JP5365078B2 - Gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas-barrier film excellent in moisture resistant heat adhesion capable of using various substrate materials and suppressing poor appearance and the degradation of gas-barrier property due to poor adhesion of the film even under severe storage conditions. <P>SOLUTION: The gas-barrier film 1A consists of a laminate composed of a substrate material (A), a primer layer (B) for vapor-deposition formed on the substrate material (A), and a vapor-deposition layer (C) formed on the primer layer (B) for vapor-deposition. The primer layer (B) for vapor-deposition consists of a resin containing an amide ester part, which is obtained by reacting at least 99 to 55 mass% of a specific ingredient (B1) and 1 to 45 mass% of a specific ingredient (B2) (wherein the total of the ingredient (B1) and the ingredient (B2) is 100 mass%). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a gas barrier film. More specifically, even in a severe storage environment required in the fields of electronics and building materials, it is possible to suppress a poor appearance and a deterioration in gas barrier performance due to poor adhesion. The present invention relates to a gas barrier film having excellent properties.

  Packaging materials used for packaging foods, non-foods, pharmaceuticals, etc., alter the oxygen, water vapor, and other contents that permeate the packaging material in order to suppress the alteration of the contents and maintain their functions and properties. It is necessary to prevent the effects of gas. Therefore, the packaging material is required to have a gas barrier property that blocks these gases.

  Conventionally, as a packaging material, a packaging material using a metal foil made of a metal such as aluminum, which is less affected by temperature, humidity and the like, as a gas barrier layer has been generally used. However, packaging materials using metal foils made of metal such as aluminum are excellent in gas barrier properties, but the contents cannot be confirmed through the packaging materials, and are treated as non-combustible materials when discarded after use. It had the drawbacks that it had to be used and the metal detector could not be used for inspection.

  Therefore, as a packaging material that overcomes these drawbacks, for example, a vapor deposition film made of an inorganic oxide such as silicon oxide, aluminum oxide, or magnesium oxide is formed on a thermoplastic resin film by a forming means such as vacuum vapor deposition or sputtering. The formed gas barrier film is shown (for example, patent documents 1 and 2). These gas barrier films have transparency that cannot be obtained with a metal foil or the like in addition to gas barrier properties such as oxygen and water vapor.

  However, even a gas barrier film suitable for the packaging material described above is rarely used alone as a packaging container or packaging material. For example, as post-processing after vapor deposition, the packaging body is subjected to various processes such as printing processing of characters and designs on the surface of the gas barrier film, pasting with other films, shape processing on packaging bodies such as containers, etc. Is done. In particular, packaging materials used for boil sterilization, retort sterilization, autoclave sterilization, and the like are sterilized through various processes, and therefore, care must be taken in the design so as not to deteriorate the performance.

For example, after making a bag by laminating the above-mentioned gas barrier film or the like with a sealant film, filling the contents and attempting boil sterilization or retort sterilization results in delamination in part of the seal part after sterilization and poor appearance In some cases, the gas barrier property is lowered from the portion, and the contents may be altered. Therefore, in boil sterilization, retort sterilization, and autoclave sterilization, there is no deterioration of gas barrier properties due to temperature and water (humidity), and there is no boil resistance, retort resistance, and autoclave resistance such as delamination does not occur. Packaging materials were sought. Therefore, as a packaging material having these performances, a packaging material composed of a laminate having a deposition primer layer containing organosilane or the like is disclosed (for example, Patent Documents 3 and 4).
U.S. Pat. No. 3,442,686 Japanese Patent Publication No.63-28017 Japanese Patent No. 037336130 International Publication No. 2004/048081 Pamphlet

In recent years, excellent gas barrier performance has been demanded not only in the fields of conventional foods, non-foods, pharmaceuticals, but also in the fields of electronics and building materials. In particular, in the solar cell-related field including both fields of electronics and building materials, it is necessary to perform product warranty for electronic products for 20 to 30 years in the same way as building materials. By performing storage evaluation, the performance of the gas barrier film in the position of glass replacement may be determined. In the information electronics field such as an organic EL display and electronic paper, evaluations under severe conditions of high temperature, high humidity, and long time are performed in acceleration acceleration tests that are not as high as solar cells.
Storage evaluation under severe conditions in solar cell applications is performed by storing for 2000 to 3000 hours at 85 ° C.-85% relative humidity. The above-described gas barrier films of Patent Documents 3 and 4 have sufficient gas barrier properties in the fields of food, non-food, pharmaceuticals, and the like. However, when these gas barrier films are stored under the above harsh conditions, poor adhesion of the gas barrier film and a decrease in gas barrier properties are observed.

Moreover, since the said evaluation method requires the evaluation time of 2000 to 3000 hours, it is calculated | required to perform a storage evaluation on further severe conditions, and PCT which preserve | saved for 100 to 200 hours under 105 degreeC-100% relative humidity ( Pressure Cooker Test) evaluation (accelerated test with pressurized steam) has also been performed.
As a base material for a gas barrier film, a polyester film is generally used, and in particular, a film made of polyethylene terephthalate (PET) is often used. Generally, if a PET film is stored in the PCT evaluation environment, it will collapse in about 100 hours with degradation due to hydrolysis. On the other hand, if a polyester film having a high glass transition temperature (Tg) such as polyethylene naphthalate (PEN) and a high degree of crystallinity is used, it is excellent in hydrolysis resistance. However, it is possible to maintain the strength properties for 200 hours or more.

  As the gas barrier film, it is more preferable to design a gas barrier film using a PET film, a PEN film, or various base materials not limited thereto depending on the required durability. However, in the PET gas barrier film provided with a deposition primer layer as in Patent Documents 3 and 4, in PCT evaluation, a significant float occurs between the substrate and the deposition primer layer in less than 50 hours, and it is practically usable. I didn't get it. Similarly, in the case of the PEN-based gas barrier film, significant floating occurred between the base material and the deposition primer layer within 20 hours, which was not practical.

