JP2020044732A - Gas barrier film and laminate - Google Patents

Abstract

To provide a gas barrier film and a laminate which are easy to manufacture and have excellent gas barrier properties and optical characteristics.SOLUTION: A gas barrier film 100 includes a substrate film 1 having an inorganic thin film layer 12, and a barrier resin layer 2. The barrier resin layer is formed of a resin composition containing a carboxy group-containing polymer (A) and a compound (B) having two or more groups selected from the group consisting of a group represented by general formula (1) and a group represented by general formula (2) in the molecule (excluding 2,2'-bis(2-oxazoline)). Rand Rare each independently a C1-4 alkyl group; p is a number of 0-4; and q is a number of 0-6.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film and a laminate.

Packaging materials used for foods, pharmaceuticals, cosmetics, precision electronic components, and the like are required to have high oxygen barrier properties and water vapor barrier properties in order to prevent deterioration of contents.
In general, since the oxygen barrier property of a thermoplastic film is not so high, various gas barrier layers such as a polyvinylidene chloride (PVDC) layer and a polyvinyl alcohol (PVA) layer are formed as a means for imparting a gas barrier property to the film. A method of depositing an inorganic material such as alumina (Al ₂ O ₃ ) or silica (SiO ₂ ) has been studied.

  A film having a PVDC layer formed thereon as a gas barrier layer is transparent and exhibits good barrier properties. However, there is a possibility that harmful gases such as acid gas may be generated when incinerated as general waste. Therefore, a shift to another material is desired from the viewpoint of environmental consideration. The film on which the PVA layer is formed exhibits excellent gas barrier properties under low humidity, but has a high hygroscopicity, and has a problem that the gas barrier properties rapidly decrease when the relative humidity is about 70% or more.

  An inorganic vapor-deposited film in which an inorganic substance such as alumina or silica is vapor-deposited on a thermoplastic plastic film is transparent and has good gas barrier properties, and does not cause the above-described problems. However, when the inorganic vapor-deposited film is bent, there is a problem that cracks are generated in the inorganic vapor-deposited layer, and the gas barrier property is significantly reduced.

  As a method of improving the bending resistance of a gas barrier film or a gas barrier laminate including a layer on which an inorganic substance is deposited, a layer comprising a cured product of an epoxy resin composition containing a predetermined epoxy resin and an epoxy resin curing agent as main components Have been proposed. For example, as an epoxy resin composition having high gas barrier properties and adhesiveness, an epoxy curing agent which is a reaction product of metaxylylenediamine or paraxylylenediamine with an unsaturated carboxylic acid having a predetermined structure and / or a derivative thereof Epoxy resin compositions containing the same have been proposed (Patent Documents 1 and 2).

  On the other hand, there has been proposed a method for forming an excellent gas barrier material in a short time without performing a heat treatment at a high temperature. For example, Patent Literature 3 discloses that a gas barrier material having excellent gas barrier properties, retort resistance, and flexibility can be formed, and a composition for forming a gas barrier material that can be cured at a lower temperature in a shorter time can be used as a polycarboxy resin. Compounds having an ether bond formed on carbon forming a double bond between the acid-based polymer (A) and nitrogen, and containing at least two ring structures (b) containing oxygen in the ether bond ( A composition for forming a gas barrier material containing B) and a dehydrating agent (C) has been proposed. Examples of the compound (B) include bisoxazolines such as 2,2'-bis (2-oxazoline).

In addition to Patent Document 3, there are known examples in which an oxazoline group-containing material is applied to a gas barrier film (for example, see Patent Documents 4 and 5).
Patent Document 4 discloses a laminated film for forming an inorganic thin film that satisfies predetermined requirements by providing a coating layer having an average thickness of 5 to 60 nm mainly composed of a resin having an oxazoline group on at least one surface of a plastic substrate film. It is disclosed that even when a laminate having an inorganic thin film is formed and subjected to a retort treatment, the laminate has excellent adhesion to an inorganic thin film and excellent gas barrier properties. Patent Literature 5 has a coating layer containing a resin having an oxazoline group as a constituent component on at least one surface of a polyester base film, has an inorganic thin film layer on the coating layer, and has a predetermined thickness on the inorganic thin film layer. It is disclosed that a laminated film having a protective layer and satisfying predetermined requirements has excellent gas barrier properties and adhesion between layers even under normal conditions and after heat treatment, and has good bending resistance and economy. Have been.

  However, Patent Document 3 does not disclose that the composition for forming a gas barrier material is applied to a base film having an inorganic thin film layer. The laminated films disclosed in Patent Literatures 4 and 5 have a configuration in which a plastic base film has a coating layer containing a resin having an oxazoline group on at least one surface, and an inorganic thin film layer is provided on the coating layer. That is, the coating layer is provided between the plastic substrate film and the inorganic thin film layer in order to improve the adhesion between the plastic substrate film and the inorganic thin film layer.

JP 2003-300271 A JP 2005-28835 A JP 2008-195787 A JP 2011-148090 A JP 2017-148992 A

  Gas barrier films have attracted attention in the optical film field as well as in the packaging material field described above. For example, a quantum dot mounted on a quantum dot (QD) display and an organic EL element mounted on an organic electroluminescence (EL) display are easily deteriorated by moisture. It is also considered effective to use it as a protective film. In these applications, it is preferable that the film has little coloring and high transparency and is excellent in optical properties so as not to hinder image display performance.

  An object of the present invention is to provide a gas barrier film and a laminate that are easy to manufacture and have excellent gas barrier properties and optical characteristics.

The present inventors have found that, in a gas barrier film and a laminate having a substrate film having an inorganic thin film layer and a barrier resin layer, a structure having the barrier resin layer on the surface of the substrate film on the inorganic thin film layer side It has been found that the above problem can be solved by forming the barrier resin layer with a resin composition containing a predetermined compound.
The present invention relates to the following [1] to [11].

[1] A gas barrier film having a base material film having an inorganic thin film layer and a barrier resin layer, wherein the gas barrier film is formed on a surface of the base film on the inorganic thin film layer side by the barrier resin. The barrier resin layer is selected from the group consisting of a carboxy group-containing polymer (A) and a group represented by the following general formula (1) and a group represented by the following general formula (2) in the molecule. Gas barrier film, which is a layer formed from a resin composition containing a compound (B) having two or more groups (excluding 2,2′-bis (2-oxazoline)).

R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, p is a number of 0 to 4, and q is a number of 0 to 6. When a plurality of R ¹ or R ² are present in the component (B), they may be the same or different from each other.
[2] The gas barrier film according to the above [1], wherein the component (A) is a polymer having a (meth) acrylic acid structural unit.
[3] The gas barrier film according to the above [2], wherein the content of the (meth) acrylic acid structural unit in the polymer having the (meth) acrylic acid structural unit is 50% by mass or more of all the structural units. .
[4] The above-mentioned [1] to [3], wherein the component (B) is at least one selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The gas barrier film according to any one of the above.

