JP2016064650A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having high level of gas barrier property.SOLUTION: There is provided a gas barrier film by arranging a first layer 2a containing zinc oxide and silicon dioxide and a second layer 2b containing following (A) to (C) on at least single side of a polymer film substrate 1 in this order. (A) is a copolymer having at least three components of at least one unsaturated compound selected from a group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester (a1), unsaturated nitrile (a2) and an unsaturated compound having a hydroxyl group (a3) as monomers with percentage of (a1) to (a3) in the copolymer of (a1):(a2):(a3)=20 to 40 mass%:10 to 30 mass%:30 to 70 mass%. (B) is a compound having an isocyanate group. (C) is a compound having two or more carboxylic acid or one or more carboxylic acid anhydride group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film that is excellent in transparency and exhibits high gas barrier properties against water vapor.

  Physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating using inorganic materials (including inorganic oxides) such as aluminum oxide, silicon oxide, and magnesium oxide on the surface of the polymer film substrate ( PVD method) or chemical vapor deposition method (CVD method) such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, photochemical vapor deposition method, etc. The transparent gas barrier film thus formed is used as a packaging material for foods, pharmaceuticals, and the like that require blocking of various gases such as water vapor and oxygen, and as an electronic device member such as a flat-screen TV and a solar battery.

  As a gas barrier property improving technique, for example, a gas containing an organic silicon compound vapor and oxygen is used to form a silicon oxide as a main component on a substrate by a plasma CVD method, and at least one kind of carbon, hydrogen, silicon and oxygen. A method of improving gas barrier properties while maintaining transparency by forming a layer made of a contained compound is used (Patent Document 1). Moreover, as a gas barrier property improving technique other than the film forming method, an organic layer that is an epoxy compound and a silicon-based oxide layer that is formed by a plasma CVD method are alternately laminated on a substrate, thereby causing cracks and defects due to film stress. A gas barrier film having a multilayer laminated structure in which the occurrence of the above is prevented is used (Patent Document 2).

JP-A-8-142252 (Claims) JP 2003-341003 A (Claims)

However, in the method of forming a gas barrier layer mainly composed of silicon oxide by the plasma CVD method, the water vapor transmission rate is 1 in an environment of a temperature of 40 ° C. and a humidity of 90% required for organic EL and electronic paper applications. In order to obtain a high gas barrier property of × 10 ⁻³ g / m ² · 24 hr · atm or less, it is necessary to increase the thickness of the layer. In such a case, the formed gas barrier layer is very dense and high. Since it is a hard layer, the silicon oxide layer is cracked by the stress of the formed layer, and there is a problem that the gas barrier property is lowered.

On the other hand, in the method of forming a gas barrier layer in which an organic layer and an inorganic layer are alternately laminated, a water vapor transmission rate is 1 × 10 ⁻³ g / m ² · 24 hr in an environment of a temperature of 40 ° C. and a humidity of 90%. In order to obtain a high gas barrier property of atm or less, several tens of layers are required, the polymer film substrate is damaged by the radiant heat of the plasma during layer formation, and warpage due to heat loss occurs. There was a problem that workability deteriorated in the post-processing.

  In view of the background of the prior art, the present invention provides a gas barrier film having a high gas barrier property in which a high gas barrier property can be obtained even when the thickness is small, and a reduction in gas barrier property and a deterioration in workability in post-processing are eliminated. It is something to be done.

The present invention employs the following means in order to solve such problems. That is,
(1) At least one surface of the polymer film substrate is in contact with the first layer containing zinc oxide and silicon dioxide and the second layer containing the following (A) to (C) in this order from the polymer film substrate. A gas barrier film characterized by being arranged.
(A) having at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester, unsaturated nitrile (a2) and hydroxyl group Copolymer (a1): a copolymer having at least three components as a monomer and an unsaturated compound (a3), wherein the proportion of (a1) to (a3) in the copolymer is as follows: a2): (a3) = 20-40% by mass: 10-30% by mass: 30-70% by mass
(B) Compound having an isocyanate group (C) Compound having two or more carboxylic acid groups or one or more carboxylic anhydride groups (2) An undercoat layer between the polymer film substrate and the first layer The gas barrier film according to (1), wherein the undercoat layer contains a polyurethane compound having an aromatic ring structure.
(3) The first layer includes at least one selected from the group consisting of aluminum (Al), gallium (Ga), tin (Sn), and indium (In). The gas barrier film according to any one of 2).
(4) The first layer contains aluminum (Al), and the first layer has a zinc (Zn) atom concentration of 10 to 35 atom% and a silicon (Si) atom concentration of 5 as measured by X-ray photoelectron spectroscopy. The gas barrier film according to any one of (1) to (3), wherein the gas barrier film has a thickness of ˜25 atom%, an aluminum (Al) atom concentration of 1 to 7 atom%, and an oxygen (O) atom concentration of 50 to 70 atom%. .
(5) The gas barrier film according to any one of (1) to (4), wherein the second layer has a thickness of 0.1 μm or more.

  A gas barrier film having a high gas barrier property against water vapor can be provided.

It is sectional drawing which showed an example of the gas barrier film of this invention. It is sectional drawing which showed an example of the gas barrier film of this invention. It is the schematic which shows typically the single wafer type sputtering apparatus for manufacturing the gas barrier film of this invention.