  There are two possible causes for this: (1) the adhesion mechanism between the polyester film and the deposition primer layer, and (2) the functional group density of the polyester film. That is, as the cause (1), the interaction existing between the polyester film and the deposition primer layer is basically intermolecular force, dipole interaction, hydrogen bond, boil sterilization, retort sterilization, autoclave Even in the close contact type that can withstand sterilization and the like, in an extremely severe storage environment such as high temperature, high humidity, and long time, a bond mode that is inherently weak to water such as hydrogen bond is considered insufficient. In addition, as the cause (2), the unit structure of PEN is equal to the unit structure of PET, but the amount of ester bond as a polar group is the same, but the number of hydrocarbon units is increased. It is conceivable that the ratio of polar groups contributing to adhesion on the film surface (this is the density of polar groups) is relatively smaller than that of PET.

  For the reasons described above, the base material is not extremely limited, and even under severe storage conditions, it suppresses poor adhesion of the laminate forming the gas barrier film and the accompanying deterioration in gas barrier properties. A gas barrier film that can be used is desired.

  Therefore, the present invention can use various base materials, and even under storage conditions much harsher than boil sterilization, retort sterilization, and autoclave sterilization, poor appearance and reduced gas barrier properties due to poor film adhesion. It aims at providing the gas barrier film excellent in moisture-and-heat-resistant adhesiveness which can suppress this.

The gas barrier film of the present invention comprises a substrate (A), a deposition primer layer (B) formed on the substrate (A), and an inorganic oxide formed on the deposition primer layer (B). And the base material (A) is a polyester film whose surface on the vapor deposition primer layer (B) side is acidified by a surface treatment, and for the vapor deposition Primer layer (B) reacts 99 to 55% by mass of the following component (B1) with 1 to 45% by mass of the following component (B2) (however, the sum of component (B1) and component (B2) is 100% by mass). The resin having an amide ester moiety obtained by mixing is compounded in an amount of 1 to 100 parts by mass in terms of metal with respect to 100 parts by mass of the total mass of the component (B1) and the component (B2). Ingredient (OS1) is the total mass It is a film which is characterized in that a layer is 1 to 100 parts by mass.
Component (B1): Oxazoline value containing oxazoline group 100-1500 g-solid / eq. An oxazoline group-containing resin.
Component (B2): An acrylic resin having an acid value of 300 to 650 mg / KOH comprising poly (meth) acrylic acid and / or a copolymer of poly (meth) acrylic acid and a comonomer.
Component (OS1): At least one selected from the group consisting of organosilanes represented by the general formula R ¹ —Si (OR ² ) ₃ , hydrolysates thereof, and derivatives thereof.
(In the above formula, R ¹ is one functional group selected from the group consisting of an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ² is an alkyl group. .)

Also, the metal compound is preferably zirconium compounds.

In the gas barrier film of the present invention, the vapor deposition layer (C) is made of at least one inorganic oxide selected from the group consisting of silicon oxide, aluminum oxide, and magnesium oxide, and has a thickness of 5 to 300 nm. Preferably there is .
Moreover, it is preferable that the thickness of the said primer layer (B) for vapor deposition is 0.01-5 micrometers.
Moreover, it is preferable that a vapor deposition overcoat layer (D) is formed on the vapor deposition layer (C).

  Various substrates can be used for the gas barrier film of the present invention. Even under storage conditions much harsher than boil sterilization, retort sterilization, and autoclave sterilization, poor appearance and gas barrier properties due to poor film adhesion. Can be suppressed, and is excellent in wet heat resistance.

  The gas barrier film of the present invention comprises a substrate (A), a deposition primer layer (B) formed on the substrate (A), and a deposition layer (B) formed on the deposition primer layer (B) ( And C). Hereinafter, embodiments of the gas barrier film of the present invention will be described in detail.

[First Embodiment]
FIG. 1 is a cross-sectional view showing a first embodiment of the gas barrier film of the present invention.
As shown in FIG. 1, the gas barrier film 1 </ b> A is a film made of a laminate in which a base material (A), a deposition primer layer (B), and a deposition layer (C) are stacked in this order.

(Base material (A))
Examples of the substrate (A) include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexanedimethanol terephthalate (PCT), and a copolymer of PET and PCT in terms of composition. Various polyester films including copolymer types such as PET-G (manufactured by Eastman Chemical Co., Ltd.), polyamide 6, polyamide 6, 6, or various polyamide (imide) films including copolymer types such as aromatic polyamide and polyimide , Polyolefin films including copolymer types such as polyethylene (PE) and polypropylene (PP), polystyrene films (PS), acrylic films such as polymethyl methacrylate (PMMA) and polyacrylonitrile (PAN) Is a film made of a copolymer of these vinyl / (meth) acrylic resins, polycarbonate (PC) film, polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene Various halogen-containing resin films such as a copolymer (FEP) can be used.
These films may be stretched or unstretched.

  The base material (A) can be properly used according to the application using the gas barrier film 1A of the present invention. Examples of the base material (A) include PET, polyamide 6, and polypropylene resin when used as a general packaging material. In the case of the gas barrier film used for the above severe environment, a high heat-resistant polyester film such as polyethylene naphthalate or polycyclohexanedimethanol terephthalate, a polycarbonate film, an acrylic film, or various halogen-containing films are used. It is preferable.

The base material (A) may contain various known additives and stabilizers. For example, an antistatic agent, an ultraviolet ray preventing agent, a plasticizer, a lubricant and the like may be used. Furthermore, in order to improve adhesion with the deposition primer layer (B), corona treatment, low temperature plasma treatment, or ion bombardment treatment may be performed. Moreover, chemical treatment, solvent treatment, or the like may be performed.
The thickness of the substrate (A) is not particularly limited.

(Primer layer for vapor deposition (B))
The primer layer (B) for vapor deposition is a layer made of a resin having an amide ester site formed by reacting at least the following component (B1) and the following component (B2). The primer layer (B) for vapor deposition plays a role of improving the wet heat resistance of the gas barrier film.

The component (B1) is an oxazoline group-containing resin containing an oxazoline group. The oxazoline group-containing resin is not particularly limited as long as it is a resin having at least two or more oxazoline groups in one molecule.
The oxazoline group-containing resin can be obtained, for example, by copolymerizing a polymerizable monomer containing an oxazoline group such as isopropenyl oxazoline together with various acrylic monomers and styrene monomers. Examples of the oxazoline group-containing resin include an oxazoline group-containing resin whose main chain is an acrylic skeleton, an oxazoline group-containing resin whose main chain is a styrene / acryl skeleton, an oxazoline group-containing resin whose main chain is a styrene skeleton, and an acrylonitrile / styrene skeleton. An oxazoline group-containing resin or the like can be used.
A component (B1) may be used individually by 1 type, and may use 2 or more types together.

