JP4755289B1 - Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film manufacturing method and a manufacturing method thereof capable of improving interlayer adhesion without preventing amidation or nitridation of a functional group located on a substrate surface and without relying on oxygen bonding. A gas barrier film is provided.
SOLUTION: A plasma processing step of performing plasma processing in advance in an environment of an atmospheric pressure of 0.1 Pa or more and 10 Pa or less under introduction of an inert gas on the surface of a plastic film as a base material, and the plasma processing step are performed. After that, a gas barrier layer laminating step comprising laminating a gas barrier layer having gas barrier properties on the surface thereof, and a gas barrier film obtained by the method were obtained.
[Selection figure] None

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 is at least at an atmospheric pressure of 0.1 Pa to 10 Pa under the introduction of an inert gas with respect to the surface of a plastic film as a base material. A plasma treatment step in which a plasma treatment is performed in advance, and a gas barrier layer lamination step in which a gas barrier layer having a gas barrier property is laminated on the surface after the plasma treatment step is performed. A method for producing a gas barrier film having hot water resistance, comprising: laminating a first polymer resin on a surface of a substrate subjected to the plasma treatment after the plasma treatment step and before the gas barrier layer lamination step. The first polymer resin laminating step is executed, and after the first polymer resin step is executed, the plastic layer is applied to the surface of the first polymer resin layer. Be running Ma process again, characterized by.

The invention according to claim 2 of the present invention is the method for producing a gas barrier film having hot water resistance according to claim 1, wherein after the gas barrier layer laminating step, a second polymer resin is formed on the surface of the gas barrier layer. It is characterized by performing a second polymer resin laminating step of laminating layers.

Invention of Claim 3 of this invention is a 3rd polymer | macromolecule further with respect to the outermost surface of the obtained gas barrier film in the manufacturing method of the gas barrier film which has the hot-water resistance of Claim 1 or Claim 2. It is characterized by performing a third polymer resin laminating step in which resins are laminated.

Invention of Claim 4 of this invention is the manufacturing method of the gas barrier film which has the hot-water resistance of any one of Claim 1 thru | or 3. WHEREIN: Most of the laminated bodies obtained by the said manufacturing method are used. It is characterized by performing a film laminating step in which a plastic film is laminated on the outer surface of the surface and an outermost layer is laminated.

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 said inert gas is argon gas or Argon / oxygen gas.

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 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 7 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 6, 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.

Invention of Claim 8 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 7, Comprising: The layer by said 1st polymer resin An olefin polymer having a thickness of 0.03 μm to 3 μm, the first polymer resin being a thermosetting resin, and the first polymer resin being dissolved in an aqueous solvent; In addition to a mixture of a silane compound, any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, dihydroxybislactotitanium Is added as a curing catalyst, and the mixing ratio of the olefin polymer and the first silane compound is the olefin polymer 1 The first silane compound is 5 to 100 parts by weight with respect to 00 parts by weight, and the first silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxy One of propyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture selected from these This thing , Characterized by.

Invention of Claim 9 of this invention is a manufacturing method of the gas barrier film which has the hot-water resistance of any one of Claim 2 thru | or 8, Comprising: The layer of said 2nd polymer resin is used. A resin having a thickness of 0.03 μm to 3 μm, the second polymer resin having thermosetting properties, and a curing reaction accelerated by epoxy ring-opening polymerization and condensation reaction;
And the second polymer resin is
(1) A mixed liquid is prepared by mixing 50 parts by weight or more of pure water with 100 parts by weight of the second silane compound in the second silane compound,
(2) To the mixed solution, either hydrochloric acid or acetic acid is added so that the mixed solution has a pH of 3 to 5 to prepare a main agent,
(3) Dilute the main agent to prepare a diluted solution,
(4) A curing catalyst for accelerating the curing of the second silane compound is added to the diluent from 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the second silane compound.
A resin obtained by sequentially executing the above procedures (1) to (4),
The second silane compound is a mixture of one or both of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane, and the curing catalyst is iron acetylacetate. It is characterized by being any one of narate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium and dihydroxybislactotitanium.