R ¹ and p are the same as above. Z ¹ is a single bond or a divalent group having 1 to 22 carbon atoms.

R ² and q are the same as above. Z ² is a single bond or a divalent group having 1 to 22 carbon atoms.
[5] The gas barrier film according to [4], wherein the component (B) is a compound represented by the general formula (3), and Z ¹ is a phenylene group.
[6] When the content of the component (B) in the resin composition is 1 g of the component (A), the group represented by the general formula (1) in the component (B) and the general formula (2) The gas barrier film according to any one of the above [1] to [5], wherein the total number of moles of the group represented by the formula (1) is 0.01 to 10 mmol.
[7] The gas barrier film according to any one of [1] to [6], wherein the inorganic substance constituting the inorganic thin film layer is at least one selected from the group consisting of silicon oxide and aluminum oxide. .
[8] The gas barrier film according to the above [7], wherein the inorganic substance constituting the inorganic thin film layer is an aluminum oxide.
[9] The gas barrier film according to any one of [1] to [8], wherein the inorganic thin film layer and the barrier resin layer are adjacent to each other.
[10] The gas barrier film according to any one of [1] to [9], wherein the base film has the inorganic thin film layer on only one surface and has only one barrier resin layer.
[11] A laminate comprising the gas barrier film according to [10] and a thermoplastic resin layer.

  The gas barrier film and the laminate of the present invention have high gas barrier properties and good optical properties, and are suitable for, for example, packaging materials and optical films for image display devices.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows one Embodiment of the gas barrier film of this invention. It is a cross section showing an embodiment of the layered product of the present invention. 13 is a schematic cross-sectional view illustrating a layer configuration of a laminate of Comparative Example 6. FIG.

[Gas barrier film]
The gas barrier film of the present invention is a gas barrier film having a base film having an inorganic thin film layer (hereinafter, also simply referred to as “base film”) and a barrier resin layer, wherein the gas barrier film is The base film has a barrier resin layer on the surface on the side of the inorganic thin film layer, and the barrier resin layer comprises a carboxy group-containing polymer (A), a group represented by the following general formula (1) in the molecule, and Formed from a resin composition containing a compound (B) having two or more groups selected from the group consisting of groups represented by the general formula (2) (excluding 2,2′-bis (2-oxazoline)) Characterized in that it is a layer formed. The gas barrier film only needs to have the base film and at least one barrier resin layer.

R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, p is a number of 0 to 4, and q is a number of 0 to 6. When a plurality of R ¹ or R ² are present in the component (B), they may be the same or different from each other.
Since the gas barrier film of the present invention has the above-described structure, the film has high gas barrier properties and good optical characteristics.
The gas barrier film of the present invention has an initial gas barrier property by having a barrier resin layer on the surface of the base film on the side of the inorganic thin film layer. In addition, since the adhesion of the barrier resin layer to the inorganic thin film layer is good, a gas barrier film and a laminate having high interlayer adhesion can be obtained.
In particular, the barrier resin layer has excellent adhesion to an inorganic thin film layer made of aluminum oxide. Therefore, when using a substrate film having an inorganic thin film layer made of aluminum oxide in the gas barrier film and the laminate of the present invention, and providing a barrier resin layer on the surface on the inorganic thin film layer side, gas barrier properties, optical properties, Further, a gas barrier film and a laminate having better interlayer adhesion can be obtained.
Hereinafter, the materials constituting the gas barrier film of the present invention will be described.

<Base film>
The base film constituting the gas barrier film of the present invention is a film comprising a base film and at least one inorganic thin film layer. The base film may have an inorganic thin film layer on at least one surface, but from the viewpoint of the bending resistance and productivity of the gas barrier film, the base film has an inorganic thin film layer on only one surface. Is preferred.

(Base film)
As the base film constituting the base film, a transparent plastic film is preferable. For example, polyolefin-based films such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, and polypropylene; polyester-based films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; nylon 6, nylon 6,6, and polymeta-xylene Polyamide film such as adipamide (N-MXD6); Polyimide film; Biodegradable film such as polylactic acid; Polyacrylonitrile film; Poly (meth) acrylic film; Polystyrene film; Polycarbonate film; Examples include a saponified vinyl acetate copolymer (EVOH) -based film, a polyvinyl alcohol-based film, and the like. Among these, in terms of transparency, strength and heat resistance, the base film is preferably a film selected from the group consisting of a polyolefin-based film, a polyester-based film, a polyamide-based film, and a polyimide-based film, and a polyester-based film is more preferable. Preferably, a polyethylene terephthalate (PET) film is more preferable.
The film may be uniaxially or biaxially stretched.

(Inorganic thin film layer)
The inorganic thin film layer is provided for providing gas barrier properties. The inorganic thin film layer can exhibit high gas barrier properties even if the thickness is small, and has good transparency. The inorganic thin film layer is preferably an inorganic vapor-deposited layer formed by a vapor deposition method.
The inorganic material constituting the inorganic thin film layer is not particularly limited as long as it is an inorganic material capable of forming a gas barrier thin film on the base film by a vapor deposition method.For example, silicon, aluminum, magnesium, calcium, zinc, tin, nickel, Examples include titanium, zirconium, carbon, and oxides, carbides, nitrides, and oxynitrides thereof. Among these, from the viewpoint of gas barrier properties, at least one selected from the group consisting of silicon oxide and aluminum oxide is preferable, and silicon oxide is more preferable. On the other hand, from the viewpoint of exhibiting good adhesion to the barrier resin layer, aluminum oxide is more preferable. The above-mentioned inorganic substances may be used alone or in combination of two or more.
The thickness of the inorganic thin film layer is preferably 5 nm or more from the viewpoint of obtaining high gas barrier properties. Further, from the viewpoint of transparency and bending resistance, the thickness is preferably 100 nm or less, more preferably 50 nm or less. The thickness is the thickness of one inorganic thin film layer.

  The method for forming the inorganic thin film layer is not particularly limited. For example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a plasma chemical vapor deposition method, a thermochemical vapor deposition method, or a photochemical vapor deposition method. A known vapor deposition method such as a chemical vapor deposition method such as a phase growth method may be used.

  The thickness of the base film composed of the base film and at least one inorganic thin film layer is preferably 5 to 300 μm, more preferably 5 to 100 μm, and still more preferably 8 to 50 μm from the viewpoint of gas barrier properties and strength. And still more preferably 10 to 40 μm.