The component (B2) is an acrylic resin obtained by copolymerizing a comonomer with poly (meth) acrylic acid and / or poly (meth) acrylic acid.
Component (B2) must have a functional group that reacts with the oxazoline group of component (B1), and (meth) acrylic acid having a carboxy group as the functional group or its ammonium salt or sodium salt (meth) A resin mainly composed of an ionic salt of acrylic acid is preferred. Moreover, as long as it has a carboxy group that reacts with the oxazoline group of the component (B1), an acrylic resin obtained by copolymerizing various comonomers may be used.

  As a comonomer, an alkyl group in which an alkyl group is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a 2-ethylhexyl group, or a cyclohexyl group ( Monomers such as (meth) acrylate; hydroxyl group-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; further (meth) acrylamide, N-alkyl (meth) acrylamide, N, N -Dialkyl (meth) acrylamide (As the alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group Etc.), N-alkoxy (meth) acrylamide, N, N-di Alkoxy (meth) acrylamide (containing alkoxy groups such as methoxy group, ethoxy group, butoxy group, isobutoxy group), N-methylol (meth) acrylamide, N-phenyl (meth) acrylamide and the like A monomer etc. can be used.

  Specifically, styrene, α-methylstyrene, vinyl methyl ether, vinyl ethyl ether, maleic acid, alkyl maleic acid monoester, fumaric acid, alkyl fumaric acid monoester, itaconic acid, alkyl itaconic acid monoester, (meth) A resin obtained by copolymerizing a comonomer such as acrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate, or butadiene with poly (meth) acrylic acid can be used as the component (B2).

The main reason for the moisture barrier heat adhesion provided to the gas barrier film 1A by the deposition primer layer (B) is the amide ester site formed by reacting the component (B1) and the component (B2).
That is, in the conventional gas barrier film, in addition to intermolecular force, dipole interaction, and hydrogen bond that contribute to moisture and heat resistance adhesion, it is formed by the reaction of the oxazoline group of component (B1) and the carboxy group of component (B2). The amide ester moiety imparts an acid / base interaction having water / heat resistant adhesion superior to hydrogen bonding, thereby improving wet heat resistant adhesion.

  The deposition primer layer (B) having an amide ester moiety can give good wet heat resistance particularly to a polyester film (base material (A)) subjected to surface treatment such as corona treatment. This is because the surface of the polyester film of the base material (A) subjected to the surface treatment shows acidity in addition to the intermolecular force, dipole interaction and hydrogen bond similar to the conventional primer layer for vapor deposition. This is probably because the amide portion of the amide ester portion of the deposition primer layer (B) exhibits basicity, and thus the wet heat resistance is improved by the acid / base interaction. Moreover, it is thought that the dipole interaction of the ester bond of a polyester film and the ester part of the amide ester site | part of the primer layer (B) for vapor deposition has also contributed to the improvement of wet heat-resistant adhesion.

  The amide ester moiety is effective not only for the polyester film subjected to the surface treatment but also for imparting wet heat resistance to the base material (A) having a basic surface such as the above-described polyamide or polyimide. This is because the amide bond part of the substrate (A) and the amide part of the amide ester part of the primer layer (B) for vapor deposition show hydrogen bond properties, which is more hydrogen bond than the conventional coating composition using hydrogen bond properties. Since the bond density due to the increase and various amide and imide films as the base material (A) are basic, the unreacted carboxy group of the deposition primer layer (B) is acidic.・ The base interaction can contribute.

  As described above, wet heat and heat adhesion can be improved by using various bonding modes adapted to the surface state of the substrate (A). Moreover, the primer layer (B) for vapor deposition of this invention is excellent in the selectivity of a base material (A), and can provide wet heat-resistant adhesiveness with respect to various base materials. However, when it is desired that the gas barrier film 1A has sufficient moisture and heat resistance even in the above-described PCT evaluation, as the substrate (A), the substrate itself has high hygroscopic polyamide, polyimide, or the like. It is preferable to use a polyester film, a polycarbonate film, an acrylic film, a halogen-containing film, or the like as compared with the above film.

The compounding ratio of component (B1) and component (B2) is mainly determined by the oxazoline value (g-solid / eq.) Due to the oxazoline group of component (B1) and the acid value (mgKOH) due to the carboxy group contained in component (B2). / G).
The component (B1) and the component (B2) are preferably blended so that the oxazoline group of the component (B1) is approximately equivalent to the carboxy group of the component (B2), and the carboxy group in the component (B2) On the other hand, it is more preferable that the oxazoline group of the component (B1) is added in an excess amount. By blending the component (B1) and the component (B2) in this manner, more and more amide ester sites can be formed and excessive unreacted carboxy groups can be reduced as much as possible. It becomes easier to improve thermal adhesion.

The component (B1) described above is a resin containing an oxazoline group, but the polymerizable monomer containing an oxazoline group in the monomer used to form the component (B1) is usually a small component (value of oxazoline value). Is great). On the other hand, the acrylic acid monomer having a reactive carboxy group in the acrylic resin such as poly (meth) acrylic acid contained in the component (B2) is a mass component (high acid value).
Therefore, in this invention, component (B1) and component (B2) are component (B1) 99-55 mass% and component (B2) 1-45 mass% (however, component (B1), component (B2), and Is 100% by mass). Thereby, the amount of oxazoline groups in component (B1) and the amount of carboxy groups in component (B2) can be adjusted as described above. Moreover, although it changes also with the copolymerization component of these components and its molar ratio (or mass ratio), it is preferable to mix | blend component (B1) 90-60 mass% and component (B2) 10-40 mass%, More preferably, 80 to 70% by mass of component (B1) and 20 to 30% by mass of component (B2) are blended.
If the component (B2) is 1% by mass or more, a sufficient crosslinking density is obtained between the component (B1) and the component (B2). It can suppress that it swells and the cohesion force of the primer layer (B) for vapor deposition falls. Moreover, if a component (B2) is 45 mass% or less, it can prevent that an unreacted carboxy group increases too much. When the amount of the amide ester moiety is small and the number of unreacted carboxy groups is too large, the wet heat resistance may be lowered particularly in the case of the substrate (A) having an acidic surface such as a polyester film.