[Gas barrier film]
The gas barrier film of the present invention has a first layer containing zinc oxide and silicon dioxide on at least one surface of a polymer film substrate, and further includes a second layer containing the following (A) to (C): It is a gas barrier film arranged in contact with the molecular film substrate in this order.
(A) having at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester, unsaturated nitrile (a2) and hydroxyl group Copolymer (a1): a copolymer having at least three components as a monomer and an unsaturated compound (a3), wherein the proportion of (a1) to (a3) in the copolymer is as follows: a2): (a3) = 20-40% by mass: 10-30% by mass: 30-70% by mass
(B) Compound having an isocyanate group (C) A compound having two or more carboxylic acid groups or one or more carboxylic anhydride groups.

  Here, the ratio of (a1) to (a3) in the copolymer refers to the mass ratio of each component of (a1) to (a3) when the entire copolymer is 100% by mass. That is, the sum of atomic weights per unit of each component can be determined from the structure of each component (here, the total sum of atomic weights per unit of each component of (a1) to (a3) is A1, A2, and A3, respectively. ). Furthermore, let the repeating number of each component of (a1)-(a3) in a copolymer be l, m, and n, respectively. At this time, the mass ratio which each component of (a1)-(a3) in a copolymer accounts is represented by (A1 * 1) :( A2 * m) :( A3 * n). This represents the ratio of (a1) to (a3) in the copolymer when the total copolymer is 100% by mass and each component is expressed by mass%.

  Hereinafter, “first layer containing zinc oxide and silicon dioxide” is simply abbreviated as “first layer”, and “second layer containing (A) to (C)” is simply abbreviated as “second layer”. There is also.

  FIG. 1 shows a cross-sectional view of an example of the gas barrier film of the present invention. The gas barrier film of the present invention comprises a polymer film substrate 1 comprising a first layer 2a containing zinc oxide and silicon dioxide on one side of the polymer film substrate 1 and a second layer 2b containing (A) to (C). It is arranged from 1 in this order. Hereinafter, the first layer 2 a and the second layer 2 b may be collectively referred to as a gas barrier layer 2. In addition to the gas barrier property of the second layer, the gas barrier layer 2 has the first layer 2a containing the above-mentioned (A) to (C) in contact with the first layer 2a containing zinc oxide and silicon dioxide. Since the defects such as pinholes and cracks on the surface are filled with the (A) to (C) contained in the second layer and the defect size is reduced by shrinkage due to curing, it has a high gas barrier property. Furthermore, the second layer is resistant to acids and alkalis, and has the effect of preventing scratches and cracks on the first layer due to external impact and wear. It is possible to realize a gas barrier film that suppresses the decrease in the temperature.

  Another example of the gas barrier film of the present invention has an undercoat layer 3 between the polymer film substrate 1 and the gas barrier layer 2 on one side of the polymer film substrate 1 as shown in FIG. It is. By having the undercoat layer 3, even if protrusions or scratches are present on the surface of the polymer film substrate 1, it can be flattened, and the gas barrier layer grows uniformly without unevenness. It becomes a gas barrier film that develops.

[Polymer film substrate]
The polymer film substrate used in the present invention preferably has a film form from the viewpoint of ensuring flexibility. The structure of the film may be a single-layer film or a film having two or more layers, for example, a film formed by a coextrusion method. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used.

  The material of the polymer film substrate used in the present invention is not particularly limited, but it is preferable to use an organic polymer as a main constituent. Examples of the organic polymer that can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, Examples include polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymer, various polymers such as polyacrylonitrile and polyacetal. Among these, it is preferable to include amorphous cyclic polyolefin or polyethylene terephthalate having excellent transparency, versatility, and mechanical properties. Further, the organic polymer may be either a homopolymer or a copolymer, and only one type may be used as the organic polymer, or a plurality of types may be blended.

  Corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, organic or inorganic matter, or a mixture thereof on the surface of the polymer film substrate on the side where the gas barrier layer is formed to improve adhesion and smoothness A pretreatment such as an undercoat layer forming treatment composed of In addition, a coating layer of an organic material, an inorganic material, or a mixture thereof may be laminated on the side opposite to the side on which the gas barrier layer is formed for the purpose of improving the slipping property at the time of winding the film.

  The thickness of the polymer film substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and is preferably 5 μm or more from the viewpoint of ensuring strength against tension or impact. Furthermore, the thickness of the polymer film substrate is more preferably 10 μm or more and 200 μm or less because of the ease of film processing and handling.

[First layer containing zinc oxide and silicon dioxide]
The gas barrier film of the present invention can exhibit high gas barrier properties when the gas barrier layer has the first layer containing zinc oxide and silicon dioxide. The reason why the gas barrier property is improved by applying the first layer containing zinc oxide and silicon dioxide is that the crystal component contained in zinc oxide and the glassy component of silicon dioxide coexist to produce fine crystals. It is presumed that the crystal growth of zinc oxide, which tends to occur, is suppressed and the particle size is reduced, so that the layer is densified and the permeation of water vapor is suppressed. In addition, the layer containing zinc oxide and silicon dioxide with suppressed crystal growth is more flexible than a thin film formed of an oxide composed of one metal element such as aluminum oxide, titanium oxide, or zirconium oxide. It is considered that cracks are less likely to occur due to heat and external stress, and it is possible to suppress a decrease in gas barrier properties.