Invention of Claim 10 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 9, Comprising: Said 1st polymer resin or said 1st Either one or both of the two polymer resins is a resin that meets one of the following (Condition A) or (Condition B).
(Condition A)
The resin is a thermosetting resin,
In addition, the resin is a mixture of an olefin polymer dissolved in an aqueous solvent and a first silane compound, and further, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisosulfate. Propoxy bis acetylacetonato titanium, dihydroxy bis lactato titanium, is added as a curing catalyst,
The mixing ratio of the olefin polymer and the first silane compound is 5 parts by weight or more and 100 parts by weight or less of the first silane compound with respect to 100 parts by weight of the olefin polymer.
The first silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercapto One of propyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane, or a mixture of a plurality selected from these.
(Condition B)
The layer thickness of the resin is 0.03 μm to 3 μm,
And the resin has a thermosetting property, and is a resin whose curing reaction is accelerated by epoxy ring-opening polymerization and condensation reaction,
And the resin is
(1) A mixed liquid is prepared by mixing 50 parts by weight or more of pure water with 100 parts by weight of the second silane compound in the second silane compound ,
(2) To the mixed solution, either hydrochloric acid or acetic acid is added so that the mixed solution has a pH of 3 to 5 to prepare a main agent,
(3) Dilute the main agent to prepare a diluted solution,
(4) A curing catalyst for accelerating the curing of the second silane compound is added to the diluent from 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the second silane compound .
A resin obtained by sequentially executing the above procedures (1) to (4),
The second silane compound is a mixture of γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane, or both,
The curing catalyst is any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactotitanium.

An invention relating to a gas barrier film having hot water resistance according to claim 11 of the present invention is manufactured by the method for manufacturing a gas barrier film having hot water resistance according to any one of claims 1 to 10. It is characterized by this.

The invention relating to the solar battery back sheet relating to the gas barrier fill according to claim 12 of the present invention is characterized by using the gas barrier film having hot water resistance according to claim 11.

  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. This is because in the production method according to the present invention, the surface of the plastic film is simply and purely physically roughened by applying a so-called vacuum plasma treatment to the surface of the plastic film as the substrate under the introduction of 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 subjecting the substrate surface to a vacuum plasma treatment under the introduction of an inert gas, a state in which substances laminated on the surface are densely aggregated is induced, and such a layer is laminated. The property can be made to be a high level having more resistance to hot water.

  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 the surface of a plastic film serving as a base material is introduced in an inert gas and in an environment of atmospheric pressure of 0.1 Pa to 10 Pa. A plasma treatment step in which a plasma treatment is performed in advance; a first polymer resin lamination step in which a first polymer resin is laminated on the surface of the substrate that has been subjected to the plasma treatment; and a gas barrier having gas barrier properties on the surface. A gas barrier layer stacking step in which layers are stacked.

Hereinafter, description will be made sequentially.
First, a 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 0.1 Pa or more and 10 Pa or less. That is, the plasma treatment in this embodiment is a vacuum plasma treatment with an inert gas introduced. (Hereinafter simply referred to as “vacuum 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 0.1 Pa or more and 10 Pa or less as described above. This is because a plasma discharge occurs when the vacuum plasma treatment is performed in the presence of argon gas within this range, and a desired effect described later can be reliably obtained. In order to obtain the effect of the vacuum plasma treatment more reliably, the atmospheric pressure range may be 2 Pa or more and 7 Pa or less. In this embodiment, it is assumed to be 4 Pa.

  In addition, the state of the vacuum plasma-treated surface of the base film after the vacuum plasma treatment according to the present embodiment is based on the result of photoelectron spectroscopy analysis (XPS), 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 vacuum plasma processing in all embodiments described later, that is, in the vacuum plasma processing in the present invention. The vacuum plasma process will be described in detail later.

  The plastic film to be a base material to be subjected to the vacuum 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, for example, 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.