  The oxazoline value of the component (B1) is 50 to 3000 g-solid / eq. It is preferable that it is 100-1500 g-solid / eq. It is more preferable that Component (B1) has an oxazoline value of 50 g-solid / eq. If it is above, it becomes easy to ensure a functional group required for adhesion | attachment. Further, the oxazoline value of the component (B1) is 3000 g-solid / eq. If it is below, the amide ester moiety is easily formed, and it becomes easy to improve the wet heat resistance.

  The acid value of component (B2) is preferably 150 to 800 mgKOH / g, and more preferably 300 to 650 mgKOH / g. If the acid value of the component (B2) is 150 mgKOH / g or more, it becomes easy to obtain a sufficient crosslinking density between the component (B1) and the component (B2), and for vapor deposition in high temperature and high humidity storage evaluation. It is easy to suppress that the primer layer (B) swells and the cohesive force of the deposition primer layer (B) decreases. Moreover, if the acid value of a component (B2) is 800 mgKOH / g or less, it will be easy to prevent that there are too many unreacted carboxy groups.

Moreover, the primer layer (B) for vapor deposition can further improve wet heat-resistant adhesion by prescribing a metal compound.
The metal compound is added to the coating composition (hereinafter referred to as “coating composition B”) composed of the component (B1), the component (B2), and the solvent that form the deposition primer layer (B). It is necessary to dissociate ions in the coating composition B (having solubility in a solvent). Many of such metal compounds are water-soluble compounds, and these water-soluble compounds can be preferably used.

As the metal compound, for example, an ammonium salt in which an aqueous solution exhibits basicity can be used. Examples of ammonium salts include zirconium compounds such as ammonium zirconium carbonate and zirconium ammonium fluoride.
In addition, aqueous solutions are acidic compounds such as zinc, iron, manganese, copper, chromium, zirconium, cobalt, and other metals, and alkali (earth) metal hydrochlorides such as sodium and calcium, sulfates, nitrates, and hydrofluoric acids. A salt can be used.
A metal compound may be used individually by 1 type, and may use 2 or more types together.

As a metal compound, it is preferable that aqueous solution is a compound which shows basicity.
That is, when a compound whose aqueous solution is acidic is used as the metal compound, the coating composition B becomes acidic, so that the oxazoline group of the component (B1) and the carboxy group of the component (B2) are contained in the coating composition B. There is a risk of gradually reacting and reducing coating suitability (effect of pot life of coating composition B). On the other hand, if a compound in which the aqueous solution is basic is used as the metal compound, the carboxy group of the component (B2) in the coating composition B can be made into an ionic salt form such as an ammonium salt or a sodium salt. The carboxy group and the oxazoline group are prevented from reacting before coating, and can react when the coating composition B is dried to form a film. Therefore, the film forming operation of the deposition primer layer (B) is facilitated.

Thus, since it is preferable that the coating composition B used for formation of the primer layer (B) for vapor deposition is a basic solution, it is preferable that the metal compound to add is a compound in which aqueous solution shows basicity. The metal compound is more preferably an ammonium salt from the viewpoint that impurities hardly remain when the coating composition B is dried to form a film.
Particularly preferred metal compounds are zirconium compounds such as zirconium ammonium carbonate and zirconium ammonium fluoride from the viewpoint of pot life and stability of the coating composition B.

  The metal compound is added to the coating composition B used for forming the deposition primer layer (B), and is ionically dissociated in this solution state. When the solvent is volatilized after the coating composition B is provided on the substrate (A) layer by various coating methods, the oxazoline group and the carboxy group react to form an amide ester site. Metal ions generated by dissociation of the compound act with unreacted carboxy groups to form ionic bridges. By this ionic crosslinking, the adhesion failure to the polyester film (acidic base material) due to the unreacted carboxy group is reduced, and the crosslinking density as the deposition primer layer (B) is improved to improve heat resistance and water resistance. Can be improved.

It is preferable that the compounding quantity of a metal compound is 1-100 mass parts in metal conversion mass (mass converted into the mass of only a metal part) with respect to 100 mass parts of total mass of a component (B1) and a component (B2). 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
If the said compounding quantity of a metal compound is 1 mass part or more, the effect by addition of a metal compound will be fully easy to be acquired. Moreover, when the said compounding quantity of a metal compound becomes more than 100 mass parts, since it is sufficient quantity to bridge | crosslink an unreacted carboxy group, the effect obtained by a metal compound hardly changes. If the metal compound is added in an excessive amount, the metal compound remains in the vapor deposition primer layer (B) as an unreacted substance. Therefore, the moisture and heat resistance of the vapor deposition primer layer (B) and There is a risk of reducing the cohesive force.

In addition, the deposition primer layer (B) is a layer that improves the adhesion to the substrate (A), and further improves the adhesion to the deposition layer (C), so that the following component (OS1) And / or the following component (MA1) is preferably blended. That is, it is preferable that only the component (OS1), only the component (MA1), or a mixture of the component (OS1) and the component (MA1) is blended.
The improvement in adhesion to the vapor deposition layer (C) by blending these components (OS1) and (MA1) affects the oxygen barrier property and water vapor barrier property rather than the laminate strength of the gas barrier film 1A.

The component (OS1) is at least one selected from the group consisting of organosilanes represented by the general formula R ¹ —Si (OR ² ) ₃ , hydrolysates thereof, and derivatives thereof. However, in the formula, R ¹ is an alkyl group, (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, one functional group selected from the group consisting of an isocyanate group, R ² is an alkyl group is there.

  Examples of the organosilane include ethyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane is mentioned. Among these, an organosilane containing an epoxy group is preferable, and glycidoxytrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, and glycidoxypropyltriethoxysilane are particularly preferable. These organosilanes are not limited to monomers, and may be derivatives such as dimers and trimers depending on the structure.

The hydrolyzate of organosilane can be obtained by a known method such as a method in which acid or alkali is directly added to these compounds to perform hydrolysis. In the method, a reaction catalyst for promoting a hydrolysis reaction of a tin compound or the like may be added as necessary.
A component (OS1) may be used individually by 1 type, and may use 2 or more types together.