<Barrier resin layer>
The barrier resin layer of the gas barrier film of the present invention comprises a carboxy group-containing polymer (A) (hereinafter, also simply referred to as a component (A)), a group represented by the following general formula (1) in the molecule, and It is formed from a resin composition containing a compound (B) having two or more groups selected from the group consisting of groups represented by formula (2) (hereinafter, also simply referred to as compound (B) or component (B)). Layer. However, the compound (B) does not include 2,2′-bis (2-oxazoline).

R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, p is a number of 0 to 4, and q is a number of 0 to 6. When a plurality of R ¹ or R ² are present in the component (B), they may be the same or different from each other.
For example, when the compound (B) is a compound having an oxazoline group which is a group included in the general formula (1), in the barrier resin layer, the carboxy group in the carboxy group-containing polymer (A) and the compound (B) The oxazoline group therein reacts with the following formula to form an amide ester bond having high gas barrier performance.

Further, since the compound (B) has two or more groups selected from the group consisting of the groups represented by the general formulas (1) and (2), it acts as a cross-linking agent, and the component (A) By the reaction with the component (B), a crosslinked structure containing an amide ester bond is formed in the barrier resin layer. By this action, more excellent gas barrier properties are developed.

(Carboxy group-containing polymer (A))
Examples of the carboxy group-containing polymer (A) used in the present invention include a polymer having a structural unit derived from a carboxy group-containing monomer, and an acid-modified polymer modified with an acid anhydride or the like. From the viewpoint of forming a crosslinked structure containing an amide ester bond and improving gas barrier properties, a polymer having a structural unit derived from a carboxy group-containing monomer is preferable.
Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, itaconic acid, and maleic acid, and are preferably at least one selected from the group consisting of acrylic acid and methacrylic acid.

From the viewpoint of improving gas barrier properties, a polymer having a (meth) acrylic acid structural unit is preferable as the component (A). The polymer having a (meth) acrylic acid structural unit is a polymer having at least one structural unit selected from the group consisting of an acrylic acid structural unit and a methacrylic acid structural unit, and further includes a polymer other than the (meth) acrylic acid structural unit. It may have a structural unit. (Meth) acrylic acid means acrylic acid or methacrylic acid.
The content of the (meth) acrylic acid structural unit in the polymer having the (meth) acrylic acid structural unit is preferably 50% by mass or more, more preferably 50% by mass or more, from the viewpoint of improving gas barrier properties. Is 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and the upper limit is 100% by mass.

  In the polymer having a (meth) acrylic acid structural unit, examples of the structural unit other than the (meth) acrylic acid structural unit include structural units derived from a monomer copolymerizable with (meth) acrylic acid. And structural units derived from alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyoxyalkylene glycol (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide and derivatives thereof, styrene, α-methylstyrene, and the like. No. (Meth) acrylate means acrylate or methacrylate.

Specific examples of the component (A) include polyacrylic acid, polymethacrylic acid, polyitaconic acid, acrylic acid-methacrylic acid copolymer, (meth) acrylic acid-alkyl (meth) acrylate copolymer, and (meth) acrylic acid. -Hydroxyalkyl (meth) acrylate copolymer, (meth) acrylic acid-alkyl (meth) acrylate-hydroxyalkyl (meth) acrylate copolymer, (meth) acrylic acid-polyoxyalkylene glycol (meth) acrylate copolymer , (Meth) acrylic acid-glycidyl (meth) acrylate copolymer, (meth) acrylic acid-hydroxyalkyl (meth) acrylate-glycidyl (meth) acrylate copolymer, (meth) acrylic acid and (meth) acrylamide or Copolymer with derivative, styrene- (meth) a Acrylic acid copolymer, styrene - copolymers of maleic acid copolymers; and the like.
Among the above, from the viewpoint of obtaining excellent gas barrier properties and availability, the component (A) includes polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymer, and (meth) acrylic acid-alkyl. At least one selected from the group consisting of a (meth) acrylate copolymer and a copolymer of (meth) acrylic acid and (meth) acrylamide or a derivative thereof is preferable, and a group consisting of polyacrylic acid and polymethacrylic acid More preferably, it is at least one member selected from the group consisting of:

As the component (A), a partially neutralized product in which a part of the carboxy groups in the carboxy group-containing polymer is neutralized by a basic compound can also be used. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and ammonia.
When the component (A) is a partially neutralized product, the degree of neutralization is not particularly limited, but from the viewpoint of obtaining excellent gas barrier properties, the molar ratio to the carboxy groups in the component (A) is preferably 30% or less. , More preferably 10% or less.

The weight average molecular weight (Mw) of the carboxy group-containing polymer (A) is not particularly limited, but is preferably 3,000 to 5,000,000, more preferably 3,000 to 2,000,000, and still more preferably 3,000 to 500,000. 3,000 to 300,000, still more preferably 5,000 to 250,000, and still more preferably 10,000 to 100,000. If Mw is 3,000 or more, it is advantageous in terms of gas barrier properties, strength, and low blocking properties of the formed barrier resin layer, and if it is 5,000,000 or less, solubility in a solvent, coating properties, Good handleability.
The Mw of the carboxy group-containing polymer (A) can be measured, for example, by gel filtration chromatography (GPC).

(Compound (B))
The component (B) used in the present invention is a compound having in its molecule two or more groups selected from the group consisting of a group represented by the following general formula (1) and a group represented by the following general formula (2), There is no particular limitation as long as it is a compound other than 2,2′-bis (2-oxazoline). 2,2′-bis (2-oxazoline) has low solubility in a solvent and is not suitable for forming a barrier resin layer.

R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, p is a number of 0 to 4, and q is a number of 0 to 6. When a plurality of R ¹ or R ² are present in the component (B), they may be the same or different from each other.
R ¹ and R ² in the above formula are preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and more preferably a methyl group. p is preferably 0 to 2, more preferably 0. In addition, q is preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.
From the viewpoint of forming more amide ester bonds by reacting with the above-mentioned component (A) in the barrier resin layer and exhibiting excellent gas barrier properties, the component (B) has a molecular weight of less than 1,000, preferably a molecular weight. It is preferably a low molecular compound having a molecular weight of 800 or less, more preferably 500 or less. From the viewpoint of forming a barrier resin layer having an appropriate crosslinking density by reacting with the component (A), among the components (B), the group represented by the general formula (1) and the general Compounds having two groups selected from the group consisting of groups represented by formula (2) are preferred.

Preferred examples of the component (B) include, for example, at least one selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4).

R ¹ and p are the same as above. Z ¹ is a single bond or a divalent group having 1 to 22 carbon atoms.