  Further, the thickness of the film used is not particularly limited, but in this embodiment, it is necessary to have a thickness that does not break even when subjected to vacuum plasma treatment, 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 a vacuum plasma treatment is performed on a surface that has been subjected to a treatment such as a corona treatment or an easy-adhesion coating, a highly harmful surface state is likely to appear in this embodiment. . This point will be described in detail again.

  When the plasma processing step for performing the vacuum plasma treatment using the argon gas on the PET film surface is completed in this way, the first polymer resin as the first layer is laminated on the surface subjected to the vacuum 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.
The first polymer resin in the present embodiment is preferably an organic-inorganic hybrid polymer. More specifically, the organic-inorganic hybrid polymer is preferably a mixture of an olefin polymer and a first silane compound. In order to avoid confusion with a silane compound in the embodiment described later, the silane compound used in the present embodiment is a first silane compound.

  It is also conceivable to add a curing catalyst to the organic-inorganic hybrid polymer. This is because the addition of the curing catalyst accelerates the crosslinking of the applied coating agent and improves the performance of the gas barrier layer. Examples of the curing catalyst to be added include iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactotitanium.

  The mixing ratio of the olefin polymer and the first silane compound is preferably 5 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the olefin polymer. .

  As the first silane compound used in the present embodiment described above, for example, tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ It is preferable to use any one of -aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture thereof. By selecting these, the pot life of the coating agent and the appearance at the time of application can be made suitable, the degree of freedom of the addition amount of the second silane compound can be easily obtained, and good gas barrier properties can be obtained. You will be able to get

  Thus, by forming an organic-inorganic hybrid polymer in which the olefin polymer and the first silane compound are mixed, the hydrophilic hydroxyl group of the olefin polymer and the reactive functional group of the silane compound are condensed and crosslinked to form a network structure. As a result, the water resistance and heat resistance can be improved, and the gas barrier properties can also be improved.

  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

  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.

  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 this embodiment, for example, any 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, in the method for manufacturing a gas barrier film having hot water resistance in the present embodiment, first, a plasma processing step of performing vacuum plasma processing is performed, and then a first polymer resin laminating step is performed on the surface thereof. Next, a gas barrier layer stacking step is performed. Here, the vacuum 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, vacuum 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 4 Pa.

  By executing the vacuum 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 “slow state” after the vacuum plasma treatment. . Further, even if this vacuum plasma treatment is performed in this embodiment, 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 vacuum plasma treatment is first performed and 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 vacuum plasma treatment, moisture and nitrogen contained in the atmosphere are prevented from inadvertently reacting with carbonyl groups that are surface functional groups 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, when actually performing vacuum plasma processing, it may be difficult to use only argon as the introduced gas in the vacuum chamber, and it may be inevitably necessary to mix oxygen. However, the mixing ratio of oxygen may be 10% or less with respect to the total amount of argon gas. For example, when a vacuum 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.

  Furthermore, by performing the vacuum 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 crushed by vacuum plasma treatment, but by laminating on the surface, the surface of the layer became smooth, so 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, vacuum plasma treatment is not simply plasma treatment, but oxygen or nitrogen existing in the atmosphere reacts with the surface of the PET film during the plasma treatment unless the vacuum treatment is performed. This is because the above-described useless oxygen bond or the like is generated.

  In order to generate the mechanism as described above, the gas barrier film manufacturing method according to the present embodiment executes vacuum plasma treatment using an inert gas as an introduction gas. Further, the atmospheric pressure is set to 0.1 Pa or more and 10 Pa or less in order to obtain a vacuum state in which unnecessary oxygen bonds are not generated.

  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 vacuum plasma treatment using an inert gas as an introduction gas, and then a silane cup is formed on the surface as a first polymer resin. 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.

(Embodiment 2)
In the method for manufacturing a gas barrier film having hot water resistance according to the first embodiment described above, it is theoretically possible not to execute the first polymer resin laminating step of laminating the first polymer resin. Therefore, here, a second embodiment will be briefly described below.

  In the first embodiment, the first polymer resin is laminated between the base film and the gas barrier layer in order to further improve the gas barrier property and ensure the interlayer adhesion. Although the first polymer resin laminating step is executed, this step is omitted in the second embodiment.