The component (MA1) is one or more metal alkoxides represented by the general formula M ¹ (OR ³ ) _n and / or a hydrolyzate thereof. In the above formula, R ³ is an alkyl group, M ¹ is a metal ion, and n is a valence of the metal ion.
Examples of the metal ions include ions such as silicon, aluminum, titanium, and zinc.
Specific examples of the metal alkoxide include, for example, tetraethoxysilane and tripropoxyaluminum. The hydrolyzate of metal alkoxide can be obtained by using the same method as the hydrolyzate of organosilane described above.
A component (MA1) may be used individually by 1 type, and may use 2 or more types together.

The compounding amount of the component (OS1) and the component (MA1) in the deposition primer layer (B) is 100 parts by mass of the total mass of the component (B1) and the component (B2), and the component (OS1) and the component (MA1). Is preferably 1 to 100 parts by mass.
When the blending amount is 1 part by mass or more, the effect of improving the adhesion with the vapor deposition layer (C) can be sufficiently obtained, and the oxygen barrier property and the water vapor barrier property can be easily improved. Moreover, when the said compounding quantity exceeds 100 mass parts, the effect which improves adhesiveness with a vapor deposition layer (C) will not change so much.

  As described above, the deposition primer layer (B) is a resin layer obtained by reacting at least the component (B1) and the component (B2), and if necessary, a metal compound or It is a layer obtained by containing a component (OS1) and a component (MA1).

The thickness of the deposition primer layer (B) is preferably 0.01 to 5 μm.
When the thickness of the deposition primer layer (B) is 0.01 μm or more, a gas barrier film having sufficient moisture and heat resistance can be easily obtained. Moreover, if the thickness of the vapor deposition primer layer (B) is 5 μm or less, the surface smoothness of the vapor deposition primer layer (B) decreases due to coating unevenness or the like during the formation of the vapor deposition primer layer (B). It is easy to suppress that. This surface smoothness is a factor that affects the oxygen barrier property and the water vapor barrier property.

(Deposition layer (C))
A vapor deposition layer (C) is a layer which consists of inorganic oxides, and is a layer which provides gas barrier property to 1 A of gas barrier films.
Examples of the material for the vapor deposition layer (C) include aluminum oxide, silicon oxide, tin oxide, magnesium oxide, and mixtures thereof. The gas barrier film 1A preferably has transparency and gas barrier properties such as oxygen barrier properties and water vapor barrier properties. Therefore, the vapor deposition layer (C) is preferably a layer made of aluminum oxide or silicon oxide. Moreover, it is not limited to the inorganic oxide mentioned above, The inorganic vapor deposition film | membrane which further provided functions other than gas barrier property may be sufficient.

The optimum condition for the thickness of the vapor deposition layer (C) varies depending on the type and configuration of the inorganic oxide used, but is generally preferably 5 to 300 nm.
If the thickness of the vapor deposition layer (C) is 5 nm or more, it is easy to obtain a uniform film having a sufficient film thickness, and it becomes easy to obtain a gas barrier film 1A that sufficiently functions as a gas barrier material. Further, if the thickness of the vapor deposition layer (C) is 300 nm or less, it becomes easy to maintain sufficient flexibility in the gas barrier film 1A, so that the gas barrier film 1A is cracked due to external factors such as bending and pulling after the film formation. It becomes difficult to occur.

(Production method)
Hereinafter, an example of a method for producing the gas barrier film 1A of the present embodiment will be described.
First, the coating composition B which forms the primer layer (B) for vapor deposition on a base material (A) is prepared. The coating composition B can be prepared by dissolving the component (B1) and the component (B2) in a solvent, and adding and mixing the metal compound, the component (OS1), and the component (MA1) as necessary. As the solvent, a water-based coating agent is preferable in consideration of the solubility of the metal compound and the like, and water is the main component, such as water alone, a mixed solution of water and alcohol, or a mixed solution of water, alcohol, and an organic solvent (small amount). An aqueous solvent is more preferable.

Next, the prepared coating composition B is applied onto the substrate (A), dried to form a film, thereby forming a deposition primer layer (B).
Examples of the coating method for coating composition B include gravure coating, gravure reverse coating, roll coating, reverse roll coating, micro gravure coating, comma coating, air knife coating, Mayer bar coating, dip coating, die coating, and spray coating. Various coating methods can be used.
Moreover, a drying method is not specifically limited, It is preferable to carry out at 60-200 degreeC.

Subsequently, a vapor deposition layer (C) is formed on the vapor deposition primer layer (B) formed on the base material (A).
As a method for forming the vapor deposition layer (C), for example, a vacuum vapor deposition method usually used for forming a vapor deposition layer in the production of a gas barrier film can be used. In addition, other thin film forming methods such as sputtering, ion plating, and plasma vapor deposition (CVD) can also be used.

As a heating means of the vacuum deposition apparatus by the vacuum deposition method, an electron beam heating method, a resistance heating method, or an induction heating method is preferable. In order to improve the adhesion between the vapor deposition layer (C) and the primer layer for vapor deposition (B) and the denseness of the vapor deposition layer (C), a plasma assist method or an ion beam assist method can also be used. Moreover, in order to improve the transparency of a vapor deposition film (C), you may perform the reactive vapor deposition which blows in oxygen gas etc. in the case of vapor deposition.
The gas barrier film 1A can be obtained by the above method.

  Since the gas barrier film 1A of the present embodiment described above has the deposition primer layer (B), even under severe storage conditions, the appearance defect and the gas barrier property decrease due to the poor adhesion of the gas barrier film. Can be suppressed, and has excellent wet heat resistance. Moreover, various base materials (A) can be used for the gas barrier film 1A.

[Second Embodiment]
Next, a second embodiment of the gas barrier film of the present invention will be described.
As shown in FIG. 2, the gas barrier film 1B of the second embodiment includes a base material (A), a deposition primer layer (B), a deposition layer (C), and a deposition overcoat layer (D) in this order. It is the film which consists of a laminated body. Since the base material (A), the deposition primer layer (B), and the deposition layer (C) are the same as those of the gas barrier film 1A of the first embodiment, the description thereof is omitted.