R ² and q are the same as above. Z ² is a single bond or a divalent group having 1 to 22 carbon atoms.
Z ¹ in the general formula (3) is preferably a divalent group having 2 to 16 carbon atoms, more preferably a single bond or a divalent group having 2 to 12 carbon atoms. Z ² in the general formula (4) is preferably a single bond or a divalent group having 2 to 16 carbon atoms, more preferably a single bond or a divalent group having 2 to 12 carbon atoms.
The divalent group in Z ¹ and Z ² may include —CO—, —COO—, —SO ₂ —, or —O—, but is preferably a hydrocarbon group, and is preferably an alkylene group or a cycloalkylene group. , An alkenylene group, an alkylidene group, or an arylene group, more preferably, an alkylene group or an arylene group. Even more preferably, it is an arylene group, even more preferably a phenylene group.
Z ¹ is preferably a phenylene group, more preferably a 1,3-phenylene group. Z ² is preferably a single bond or a phenylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group.
Among the above, the component (B) is a compound represented by the general formula (3), and a compound in which Z ¹ is a phenylene group is preferable.

Specific examples of the component (B) include compounds represented by the general formula (3), that is, 2,2′-bis (4-methyl-2-oxazoline) and 2,2′-bis (5-methyl- 2-oxazoline), 2,2′-bis (5,5′-dimethyl-2-oxazoline), 2,2′-bis (4,4,4 ′, 4′-tetramethyl-2-oxazoline), , 2 '-(1,2-phenylene) bis (2-oxazoline), 2,2'-(1,3-phenylene) bis (2-oxazoline) [1,3-bis (4,5-dihydro-2) -Oxazolyl) benzene], 2,2 '-(1,4-phenylene) bis (2-oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p -Phenylenebis (4,4-dimethyl-2-oxazoline), 2,2′-m-phenylenebis (4-methyl-2-oxazoline), 2,2′-m-phenylenebis (4,4′-dimethyl-2-oxazoline), 2,2′-ethylenebis (2-oxazoline), 2,2′- Tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-oxazoline) 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-3,3'-diphenoxy Bisoxazolines such as ethanebis (2-oxazoline), 2,2′-cyclohexylenebis (2-oxazoline), and 2,2′-diphenylenebis (2-oxazoline); represented by the formula (4) Conversion 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H-1,3-oxazine), , 2′-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′- Butylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-p / p ′ Bisoxa such as -diphenylenebis (5,6-dihydro-4H-1,3-oxazine) Gins are mentioned, and one or more of these can be used in combination.
Among the above, bisoxazolines are preferable as the component (B), and 2,2 ′-(1,2-phenylene) bis (2-oxazoline) and 2,2 ′-(1,3-phenylene) bis (2 -Oxazoline) [1,3-bis (4,5-dihydro-2-oxazolyl) benzene] and at least one selected from the group consisting of 2,2 '-(1,4-phenylene) bis (2-oxazoline). Species is more preferable, and at least selected from the group consisting of 2,2 ′-(1,3-phenylene) bis (2-oxazoline) and 2,2 ′-(1,4-phenylene) bis (2-oxazoline) One type is more preferred, and 2,2 ′-(1,3-phenylene) bis (2-oxazoline) is even more preferred.

  In the resin composition forming the barrier resin layer, the content of the component (B) is based on 1 g of the component (A) and the group represented by the general formula (1) in the component (B) and the general formula (2). )), The total number of moles of the group is preferably 0.01 to 10 mmol, more preferably 0.1 to 8 mmol, further preferably 0.5 to 7 mmol, still more preferably 1 to 7 mmol, and still more preferably 1 to It is from 0.5 to 5 mmol, more preferably from 2 to 5 mmol. Good gas barrier properties are obtained when the total mole number of the group represented by the general formula (1) and the group represented by the general formula (2) in the component (B) is at least 0.01 mmol per 1 g of the component (A). When it is 10 mmol or less, the solubility in the composition is good. Further, the total mole number of the group represented by the general formula (1) and the group represented by the general formula (2) in the component (B) per 1 g of the component (A) is 0.1 mmol or more, preferably 0.1 mol. When the amount is 5 mmol or more, more preferably 1 mmol or more, still more preferably 1.5 mmol or more, and still more preferably 2 mmol or more, the gas barrier property is good, and especially when the inorganic thin film layer is an aluminum oxide, the water vapor barrier property is improved. I do.

(Inorganic particles)
The barrier resin layer and the resin composition forming the same may further contain inorganic particles. When inorganic particles are contained, the gas barrier film having an inorganic thin film layer can have improved bending resistance and the like.
The inorganic particles may be spherical inorganic particles or non-spherical inorganic particles, and are preferably non-spherical inorganic particles from the viewpoint of easily exhibiting gas barrier properties. The shape of the non-spherical inorganic particles may be a three-dimensional shape other than a spherical shape (substantially perfect spherical shape), and examples thereof include a plate shape, a scale shape, a column shape, a chain shape, and a fiber shape. A plurality of plate-like or scale-like inorganic particles may be laminated to form a layer. Among these, from the viewpoint of improving gas barrier properties and bending resistance, plate-like, flake-like, columnar, or chain-like inorganic particles are preferable, and plate-like, flake-like, or columnar inorganic particles are more preferable, and the plate-like shape is preferable. Alternatively, scaly inorganic particles are more preferable.

Examples of the inorganic substance constituting the inorganic particles include silica, alumina, mica (mica), talc, aluminum, bentonite, smectite and the like. Among these, at least one selected from the group consisting of silica, alumina, and mica is preferable, and at least one selected from the group consisting of silica and alumina is more preferable from the viewpoint of improving gas barrier properties and bending resistance.
The above-mentioned inorganic particles may be surface-treated as necessary for the purpose of increasing the dispersibility in the resin composition and improving the transparency of the obtained gas barrier film. Among them, the inorganic particles are preferably coated with an organic material, and at least one selected from the group consisting of silica and alumina coated with an organic material from the viewpoint of improving gas barrier properties, bending resistance, and transparency. Species are more preferred. From the viewpoint of gas barrier properties and bending resistance, silica coated with an organic material is more preferable, and from the viewpoint of transparency, alumina coated with an organic material is more preferable.

  The average particle size of the inorganic particles is preferably 1 to 2,000 nm, more preferably 1 to 1,500 nm, still more preferably 1 to 1,000 nm, still more preferably 1 to 800 nm, and still more preferably 1 to 500 nm, The range is even more preferably 5 to 300 nm, still more preferably 5 to 200 nm, still more preferably 5 to 100 nm, and still more preferably 8 to 70 nm. When the average particle size is 1 nm or more, the preparation of the inorganic particles is easy, and when the average particle size is 2,000 nm or less, the gas barrier properties, the bending resistance, and the transparency are all good. Note that the average particle size is the average particle size of the primary particles.

