JP2003326646A - Gas barrier film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enhance usefulness of a gas barrier film. <P>SOLUTION: This gas barrier film is constituted by laminating a plastic film (A) and a covering layer (B) which is formed by using a composition including an organosilicon compound and/or a hydrolytic condensate thereof; the organosilicon compound is expressed by formula: R<SP>1</SP><SB>x</SB>Si(OR<SP>2</SP>)<SB>y</SB>(wherein R<SP>1</SP>is an alkyl group which can have a functional group which does not react with a hydrogen atom or active hydrogen; R<SP>2</SP>is a hydrogen atom or an alkyl group; x represents an integer greater than/equal to zero; y represents an integer greater than/equal to one; and a relationship between x and y is expressed by equation: x+y=4); and in the plastic film (A), a ratio (E'<SB>50</SB>/E'<SB>100</SB>) between a storage elastic modulus E'<SB>50</SB>at 50°C and a storage elastic modulus E'<SB>100</SB>at 100°C is in the range of 1.0-5.0, when viscoelasticity is measured at a frequency of 10 Hz in a tensile mode. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a gas barrier film having extremely low permeability to gases such as oxygen, carbon dioxide, and water vapor, and more specifically, it has high thermal stability and is composed of a plastic film and a coating layer. The present invention relates to a gas barrier film capable of effectively suppressing a decrease in gas barrier property due to peeling.

[0002]

2. Description of the Related Art In recent years, in the fields of packaging, medical treatment and the like, there is an increasing demand for gas barrier films having extremely low permeability to gases such as oxygen, nitrogen, carbon dioxide and water vapor.

As a method for producing a gas barrier film, the film itself is formed from a material having a gas barrier property such as an ethylene-vinyl alcohol copolymer, a vinylidene chloride copolymer, an aromatic nylon, and the like. There are methods such as laminating or coating a material having the above with a film base material, laminating an aluminum foil on the film base material, and depositing a metal oxide on the surface of the film base material.

However, none of these gas barrier materials can be said to satisfy all of moisture resistance, environmental resistance, transparency and flexibility. Specifically, the ethylene-vinyl alcohol copolymer and the aromatic nylon have a significantly reduced gas barrier property as the humidity of the atmosphere increases. Since the vinylidene chloride-based copolymer contains chlorine atoms, it may cause pollution. When the aluminum foil is laminated on the film substrate, the gas barrier film becomes opaque and the contents of the package cannot be confirmed. Further, when a metal oxide is vapor-deposited on the surface of the gas barrier film, cracks are likely to occur in the vapor deposition layer, and the gas barrier property is deteriorated.

In order to solve these problems, the present inventors have already proposed a gas barrier coating agent and a gas barrier film having a film containing a polysiloxane polymer formed on the surface thereof. (JP-A-8-
295848, etc.). Such a gas barrier film retains high gas barrier properties and is excellent in moisture resistance, environment resistance, transparency and flexibility, and can be said to be extremely useful when applied to various applications.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to further enhance the usefulness of a gas barrier film having a layer composed of the above polysiloxane polymer.

[0007]

The present invention which solves the above-mentioned problems includes a plastic film (A) and the following formula (1):

[0008]

[Chemical 3]

(Wherein R ¹ is a hydrogen atom or an alkyl group which may have a functional group, R ² is a hydrogen atom or an alkyl group, x is an integer of 0 or more, and y is 1
It is an integer greater than or equal to x + y = 4, and x or y is 2
In the above cases, R ¹ or R ² may be different) a coating layer (B) formed using a composition containing an organosilicon compound represented by The plastic film (A) is a gas barrier film obtained by laminating the above, and the plastic film (A) has a storage elastic modulus E ′ _{50 at 50} ° C. and a storage at 100 ° C. when viscoelasticity is measured at a frequency of 10 Hz by a tensile mode. 'ratio of ₁₀₀ (E' modulus E ₅₀ / E _'100) is 1.0
It is a film for gas barriers, which is 5.0.

In the present invention, the plastic film (A), the organic compound (b-i) having a nitrogen atom to which active hydrogen is bonded in the molecule, and the active hydrogen are reacted with each other to chemically bond with the nitrogen atom. A gas barrier film comprising a coating layer (B) formed by using a composition obtained by reacting an organic compound (b-ii) having a functional group capable of forming in a molecule, and a coating layer (B). The plastic film (A) has a frequency of 1 depending on the tension mode.
When measured viscoelasticity at 0 Hz, the ratio of the ₁₀₀ 'the storage modulus E at ₅₀ to 100 ° C.' the storage modulus E at _{50 ℃ (E '50 / E} ' 100), 1.0~5 It is a film for gas barriers characterized by being 0.0.

In the present invention, the plastic film (A), the organic compound (b-i) having a nitrogen atom to which active hydrogen is bonded in the molecule, and the active hydrogen are reacted with each other to chemically bond with the nitrogen atom. A gas barrier film comprising a coating layer (B) formed by using a composition obtained by reacting an organic compound (b-ii) having a functional group capable of forming in a molecule, and a coating layer (B). The adhesive strength between the plastic film (A) and the coating layer (B) is
The film for gas barrier is characterized by having a thickness of 250 gf / 15 mm or more.

The inventors of the present invention have conducted extensive studies to further improve the characteristics of the gas barrier film having excellent characteristics, and have found that there is a correlation between the storage elastic modulus or the adhesion strength and the thermal stability. . That is, the gas barrier film having the storage elastic modulus of the plastic film and the adhesion strength between the plastic film and the coating layer satisfying the above-specified values has very good thermal stability. Therefore, the gas barrier film of the present invention can maintain excellent gas barrier properties even under extremely severe conditions (for example, boiling at high temperature).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The gas barrier film of the present invention comprises at least a plastic film (A) and a coating layer (B) laminated together. Below are the components,
The plastic film (A) and the coating layer (B) will be mainly described in detail.