The first layer containing zinc oxide and silicon dioxide in the present invention is selected from the group consisting of aluminum (Al), gallium (Ga), tin (Sn), and indium (In) as long as it contains zinc oxide and silicon dioxide. At least one of the above may be included. Further, oxides, nitrides, sulfides, or mixtures of these elements may be included. Aluminum (Al), gallium (Ga), tin (Sn) and indium (In) are elements of group numbers 3B and 4B in the periodic table, and zinc (Zn) and silicon (Si) contained in the first layer Since the number of valence electrons is the same and the physical and chemical affinity is high, crystal growth of the first layer can be further suppressed, and the gas barrier property can be improved. Among these, aluminum (Al), which is an element having a small atomic radius and low hardness, is more preferable because it can densify the first layer and has excellent flexibility. As the first layer containing aluminum (Al), for example, a layer composed of the following coexisting phase containing zinc oxide and silicon dioxide that can provide high gas barrier properties is preferably used.
(I) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide Details of the layer comprising this coexisting phase will be described later.

  The thickness of the first layer used in the present invention is preferably 10 nm or more and 500 nm or less. When the thickness of the layer is thinner than 10 nm, there are places where the gas barrier property cannot be sufficiently secured, and the gas barrier property may vary in the polymer film substrate surface. In addition, when the thickness of the layer is greater than 500 nm, the stress remaining in the layer increases, so that cracks are likely to occur in the first layer due to bending or external impact, and the gas barrier properties may decrease with use. is there. Therefore, the thickness of the first layer is preferably 10 nm or more and 500 nm or less, and more preferably 20 nm or more and 200 nm or less from the viewpoint of ensuring flexibility. The thickness of the first layer can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).

  The center layer average roughness SRa of the first layer used in the present invention is preferably 10 nm or less. When SRa is larger than 10 nm, the uneven shape on the surface of the first layer becomes large, and large gaps and defects are formed between the sputtered particles. Therefore, the first layer is filled with the second layer, and the first layer is contracted by curing. The defect size on the surface cannot be made sufficiently small, and the effect of improving the gas barrier property may be difficult to obtain. Accordingly, the SRa of the first layer is preferably 10 nm or less, more preferably 7 nm or less.

  The SRa of the first layer in the present invention can be measured using a three-dimensional surface roughness measuring machine.

  In the present invention, the method for forming the first layer is not particularly limited. For example, the first layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. Among these methods, the sputtering method is preferable because the first layer can be easily and precisely formed.

[Layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide]
The details of the coexisting phase suitably used as the first layer containing zinc oxide and silicon dioxide in the present invention will be described. The first layer preferably comprises the following coexisting phases (i) to (iii).
(I) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide The “coexistence phase of (i) to (iii)” is referred to as “coexistence phase of zinc oxide-silicon dioxide-aluminum oxide” or “ZnO—SiO ₂ — It may be abbreviated as “Al ₂ O ₃ ”. Also, silicon (SiO ₂₎ dioxide, the generation time of the condition, those slightly deviated from the composition ratio of silicon and oxygen on the left formula (SiO~SiO ₂₎ although it is possible to produce silicon dioxide or SiO ₂ It shall be written as Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc oxide and aluminum oxide. Regardless of the deviation of the composition ratio depending on the conditions at the time of production, zinc oxide or ZnO, aluminum oxide or Al, respectively. _It shall be expressed as ₂ O ₃ .

  The reason why the gas barrier property is improved by applying a layer comprising a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide as the first layer of the gas barrier layer in the gas barrier film of the present invention is the layer containing zinc oxide and silicon dioxide In addition, the coexistence of aluminum oxide further suppresses the crystal growth compared to the case of coexistence of zinc oxide and silicon dioxide alone, so that the deterioration of gas barrier properties due to the generation of cracks can be suppressed. it is conceivable that.

  The composition of the layer comprising the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide can be obtained by measuring by X-ray photoelectron spectroscopy (XPS method) as described later. Here, the composition of the first layer in the present invention is represented by an atomic concentration ratio of each element measured by the XPS method after removing by etching about 5 nm from the outermost layer of the first layer. Zinc (Zn) atom concentration measured by X-ray photoelectron spectroscopy is 10 to 35 atom%, silicon (Si) atom concentration is 5 to 25 atom%, aluminum (Al) atom concentration is 1 to 7 atom%, oxygen (O) atom The concentration is preferably 50 to 70 atom%.