  When the inorganic particles are plate-like, scale-like, columnar, or fibrous non-spherical inorganic particles, the aspect ratio is preferably from 2 to 700, and more preferably from 3 to 500. When the aspect ratio is 2 or more, good gas barrier properties are easily developed.

The average particle diameter and the aspect ratio of the inorganic particles can be determined by, for example, observing using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and averaging three or more measured values. The average particle diameter and the aspect ratio of the inorganic particles present in the barrier resin layer may be determined, for example, by embedding the gas barrier film in an epoxy resin and then performing ion milling on the cross section of the film using an ion milling device. It can be obtained by preparing an observation sample and observing and measuring the cross section of the obtained sample in the same manner as described above.
When the average particle diameter of the inorganic particles is less than 100 nm and it is difficult to measure the average particle diameter by the above method, the average particle diameter can be measured by, for example, the BET method.

The method for producing the inorganic particles is not particularly limited, and a known method can be used.
From the viewpoints of ease of preparation of the inorganic particles, ease of blending into the resin composition, and dispersibility, in the present invention, it is preferable to prepare a dispersion of the inorganic particles and blend the dispersion with the resin composition. The dispersion medium of the inorganic particle dispersion is not particularly limited, and either water or an organic solvent can be used. As the organic solvent, a polar solvent is preferable from the viewpoint of dispersibility of the inorganic particles, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol, 2-ethoxyethanol, and 2-propoxy are preferable. Protic polar solvents such as ethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, N, N-dimethylformamide, N, N-dimethylacetamide And aprotic polar solvents such as dimethylsulfoxide and N-methylpyrrolidone.
From the viewpoint of the dispersibility of the inorganic particles, the dispersion medium is preferably at least one selected from the group consisting of water and a protic polar solvent, and from the viewpoint of the dispersibility of the particles, and the miscibility of the dispersion and the resin composition. Is more preferably a protic polar solvent, and even more preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol and 2-propanol.

  When inorganic particles are used, the content of the inorganic particles in the resin composition forming the barrier resin layer is preferably from 0.5 to 10.0 parts by mass, more preferably from 100 to 100 parts by mass of the component (A). Is 1.0 to 8.0 parts by mass, more preferably 1.5 to 6.0 parts by mass. When the content of the inorganic particles in the resin composition is 0.5 parts by mass or more based on 100 parts by mass of the component (A), the obtained gas barrier film has a good effect of improving the bending resistance. Further, when the content is 10.0 parts by mass or less, the gas barrier properties and transparency of the obtained gas barrier film are maintained in good ranges.

<Other ingredients>
To the resin composition forming the barrier resin layer, a thermosetting resin, a wetting agent, a tackifier, an antifoaming agent, a curing accelerator, and a rust preventive are added as necessary within a range that does not impair the effects of the present invention. You may mix additives, such as an agent, a pigment, and an oxygen scavenger. The total content of these additives in the resin composition is preferably 10% by mass or less, more preferably 0.001 to 5% by mass.

  From the viewpoint of obtaining the effects of the present invention, the total content of the component (A) and the component (B) in the solid content of the barrier resin layer and the resin composition forming the same is preferably 60% by mass or more, It is more preferably at least 70% by mass, further preferably at least 80% by mass, even more preferably at least 85% by mass, and the upper limit is 100% by mass. The “solid content of the resin composition” means a component excluding water and a solvent in the resin composition.

The resin composition for forming the barrier resin layer is prepared, for example, by blending a predetermined amount of the component (A), the component (B), and, if necessary, the inorganic particles or a dispersion thereof, an additive, and a solvent. It can be prepared by stirring and mixing using a known method and apparatus. The order of mixing the components is not particularly limited, but a solution is prepared by dissolving the components (A) and (B) in a solvent, and then the solution of the component (A) and the solution of the component (B) are mixed. Mixing is preferred.
The solvent used in the above solution is not particularly limited as long as it is a solvent capable of dissolving each component, but the polar solvent exemplified as the dispersion medium of the inorganic particle dispersion is preferable, a protic polar solvent is more preferable, and methanol, ethanol, At least one selected from the group consisting of 1-propanol and 2-propanol is more preferred.

  The thickness of the barrier resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, further preferably 0.5 μm or more, and still more preferably 0.8 μm or more, from the viewpoint of gas barrier properties and bending resistance. is there. In addition, from the viewpoint of the transparency of the gas barrier film, the thickness is preferably 20 μm or less, more preferably 10 μm or less, further preferably 8.0 μm or less, still more preferably 5.0 μm or less, and still more preferably 3.5 μm or less. is there. The thickness is the thickness of one layer of the barrier resin layer.

<Layer structure of gas barrier film>
The gas barrier film of the present invention has the base film having an inorganic thin film layer and at least one barrier resin layer, and has a barrier resin layer on a surface of the base film on the inorganic thin layer side. What is necessary is just a structure which has. From the viewpoint of obtaining the effects of the present invention, the gas barrier film of the present invention preferably has a configuration in which the base film has an inorganic thin film layer on only one side and has only one barrier resin layer. Further, it is preferable that the inorganic thin film layer and the barrier resin layer are adjacent to each other.
As a preferred layer configuration of the gas barrier film, for example, the configuration of FIG. FIG. 1 is a schematic cross-sectional view showing one embodiment of the gas barrier film of the present invention. A gas barrier film 100 has a base film 1 having an inorganic thin film layer 12 on one surface and a surface on the inorganic thin film layer 12 side. This is a configuration in which the barrier resin layer 2 is provided. The base film 1 is obtained by forming an inorganic thin film layer 12 on one surface of a base film 11. In FIG. 1, the inorganic thin film layer 12 and the barrier resin layer 2 are adjacent to each other. Further, as shown in FIG. 1, the gas barrier film of the present invention preferably has no film other than the base film.
However, the gas barrier film of the present invention is not limited to the layer configuration shown in FIG. 1, and may have, for example, two or more barrier resin layers. In addition, for example, in the gas barrier film of FIG. 1, a primer is provided between the base film 1 and the barrier resin layer 2 or on the upper surface (the surface not adjacent to the base film 1) of the barrier resin layer 2. A configuration having a layer, a protective layer, and the like may be used.

<Production method of gas barrier film>
The method for producing the gas barrier film of the present invention is not particularly limited, and a known method can be used. For example, as a method of manufacturing the gas barrier film having the configuration shown in FIG. 1, a resin composition for forming a barrier resin layer is formed on the surface of the base film on which the inorganic thin film layer is formed on one surface of the base film. A method of forming a barrier resin layer by applying a desired thickness and then heating to form a barrier resin layer may be used.
Examples of the application method when applying the resin composition include, for example, bar coat, Meyer bar coat, air knife coat, gravure coat, reverse gravure coat, micro gravure coat, micro reverse gravure coat, die coat, slot die coat, vacuum die coat, dip Coating, spin coating, roll coating, spray coating, brush coating and the like can be mentioned. Among them, a bar coat, a roll coat or a spray coat is preferable, and a gravure coat, a reverse gravure coat, a micro gravure coat, or a micro reverse gravure coat is industrially preferable.