[0014] a plastic film (A) is, 'storage modulus at ₅₀ and 100 ° C. E' storage modulus E at 50 ° C. ₁₀₀
The ratio of the _{(E '50 / E' 100} ) is preferably 1.0 to 5.0. Storage modulus E _'50 at 50 ° C. and 100
The ratio of the storage modulus E _'100 at ° C. (hereinafter, for convenience also referred to as "storage modulus ratio") when it is such a range is for the resulting gas barrier film has excellent thermal stability . The storage elastic modulus is an elastic modulus that is in the same phase as a vibration stress when a cyclic load is applied, and is also called a dynamic elastic modulus. In general, the larger the value, the more difficult it is to deform. Accordingly, E _'50 / E' ₁₀₀ that is large,
It means that the plastic film (A) is easily deformed at high temperature. Conversely, E _'50 / E' that ₁₀₀ is small, a plastic film (A) which means that difficult to deform at high temperatures. Since the storage elastic modulus may vary depending on the frequency used at the time of measurement, the frequency used is 10 Hz in the present application. The tension mode is used as the measurement mode. The storage elastic modulus can be measured using a commercially available measuring instrument. For example, it can be measured using a solid viscoelasticity analyzer RSAII manufactured by Rheometric Scientific.

Plastic film (A) and coating layer
The film for gas barrier laminated with (B) is constant
Plastic film while held at temperature
Storage elastic modulus ratio with respect to adhesion between (A) and coating layer (B)
Is considered to be essentially non-issue. But
For example, the gas barrier film is sterilized by boiling at 90 ° C.
When exposed to
It has a great influence on the adhesion between the rum (A) and the coating layer (B).
I'm sorry. Storage modulus of plastic film (A)
Ratio (E '₅₀/ E '₁₀₀) Is the storage elastic modulus ratio of the coating layer (B)
If it is small, the plastic film (A) will deform
On the other hand, it is difficult for the coating layer (B) to be easily deformed.
It This will deform the gas barrier film at high temperatures.
Problems such as cracks in the coating layer (B) when applied
Occurs, resulting in deterioration of the gas barrier property. vice versa,
Storage modulus ratio for plastic film (A)
(E ’₅₀/ E ' ₁₀₀) Is the storage elastic modulus ratio of the coating layer (B)
On the other hand, if it is large, the plastic film (A) will deform
Although it is easy, the coating layer (B) is not easily deformed.
It This will deform the gas barrier film at high temperatures.
When applied, it softens the plastic film (A) and a coating layer
(B) cannot follow and peels off or cracks occur.
There is a risk of All of these problems are gas barrier properties
Cause a drop in.

These problems do not depend only on the storage elastic modulus ratio of the plastic film (A), but of course occur with respect to the storage elastic modulus ratio of the coating layer (B). As a result of considering the coating layer (B) constituent material and the like in the present invention, the inventors of the present invention show excellent thermal stability when the storage elastic modulus ratio of the plastic film (A) is 1.0 to 5.0. It has been found that a gas barrier film having the same can be obtained. Therefore, the first gas barrier film of the present invention is characterized in that the storage elastic modulus ratio of the plastic film (A) is 1.0 to 5.0. When the storage elastic modulus ratio is less than 1.0, the flexibility of the plastic film (A) is relatively inferior, so that the coating layer may be cracked and the gas barrier property may be deteriorated. On the other hand, when the storage elastic modulus ratio is more than 5.0, the flexibility of the coating layer (B) is relatively poor, so that peeling or cracking occurs between the plastic film (A) and the coating layer (B), and for a gas barrier. The gas barrier property of the film may decrease.

The plastic film (A) is preferably selected so as to have a storage elastic modulus ratio of 1.0 to 5.0. Suitable materials include polypropylene film, polyester film and polyamide film. To be From the viewpoint of thermal stability, a polyester film or a polyamide film is more preferable. Considering the film strength, the polyester film is particularly preferable.

Examples of the polyester include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polyethylene naphthalate (PEN). Examples of the polyamide include poly ε-caprolactam, polyhexamethylene adipamide, and polymetaxylylene adipamide. The plastic film (A) may be unstretched, or may be uniaxially or biaxially stretched or rolled. Further, these plastic films (A) may be synthesized by polymerization,
A commercially available film may be used.

The shape of the plastic film (A) is not particularly limited and may be determined in consideration of the intended use and workability. The thickness is also not particularly limited, but if it is too thin, the film strength may be insufficient, and if it is too thick, the risk of cracking increases. Therefore, the plastic film (A) generally has a thickness of 5 to 500 μm, preferably 7 to 50 μm, and more preferably 10 to 30 μm.

The coating layer (B) is formed by preparing in advance a composition used for forming the coating layer (B) (hereinafter, also referred to as "coating layer composition") and applying the composition. It Regarding the method for preparing the composition for the coating layer, the method described in JP-A-8-295848 can be appropriately referred to.

One embodiment of the coating layer composition contains the organosilicon compound represented by the above formula (1) and / or its hydrolytic condensate.

In the formula (1), R ¹ is a hydrogen atom or an alkyl group which may have a functional group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, Examples thereof include branched alkyl groups such as sec-butyl group, and cyclic (alicyclic) alkyl groups such as cyclopropyl group and cyclobutyl group. Among these, a methyl group or an ethyl group is preferable from the viewpoint of easiness of reaction in forming the dense coating layer (B).
The functional group that can be contained in the alkyl group is not particularly limited, and examples thereof include an amino group, an epoxy group, a (meth) acryl group, a thiol group, a hydroxyl group, and a vinyl group. In particular, when it has a vinyl group, it has an effect of improving heat resistance. In addition, R ¹ is, when x is 2 or more,
It may be the same or different.

In the above formula (1), R ² is a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a linear alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an isopropyl group, an isobutyl group, a tert-butyl group, Examples thereof include branched alkyl groups such as sec-butyl group, and cyclic (alicyclic) alkyl groups such as cyclopropyl group and cyclobutyl group. Among these, a methyl group or an ethyl group is preferable from the viewpoint of easiness of reaction in forming the dense coating layer (B). When y is 2 or more, R ^{2 s} may be the same or different.