  By omitting the thickness, the thickness of the entire laminate can be reduced as much as possible, and the manufacturing process can be omitted, which can contribute to cost reduction required for manufacturing.

  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 the vacuum plasma treatment using the inert gas as the introduction gas, the above-mentioned 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 manufacturing a gas barrier film having hot water resistance according to the present embodiment, the gas barrier film having hot water resistance having the configuration of base film / gas barrier layer can be obtained. .

(Embodiment 3)
Next, in the method for manufacturing a gas barrier film having hot water resistance according to the first embodiment described above, a second polymer resin is further laminated on the surface of the gas barrier layer after completing all the steps. A method for producing a gas barrier film having a hot water resistance obtained by executing a molecular resin lamination step will be described as a third embodiment.

  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, gas barrier properties can be improved while ensuring flexibility.

  The second polymer resin is preferably a layer that has thermosetting properties, and further has a curing reaction 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 bonds (oxygen defects) 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. The silane compound in the following description of the present embodiment is a second silane compound. This is to avoid confusion with the silane compound described above. The second silane compound and the first silane compound may be the same silane compound or different silane compounds. I do not care.

This second polymer resin is obtained as follows.
The second silane compound is mixed with 50 parts by weight or more of pure water with respect to 100 parts by weight of the second silane compound to prepare a mixed solution, and then either hydrochloric acid or acetic acid is added to the mixed solution. The main solution is prepared by adding the mixed solution so that the pH is 3 to 5, then the main agent is diluted to prepare a diluted solution, and then the curing of the second silane compound is promoted. The curing catalyst is obtained by adding 1 part by weight or more and 10 parts by weight or less to the diluent with respect to 100 parts by weight of the second silane compound.

  In addition, it is preferable that the hydrochloric acid used in the said method is 1N hydrochloric acid, for example. In addition, the main agent is diluted with a diluent, and for this, a solution or solvent that can improve the film-forming property and dissolve the curing catalyst described later may be used.

  More specifically, 100 parts by weight of the second silane compound having an epoxy group and 100 parts by weight of pure water with respect to 100 parts by weight of the second silane compound are mixed and stirred. In addition, 1N hydrochloric acid or acetic acid is added in an amount of 1 part by weight or more and 4 parts by weight or less to 100 parts by weight of the second silane compound in order to promote hydrolysis. The obtained main agent is stirred for 1 hour, and then the main agent is diluted with a dilute solution for improving the film-forming property of the second polymer resin layer, and then the second polymer resin is cured to this. It is obtained by adding a curing catalyst for promotion in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the second silane compound.

  In addition, 1N hydrochloric acid or acetic acid is added in an amount of 1 to 4 parts by weight with respect to 100 parts by weight of the second silane compound, and this value is 1.5 parts by weight. By doing so, a more preferable pH is obtained, so that the workability is favorable and the hydrolyzability is excellent.

  Moreover, although the said main ingredient is diluted with the dilution solution for improving the film formation property of 2nd polymer resin, if this dilution solution is a well-known thing, it will not specifically limit. In the present embodiment, it is preferable to obtain an isopropyl alcohol / n-butanol = 1/1 solution. Note that the blending ratio of isopropyl alcohol / n-butanol is not necessarily limited to 1/1, but by using this ratio, the concentration of the main agent is easily formed. That is, the concentration is suitable for forming a layer having good leveling and being less prone to cracking, and the film has excellent wettability.

  Further, a curing catalyst for accelerating the curing of the second polymer resin is added in an amount of 1 part by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the second silane compound. When the amount is from 2 parts by weight to 8 parts by weight, a preferable result is obtained, and when the amount is further 4 parts by weight, a more preferable result is obtained. That is, curing is effectively promoted. The curing catalyst used here is preferably a metal complex, for example, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, diisopropoxybisacetylacetonatotitanium, dihydroxybislacta. It is preferable to use titanium, especially aluminum acetylacetonate. Even in other cases, use of, for example, tin tetrachloride is suitable. And, by adding 4 parts by weight of aluminum acetylacetonate to 100 parts by weight of the second silane compound to the main agent, the added aluminum acetylacetonate acts as a reaction catalyst. Simultaneously, the addition reaction between the silanol group and the epoxy group and the ring opening reaction of the epoxy group are promoted, and as a result, the formation of the second polymer resin layer can be accelerated.