  When the zinc (Zn) atom concentration is higher than 35 atom% or the silicon (Si) atom concentration is lower than 5 atom%, the silicon dioxide and / or aluminum oxide that suppresses the crystal growth of zinc oxide is insufficient. Defects may increase and sufficient gas barrier properties may not be obtained. When the zinc (Zn) atom concentration is less than 10 atom% or the silicon (Si) atom concentration is more than 25 atom%, the amorphous component of silicon dioxide inside the layer may increase and the flexibility of the layer may decrease. is there. Further, when the aluminum (Al) atomic concentration is higher than 7 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that the hardness of the film is increased, and cracks are easily generated against heat and external stress. There is a case. When the aluminum (Al) atomic concentration is less than 1 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved, so the flexibility may decrease. In addition, when the oxygen (O) atom concentration is higher than 70 atom%, the amount of defects in the first layer increases, so that a desired gas barrier property may not be obtained. If the oxygen (O) atom concentration is less than 50 atom%, the oxidation state of zinc, silicon, and aluminum becomes insufficient, crystal growth cannot be suppressed, and the particle diameter becomes large, so that the gas barrier property may be lowered. From this viewpoint, the zinc (Zn) atom concentration is 15 to 32 atom%, the silicon (Si) atom concentration is 10 to 20 atom%, the aluminum (Al) atom concentration is 1 to 4 atom%, and the oxygen (O) atom concentration is 50 to 64 atom%. % Is more preferable.

  The components contained in the layer comprising the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide are not particularly limited as long as zinc oxide, silicon dioxide and aluminum oxide are in the above composition and are the main components. For example, aluminum (Al) , Including metal oxides formed from titanium (Ti), zirconium (Zr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd), etc. It doesn't matter. Here, the main component means 50% by mass or more of the composition of the first layer, preferably 60% by mass or more, and more preferably 80% by mass or more.

  The composition of the layer composed of the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide is formed with the same composition as the mixed sintered material used at the time of forming the layer. It is possible to adjust the composition of the first layer by using a sintered material.

  The composition of the layer composed of the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide can be determined by using X-ray photoelectron spectroscopy to determine the composition ratio of zinc, silicon, aluminum, oxygen, and contained elements. X-ray photoelectron spectroscopy is a method for detecting elemental information from the binding energy values of bound electrons obtained by detecting photoelectrons emitted from the surface when the surface of a sample placed in an ultra-high vacuum is irradiated with soft X-rays. Further, each detected element can be quantified from the peak area ratio of the binding energy.

  When an inorganic layer or resin layer is laminated on a layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide, the thickness of the inorganic layer or resin layer measured by cross-sectional observation with a transmission electron microscope is ionized. After removal by etching or chemical treatment, a layer consisting of a zinc oxide-silicon dioxide-aluminum oxide coexisting phase of about 5 nm thick can be removed by argon ion etching and analyzed by X-ray photoelectron spectroscopy.

  Method for forming a layer comprising a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide on a polymer film substrate (or on a layer provided on the polymer film substrate (for example, on an undercoat layer described later)) Is not particularly limited, and can be formed by a vacuum deposition method, a sputtering method, an ion plating method or the like using a mixed sintered material of zinc oxide, silicon dioxide and aluminum oxide. When using a single material of zinc oxide, silicon dioxide, and aluminum oxide, form a film of zinc oxide, silicon dioxide, and aluminum oxide simultaneously from separate vapor deposition sources or sputter electrodes, and mix them to the desired composition. Can be formed. Among these methods, the method for forming the first layer of the gas barrier layer of the gas barrier film of the present invention is more preferably a sputtering method using a mixed sintered material from the viewpoint of gas barrier properties and composition reproducibility of the formed layer. .

[Second layer containing (A) to (C)]
Next, the second layer including (A) to (C) will be described in detail.

The gas barrier film of the present invention significantly improves the gas barrier property by arranging the second layer containing the following (A) to (C) in contact with the first layer containing zinc oxide and silicon dioxide. It is something that can be done.
(A) having at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester, unsaturated nitrile (a2) and hydroxyl group Copolymer (a1): a copolymer having at least three components as a monomer and an unsaturated compound (a3), wherein the proportion of (a1) to (a3) in the copolymer is as follows: a2): (a3) = 20-40% by mass: 10-30% by mass: 30-70% by mass
(B) Compound having an isocyanate group (C) A compound having two or more carboxylic acid groups or one or more carboxylic anhydride groups.

  Factors that determine gas barrier properties in the second layer include cohesive energy, free volume, crystallinity, orientation, and the like. These factors are often attributed to side chain functional groups in the polymer structure. That is, polymer chains containing functional groups capable of intermolecular interaction such as hydrogen bonding or electrostatic interaction in the structure tend to strongly aggregate using the interaction force as a driving force. As a result, the cohesive energy and orientation are increased, the free volume is decreased, and the gas barrier property is improved. On the other hand, when the polymer structure contains a sterically bulky functional group, it is considered that the gas barrier property is lowered because the aggregation of the polymer is prevented and the free volume is increased. Furthermore, it can be considered that when the intermolecular interaction is increased, the driving force for strongly agglomerating and reducing the free volume space is increased, and as a result, the aggregation density of the polymer is increased. A detailed description of each component (A) to (C) in the second layer of the present invention contributing to gas barrier properties will be described later.

  Moreover, since the gas barrier film of the present invention is filled with defects (A) to (C) contained in the second layer into defects such as pinholes and cracks on the surface of the first layer, and the defect size is reduced by shrinkage due to curing. In addition to the gas barrier properties of the second layer itself, the gas barrier is further improved. The effect of improving the gas barrier property is that the first layer contains zinc oxide and silicon dioxide, so that the particle size is small and the size and shape of the particles of the first layer easily penetrate into the resin of the second layer. It is presumed that it is arranged in Further, since the hydroxyl group of the second layer forms a hydrogen bond with the silicon dioxide of the first layer, it is considered that the bonding force between the layers becomes stronger and contributes to improvement of gas barrier properties.