In the above formula (1), x is an integer of 0 or more, y is an integer of 1 or more, and x + y = 4.
Although not particularly limited, in consideration of heat resistance, boiling resistance, and water resistance of the coating layer (B) formed, x =
It is preferred that 0 and y = 4.

Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, Diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ- Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyi Alkoxysilanes such as triethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane and complex compounds thereof, Methyltriacetoxysilane, trimethylsilanol, and polymeric organosilicon compounds containing these compounds are mentioned. Among these, the coating layer (B)
Considering the moisture resistance and water resistance of the above, tetramethoxysilane and tetraethoxysilane are preferable. In addition, these may be used individually by 1 type, or may be used in combination of 2 or more type.

The hydrolytic condensate of the organosilicon compound is a compound obtained by hydrolytic condensation of the organosilicon compound represented by the above formula (1). Instead of the organic silicon compound or in addition to the organic silicon compound, the hydrolysis-condensation product of the organic silicon compound may be contained because the organic compound and the organic silicon compound in the coating layer (B) are not formed. This is because it is preferable to hydrolyze and condense these in advance in order to prevent intentional drying. That is, the coating layer composition of the present invention may contain an organosilicon compound, or may contain a hydrolyzed condensate of the organosilicon compound. Of course, both may be included. These hydrolysis-condensation reactions also proceed with water present in the air, but the reaction efficiency may be improved by using a known catalyst such as acid or base. Further, in consideration of workability, it is preferable to carry out the hydrolysis reaction in a solvent.

The composition for the coating layer containing the organosilicon compound represented by the above formula (1) and / or its hydrolysis-condensation product may contain other components. For example, the organic compound (b-i), the organic compound (b-ii), and the like described later may be contained.

Another embodiment of the coating layer composition is an organic compound (b) having a nitrogen atom to which active hydrogen is bonded in the molecule.
-I), an organic compound having in the molecule thereof a functional group capable of reacting with the active hydrogen to form a chemical bond with the nitrogen atom (b)
-Ii) is obtained by reacting with. In preparing the coating layer composition, the following formula (2):

[0029]

[Chemical 4]

Organosilicon compound (b-iii) represented by
And / or the hydrolysis condensate (b-iv) thereof may be further reacted.

The organic compound (b-i) is not particularly limited as long as it has a nitrogen atom to which active hydrogen is bonded in the molecule. In the present application, active hydrogen refers to a hydrogen atom which is highly reactive and reacts with various reagents, and specifically, -NH- (wherein, N is not bonded to any other hydrogen atom) or -NH. It exists as ₂ in the molecule. When the composition comprising the organic compound (b-i) is contained in the coating layer composition, it is particularly effective in increasing the flexibility of the coating layer (B) formed.

The molecular weight of the organic compound (b-i) is not particularly limited, but a polymer compound is preferable in view of the film-forming property and flexibility of the coating layer (B) to be formed. . If the number average molecular weight of the polymer compound as the organic compound (b-i) is too small, the coating layer (B) formed may be inferior in flexibility, or the plastic film (A) or another coating layer (B) may be formed. ) There is a possibility that the film-forming property when coating and laminating on top may be poor. Therefore, the number average molecular weight of the polymer compound as the organic compound (b-i) is 25
It is preferably 0 or more, more preferably 300 or more. On the other hand, if the number average molecular weight is too large, the transparency of the coating layer (B) formed may be inferior.
The flexibility of the coating layer (B) may be poor. Therefore, the number average molecular weight of the polymer compound as the organic compound (b-i) is preferably 200,000 or less, and 1000
It is more preferably 00 or less, and particularly preferably 10,000 or less. However, organic compounds with a complex structure that cannot be measured by the number average molecular weight (b-
It can be used as i), and these are not excluded in the present invention.

Specific examples of the organic compound (b-i) include:
Examples thereof include low molecular weight compounds such as ethanolamine, and high molecular weight compounds such as polyalkyleneimine and polyallylamine.

As the polyalkyleneimine, polymethyleneimine, polyethyleneimine, polypropyleneimine, polyisopropyleneimine, polybutyleneimine,
Examples thereof include polyisobutylene imine. The polyalkyleneimine can be prepared by using various known synthesis methods, or a commercially available product may be used. For example, Epomin series manufactured by Nippon Shokubai Co., Ltd .; Epomin SP-00
3, Epomin SP-006, Epomin SP-012, Epomin SP-018, Epomin SP-103, Epomin SP-110, Epomin SP-200, Epomin SP-
300, Epomin SP-1000, Epomin SP-10
Polyethyleneimine such as 20 (both are trade names) can be used. As the polyallylamine, those synthesized by various known methods can be used, and PAA-L and PAA-H (both are trade names) manufactured by Nitto Boseki Co., Ltd. can be used. These may be used alone or in combination of two or more. Among the above-listed organic compounds (bi), polyalkyleneimine is preferable, and polyethyleneimine is particularly preferable, in consideration of transparency, heat resistance, flexibility and adhesiveness of the coating layer (B).

The organic compound (b-ii) is the organic compound (b
There is no particular limitation as long as it has a functional group in the molecule capable of reacting with active hydrogen bonded to the nitrogen atom contained in -i) to form a chemical bond with this nitrogen atom. Such a functional group is not particularly limited, but an epoxy group, a carboxyl group, an isocyanate group,
Examples thereof include thioisocyanate group, oxazolinyl group, (meth) acryl group, aldehyde group, ketone group and alkyl halide group. An epoxy compound having an epoxy group is preferable in view of easiness of reaction with active hydrogen bonded to nitrogen atom and hot water resistance. The organic compound (b-
Including the component (ii) in the coating layer composition is particularly effective in improving the film-forming property of the coating layer composition.