  After the application of the resin composition, heating is performed to cause the components (A) and (B) to react with each other and to volatilize water and the solvent in the resin composition. The heating conditions can be appropriately selected. For example, the heating can be performed under the conditions of a heating temperature of 60 to 180 ° C. and a heating time of 5 to 180 seconds.

<Characteristics of gas barrier film>
The gas barrier film of the present invention has excellent gas barrier properties. For example, the oxygen permeability (cc / m ² · day · atm) at 23 ° C. and a relative humidity of 60% of the base film to be used is determined by the oxygen permeability (cc / m ² ) of the gas barrier film at a temperature of 23 ° C. and a relative humidity of 60%. ^The value (hereinafter also referred to as “OTR improvement rate”) divided by ( ² · day · atm) is preferably 2 or more, more preferably 5 or more, and still more preferably 10 or more.
Further, 40 ° C. of the substrate film to be used, water vapor permeability at 90% relative humidity the ^{(g / m 2 · day)} , 40 ℃ gas barrier film, water vapor permeability at a relative humidity of 90% (g / ^{m 2} · day) (hereinafter also referred to as “WVTR improvement rate”) is preferably 1.2 or more, more preferably 1.5 or more, further preferably 2 or more, and still more preferably 2.5 or more.
The oxygen permeability and the water vapor permeability of the gas barrier film are specifically determined by the methods described in Examples.

It is preferable that the gas barrier film of the invention has little coloring and high transparency. In particular, when used as an optical film for an image display device, such as a protective film for a quantum dot in a quantum dot display or a protective film for an organic EL element in an organic EL display, it is required to have low coloring and high transparency.
From the above viewpoint, the YI value of the gas barrier film of the present invention is preferably 2.5 or less, more preferably 2.0 or less, and further preferably 1.5 or less. The YI value can be measured according to JIS K7373: 2006.
The haze of the gas barrier film of the present invention is preferably 10% or less, more preferably 7% or less, and still more preferably 5% or less. Haze can be measured according to JIS K7136: 2000.
Further, the total light transmittance of the gas barrier film of the present invention is preferably 85% or more, more preferably 88% or more. The total light transmittance can be measured according to JIS K7361-1: 1997.

[Laminate]
The laminate of the present invention has the above-described gas barrier film of the present invention and a thermoplastic resin layer. As a preferable configuration, for example, the surface on the barrier resin layer side in the gas barrier film of the present invention (the surface (upper surface) on the barrier resin layer 2 side in the gas barrier film 100 in FIG. 1) or the opposite surface (FIG. And a structure in which a thermoplastic resin layer is laminated on the surface (lower surface) on the base film 11 side in the gas barrier film 100 of (1).
In the laminate, an arbitrary layer such as a primer layer, an ink layer, an adhesive layer, a surface protection layer, and a vapor deposition layer may be further laminated between the gas barrier film and the thermoplastic resin layer. The laminate of the present invention may have two or more gas barrier films of the present invention and two or more thermoplastic resin layers.

It is preferable to use a thermoplastic resin film as the thermoplastic resin layer. As the thermoplastic resin film, the transparent plastic film exemplified in the base film constituting the base film is preferable. The surface of the thermoplastic resin film may be subjected to a surface treatment such as a flame treatment or a corona discharge treatment. Further, as the thermoplastic resin film, a film containing an ultraviolet absorber, a coloring agent, or the like, or a film having a primer layer, an ink layer, a surface protective layer, a vapor deposition layer, or the like on the surface can also be used.
The thickness of the thermoplastic resin layer is preferably from 10 to 300 μm, more preferably from 10 to 100 μm.

Preferred layer configurations of the laminate of the present invention include, for example, a configuration in which the gas barrier film and the thermoplastic resin film are directly laminated, and a configuration in which the gas barrier film and the thermoplastic resin film are laminated via an adhesive layer. And the like. Among them, a configuration in which a gas barrier film and a thermoplastic resin film are laminated via an adhesive layer is preferable.
When the gas barrier film and the thermoplastic resin film are laminated with an adhesive layer interposed therebetween, it is preferable that the surface of the gas barrier film on the side of the barrier resin layer and the thermoplastic resin film face each other and laminated. . In this case, the layer configuration of the laminate is as shown in FIG. FIG. 2 is a schematic sectional view showing an embodiment of the laminate of the present invention. In FIG. 2, a laminate 200 is formed by laminating the surface of the gas barrier film 100 on the side of the barrier resin layer 2 and the thermoplastic resin film 3 with the adhesive layer 4 interposed therebetween. In this configuration, the inorganic thin film layer 12, the barrier resin layer 2, the adhesive layer 4, and the thermoplastic resin film 3 are laminated in this order.

The method for producing the laminate is not particularly limited. For example, as a method of manufacturing a laminate in which a gas barrier film and a thermoplastic resin film are directly laminated, the above-described barrier resin layer forming surface is formed on the inorganic thin film layer side surface of the base film constituting the gas barrier film. Immediately after the application of the resin composition, a thermoplastic resin film is adhered to the application surface by a nip roll or the like, and then the resin composition is heated by the above-described method. In this case, the resin composition constituting the barrier resin layer also plays a role of bonding the base resin film and the thermoplastic resin film in the gas barrier film.
As a method for producing a laminate in which a gas barrier film and a thermoplastic resin film are laminated via an adhesive layer, one side of the gas barrier film produced by the above-described method, or an adhesive on one side of the thermoplastic resin film. There is a method in which an adhesive constituting a layer is applied, and then the other film is attached and laminated.
As the adhesive constituting the adhesive layer, a known adhesive such as a urethane-based adhesive, an acrylic-based adhesive, or an epoxy-based adhesive can be used. The thickness of the adhesive layer is not particularly limited, but is preferably from 0.1 to 30 μm, more preferably from 1 to 20 μm, and still more preferably from 2 to 20 μm, from the viewpoint of achieving both adhesion and transparency.

<Application>
Since the gas barrier film and the laminate of the present invention have excellent gas barrier properties and optical properties, they are suitable for use as packaging materials for protecting foods, pharmaceuticals, cosmetics, precision electronic components, and the like. When used as a packaging material, the gas barrier film and the laminate of the present invention may be used as a packaging material as they are, or another layer or film may be further laminated.
In addition, gas barrier films and laminates having particularly good water vapor barrier properties and optical properties include optical films for image display devices, such as protective films for quantum dots in quantum dot displays and organic EL elements in organic EL displays. It is also suitable. The embodiment as the protective film is, for example, a protective film for an organic EL element, in an organic EL display device, the gas barrier of the present invention is provided on the surface on the side where the organic EL element is formed and on the viewer side of the display device. And a mode in which a conductive film is provided.