(At least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester)
With respect to at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester used for copolymer (A), As acid esters, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t- Examples include butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, and fumaric acid.

  Examples of other monomers include styrene, α-methylstyrene, butadiene, ethylene, vinyl acetate and the like.

  Of these, unsaturated carboxylic acid esters are preferred. Of unsaturated carboxylic acid esters, methyl methacrylate and methyl acrylate are particularly preferable, and methyl methacrylate is more preferable.

  When the blending amount of (a1) increases, the relative amount of the unsaturated nitrile (a2) and the unsaturated compound (a3) having a hydroxyl group in the copolymer decreases, and gas barrier properties are not sufficiently exhibited, There are cases where the coating film strength and adhesion resistance due to the lack of structure are insufficient.

(Unsaturated nitrile (a2))
As the unsaturated nitrile (a2) used in the copolymer (A), acrylonitrile is preferable. Acrylonitrile has a nitrile group in its molecular structure, and has a strong ability to form hydrogen bonds because the nitrile group is a highly polarized functional group. That is, the coating film formed from the copolymer (A) containing acrylonitrile as a constituent component has gas barrier properties due to the contribution of the nitrile group of acrylonitrile. The gas barrier property can be adjusted by the content of acrylonitrile.

  When the amount of the unsaturated nitrile (a2) is increased, the solubility of the copolymer in the organic solvent is lowered, which not only hinders the increase in molecular weight during polymerization but also makes it difficult to form a paint. Furthermore, it may become impractical because the film-forming property and transparency of the coating film are lowered. On the other hand, when the blending amount decreases, the gas barrier property improving effect of the gas barrier layer may be insufficient.

(Unsaturated compound having a hydroxyl group (a3))
As described above, it is preferable to increase the content of the unsaturated nitrile (a2) in the copolymer (A) from the viewpoint of improving gas barrier properties. However, polyacrylonitrile, which is an unsaturated nitrile (a2), has a high glass transition temperature of about 300 ° C., and it requires treatment at a high temperature to form a film. It is preferable to lower the temperature of the membrane. In addition, as described above, factors that determine gas barrier properties include cohesive energy, free volume, crystallinity, orientation, etc., but a method using a monomer component having a highly polar functional group as a monomer for copolymerization Is one means of improving the gas barrier property. From such a viewpoint, it is preferable to use an unsaturated compound (a3) having a hydroxyl group that functions as a functional group exhibiting high cohesive force and having a hydroxyl group in the present invention. In addition, when the unsaturated compound (a3) having a hydroxyl group is contained in the second layer, a first layer composed of an inorganic compound is formed to form a crosslinked structure with the compound (B) having an isocyanate group. It adheres strongly and can develop coating film strength and adhesion resistance.

  Examples of the unsaturated compound (a3) having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2 -Monomers of unsaturated compounds such as hydroxy vinyl ether, polyethylene glycol methacrylate, polypropylene glycol monoacrylate and polypropylene glycol monomethacrylate. These unsaturated compounds having a hydroxyl group can be selected singly or in combination of two or more. Of these unsaturated compounds having a hydroxyl group, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is preferable because good polymerization stability is obtained and reactivity with an isocyanate group is good. Ethyl methacrylate is particularly preferred.

  In the copolymer (A), the film-forming property and gas barrier property of the second layer and the number of crosslinking points with the compound (B) having an isocyanate group vary depending on the content of the unsaturated compound (a3) having a hydroxyl group. As a result, heat resistance, coating film hardness, and the like change. When the blending amount of the unsaturated compound (a3) decreases, the cohesive force between the resin chains derived from the hydroxyl group may not work sufficiently, and the gas barrier property may not be improved. Further, the number of crosslinking points formed by the progress of the crosslinking reaction between the hydroxyl group and the isocyanate group of the compound (B) having an isocyanate group may not be sufficient, and the heat resistance of the second layer may not be sufficiently exhibited. . On the other hand, when the amount of the unsaturated compound (a3) having a hydroxyl group increases, the number of hydroxyl groups in the copolymer increases, so that it is necessary to increase the amount of the compound (B) having an isocyanate group, and at the same time, it has an isocyanate group. The isocyanate group of the compound (B) is likely to remain unreacted and may cause a problem such as blocking. Furthermore, since the contents of (a2) and (B) described later are reduced, the gas barrier property improving effect is reduced, and the film forming property of the coating film may be lowered.

(Ratio of (a1), (a2), (a3) in copolymer (A))
As described above, there is a suitable range for the ratio of (a1), (a2), and (a3) in the copolymer (A). For example, the ratio of the unsaturated nitrile (a2) is determined by the solubility of the copolymer (A) in an organic solvent, the prevention of molecular weight increase during polymerization, the film-forming property of the coating film, the transparency, the gas barrier of the second layer From the viewpoint of properties, the proportion in the copolymer (A) is preferably 10 to 30% by mass, more preferably 10 to 25% by mass.