The organic compound (b-ii) is not particularly limited, but may be 2-ethylhexyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether. Glycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl Aliphatic mono- and diglycidyl ethers such as ether and trimethylolpropane diglycidyl ether; Se roll triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) isocyanurate, trimethylolpropane triglycidyl ether,
Polyglycidyl ethers such as pentaerythritol tetraglycidyl ether; Aliphatic and aromatic mono- and diglycidyl esters such as adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester and phenylglycidyl ether; Bisphenol A diglycidyl ether, Glycidyls having an aromatic ring such as resorcinol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol F diglycidyl ether or its hydrogenated ring (including nuclear substituted derivatives); oligomer having a glycidyl group as a functional group Kinds; hexamethylene diisocyanate, tolylene diisocyanate, 1,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, trif Methane triisocyanate, tolidine diisocyanate, xylylene diisocyanate, diisocyanate such as dicyclohexylmethane diisocyanate; tartrate, dicarboxylic acids such as adipic acid; a carboxyl group-containing polymers such as polyacrylic acid; oxazolinyl group-containing polymer and the like.

These may be used alone or in combination of two or more. In addition, among the organic compounds (b-ii) exemplified above, an organic compound having an aromatic ring or an aliphatic ring is preferable. By using an organic compound having an aromatic ring or an aliphatic ring, the water resistance of the coating layer (B) can be improved.

The organic compound (b-ii) has the following formula (3):

[0039]

[Chemical 5]

A functional group represented by (hereinafter referred to as "SiOR
⁵ group ”) is also included in the molecule. In the formula,
R ⁵ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is a linear alkyl group,
It may be either a branched alkyl group or a cyclic (alicyclic) alkyl group. Among the alkyl groups, a methyl group or an ethyl group is preferable from the viewpoint of making the coating layer (B) dense.

[0041] When the in organic compound (b-ii) has a SiOR ⁵ group proceeds hydrolysis condensation in ⁵ groups SiOR before the reaction with the organic compound (b-i) or after the reaction. In addition, cohydrolytic condensation proceeds with the hydrolyzable condensing group contained in the organic silicon compound described later. Due to the action of these polycondensation, it is possible to quickly form a dense coating layer (B) having excellent hard coat properties. It also has the effect of increasing the adhesion of the coating layer (B). When the organic compound (b-i) is a low molecular weight compound, it may be hydrolyzed and condensed before the reaction with the organic compound (b-ii).

Organic compounds having a SiOR ⁵ group (b-i
Specific examples of i) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ. -Glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Silane coupling agent having an epoxy group such as ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane and a SiOR ⁵ group (Hereafter, simply epoxy resin-containing sila Coupling agent is be omitted); .gamma. isocyanoacetate trimethoxysilane, .gamma. isocyanoacetate triethoxysilane,
γ-isocyanopropylmethyldimethoxysilane, γ-
Examples thereof include a silane coupling agent containing an isocyanate group such as isocyanopropylmethyldiethoxysilane and a SiOR ⁵ group (hereinafter, simply referred to as a silane coupling agent containing an isocyanate group). These may be used alone or in combination of two or more.

The organosilicon compound (b-iii) is a compound represented by the above formula (2). R ³ is a hydrogen atom or an alkyl group. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, specifically, a methyl group,
Linear alkyl groups such as ethyl group, propyl group, butyl group, branched alkyl groups such as isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, and cyclic (alicyclic) alkyl groups such as cyclopropyl group and cyclobutyl group. Can be mentioned. Among these, a methyl group or an ethyl group is preferable from the viewpoint of easiness of reaction in forming the dense coating layer (B). In addition, an organic compound (b-
When i) is included in the composition for the coating layer, it may have a functional group that does not react with the active hydrogen bonded to the nitrogen atom contained in the organic compound (b-i). Organic compound (b
The functional group which does not react with the active hydrogen contained in -i) is not particularly limited, but includes a vinyl group. When it has a vinyl group, it has the effect of improving heat resistance. When a is 2 or more, R ³ may be the same or different. Since R ⁴ , a, and b are the same as those described in relation to the above formula (1), description thereof will be omitted here. Specifically, R ^{2 corresponds} to R ⁴ , x corresponds to a, and y corresponds to b. The hydrolytic condensation product (b-iv) of the organosilicon compound is a compound obtained by hydrolytic condensation of the organosilicon compound (b-iii) represented by the above formula (2). Since the hydrolysis-condensation product (b-iv) of the organosilicon compound is the same as that described in the above formula (1), the description thereof will be omitted.

The organosilicon compound (b-iii)
And the hydrolysis-condensation product (b-iv) thereof are the same as the organic compound (b-ii) in that they do not have a functional group capable of reacting with the active hydrogen bonded to the nitrogen atom of the organic compound (b-i). Is clearly different.

The compound used in preparing the composition for the coating layer may be selected in consideration of the obtained properties. In the case of selecting from the above (b-i) to (b-iv),
Polyethyleneimine as (b-i), epoxy group-containing silane coupling agent as (b-ii), (b-iii)
Tetramethoxysilane or tetraethoxysilane as, or (b-i) an amino group-containing silane coupling agent, (b-ii) an epoxy compound having an aromatic ring or an aliphatic ring, (b-iii) Tetramethoxysilane or tetraethoxysilane is used. Hereinafter, the case of producing a coating layer composition using the above (b-i) to (b-iv) will be described, but the present invention is not limited to the following embodiments.

In order to produce a coating layer composition from the above (b-i) to (b-iv), first, the above-mentioned (b-i)
And (b-ii), and (b-iii) and / or as required.
Alternatively, (b-iv) is reacted to prepare a composition in which these are reacted. The reaction medium is a solvent (b-
The same compounds as v) can be used. Above (b
-I) to (b-iv) are reacted with each other to obtain a composition, and the amount to be added should be determined depending on the presence or absence of other additives, and should not be uniquely defined. No, but normal amounts are specified below.