(Deposition overcoat layer (D))
The overcoat layer (D) for vapor deposition is a layer that plays a role of improving gas barrier properties. Even a layer structure such as the gas barrier film 1A of the first embodiment shows sufficient gas barrier properties, but the gas barrier properties are further improved by forming the deposition overcoat layer (D).
The overcoat layer (D) for vapor deposition is formed by a coating composition (hereinafter referred to as “coating composition D”) containing two or more compounds having the component (D1) and the component (D2) as essential components. be able to.

As the component (D1), a water-soluble polymer can be used, and examples thereof include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, and sodium alginate. Of these, polyvinyl alcohol is particularly preferable.
A component (D1) may be used individually by 1 type, and may use 2 or more types together.

Component (D2) is a component that is blended in consideration of adhesion to the vapor deposition layer (C), intermolecular restraint of component (D1), and the following component (OS2) and / or component (MA2) Can be used. That is, only the component (OS2) may be used, only the component (MA2) may be used, or a mixture of the component (OS2) and the component (MA2) may be used.
A component (D2) may be used individually by 1 type, and may use 2 or more types together.

The component (OS2) is at least one selected from the group consisting of organosilanes represented by the general formula R ⁴ —Si (OR ⁵ ) ₃ , hydrolysates thereof, and derivatives thereof. In the above formula, R ⁴ is one functional group selected from the group consisting of an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ⁵ is an alkyl group. is there.
Specific examples of the organosilane, its hydrolyzate, and derivatives thereof are the same as those mentioned for the component (OS1) of the deposition primer layer (B).
A component (OS2) may be used individually by 1 type, and may use 2 or more types together.

The component (MA2) is one or more metal alkoxides represented by the general formula M ² (OR ⁶ ) _m and / or a hydrolyzate thereof. In the above formula, R ⁶ is an alkyl group, M ² is a metal ion, and m is a valence of the metal ion.
Specific examples of the metal alkoxide and / or the hydrolyzate thereof include the same materials as those described for the component (MA1) of the deposition primer layer (B).
A component (MA2) may be used individually by 1 type, and may use 2 or more types together.
The component (D2) in the vapor deposition overcoat layer (D) may be appropriately determined so that effects such as gas barrier properties and intermolecular restraint of the component (D1) can be sufficiently obtained.

The thickness of the overcoat layer (D) for vapor deposition is preferably 0.01 to 5 μm.
When the thickness of the overcoat layer (D) for vapor deposition is 0.01 μm or more, sufficient adhesion to the vapor deposition layer (C) and intermolecular constraint of the component (D1) can be obtained sufficiently, and gas barrier properties can be obtained. The improvement effect is easily obtained. Moreover, if the thickness of the overcoat layer (D) for vapor deposition is 5 μm or less, it is easy to prevent cracks.

  Moreover, the overcoat layer (D) for vapor deposition may contain components other than the component (D1) and the component (D2). Examples of other components include a thickener, a viscosity modifier, a leveling agent, and an antifoaming agent.

(Production method)
Hereinafter, an example of the manufacturing method of the gas barrier film 1B will be described. The method for forming the deposition primer layer (B) on the substrate (A) and the method for forming the deposition layer (C) on the deposition primer layer (B) are the same as those of the gas barrier film 1A of the first embodiment. The method can be used.
After forming the vapor deposition layer (C), a vapor deposition overcoat layer (D) is formed on the vapor deposition layer (C).

The coating composition D is prepared by adding component (D1) and component (D2) to a solvent, mixing and dissolving. As the solvent used for the preparation of the coating composition D, the same solvent as the coating composition B can be used. Next, the prepared coating composition D is applied onto the vapor deposition layer (C), dried and formed into a film, and the gas barrier film 1B is obtained by forming the vapor deposition overcoat layer (D).
As the coating method of the coating composition D, the same method as the coating method of the coating composition B can be used.
Moreover, the drying method after coating is not specifically limited, It is preferable to carry out at 60-200 degreeC.

  The gas barrier film 1B according to the second embodiment described above has excellent gas barrier properties, and can suppress a decrease in adhesion even under a severe environment under high temperature and high humidity such as PCT evaluation. It is expected that evaluation methods such as the electronics field and building materials field can be developed even for harsh product items.

  As described above, as a result of the study by the present inventor, in addition to the conventional adhesion mechanism, by providing an acid-base interaction by the amide ester site, it is possible to impart excellent moisture and heat resistance adhesion to the gas barrier film. I was able to find it. Since the gas barrier film of the present invention is excellent in wet heat and heat adhesion, it can suppress a decrease in the adhesion even under severe conditions, and can sufficiently maintain the gas barrier property.

In addition, the gas barrier film of this invention is not limited to the gas barrier film illustrated in FIG.1 and FIG.2. For example, it may be a gas barrier film in which another layer is provided on the vapor deposition overcoat layer (D) of the gas barrier film 1B for the purpose of further improving the wet heat resistance.
Moreover, if a layer like the primer layer (B) for vapor deposition in this invention is used, various functions which are excellent in heat-and-moisture-resistant adhesiveness by forming the inorganic vapor deposition film which has another function instead of a vapor deposition layer (C). It is thought that it can also be developed as a vapor deposited film.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
The materials used in this example are shown below.
[Base material (A)]
About the base material (A), since it is a factor which influences the adhesiveness in the gas barrier film of this invention, the highly durable base material for PCT evaluation was selected especially. In addition, for the purpose of confirming the substrate selectivity, as a reference example, a nylon substrate that is not usually used for applications in which PCT evaluation is performed was similarly examined.
A-1: Polyethylene terephthalate (PET) film (trade name: Lumirror, manufactured by Toray, thickness 12 μm)
A-2: Polyethylene naphthalate (PEN) film (trade name: Teonex, manufactured by Teijin, thickness 12 μm)
A-3: Polycarbonate (PC) film (trade name: Polycaace, manufactured by Sumitomo Bakelite, thickness 15 μm)
(Other base materials)
A'-1: Nylon (ONy) film (trade name: Emblem, manufactured by Unitika, 15 μm)

[Primer layer for vapor deposition (B)]
(Ingredient (B1))
B1-1: A water-soluble oxazoline group-containing acrylic resin (oxazoline value 220 g-solid / eq.) Obtained by introducing an oxazoline group-containing compound into a copolymerized acrylic resin having methyl (meth) acrylate (MMA) as the main skeleton.