  The ratio of the unsaturated compound (a3) having a hydroxyl group is the film forming property and gas barrier property of the second layer, the number of crosslinking points with the compound (B) having an isocyanate group, heat resistance, coating film hardness, and resin chain derived from the hydroxyl group. From the viewpoint of cohesive strength between them, the proportion of the copolymer (A) is 30 to 70% by mass, preferably 40 to 60% by mass.

  Moreover, as a ratio (mass ratio) in the copolymer (A) of the unsaturated nitrile (a2) and the unsaturated compound (a3) having a hydroxyl group, (a2) :( a3) is 10% by mass: 70% by mass. % To 30% by mass: 30% by mass, preferably 20% by mass: 50% by mass to 30% by mass: 50% by mass.

  The proportion of (a1) in the copolymer (A) is preferably 20 to 40% by mass and more preferably 25 to 35% by mass from the viewpoints of gas barrier properties, coating film strength, and adhesion resistance.

  Further, at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester, unsaturated nitrile (a2), and an unsaturated group having a hydroxyl group. The ratio (mass ratio) in the copolymer (A) with the saturated compound (a3) is (a1) :( a2) + (a3) = 40% by mass: 60% by mass to 20% by mass: 80% by mass. Preferably, (a1) :( a2) + (a3) = 35% by mass: 65% by mass to 25% by mass: 75% by mass.

(Compound having an isocyanate group (B))
In the present invention, the compound (B) having an isocyanate group can be used to crosslink the copolymer (A). When the copolymer (A) is applied alone, gas barrier properties are exhibited, but physical properties such as coating strength and adhesion resistance tend not to be obtained. Therefore, it is preferable to use as the curing agent a compound (B) having an isocyanate group that reacts with a hydroxyl group that the copolymer (A) has as a side chain. By including the compound (B) having an isocyanate group, a crosslinked structure is generated, which is preferable because a second layer having physical properties such as gas barrier properties, coating film strength, and adhesion resistance is formed. Examples of the compound having an isocyanate group include aromatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates.

  Examples of aromatic diisocyanates that can be used include m- or p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), 4,4′-, 2,4′- or 2, Examples include 2'-diphenylmethane diisocyanate (MDI), 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenyl ether diisocyanate, and the like.

  Examples of the araliphatic diisocyanate that can be used include 1,3- or 1,4-xylylene diisocyanate (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate (TMXDI), and the like.

  Examples of alicyclic diisocyanates that can be used include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4 ′. -, 2,4'- or 2,2'-dicyclohexylmethane diisocyanate (hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4-bis (Isocyanate methyl) cyclohexane (hydrogenated XDI) and the like can be exemplified.

  Examples of the aliphatic diisocyanate that can be used include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-, 2,3-, or 1,3- Examples include butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate.

  These include urethane-modified products, allophanate-modified products, urea-modified products, biuret-modified products, uretdione-modified products, uretoimine-modified products, isocyanurate-modified products, and carbodiimide-modified products. These may be used alone or in combination.

  Furthermore, you may use the partial condensate of the isocyanate compound illustrated above, the compound etc. which have a hydroxyl group, 1 type of various derivatives, or these 2 or more types. For example, a wide range of diols from various low molecular weight diols to oligomers, and partial condensates with trifunctional or higher functional polyols as required.

  Considering the gas barrier property of the second layer formed by the cross-linking reaction product of the copolymer (A) and the compound (B) having an isocyanate group, among these compounds having an isocyanate group, 1,3-xylene diisocyanate (XDI) and its partial condensate and / or 1,4-xylene diisocyanate (XDI) and its partial condensate are preferred. The three-dimensional structure of the crosslinked product greatly affects the gas barrier property. In order to develop gas barrier properties, it preferably has a xylene diisocyanate skeleton.

  In the present invention, the blending ratio of the copolymer (A) constituting the second layer and the compound (B) having an isocyanate group is not particularly limited, but the compound (B) having an isocyanate group is too small. And the copolymer (A) are not sufficiently cross-linked, and the coating film not only causes poor curing, but also does not exhibit sufficient coating strength, and adhesion resistance with the base film. Etc. may be insufficient. In addition, when the compounding amount of the compound (B) having an isocyanate group is too large, it not only causes blocking, but also causes an inconvenience in post-processing such as excess isocyanate compound moving to another layer. There is.

(Compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups)
In the present invention, a compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups can be used as a material for forming the second layer. Thereby, since the adhesive force between the 1st layer comprised by an inorganic compound and a 2nd layer improves, it is preferable. The carboxyl group or carboxylic anhydride group has a property of easily coordinating with the element-oxygen bond in an inorganic substance such as an aluminum-oxygen bond or silicon-oxygen bond that the material such as alumina or silica forming the first layer has. Have Therefore, the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups on the surface of the first layer is coordinated by blending and applying to the resin composition forming the second layer. Thus, the surface becomes organic, and the adhesion with the resin forming the second layer can be improved. Furthermore, when the first layer is an inorganic oxide, the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups is coordinated on the surface of the inorganic oxide, Since it becomes difficult for the water | moisture content in it to osmose | permeate the 1st layer comprised with an inorganic compound, the effect that it becomes difficult to produce the fall of adhesive force is also acquired.

  Examples of the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups in one molecule include phthalic acid, terephthalic acid, isophthalic acid, sebacic acid, azelaic acid, adipic acid, trimellitic acid, Examples include 2,6-naphthalenedicarboxylic acid, maleic acid, succinic acid, malic acid, citric acid, isocitric acid, and tartaric acid.