  This point will be described in more detail. By applying the second polymer resin, a second polymer resin layer mainly composed of a silane compound is formed. At this time, if the silane compound alone is used, the condensation reaction rate is extremely slow. The curing reaction process takes time and is therefore not suitable for actual high-speed machining operations. However, if a curing catalyst is added to the second polymer resin mainly composed of a silane compound, the curing catalyst functions to promote the reaction, so the second polymer to which the curing catalyst is added. When the resin is applied, not only the condensation reaction of the silane compound, but also the addition reaction between the epoxy group and the silanol group and the ring opening reaction of the epoxy group will be added, and the curing reaction process will be accelerated accordingly. As a result, the gas barrier film according to the present embodiment can be used for high-speed processing such as roll-to-roll processing. Further, since the chemical bond with the gas barrier layer becomes strong, the effect of supplementing the gas barrier property of the gas barrier layer can be improved.

  And since the 2nd polymer resin layer formed as a result has an organic functional group in polysiloxane frame | skeleton, the gas barrier film which has the hot water resistance concerning this Embodiment can ensure flexibility. become. Furthermore, since the gas barrier property can be ensured by having a polysiloxane skeleton, the original gas barrier property can be complemented, and the scratch resistance and stain resistance can be further improved. In the present embodiment, as described above, aluminum acetylacetonate is used as a curing catalyst, but other aluminum complexes may be used, and other known curing catalysts may be used.

  Here, the second silane compound is a mixture of one or both of γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane. Preferably, the above state, that is, the curing process of the second polymer resin is easily promoted. Furthermore, by selecting these, cracks are less likely to occur and the wettability to the film can be made more suitable. Moreover, the effect that adhesion strength improves by the chemical bond with the sealant adhesive agent of an unreacted functional group by selecting these is also acquired. And the effect which improves crack resistance etc. more as originally aimed is also acquired.

  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.

  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.

  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.

(Embodiment 4)
Next, in the method for manufacturing a gas barrier film having hot water resistance according to the second embodiment, after completion of all the steps, the second polymer resin in which the second polymer resin layer is further laminated on the surface of the gas barrier layer. A method for manufacturing a gas barrier film having a hot water resistance obtained by executing a lamination process will be briefly described as a fourth embodiment.

  The method for producing a gas barrier film having hot water resistance according to this embodiment is, after all, for protecting the gas barrier layer of the gas barrier film obtained by directly laminating the gas barrier layer on the base film and supplementing the gas barrier property. For this purpose, the second polymer resin described above is laminated, and the purpose thereof is the same.

  The manufacturing method according to the fourth embodiment may be used in accordance with the film thickness, gas barrier properties, and further manufacturing process requirements required for the gas barrier film. Details are as described above, and detailed description is omitted here.

  According to the method for producing a gas barrier film having hot water resistance according to the present embodiment thus performed, the gas barrier film having hot water resistance having the configuration of base film / gas barrier layer / second polymer resin. Can be obtained.

(Embodiment 5)
Finally, a method for manufacturing a gas barrier film having hot water resistance for obtaining a configuration in which the elements described so far are further combined will be described as a fifth embodiment.

The fifth embodiment is executed according to the following procedure.
First, after performing a plasma treatment step for performing a plasma treatment in advance in an atmosphere of an atmospheric pressure of 0.1 Pa or more and 10 Pa or less under introduction of an inert gas, on the surface of a plastic film as a base material,
(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.

(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 vacuum 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.

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

  The method for producing a gas barrier film having hot water resistance according to the present invention and the gas barrier film having hot water resistance to be obtained will be further described below with examples, but the present invention is not limited to these examples. Absent. Moreover, the gas barrier film used for each Example was obtained by the manufacturing method already demonstrated in 1st Embodiment-5th Embodiment, and what was used for the comparative example was also manufactured according to it. Note that it was obtained by the method.