(Component (B2))
In this example, since a comparative study was performed using components similar to the component (B1), the component (B2) was limited to one type.
B2-1: Ammonium salt of water-soluble poly (acrylic acid-hydroxyethyl methacrylate) copolymer (acid value 600 mgKOH / g)

(Other ingredients)
As a comparison with the component (B1) that reacts with the component (B2) to form an amide ester site, a water-soluble resin or a water-soluble compound that can react with the component (B2) to obtain another binding mode was used. .
B1'-1: Water-soluble low-molecular-weight glycidyl compound (manufactured by Nagase Chemtech)
B1'-2: Water-soluble polyallylamine (manufactured by Toyobo)

In addition, as a component for forming a primer layer for vapor deposition for comparison, Component B3-1 comprising a mixture of a solvent-based acrylic polyol, a polyisocyanate compound, and a silane coupling agent was used. The preparation method of component B3-1 is as follows.
A dilution solvent is prepared by mixing acrylic polyol (manufactured by Mitsubishi Rayon) with 2- (epoxycyclohexyl) ethyltrimethylsilane (hereinafter referred to as “EETMS”), which is a silane coupling agent. Next, a component obtained by diluting a mixed solution in which metaxylylene diisocyanate, which is a polyisocyanate compound, is added so that the amount of isocyanate groups is equal to the amount of hydroxyl groups of acrylic polyol to an arbitrary concentration is used as Component B3-1. It was.

(Metal compound)
In this example, the vapor deposition primer layer (B) was limited to a zirconium compound that can be formed most stably.
M-1: Ammonium zirconium carbonate

(Ingredient (OS1))
In this example, organosilane that can form the deposition primer layer (B) most stably was used.
OS1-1: Glycidoxypropyltriethoxysilane

Moreover, about the vapor deposition layer (C) and the overcoat layer (D) for vapor deposition, in order to see the influence of a base material (A) and the primer layer (B) for vapor deposition, conditions were each fixed.
[Deposition layer (C)]
Inorganic oxide: silicon oxide

[Deposition overcoat layer (D)]
D1-1: Completely saponified ethylene-vinyl acetate copolymer (polyvinyl alcohol)
D2-1: Silane compound (Shin-Etsu Silicone)

Hereinafter, examples and comparative examples will be described.
[Example 1]
Component B1-1 (80 parts by mass) and Component B2-1 (20 parts by mass) are diluted with distilled water / ethanol mixed solvent (mixing ratio 70/30) so that the final solid content is 0.5%. Coating composition B was prepared and applied using a gravure coater (a plate was fixed) so that the dry coating amount was in the range of 0.05 to 0.1 μm. The coating composition B applied to the substrate A-1 was dried and formed into a film so that the base material temperature was about 95 to 100 ° C., and subjected to thermal crosslinking at that temperature.
Next, on the primer layer (B) for vapor deposition formed on the base material (A), a vapor deposition layer (C) was provided with a silica vapor deposition film (about 30 to 50 nm) by a PVD (Physical Vapor Deposition) method ( Deposition layer C-1). Furthermore, the coating composition D which mix | blended component D2-1 with component D1-1 is applied on a vapor deposition layer (C) by the gravure coating method, and it is dried and manufactured so that a base material temperature may be about 100-110 degreeC. A gas barrier film (FIG. 2) was prepared by forming an overcoat layer (D) for vapor deposition (deposition overcoat layer D-1) having a dry thickness of 0.5 μm.

[Examples 2 to 9]
A gas barrier film was prepared in the same manner as in Example 1 except that the composition and composition of the base material (A) and the primer layer for vapor deposition (B) were changed as shown in Table 1. In addition, component OS1-1 was added so that solid content concentration might be 5 mass% in the coating composition B.

[Comparative Examples 1-5]
A gas barrier film was prepared in the same manner as in Example 1 except that the composition and composition of the base material (A) and the primer layer for vapor deposition (B) were changed as shown in Table 1. In addition, component OS1-1 was added so that solid content concentration might be 5 mass% in the coating composition B.

[Reference Example 1]
A gas barrier film was produced in the same manner as in Example 1 except that the base material A′-1 was used instead of the base material A-1 and the composition and formulation of the deposition primer layer (B) were changed as shown in Table 1. It was created. In addition, component OS1-1 was added so that solid content concentration might be 5 mass% in the coating composition B.
Table 1 shows the layer structures of the gas barrier films obtained in Examples, Comparative Examples, and Reference Examples. However, the compounding quantity of M-1 in Table 1 is a metal conversion mass.

Hereinafter, the evaluation method of the gas barrier film in a present Example is demonstrated.
[Evaluation method]
Hydrolysis resistance by dry laminating technique on both sides of the obtained gas barrier film using an adhesive for dry laminating (ADH) (manufactured by Toyo Ink) composed of polycarbonate urethane diol (main agent) and polyisocyanate (curing agent) An evaluation sample was prepared by forming a polyester film (trade name: X10S, manufactured by Toray Industries, Inc., 125 μm) having excellent properties (FIG. 3). The evaluation sample (referred to as A4 cut sample) was placed in a PCT evaluation tester (manufactured by Oyo), stored in a 105 ° C-100% relative humidity environment, laminate strength after 48, 96, and 196 hours, and oxygen. Barrier properties and water vapor barrier properties were measured.

(Lamination strength)
The laminate strength (unit: N / 15 mm) is measured on the vapor deposition surface side corresponding to the X part of FIG. 3 (laminated portion of the base material (A), the vapor deposition primer layer (B) and the vapor deposition layer (C)). Then, evaluation was performed under the condition of a peeling rate of 300 mm / min by T-type peeling using a strip test piece having a width of 15 mm. Moreover, the peeling surface analysis at that time was performed by IR method (infrared absorption method) and XPS method (X-ray excitation photoelectron spectroscopy), and the peeling surface was specified. The laminate strength was determined according to the following criteria.
○: The laminate strength is 1 N / 15 mm or more.
X: The laminate strength is less than 1 N / 15 mm.