  Examples of the compound having a carboxylic anhydride group include maleic anhydride, succinic anhydride, trimellitic anhydride, tetrabasic acid anhydride, etc., but especially when coating on a highly polar substrate film such as metal. Compounds having two or more anhydrides, such as basic acid anhydrides, are good. Tetrabasic acid anhydrides include benzophenone tetracarboxylic acid anhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl -3-Cyclohexene-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride (pyromellitic anhydride) and the like. Of these, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride and 1,2,4,5-benzenetetracarboxylic acid It is preferable to use an anhydride (pyromellitic anhydride). The addition amount of (C) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the sum of the copolymer (A) used for forming the second layer and the compound (B) having an isocyanate group. From the viewpoint of the temporal stability of the layer, 0.1 to 10 parts by mass is more preferable. When the addition amount is less than 0.1 parts by mass, the coordination efficiency of the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups is reduced, and sufficient adhesion is obtained. It may not be obtained. On the other hand, when it is added in an amount of more than 20 parts by mass, it has a function of inhibiting reactions other than the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups, so that the gas barrier property of the coating film May decrease.

  Moreover, the compound which superposed | polymerized the compound (C) which has two or more carboxylic acid groups or one or more carboxylic anhydride groups in the said molecule | numerator can also be used. The number average molecular weight of the compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups in one molecule is preferably 1,000 or less.

(Silane compound (D))
In this invention, it is also preferable to use the silane compound (D) which has an organic functional group and a hydrolyzable functional group in 1 molecule as a material which forms a 2nd layer. The organic functional group forms a bond with the organic group in the second layer, and the hydrolyzable functional group forms an oxysilane bond with the first layer composed of an inorganic compound, whereby the first layer and the second layer There is an effect of improving the adhesive strength of.

  In addition, the hydroxyl group in the copolymer (A) undergoes a crosslinking reaction with the isocyanate group of the compound (B) having an isocyanate group, and the hydrolyzable functional group in the silane compound (D) is hydrolyzed. When the hydroxyl group to be bonded to the hydroxyl group on the surface of the first layer composed of the inorganic compound, the adhesion between the first layer composed of the inorganic compound and the second layer is further improved and strengthened. Therefore, it is preferable.

  The silane compound (D) is one selected from the group consisting of an amino group, a vinyl group, and an epoxy group as an organic functional group from the viewpoint of ensuring adhesion resistance between the first layer and the second layer composed of an inorganic compound. It is preferable to have the above functional group. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxy Silane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Examples include diethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These silane compounds may be used alone or in combination of two or more.

  The addition amount of the silane compound (D) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the sum of the copolymer (A) used for forming the second layer and the compound (B) having an isocyanate group. From the viewpoint of the temporal stability of the second layer, 0.1 to 2 parts by mass is more preferable. When the addition amount is less than 0.1 parts by mass, the effect of the silane compound is small, and sufficient adhesion may not be obtained. On the other hand, when more than 10 parts by mass is added, the silane compound (D) acts like a plasticizer in the second layer, so that the gas barrier property of the coating film may be lowered.

  The silane compound (D) contains at least one hydroxyl group such as silanol, which is a compound in which a hydroxyl group is bonded to a silicon atom, by blending water and a solvent and hydrolyzing the mixture using a known technique. A silane compound is prepared. Solvents that can be used include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, methanol, ethanol and the like.

(Other additives)
As long as the characteristics of the second layer according to the present invention are not impaired, a heat stabilizer, an antioxidant, a reinforcing agent, a pigment, a deterioration preventing agent, a weathering agent, a flame retardant, a plasticizer, a release agent, a lubricant, etc. May be added.

  Examples of heat stabilizers, antioxidants and deterioration inhibitors that can be used include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and mixtures thereof.

  Examples of reinforcing agents that can be used include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, and oxidation. Examples include zinc, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate whisker, boron nitride, graphite, glass fiber, and carbon fiber.

  An inorganic layered compound may be mixed in the second layer according to the present invention. Preferable examples of the inorganic layered compound include montmorillonite, beidellite, saponite, hectorite, saconite, vermiculite, fluoric mica, muscovite, paragonite, phlogopite, leoprite, margarite, clintonite, anandite, etc. Swellable fluoromica or montmorillonite is particularly preferred. These inorganic layered compounds may be naturally occurring, artificially synthesized or modified, or those treated with an organic material such as an onium salt.

[Method for forming second layer]
In the present invention, the copolymer (A) is added with a compound (B) having an isocyanate group, a compound (C) having two or more carboxylic acid groups or one or more carboxylic anhydride groups, and a silane compound (D). It is preferable to mix and crosslink using a known technique to form the second layer. The copolymer (A) can be dissolved in, for example, a propyl acetate-propylene glycol monomethyl ether-n-propyl alcohol mixed solution and mixed with the above-described compound (B) having an isocyanate group. Next, a predetermined amount of the copolymer (A) solution and the isocyanate group-containing compound (B) are mixed and dissolved in a solvent to obtain a coating liquid (coating material) for the second layer. Can do. Solvents that can be used include toluene, xylene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylformamide, dimethylacetamide, methanol, ethanol, water and the like.