Next, the present invention will be described specifically with reference to examples. However, the present invention is not limited at all by these examples.
The measurement and evaluation in this example were performed by the following methods.

<Thickness of barrier resin layer>
The measurement was performed using a multilayer film thickness measuring device (“DC-8200” manufactured by Gunze Co., Ltd.).

<Oxygen permeability of film (cc / m ² · day · atm)>
The oxygen transmission rate (OTR) was measured using an oxygen transmission rate measuring apparatus (“OX-TRAN 2/21” manufactured by Modern Control) under the conditions of 23 ° C. and 60% relative humidity.

<Moisture water vapor transmission rate (g / m ² · day)>
Using a water vapor transmission rate measuring apparatus (“PERMATRAN-W 1/50” manufactured by MOCON), the measurement was continuously performed under the conditions of 40 ° C. and a relative humidity of 90%. WVTR).

<YI>
Based on JIS K7373: 2006, it was measured using a color / turbidity simultaneous measuring device (“COH400” manufactured by Nippon Denshoku Industries Co., Ltd.).

<Haze>
Based on JIS K7136: 2000, it was measured using a color / turbidity simultaneous measurement device (“COH400” manufactured by Nippon Denshoku Industries Co., Ltd.).

<Total light transmittance>
Based on JIS K7361-1: 1997, it was measured using a color / turbidity simultaneous measurement device (“COH400” manufactured by Nippon Denshoku Industries Co., Ltd.).

<Peel strength (g / 15 mm)>
According to the method specified in JIS K6854-3: 1999, the peel strength of the laminate was measured at a peel rate of 300 mm / min by a T-type peel test.

<Peeling interface>
In the measurement of the peel strength of the laminate, it was visually observed at which layer interface the laminate was peeled.

Production Example 1 (Production of resin composition A)
As the component (A), (A-1) polyacrylic acid (Mw 25,000, “polyacrylic acid 25,000” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and as the component (B), (B-1) 2,2 '-(1,3-phenylene) bis (2-oxazoline) (1,3-PBO, "1,3-bis (4,5-dihydro-2-oxazolyl) benzene" manufactured by Tokyo Chemical Industry Co., Ltd.) used.
A 10% by weight methanol solution of polyacrylic acid and a 10% by weight methanol solution of 1,3-PBO were prepared, and 10 g of the obtained polyacrylic acid solution and 3 g of 1,3-PBO solution were mixed to obtain a resin composition. The product A was obtained.

Production Example 2 (Production of resin composition B)
10 g of a polyacrylic acid solution and 3 g of a 1,3-PBO solution prepared in the same manner as in Production Example 1, and a 10% by mass ethanol dispersion of plate-like alumina particles (KOS-A2EOK5-10 manufactured by Kawaken Fine Chemical Co., Ltd.) , 0.2 g of alumina particles (average primary particle diameter: 20 nm) to obtain a resin composition B.

Production Examples 3 to 6 (Production of resin compositions C to F)
10% by mass methanol solution of polyacrylic acid, 10% by mass methanol solution of 1,3-PBO prepared in the same manner as in Production Example 1, and 10% by mass ethanol dispersion of plate-like alumina particles used in Production Example 2 Were mixed at the ratios shown in Table 1 to obtain resin compositions C to F.

Production Example 7 (Production of Comparative Resin Composition A)
A 10% by mass methanol solution of the polyacrylic acid (Mw 25,000, “Polyacrylic acid 25,000” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) used in Production Example 1 was prepared, and this was referred to as Comparative Resin Composition A. did.

Production Example 8 (Production of Comparative Resin Composition B)
10 g of a 10% by mass methanol solution of polyacrylic acid prepared in the same manner as in Production Example 1 and a 10% by mass ethanol dispersion of plate-like alumina particles ("KOS-A2EOK5-10" manufactured by Kawaken Fine Chemicals Co., Ltd.) Comparative resin composition B was obtained by mixing with 5 g.

Production Examples 9 to 11 (Production of Resin Compositions GI)
A 10% by mass methanol solution of polyacrylic acid prepared in the same manner as in Production Example 1 and a 10% by mass methanol solution of 1,3-PBO were mixed at the ratio shown in Table 1 to obtain resin compositions G to I. Was.

Production Examples 12 and 13 (Production of resin compositions J and K)
Except that (A-2) polyacrylic acid (Mw 5,000, “Polyacrylic acid 5,000” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the component (A), the same procedure as in Production Example 1 was carried out. A 10% by mass methanol solution of polyacrylic acid was prepared. This solution and a 10% by mass methanol solution of 1,3-PBO were mixed at the ratio shown in Table 1 to obtain resin compositions J and K.

Production Examples 14 and 15 (Production of resin compositions L and M)
Except that (A-3) polyacrylic acid (Mw 250,000, "Polyacrylic acid 250,000" manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as the component (A), the same procedure as in Production Example 1 was carried out. A 10% by mass methanol solution of polyacrylic acid was prepared. This solution and a 10% by mass methanol solution of 1,3-PBO were mixed at the ratio shown in Table 1 to obtain resin compositions L and M.
Table 1 shows the composition.

Production Example 16
An attempt was made to prepare a 10% by mass methanol solution using (2) -bis (2-oxazoline) as the (B) ′ component, but the solubility in methanol was low and the solution could not be prepared.

[Production and evaluation of gas barrier film]
Example 1
As the substrate film, a silica-deposited PET (“Tech Barrier L” manufactured by Mitsubishi Plastics, Inc., thickness: 12 μm) in which silicon oxide (silica) was deposited on one side of PET was used. The resin composition A obtained in Production Example 1 was coated on the silica-deposited surface with a bar coater No. 8 and dried at 100 ° C. for 60 seconds to obtain a gas barrier film having the configuration shown in FIG. 1 and having a 1.65 μm-thick barrier resin layer on the silica-deposited surface of the base film.
Various evaluations were performed using the obtained films by the methods described above. Table 2 shows the results.

Examples 2-6, Comparative Examples 1-2
Except that the thickness of the resin composition and the barrier resin layer used were changed as shown in Table 2, a gas barrier film was produced in the same manner as in Example 1, and various evaluations were made. Table 2 shows the results.

Comparative Example 3
Various evaluations were performed using the silica-deposited PET, which is the substrate film used in Examples 1 to 6 and Comparative Examples 1 and 2, by the above method. Table 2 shows the results.