(Gas barrier properties)
The oxygen barrier property (unit: cc / m ² / day / atm) was measured using oxytolan (manufactured by Modern Control Co., Ltd.). Moreover, water vapor | steam barrier property (unit: g / m < ² > / day) was measured using Permatran (made by Modern Control Co., Ltd.). The gas barrier properties were evaluated according to the following criteria.
○: At least one of the measured values for oxygen barrier property and water vapor barrier property is less than 5 times from the initial value.
X: The measured values for oxygen barrier properties and water vapor barrier properties are both five times or more from the initial values.

Moreover, in evaluation in a present Example, since base material (A) itself deterioration arises besides adhesiveness, about PET film of base material A-1, the evaluation period was made into 96 hours.
On the other hand, the ONy film of the base material A-4 is greatly affected by wrinkles and the like because the base material significantly absorbs moisture due to the influence of humidity in the PCT evaluation. For this reason, since it is difficult to accurately evaluate the laminate strength and gas barrier properties, the substrate A-4 was not judged for gas barrier properties. The laminate strength was measured by the above-described method at a level where there was no wrinkle effect, and when it was difficult to evaluate the strength accurately due to the wrinkle effect, it was evaluated as sensory adhesion by hand peeling.
Table 2 shows the measurement results of the laminate strength and gas barrier properties for the gas barrier films in Examples, Comparative Examples, and Reference Examples, and Table 3 shows the determination results. However, the measurement result after 96 hours of Reference Example 1 in Table 2 indicated “difficult to measure”, but had sufficient adhesion in evaluation by hand peeling.

As shown in Tables 2 and 3, in Examples 1 to 9, which are gas barrier films of the present invention, having an amide ester moiety allows PCT evaluation by storage at 105 ° C.-100% relative humidity. Moreover, the fall of the gas barrier property by the adhesion defect between a base material (A) and the primer layer (B) for vapor deposition was suppressed.
Moreover, it was confirmed from the comparison with the gas barrier film of Example 1 and 5 that the gas barrier film of Example 2 and 6 is improving the heat-and-moisture resistant adhesiveness by containing a metal compound.
In addition, the gas barrier films of Examples 3 and 7 are compared with the gas barrier films of Examples 1 and 5, and by containing organosilane, the oxygen barrier property is not greatly improved, but the water vapor barrier property is further improved. Confirmed to do.
In addition, the gas barrier films of Examples 4 and 8 are compared with the gas barrier films of Examples 1 and 5, and both contain the metal compound and the organosilane, thereby improving both the wet heat resistance and the water vapor barrier property. It was confirmed.
Moreover, from the result of the reference example 1, it was confirmed that the primer layer (B) for vapor deposition in this invention has wide selectivity of a base material (A).

On the other hand, in Comparative Example 1 in which the deposition primer layer (B) was formed from a component that reacts with the component (B2) but does not form an amide ester site, poor adhesion occurred after 96 hours, and the gas barrier properties decreased.
Moreover, in Comparative Example 2, since an amine compound having high reactivity was used, a reaction occurred before the coating composition B was applied, and a deposition primer layer could not be formed.
Further, in Comparative Examples 3 and 4 in which the deposition primer layer was formed by the conventional method, the gas barrier property was lowered due to poor adhesion in the PCT evaluation.
Moreover, in the comparative example 5, although the component (B1) and the component (B2) were used, the wet heat-resistant adhesiveness was inferior compared with the Example. This is considered to be because the amount of the carboxyl group of the component (B2) was excessive and the adhesion with the acidic substrate was lowered.

  Since the gas barrier film of the present invention is excellent in moisture and heat resistance adhesion, the adhesion and gas barrier properties are reduced even in applications that require storage evaluation under severe conditions under moisture and heat resistance, such as the field of electronic components and building materials. Can be suppressed. In addition, it has sufficient performance as moisture and heat resistance to conventional boil and retort sterilization, so it can also be used as a gas barrier film for packaging materials that require conventional high-temperature sterilization in the fields of food, non-food, pharmaceuticals, etc. be able to.

It is sectional drawing which showed an example of embodiment of the gas barrier film of this invention. It is sectional drawing which showed the other embodiment example of the gas barrier film of this invention. It is sectional drawing of the evaluation sample used for evaluation in a present Example.

Explanation of symbols

  1A, 1B Gas barrier film A Base material B Deposition primer layer C Deposition layer D Deposition overcoat layer ADH Dry laminate adhesive DS Polyester film X Laminate strength measurement site

Claims (5)

A base material (A), a deposition primer layer (B) formed on the base material (A), and a deposition layer (C) made of an inorganic oxide formed on the deposition primer layer (B) And a laminate including
The base material (A) is a polyester film whose surface on the vapor deposition primer layer (B) side is acidified by surface treatment,
The said primer layer (B) for vapor deposition is 99-55 mass% of the following component (B1), and the following component (B2) 1-45 mass% (however, the sum total of a component (B1) and a component (B2) is 100 mass%). 1 to 100 parts by mass of metal compound in terms of metal with respect to 100 parts by mass of the total of component (B1) and component (B2) The gas barrier film is a layer containing 1 to 100 parts by mass of the following components (OS1) in total mass.
Component (B1): Oxazoline value containing oxazoline group 100-1500 g-solid / eq. An oxazoline group-containing resin.
Component (B2): An acrylic resin having an acid value of 300 to 650 mg / KOH comprising poly (meth) acrylic acid and / or a copolymer of poly (meth) acrylic acid and a comonomer.
Component (OS1): At least one selected from the group consisting of organosilanes represented by the general formula R ¹ —Si (OR ² ) ₃ , hydrolysates thereof, and derivatives thereof.
(In the above formula, R ¹ is one functional group selected from the group consisting of an alkyl group, a (meth) acryloyl group, a vinyl group, an amino group, an epoxy group, and an isocyanate group, and R ² is an alkyl group. .)   The gas barrier film according to claim 1, wherein the metal compound is a zirconium compound.   The said vapor deposition layer (C) consists of an at least 1 sort (s) or more inorganic oxide selected from the group which consists of a silicon oxide, an aluminum oxide, and a magnesium oxide, and thickness is 5-300 nm. Gas barrier film.   The gas barrier film as described in any one of Claims 1-3 whose thickness of the said primer layer (B) for vapor deposition is 0.01-5 micrometers.   The gas barrier film according to any one of claims 1 to 4, wherein an overcoat layer (D) for vapor deposition is formed on the vapor deposition layer (C).

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