The compounding amount of the organic compound (b-i) is such that the constituents of the composition for the coating layer (excluding the solvent (b-v)).
5 to 70% by mass, preferably 10 to 60% by mass, and more preferably 15 to 40% by mass with respect to the total compounding amount of
Is the range.

The compounding amount of the organic compound (b-ii) is such that the constituents of the composition for the coating layer (excluding the solvent (b-v)).
It is usually in the range of 5 to 50% by mass, preferably 7 to 35% by mass, and more preferably 10 to 20% by mass with respect to the total blending amount.

When the organosilicon compound (b-iii) and / or its hydrolyzed condensate (b-iv) is blended, the blending amount is such that the constituents of the coating layer composition (provided that the solvent (b It is usually 10 to 80% by mass, preferably 20 to 70% by mass, and more preferably 30 to 60% by mass with respect to the total blended amount of (excluding -v). In addition,
The "blending amount of the organosilicon compound (b-iii) and / or its hydrolysis-condensation product (b-iv)" means the total blending amount of both, and only one of them is for the coating layer. When it is contained in the composition, it means the blending amount of one of them.

The solvent (bv) in which (b-i) to (b-iv) are mixed is an organic compound (b-i), an organic compound (b-ii), an organic silicon compound (b-iii). And / or a hydrolyzed condensate of an organosilicon compound (b-iv),
Also, it is not particularly limited as long as it can dissolve these reaction products, and specifically, alcohols such as methanol, ethanol, 2-propanol, butanol and ethylene glycol; ketones such as acetone and methyl ethyl ketone. Aromatic hydrocarbons such as toluene, benzene and xylene; Hydrocarbons such as hexane, heptane and octane; Acetates such as methyl acetate and ethyl acetate; Others, such as ethylphenol ether, propyl ether, tetrahydrofuran and water Can be mentioned. Of these, alcohols such as methanol and ethanol are preferable because they are excellent in stability during hydrolysis reaction and storage stability. The solvent may be selected in consideration of compatibility with the components (b-i) to (b-iv) used.

The compounding amount of the solvent (bv) is not particularly limited, but it is usually when the total mass of the coating layer composition (including the solvent (bv) here is 100% by mass). 20
To 97 mass%, preferably 50 to 95 mass%, more preferably 70 to 95 mass%, and particularly preferably 75 to 90 mass%. When the compounding amount of the solvent (b-v) is less than 20% by mass, the reaction stability of the coating layer composition may be poor, and the viscosity of the coating layer composition may increase during coating. Therefore, uniform coating may not be possible. On the other hand, 9
If it exceeds 7% by mass, the productivity when forming the coating layer (B) may be poor, and the concentration of the active ingredient may be too low, so that the required thickness of the coating layer (B) cannot be secured. There are cases.

Further, a curing catalyst, a wettability improver, a plasticizer,
Various additives such as a defoaming agent and a thickening agent may be further added in an appropriate amount as long as the characteristics of the coating layer composition are not impaired.

The method for producing the coating layer composition is not particularly limited, and the following method can be used, for example.

(1) Organic compound (b-i), organic compound (b-ii), organic silicon compound (b-iii) and / or its hydrolyzed condensate (b-iv), solvent (b) -V) and a method of reacting a compounding component containing (optionally other components), (2) a solvent (b-
v), the organic compound (b-i) and the organic compound (b-i)
i) and then reacting with an organosilicon compound (b-i
ii) and / or a method of adding a hydrolyzed condensate (b-iv) thereof, (3) in a solvent (bv) containing the organic compound (b-i), the organic compound (b-ii) and the organosilicon The method of hydrolyzing and condensing the compound (b-iii) and the like can be mentioned, but the method is not limited thereto. The solvent (bv) is preferably supplemented or added in an appropriate manner depending on the preparation stage and method.

The reaction condition is that the organic compound (b-
It is preferable that the unreacted substance i) is not substantially left. This is because if the unreacted organic compound (b-i) remains, the stability of the obtained coating layer (B) may decrease. For example, at 30 to 80 ° C., 0.5
The reaction may be performed for about 5 hours.

The coating layer (B) is formed using the composition for coating layer thus prepared. Various coating methods and printing methods can be used to apply the composition for the coating layer. For example, roll coating method, dip coating method, bar coating method, nozzle coating method, die coating method, spray coating method, spin coating method, curtain coating method,
Various printing methods such as flow coating method, screen printing, gravure printing, curved surface printing and the like can be mentioned. You may combine these. Usually, the coating layer composition,
The coating layer (B) is dried so that the thickness thereof is 0.1 to 3.0 μm, preferably 0.3 to 1.5 μm.
When the thickness of the coating layer (B) after drying is less than 0.1 μm, sufficient gas barrier properties may not be exhibited. On the other hand, when the thickness of the coating layer (B) after drying exceeds 3.0 μm, the gas barrier property may be deteriorated due to the generation of cracks and insufficient adhesion strength.

After coating, the composition for the coating layer is cured and dried. In the case of heating, it is preferable to heat the plastic film (A) at a temperature not higher than the heat resistant temperature. Here, the heat resistant temperature of the plastic film means an upper limit temperature at which the properties of the plastic film can be substantially maintained, and means a glass transition point, a crystallization temperature or a decomposition point. The curing and drying conditions are not particularly limited, but in order to quickly form the coating layer (B), it is 60
It is recommended to perform the treatment at ˜120 ° C. for 1 to 300 seconds. It may be dried in the presence of steam or mist.

Coating layer (B) even in a hot and humid environment
In order to exhibit a very high gas barrier property, it is preferable to carry out aging treatment after curing and drying. Examples of the aging treatment include a heat treatment (for example, heat treatment at 40 to 60 ° C. for 1 to 7 days) and a corona treatment.

When the coating layer composition is coated to form the coating layer (B), the coating layer composition having the same composition may be coated several times.
The coating layer composition having different compositions may be coated several times to form the coating layer (B) into a multi-layer structure.