Examples 7 to 17, Comparative Example 4
The substrate film to be used was changed to an alumina-deposited PET in which aluminum oxide (alumina) was vapor-deposited on one side of PET (“Barrierox 1011HG (no coating)” manufactured by Toray Film Processing Co., Ltd., thickness: 12 μm), A gas barrier film was produced in the same manner as in Example 1, except that the thickness of the resin composition used and the thickness of the barrier resin layer were changed as shown in Table 2, and various evaluations were made. Table 2 shows the results.

Comparative Example 5
Various evaluations were performed by the above method using the alumina-deposited PET as the base film used in Examples 7 to 17 and Comparative Example 4. Table 2 shows the results.

  As shown in Table 2, the gas barrier film of the present invention has excellent gas barrier properties, and also has good optical properties because of low YI value and Haze value and high total light transmittance.

[Production of laminate and evaluation of interlayer adhesion]
Example 18
As the substrate film, a silica-deposited PET (“Tech Barrier L” manufactured by Mitsubishi Plastics, Inc., thickness: 12 μm) in which silicon oxide (silica) was deposited on one side of PET was used. The resin composition A obtained in Production Example 1 was coated on the silica-deposited surface with a bar coater No. 8 and dried by heating at 100 ° C. for 60 seconds to obtain a gas barrier film having a configuration shown in FIG. 1 and having a barrier resin layer on the silica-deposited surface of the substrate film.
On the barrier resin layer of the obtained gas barrier film, 15 parts by mass of a polyester resin component (“AD-502” manufactured by Toyo Morton Co., Ltd.) as a urethane adhesive, and a polyisocyanate component (Toyo Morton Co., Ltd.) (CAT-RT85) manufactured by Bar Coater Co., Ltd.) containing 1.05 parts by mass of an ethyl acetate solution (solid content: 20% by mass). 12 and dried at 80 ° C. for 10 seconds, and then a 40 μm-thick linear low-density polyethylene film (LLDPE, “TUX MC-S” manufactured by Mitsui Chemicals Tosello Co., Ltd.) was applied. By laminating with a nip roll, a laminate having the configuration shown in FIG. 2 was obtained.
Using the obtained laminate, the measurement of the peel strength and the observation of the peel interface were performed by the above method. Table 3 shows the results.

Examples 19 to 21
A laminate was prepared in the same manner as in Example 18 except that the resin composition used was changed as shown in Table 3, and the peel strength was measured and the peel interface was observed. Table 3 shows the results.

Example 22
Except that, as the base film, an alumina-deposited PET (available from Toray Film Processing Co., Ltd., “Barrierox 1011HG (no coat)”, thickness: 12 μm) in which aluminum oxide (alumina) was deposited on one side of PET was used. A laminate was prepared in the same manner as in Example 18, and the peel strength was measured and the peel interface was observed. Table 3 shows the results.

Examples 23 to 25
A laminate was prepared in the same manner as in Example 22 except that the resin composition used was changed as shown in Table 3, and the peel strength was measured and the peel interface was observed. Table 3 shows the results.

Comparative Example 6
Except that the barrier resin layer was not formed, an alumina-deposited PET, an adhesive layer, and LLDPE were sequentially laminated in the same manner as in Example 22 to produce a laminate 200 ′ having the configuration shown in FIG. The peel strength was measured and the peel interface was observed. Table 3 shows the results.

  As shown in Table 3, the laminates of Examples 22 to 25 using alumina-deposited PET as the base film had a large peel strength value and the peel interface was between the adhesive layer and the LLDPE. It can be seen that the adhesion between the alumina vapor deposition layer and the barrier resin layer is high. The laminates of Examples 18 to 21 using silica-deposited PET as the base film had lower adhesion between the deposited layer and the barrier resin layer than Examples 22 to 25.

  Since the gas barrier film and the laminate of the present invention have high gas barrier properties and good optical properties, they are suitable for, for example, packaging materials and optical films for image display devices.

Reference Signs List 100 gas barrier film 1 base film 11 base film 12 inorganic thin film layer 2 barrier resin layer 3 thermoplastic resin film (thermoplastic resin layer)
4 Adhesive Layer 200 Laminate 200 ′ Laminate of Comparative Example 6

Claims (11)

A substrate film having an inorganic thin film layer, a gas barrier film having a barrier resin layer,
The gas barrier film has the barrier resin layer on the surface of the substrate film on the side of the inorganic thin film layer, and the barrier resin layer comprises a carboxy group-containing polymer (A) and the following general formula in a molecule: Compound (B) having two or more groups selected from the group consisting of a group represented by (1) and a group represented by the following general formula (2) (however, excluding 2,2′-bis (2-oxazoline) ), Which is a layer formed from a resin composition containing:

R ¹ and R ² are each independently an alkyl group having 1 to 4 carbon atoms, p is a number of 0 to 4, and q is a number of 0 to 6. When a plurality of R ¹ or R ² are present in the component (B), they may be the same or different from each other.   The gas barrier film according to claim 1, wherein the component (A) is a polymer having a (meth) acrylic acid structural unit.   The gas barrier film according to claim 2, wherein the content of the (meth) acrylic acid structural unit in the polymer having the (meth) acrylic acid structural unit is 50% by mass or more of all the structural units. The component (B) according to any one of claims 1 to 3, wherein the component (B) is at least one selected from the group consisting of a compound represented by the following general formula (3) and a compound represented by the following general formula (4). The gas barrier film according to the above.

R ¹ and p are the same as above. Z ¹ is a single bond or a divalent group having 1 to 22 carbon atoms.

R ² and q are the same as above. Z ² is a single bond or a divalent group having 1 to 22 carbon atoms. The gas barrier film according to claim 4, wherein the component (B) is a compound represented by the general formula (3), and Z ¹ is a phenylene group.   The content of the component (B) in the resin composition is represented by the group represented by the general formula (1) in the component (B) and the general formula (2) based on 1 g of the component (A). The gas barrier film according to any one of claims 1 to 5, wherein the total number of moles of the group is 0.01 to 10 mmol.   The gas barrier film according to any one of claims 1 to 6, wherein the inorganic substance constituting the inorganic thin film layer is at least one selected from the group consisting of silicon oxide and aluminum oxide.   The gas barrier film according to claim 7, wherein the inorganic substance constituting the inorganic thin film layer is aluminum oxide.   The gas barrier film according to any one of claims 1 to 8, wherein the inorganic thin film layer and the barrier resin layer are adjacent to each other.   The gas barrier film according to any one of claims 1 to 9, wherein the base film has the inorganic thin film layer only on one side and has only one barrier resin layer.   A laminate comprising the gas barrier film according to claim 10 and a thermoplastic resin layer.