(Description of each member and device)
Polymer resin film as substrate: PET film (“NS” thickness 12 μm, manufactured by Teijin Ltd.)
First polymer resin: Shin-Etsu Chemical Co., Ltd.
Product Name: KBM403
Lamination thickness: 0.2 μm
Second polymer resin: Shin-Etsu Chemical Co., Ltd.
Product name: KBE403
Lamination thickness: 0.2 μm
Gas barrier layer: SiOx (1.0 ≦ x ≦ 2.0) Thickness 0.015 μm

(Explanation on vacuum plasma treatment)
Gas introduced during vacuum plasma treatment: Argon Vacuum degree during vacuum plasma treatment: 4 Pa

(Preparation of the first polymer resin layer)
KBM403 50 parts by weight Water 50 parts by weight Hydrochloric acid (35%) 0.07 parts by weight After preparing a mixture of these and hydrolyzing,
Add IPA / n-butanol = 575/575 (parts by weight) and dilute.
Further, 2 parts by weight of a curing catalyst (aluminum acetylacetonate) is added to complete the preparation.

(Preparation of second polymer resin layer)
KBE403 50 parts by weight Water 50 parts by weight Hydrochloric acid (35%) 0.07 parts by weight After preparing a mixture of these and hydrolyzing them,
Add IPA / n-butanol = 575/575 (parts by weight) and dilute.
Further, 2 parts by weight of a curing catalyst (aluminum acetylacetonate) is added to complete the preparation.

(Explanation regarding measurement of gas barrier properties)
Gas barrier performance measurement method Moisture and heat resistance test: 85 ° C. hot water test was allowed to stand for 2 weeks and then at 85 ° C. and 85% humidity for 1000 hours.
The obtained gas barrier film was subjected to a permeation humidity test according to JIS Z 0208. (Cup method)
Moreover, the measurement regarding moisture permeability was performed according to JIS K7129. (Mocon method moisture permeability)
Moreover, the measurement regarding oxygen permeability was performed according to JISK7126. (Mocon oxygen)

(Configuration of each example and comparative example)
Example 1-1 Base material / first polymer resin layer / gas barrier layer Example 1-2 Base material / first polymer resin layer / gas barrier layer Example 2 Base material / gas barrier layer Example 3-1 Base material / First polymer resin layer / gas barrier layer / second polymer resin layer Example 3-2 Base material / first polymer resin layer / gas barrier layer / second polymer resin layer Example 4 Base material / gas barrier layer / second 2 Polymer resin layer Example 5 Base material / first polymer resin layer / gas barrier layer / first polymer resin layer / gas barrier layer

As mentioned above, in each Example, the laminated body was laminated | stacked after performing the vacuum plasma processing by performing the vacuum plasma processing process with respect to the surface of a base material.
Further, in Example 1-2 and Example 3-2, the surface of the first polymer resin layer was again subjected to the vacuum plasma treatment, and further laminated.

Comparative example 1 Base material / first polymer resin layer / gas barrier layer comparative example 2 Base material / gas barrier layer comparative example 3 Base material / first polymer resin layer / gas barrier layer / second polymer resin layer comparative example 4 Base material / Gas barrier layer / second polymer resin layer comparative example 5 base material / first polymer resin layer / gas barrier layer / first polymer resin layer / gas barrier layer

In Comparative Examples 1, 3, and 5, the substrate surface was subjected to plasma treatment using oxygen as an introduction gas.
In Comparative Examples 2 and 4, the gas barrier layer was laminated on the substrate surface without any pretreatment.

The following items were examined for each example and each comparative example.
・ Barrier property 1
A sample obtained by dry-laminating a laminated film of each example and comparative example with a CPP (manufactured by Toyobo Co., Ltd .: trade name “CT-P1146”) having a thickness of 60 μm by a conventionally known method was used as a sample.
The obtained sample was immersed in hot water at 125 ° C. for 30 minutes.
The barrier properties before and after that were measured. It is described in the table as “initial” before immersion, and “after letting” after immersion. Note that (OTR / WVTR) is oxygen permeability / water vapor permeability.