One of the purposes of the present invention is to ensure sufficient gas barrier properties by preventing peeling between the plastic film (A) and the coating layer (B), but to prevent peeling. Preferably has a high adhesion strength between the plastic film (A) and the coating layer (B). Having a high adhesion strength makes it possible to secure sufficient gas barrier properties even under high temperature and severe conditions.
That is, the second aspect of the present invention is the plastic film (A)
And a coating layer (B), which is a gas barrier film in which the adhesion strength between the plastic film (A) and the coating layer (B) is 250 gf / 15 mm or more. With such adhesion strength, it is possible to effectively prevent deterioration of the gas barrier property of the gas barrier film due to peeling of the plastic film (A) and the coating layer (B). However, suitable adhesion strength between the plastic film (A) and the coating layer (B) may depend on the type of the plastic film (A). Plastic film (A)
If is a polypropylene film, 350 gf
/ 15 mm or more is more preferable. When the plastic film (A) is a polyester film or a polyamide film, it is more preferably 500 gf / 15 mm or more, still more preferably 600 gf / 15 mm or more. Generally, the higher the adhesion strength, the more preferable, and the upper limit is not particularly limited.

The adhesion strength can also be used as a specific index having a gas barrier property at high temperatures. In the present application, the adhesion strength between the plastic film (A) and the coating layer (B) after boiling for 20 minutes in water at 95 ° C. is 2
It is preferably 50 gf / 15 mm or more. With such adhesion strength, sufficient gas barrier properties can be ensured even after treatment such as boiling sterilization. However, also in this case, the suitable adhesion strength between the plastic film (A) and the coating layer (B) depends on the type of the plastic film (A). When the plastic film (A) is a polypropylene film, it is preferably 250 gf / 15 mm or more.
When the plastic film (A) is a polyester film or a polyamide film, 500 gf /
More preferably 15 mm or more, 600 gf /
It is even more preferably 15 mm or more.

The adhesion strength can be measured by the peeling method described in the examples.

As a specific index having a gas barrier property at high temperature, the oxygen permeability may be directly measured.
In the present application, the oxygen permeability of the gas barrier film after boiling in 95 ° C. water for 20 minutes is 20 ° C. 90%.
20 cm ³ / (m ² · 24 hrs · atm) at Rh
The following is preferable. It can be said that such an oxygen permeability has sufficient performance as a film for an oxygen gas barrier. The oxygen permeability of the gas barrier film can be measured using a commercially available device.

A sealant layer (C) may be further laminated on the gas barrier film. The gas barrier film including the sealant layer (C) is generally laminated in the order of plastic film (A) / coating layer (B) / sealant layer (C), but these must be laminated in this order. Instead, the order may be changed in some cases. Further, a known layer such as an adhesive layer for laminating the sealant layer (C) may be added. As the sealant layer (C), a polyolefin film,
A film having various heat-sealing properties such as an ethylene vinyl alcohol copolymer film can be used.
More preferable examples include a low density polyethylene film, an unstretched polypropylene film, and an ethylene vinyl acetate copolymer film. Sealant layer (C)
The thickness is preferably 10 to 200 μm, and 20 to 100 μm.
μm is more preferable, and 30 to 70 μm is particularly preferable.

[0065]

EXAMPLES Next, the usefulness of the present invention will be specifically described with reference to Examples and Comparative Examples. The apparatus and conditions used for measuring each physical property are as follows.

<Measurement of Storage Elastic Modulus> A solid viscoelasticity analyzer RSAII manufactured by Rheometric Scientific was used. Measurement mode is pull mode, frequency is 1
It was set to 0 Hz. The temperature range was from 25 ° C to 140 ° C, and the temperature was raised at a rate of 3 ° C / min. The measurement atmosphere was air.

<Adhesion strength measurement> The adhesion strength was measured by a peeling method using a gas barrier film having a sealant layer. First, the sealant layers are adhered to each other by applying a pressure of ² kg / cm ² at 200 ° C. for 1 second to form a plastic film (A) / covering layer (B) / sealant layer (C) / sealant layer (C) / Two gas barrier films were laminated in the order of coating layer (B) / plastic film (A). After that, the one gas barrier film and the other gas barrier film were pulled in opposite directions. The pulling speed at that time was 100 mm / min. Among the laminated layers, the adhesive strength between the plastic film (A) and the coating layer (B) was the weakest, so the plastic film (A) and the coating layer (B) were first peeled off. The strength at this time was defined as the adhesion strength (gf / 15 mm).

<Measurement of Oxygen Permeability> An oxygen permeability measuring device MH manufactured by Modern Controls was used. 20 ℃
It was measured at 30% Rh and 20 ° C. 90% Rh.

<Synthesis Example 1: Preparation of coating layer composition 1> Polyethyleneimine (18) was used as the organic compound (bi).
g: A mixed solution containing Epomin SP-018 manufactured by Nippon Shokubai Co., Ltd., γ-glycidoxypropyltrimethoxysilane (17 g) as the organic compound (b-ii), and methanol (520 g) as the solvent (b-v). At 60 ° C for 3
The reaction was carried out for a period of time and cooled to room temperature. Next, a mixed liquid of water (13 g) and methanol (50 g) was added to this reaction liquid, and the mixture was reacted at room temperature for 24 hours to obtain coating layer composition 1.

<Synthesis Example 2: Preparation of coating layer composition 2> Polyethyleneimine (18) as the organic compound (b-i)
g: A mixed solution containing Epomin SP-018 manufactured by Nippon Shokubai Co., Ltd., γ-glycidoxypropyltrimethoxysilane (17 g) as the organic compound (b-ii), and methanol (520 g) as the solvent (b-v). At 60 ° C for 3
The reaction was carried out for a period of time and cooled to room temperature. Next, a mixed solution of water (13 g) and methanol (50 g) was added to this reaction solution and reacted for 30 minutes, and further hydrolytic condensation of tetramethoxysilane as a hydrolytic condensate (b-iv) of an organosilicon compound. Thing (135 g: Tama Chemical Industry Co., Ltd., M
A mixture of silicate 51) and methanol (250 g) was added. This was reacted at room temperature for 24 hours to obtain a coating layer composition 2.

