and this plasma treatment process is the same as that already described, and therefore, further detailed description is omitted here.

  In addition, various embodiments according to the present invention have been described above, and in order to further improve the gas barrier property on the surface of the gas barrier film having hot water resistance obtained by each manufacturing method. It is also conceivable to execute a third polymer resin lamination step of laminating the third polymer resin. A suitable third polymer resin in this case may be the same as the first polymer resin or the second polymer resin already described, and the detailed description thereof is omitted here.

  Further, various embodiments according to the present invention have been described above. Among them, a gas barrier is obtained by laminating a plastic film on the outermost surface of a gas barrier film having hot water resistance obtained by each manufacturing method. It is also possible to improve the performance. In this case, the plastic film is not particularly limited, but it can be said that, for example, a thickness of 25 μm to 70 μm is suitable, and a PP film or a PE film is preferably used as a specific material. However, further detailed explanation is omitted here.

  Further, the gas barrier film having hot water resistance obtained by the various embodiments according to the present invention described above has so-called high barrier properties. It can be used as a sheet. This is provided in order to protect that the main structure of the solar cell is vulnerable to gas such as water vapor, and the higher the performance of the gas barrier, the more suitable it can be used. Since the specific utilization method is the same as that of the back sheet of a conventionally known solar cell, further detailed description is omitted here.

Claims (8)

at least,
A plasma treatment step in which a plasma treatment is performed in advance in an environment of an atmospheric pressure of 1 × 10 ⁻¹ to 1 × 10 ⁻³ Torr under introduction of an inert gas on the surface of a plastic film serving as a substrate;
Performing a first polymer resin laminating step of laminating a first polymer resin obtained by adding scaly silica having a silanol group to the main agent on the surface of the substrate subjected to the plasma treatment;
A gas barrier layer laminating step in which a gas barrier layer having a gas barrier property is laminated on the surface after the first polymer resin laminating step is performed;
After the gas barrier layer lamination step,
A second polymer resin lamination step in which a second polymer resin obtained by adding scaly silica having a silanol group to the main agent is laminated on the surface of the gas barrier layer;
With
The plasma treatment is a glow discharge plasma treatment;
On the surface of the base material subjected to the glow discharge plasma treatment process, any metal belonging to Group 4 to Group 12 of the fourth period in the periodic table or an alloy of metals within the range adheres. To become a,
A method for producing a gas barrier film having hot water resistance, characterized by: A method for producing a gas barrier film having hot water resistance according to claim 1,
In a cross-sectional view of the first or second polymer resin layer to which the scaly silica having a silanol group is added,
The labyrinth having the silanol group is dispersed in a substantially horizontal direction and stacked in layers so as to alternate in the cross-sectional thickness direction, and the labyrinth effect is exhibited.
A method for producing a gas barrier film having hot water resistance , characterized by:
A method for producing a gas barrier film having hot water resistance according to claim 1 or 2,
The scaly silica having a silanol group is in the range of 0.01 wt% or more and 1 wt% or less with respect to the main component solid content concentration of the first or second polymer resin layer;
A method for producing a gas barrier film having hot water resistance characterized by the above.
A method for producing a gas barrier film according to any one of claims 1 to 3,
Either one or both of the first polymer resin and the second polymer resin is a silane coupling agent, or a polymer resin mainly composed of a silane coupling agent,
A method for producing a gas barrier film, characterized in that A method for producing a gas barrier film having hot water resistance according to any one of claims 1 to 4,
The substance constituting the gas barrier layer is any one of the group consisting of silicon, titanium, tin, zinc, aluminum, indium, and magnesium, or any of oxides, nitrides, or compounds thereof, or the group. A plurality of oxides, nitrides, or compounds thereof,
The gas barrier layer is laminated by a vacuum deposition method;
A method for producing a gas barrier film having hot water resistance, characterized by: A method for producing a gas barrier film having hot water resistance according to any one of claims 1 to 5,
The gas barrier layer is silicon oxide represented by SiOx, and x is 1.0 ≦ x ≦ 2.0,
A method for producing a gas barrier film having hot water resistance, characterized by: It is manufactured by the method for manufacturing a gas barrier film according to any one of claims 1 to 6.
A gas barrier film characterized by Using the gas barrier film according to claim 7;
A solar battery back sheet characterized by