-Barrier property 2 and adhesion | attachment What laminated | stacked the plastic film on both surfaces of the laminated film of each Example and the comparative example as follows was made into the sample.
Weather-resistant PET having a thickness of 50 μm (product name “K1653” manufactured by Toyobo Co., Ltd.) / Laminated film of Example or Comparative Example / White PET having a thickness of 188 μm (product name “TR55” manufactured by Toyobo Co., Ltd.)
The obtained sample was exposed to the following environment.
1) It was immersed in 85 degreeC warm water for 2 weeks.
2) It was left for 1000 hours in a temperature of 85 degrees and humidity of 85%.
After satisfying each condition, the gas barrier properties measured by the above-mentioned “cup method”, “moisture permeability through the mocon method” and “mocon method oxygen” are described in the table.
Further, regarding the adhesion, the adhesion at the boundary surface of the laminated film of Example or Comparative Example was measured in a weather resistant PET having a thickness of 50 μm (product name “K1653” manufactured by Toyobo Co., Ltd.) in the configuration of the above sample.
The measuring method was T-type peeling: tensile speed 300 mm / min.
Further, as in the previous test, the degree of adhesion of the obtained sample was measured in the same manner before and after immersing the obtained sample in 125 ° C. hot water for 30 minutes. The result is described in the column labeled “adhesion” in the table.

  As can be seen from the above results, it can be seen that the gas barrier film according to the present invention has high barrier properties.

  More specifically, it can be understood that the gas barrier film according to the present invention is much more preferable in terms of interlayer adhesion by performing the lamination after the plasma treatment of the base film. Incidentally, it can be seen that the interlaminar adhesion is further improved when the first polymer resin layer is subjected to plasma treatment.

  Further, in the present invention, it is understood that the interlaminar adhesion is better as compared with the case where the plasma treatment of the comparative example is performed because the vacuum plasma treatment using argon gas as the introduction gas is used instead of the simple plasma treatment. As already explained, this is a proof that when oxygen or nitrogen is used for plasma treatment, oxygen bonds that have been inadvertently broken are broken by water vapor, resulting in delamination. Think of things.

  Incidentally, in this embodiment, an example in which the first polymer resin is directly laminated without performing plasma treatment on the surface of the base material is not shown, but this causes a phenomenon called “repellency” even if such lamination is attempted. This is because it was impossible to laminate the layers, that is, as a result, a laminate could not be obtained.

Claims (12)