<Example 1> Plastic film (A)
As a storage elastic modulus E _'50 at 50 ° C. is 1.3 × 10 ⁵
N / cm ^2, the storage modulus at 100 ° C. E _'100 is 0.9 ×
A nylon film having a thickness of 10 ⁵ N / cm ² and a thickness of 15 μm [(E ′ ₅₀ / E ′ ₁₀₀ ) = 1.4] was prepared. On this film, the coating layer composition 1 obtained in Synthesis Example 1 was applied by a bar coater so that the thickness after drying was 1 μm,
It was dried at 90 ° C. and 10% Rh for 10 seconds, and further dried at 100 ° C. for 10 seconds. Then, it was aged at 50 ° C. for 7 days to obtain a gas barrier film 1 in which the plastic film (A) and the coating layer (B) were laminated.

Oxygen permeability of this gas barrier film 1
Is 2.5 cm at 20 ° C and 30% Rh ³/ (M²・ 24 hours
s ・ atm), 10.1 ° C at 20 ° C 90% Rh³/
(M²・ 24 hrs ・ atm). The result is
The results are shown in Table 1 below.

Example 2 On the gas barrier film 1 obtained in Example 1, a sealant layer (C) having a thickness of 6 was formed.
A 0 μm unstretched polypropylene film (CPP) was laminated using a urethane adhesive to obtain a gas barrier film 2.

Oxygen permeability of this gas barrier film 2
Is 2.5 cm at 20 ° C and 30% Rh ³/ (M²・ 24 hours
s ・ atm), 7.1 cm at 20 ° C and 90% Rh³/ (M²
・ 24 hrs ・ atm). Adhesion strength is 550g
It was f / 15 mm.

Further, this gas barrier film 2
It was boiled for 20 minutes in water at 0 ° C. When the oxygen permeability after boiling was measured, it was 7.8 cm at 20 ° C. and 30% Rh.
^{3 / (m 2 · 24hrs ·} atm), was 15.9 cm ³ / at ^{20 ℃ 90% Rh (m 2} · 24hrs · atm). The adhesion strength was 530 gf / 15 mm.

<Example 3> Plastic film (A)
As a storage elastic modulus E _'50 at 50 ° C. is 1.3 × 10 ⁵
N / cm ^2, the storage modulus at 100 ° C. E _'100 is 0.9 ×
A nylon film having a thickness of 10 ⁵ N / cm ² and a thickness of 15 μm [(E ′ ₅₀ / E ′ ₁₀₀ ) = 1.4] was prepared. On this film, the coating layer composition 2 obtained in Synthesis Example 2 was applied by a bar coater so that the thickness after drying was 1 μm,
It was dried at 90 ° C. and 10% Rh for 10 seconds, and further dried at 100 ° C. for 10 seconds. Then, it was aged at 50 ° C. for 7 days to obtain a gas barrier film 3 in which the plastic film (A) and the coating layer (B) were laminated.

Oxygen permeability of this gas barrier film 3
Is 2.3 cm at 20 ° C. and 30% Rh ³/ (M²・ 24 hours
s-atm), 0.6 cm at 20 ° C 90% Rh³/ (M²
・ 24 hrs ・ atm). <Example 4> Gas barrier film obtained in Example 3
On the top of No. 3 as a sealant layer (C) with a thickness of 60 μm
Expanded polypropylene film (CPP) with urethane adhesive
And use them to form the gas barrier film 4.
It was

Oxygen permeability of this gas barrier film 4
Is 1.2 cm at 20 ° C and 30% Rh ³/ (M²・ 24 hours
s ・ atm), 0.3 cm at 20 ° C, 90% Rh³/ (M²
・ 24 hrs ・ atm). Adhesion strength is 570g
It was f / 15 mm.

Further, this gas barrier film 4
It was boiled for 20 minutes in water at 0 ° C. When the oxygen permeability after boiling was measured, it was 1.5 cm at 20 ° C and 30% Rh.
^{It was 3} / (m ² · 24 hrs · atm) and 0.9 cm ³ / (m ² · 24 hrs · atm) at 20 ° C. and 90% Rh.
The adhesion strength was 560 gf / 15 mm.

<Example 5> Plastic film (A)
Has a storage elastic modulus E ′ ₅₀ at 50 ° C. of 1.2 × 10 ⁵
N / cm ^2, the storage modulus at 100 ° C. E _'100 is 1.1 ×
A PET film [(E ′ ₅₀ / E ′ ₁₀₀ ) = 1.1] having a thickness of 10 ⁵ N / cm ² and a thickness of 15 μm was prepared. Otherwise in the same manner as in Example 3, a gas barrier film 5 was obtained.

Oxygen permeability of this gas barrier film 5
Is 1.7 cm at 20 ° C. and 30% Rh ³/ (M²・ 24 hours
s · atm), 0.5 cm at 20 ° C, 90% Rh³/ (M²
・ 24 hrs ・ atm).

<Example 6> On the gas barrier film 5 obtained in Example 5, a sealant layer (C) having a thickness of 5 was formed.
0 μm linear low density polyethylene film (LLDP
E) was laminated using a urethane adhesive to obtain a gas barrier film 6.

Oxygen permeability of this gas barrier film 6
Is 1.6 cm at 20 ° C and 30% Rh ³/ (M²・ 24 hours
s ・ atm), 0.3 cm at 20 ° C, 90% Rh³/ (M²
・ 24 hrs ・ atm). Adhesion strength is 630g
It was f / 15 mm.