at least,
A plasma treatment step of performing a plasma treatment in advance under an environment of an atmospheric pressure of 0.1 Pa to 10 Pa, with an inert gas introduced, on the surface of the plastic film serving as a substrate;
A gas barrier layer stacking step in which a gas barrier layer having a gas barrier property is stacked on the surface after performing the plasma treatment step;
Comprising
A method for producing a gas barrier film having hot water resistance, characterized by:
After the plasma treatment step and before the gas barrier layer lamination step,
Performing a first polymer resin laminating step of laminating a first polymer resin on the surface of the substrate subjected to the plasma treatment;
After performing the first polymer resin step, the plasma treatment step is performed again on the surface of the first polymer resin layer.
A method for producing a gas barrier film having hot water resistance, characterized by: In the manufacturing method of the gas barrier film which has the hot-water resistance of Claim 1,
After the gas barrier layer lamination step,
Performing a second polymer resin lamination step in which a second polymer resin is laminated on the surface of the gas barrier layer;
A method for producing a gas barrier film having hot water resistance, characterized by: In the method for producing a gas barrier film having hot water resistance according to claim 1 or 2,
Performing a third polymer resin lamination step in which a third polymer resin is further laminated on the outermost surface of the obtained gas barrier film;
A method for producing a gas barrier film having hot water resistance, characterized by: The method for producing a gas barrier film having hot water resistance according to any one of claims 1 to 3,
Performing a film laminating step in which a plastic film is laminated on the outermost surface of the outermost surface of the laminate obtained by the manufacturing method and the outermost layer is laminated;
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 4,
The inert gas is argon gas or argon / oxygen gas;
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 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 6,
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: A method for producing a gas barrier film having hot water resistance according to any one of claims 1 to 7,
The layer thickness of the first polymer resin is 0.03 μm to 3 μm,
And the first polymer resin is a thermosetting resin,
In addition, the first polymer resin is a mixture of an olefin polymer dissolved in an aqueous solvent and a first silane compound, and further, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, four One of tin chloride, diisopropoxy bisacetylacetonato titanium, dihydroxy bis lactato titanium, added as a curing catalyst,
The mixing ratio of the olefin polymer and the first silane compound is 5 parts by weight or more and 100 parts by weight or less of the first silane compound with respect to 100 parts by weight of the olefin polymer.
The first silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercapto One of propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, or a mixture of a plurality selected from these,
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 2 to 8,
The layer thickness of the second polymer resin is 0.03 μm to 3 μm,
And the second polymer resin has a thermosetting property, and is a resin whose curing reaction is accelerated by epoxy ring-opening polymerization and condensation reaction,
And the second polymer resin is
(1) A mixed liquid is prepared by mixing 50 parts by weight or more of pure water with 100 parts by weight of the second silane compound in the second silane compound,
(2) To the mixed solution, either hydrochloric acid or acetic acid is added so that the mixed solution has a pH of 3 to 5 to prepare a main agent,
(3) Dilute the main agent to prepare a diluted solution,
(4) A curing catalyst for accelerating the curing of the second silane compound is added to the diluent from 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the second silane compound.
A resin obtained by sequentially executing the above procedures (1) to (4),
The second silane compound is a mixture of γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane, or both,
The curing catalyst is any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, dihydroxybislactotitanium,
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 9,
Either or both of the first polymer resin and the second polymer resin are resins that meet one of the following (Condition A) or (Condition B):
A method for producing a gas barrier film having hot water resistance, characterized by:
(Condition A)
The resin is a thermosetting resin,
In addition, the resin is a mixture of an olefin polymer dissolved in an aqueous solvent and a first silane compound, and further, iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisosulfate. Propoxy bis acetylacetonato titanium, dihydroxy bis lactato titanium, is added as a curing catalyst,
The mixing ratio of the olefin polymer and the first silane compound is 5 parts by weight or more and 100 parts by weight or less of the first silane compound with respect to 100 parts by weight of the olefin polymer.
The first silane compound is tetramethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercapto One of propyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane, or a mixture of a plurality selected from these.
(Condition B)
The layer thickness of the resin is 0.03 μm to 3 μm,
And the resin has a thermosetting property, and is a resin whose curing reaction is accelerated by epoxy ring-opening polymerization and condensation reaction,
And the resin is
(1) A mixed liquid is prepared by mixing 50 parts by weight or more of pure water with 100 parts by weight of the second silane compound in the second silane compound ,
(2) To the mixed solution, either hydrochloric acid or acetic acid is added so that the mixed solution has a pH of 3 to 5 to prepare a main agent,
(3) Dilute the main agent to prepare a diluted solution,
(4) A curing catalyst for accelerating the curing of the second silane compound is added to the diluent from 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the second silane compound .
A resin obtained by sequentially executing the above procedures (1) to (4),
The second silane compound is a mixture of γ-glycidoxypropyltrimethoxysilane or γ-glycidoxypropyltriethoxysilane, or both,
The curing catalyst is any one of iron acetylacetonate, zinc acetylacetonate, aluminum acetylacetonate, tin tetrachloride, diisopropoxybisacetylacetonatotitanium, and dihydroxybislactotitanium.
It is manufactured by the method for manufacturing a gas barrier film having hot water resistance according to any one of claims 1 to 10.
A gas barrier film having hot water resistance, characterized by Using a gas barrier film having hot water resistance according to claim 11;
A solar battery back sheet characterized by