The gas barrier film 6 is made
It was boiled for 20 minutes in water at 0 ° C. When the oxygen permeability after boiling was measured, it was 2.3 cm at 20 ° C. and 30% Rh.
^{It was 3} / (m ² · 24 hrs · atm) and 0.8 cm ³ / (m ² · 24 hrs · atm) at 20 ° C. and 90% Rh.
The adhesion strength was 620 gf / 15 mm.

<Comparative Example 1> Plastic film (A)
Has a storage elastic modulus E ′ ₅₀ at 50 ° C. of 1.0 × 10 ⁵
N / cm ^2, the storage modulus at 100 ° C. E _'100 0.08
A polyethylene film (PE) [(E ′ ₅₀ / E ′ ₁₀₀ ) = 12.5] having a thickness of 30 μm and a density of × 10 ⁵ N / cm ² was prepared. On this film, the coating layer composition 1 obtained in Synthesis Example 1 was applied by a bar coater so that the thickness after drying was 1 μm, and dried at 90 ° C. and 10% Rh for 10 seconds,
Further, it was dried at 100 ° C. for 10 seconds. After that, 50 ℃
After aging for 7 days, a comparative gas barrier film 1 in which the plastic film (A) and the coating layer (B) were laminated was obtained.

Oxygen permeability of comparative gas barrier film 1
Is 145 cm at 20 ° C and 30% Rh ³/ (M²・ 24 hours
s ・ atm), 127 cm at 20 ° C and 90% Rh³/ (M²
・ 24 hrs ・ atm).

Comparative Example 2 On the comparative gas barrier film 1 obtained in Comparative Example 1, a non-stretched polypropylene film (CPP) having a thickness of 60 μm was used as a sealant layer (C).
Were laminated using a urethane adhesive to obtain a comparative gas barrier film 2.

The oxygen permeability of this comparative gas barrier film 2 was 134 cm ³ / (m ² · 24 at 20 ° C. and 30% Rh.
hrs / atm), 121 cm ³ / at 20 ° C and 90% Rh
(M ² · 24 hrs · atm). Adhesion strength is 1
It was 5 gf / 15 mm.

The comparative gas barrier film 2 was boiled in water at 95 ° C. for 20 minutes. When the oxygen permeability after boiling was measured, it was 20 ° C 30% Rh, 20 ° C
Both 90% Rh is 1000 cm ³ / (m ² · 24 hrs ·
atm) was exceeded. Also, the adhesion strength is 10 gf / 1
It was less than 5 mm.

[0090]

[Table 1]

As shown in Table 1, it can be confirmed that the gas barrier film of the present invention is excellent in thermal stability.

[0092]

The gas barrier film having the storage elastic modulus of the plastic film and the adhesion strength between the plastic film and the coating layer satisfying the specified values defined in the present invention has very excellent thermal stability. Therefore, the gas barrier film of the present invention can maintain excellent gas barrier properties even under extremely severe temperature conditions.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08L 23:12 C08L 23:12 67:00 67:00 77:00 77:00 F-term (reference) 4F006 AA35 AA38 AB32 BA05 CA07 CA09 DA04 4F100 AH06B AK01A AK07 AK31B AK48 AK51G AK52B AR00C AT00A BA02 BA03 BA07 BA10A BA10C BA15 EH46 GB15 JD02 JD03 JJ03 JK06 JK06A JK06BJC07A00

Claims (5)

[Claims] 1. A plastic film (A) and the following formula (1): (In the formula, R ¹ is a hydrogen atom or an alkyl group which may have a functional group, R ² is a hydrogen atom or an alkyl group, x is an integer of 0 or more, and y is an integer of 1 or more. And x + y = 4, and when x or y is 2 or more, R ¹ or R ² may be different) and / or a composition containing a hydrolyzed condensate thereof. A coating film (B) formed by using a gas barrier film, wherein the plastic film (A) is 50 ° C. when viscoelasticity is measured in a tensile mode at a frequency of 10 Hz. gas barrier film ratio of ₁₀₀ 'the storage modulus E at ₅₀ to 100 ° C.' storage modulus E (E _'50 / E' _100), characterized in that 1.0 to 5.0 in . 2. A plastic film (A), an organic compound (b-i) having a nitrogen atom to which active hydrogen is bonded in its molecule, and a compound capable of reacting with the active hydrogen to form a chemical bond with the nitrogen atom. A gas barrier film, comprising: a coating layer (B) formed by using a composition obtained by reacting an organic compound (b-ii) having a functional group in the molecule; The plastic film (A) has a ratio (E ′ ₅₀ / E ′ ₅₀ / storage modulus E ′ _{50 at 50} ° C. to storage modulus E ′ _{100 of} 50 ° C. when viscoelasticity is measured at a frequency of 10 Hz in a tensile mode. E '
₁₀₀ ) is 1.0-5.0, The film for gas barriers characterized by the above-mentioned. 3. A plastic film (A), an organic compound (b-i) having a nitrogen atom to which active hydrogen is bonded in the molecule, and a compound capable of reacting with the active hydrogen to form a chemical bond with the nitrogen atom. A gas barrier film, comprising: a coating layer (B) formed by using a composition obtained by reacting an organic compound (b-ii) having a functional group in the molecule; A film for gas barrier, wherein the adhesion strength between the plastic film (A) and the coating layer (B) is 250 gf / 15 mm or more. 4. The coating layer (B) contains, in addition to the organic compound (b-i) and the organic compound (b-ii),
Furthermore, the following formula (2): (In the formula, R ³ is a hydrogen atom or an alkyl group which may have a functional group that does not react with the active hydrogen, R ⁴ is a hydrogen atom or an alkyl group, and a is an integer of 0 or more, b is an integer of 1 or more, a + b = 4, and a
Or when b is 2 or more, R ³ or R ⁴ may be different) by reacting with an organosilicon compound (b-iii) and / or its hydrolyzed condensate (b-iv) The gas barrier film according to claim 2, which is formed by using the obtained composition. 5. The gas barrier film according to claim 1, further comprising a sealant layer (C).