  There is no restriction | limiting in particular as a method of manufacturing this 2nd layer in this invention, It can manufacture by the method corresponding to a base film. For example, printing methods such as offset printing method, gravure printing method, silk screen printing method, roll coating method, dip coating method, bar coating method, die coating method, knife edge coating method, gravure coating method, kiss coating method, spin coating method The coating liquid may be coated using a method such as a combination of these.

  The thickness of the second layer provided on the first layer is preferably 0.1 μm or more from the viewpoint of having a high water vapor permeability. Moreover, from the viewpoint of external impact and wear resistance, it is more preferably 0.3 μm or more. The upper limit of the thickness of the second layer is not particularly limited, but is preferably 3 μm, more preferably 2 μm. That is, the thickness of the second layer is preferably 0.1 to 3 μm, and more preferably 0.3 to 2 μm. When the thickness of the second layer is 0.1 μm or more, the gas barrier properties can be sufficiently improved and the effect of preventing scratches and cracks on the first layer due to external impact and wear can be obtained. It is preferable because the second layer with less defects such as film breakage and repellency can be formed. On the other hand, if the thickness of the second layer is 3 μm or less, the solvent is sufficiently dried even if the drying conditions at the time of coating are low temperature and for a short time. It is preferable that problems such as

  In the present invention, when the second layer is formed and laminated on the first layer by coating, it is preferably 70 ° C or higher, more preferably 90 ° C or higher, although it depends on the solvent used in the coating liquid (coating agent). It is better to dry at temperature. When the drying temperature is lower than 70 ° C., the coating film is not sufficiently dried, and it may be difficult to obtain a film having sufficient gas barrier properties. In the formation of the second layer, the crosslinking reaction between the copolymer (A) and the compound (B) having an isocyanate group proceeds mainly during the drying, but an aging treatment is performed for the purpose of further promoting the crosslinking reaction. You can also The crosslinking reaction further proceeds by the aging treatment, and the coating film strength, gas barrier property, adhesion resistance and the like can be further improved.

[Undercoat layer]
The gas barrier film of the present invention is provided with an undercoat layer containing a polyurethane compound having an aromatic ring structure between the polymer film substrate and the first layer in order to improve gas barrier properties and flex resistance. It is preferable. If there are defects such as protrusions and scratches on the polymer film substrate, pinholes and cracks also occur in the first layer laminated on the polymer film substrate starting from the defects, causing gas barrier properties and bending resistance. Since the property may be impaired, it is preferable to provide the undercoat layer of the present invention. In addition, even when the difference in thermal dimensional stability between the polymer film substrate and the first layer is large, the gas barrier property and the bending resistance may be lowered. Therefore, it is preferable to provide an undercoat layer. In addition, the undercoat layer used in the present invention preferably contains a polyurethane compound having an aromatic ring structure from the viewpoint of thermal dimensional stability and flex resistance, and further contains an ethylenically unsaturated compound and a photopolymerization initiator. It is more preferable to contain an organosilicon compound and / or an inorganic silicon compound.

  The polyurethane compound having an aromatic ring structure used in the present invention has an aromatic ring and a urethane bond in the main chain or side chain. For example, an epoxy (meth) having a hydroxyl group and an aromatic ring in the molecule. It can be obtained by polymerizing acrylate, diol compound and diisocyanate compound.

  As epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule, diepoxy compounds of aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, hydroquinone, etc. And a (meth) acrylic acid derivative.

  Examples of the diol compound include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl Glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4, 4-tetramethyl-1,3-cyclobutanediol, 4,4′-thiodiph Diol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4 '-Isopropylidenephenol, 4,4'-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, and the like can be used. These can be used alone or in combination of two or more.

  Examples of the diisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, and 4,4-diphenylmethane diisocyanate. Aromatic diisocyanate compounds such as aromatic diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, etc. Aliphores such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Systems isocyanate compound, diisocyanate, aromatic aliphatic isocyanate compounds such as tetramethyl xylylene diisocyanate. These can be used alone or in combination of two or more.

  The component ratio of the epoxy (meth) acrylate having a hydroxyl group and an aromatic ring in the molecule, a diol compound, and a diisocyanate compound is not particularly limited as long as it has a desired weight average molecular weight. The weight average molecular weight (Mw) of the polyurethane compound having an aromatic ring structure in the present invention is preferably 5,000 to 100,000. A weight average molecular weight (Mw) of 5,000 to 100,000 is preferable because the resulting cured film has excellent thermal dimensional stability and flex resistance. In addition, the weight average molecular weight (Mw) in this invention is the value measured using the gel permeation chromatography method and converted with standard polystyrene.

  Examples of the ethylenically unsaturated compound include di (meth) acrylates such as 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and penta Multifunctional (meth) acrylates such as erythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate And epoxy acrylates such as bisphenol F type epoxy di (meth) acrylate and bisphenol S type epoxy di (meth) acrylate. Among these, polyfunctional (meth) acrylates excellent in thermal dimensional stability and surface protection performance are preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.

  The content of the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, the total amount with the polyurethane compound having an aromatic ring structure is in the range of 5 to 90% by mass. It is preferable that it is in the range of 10 to 80% by mass.

  The material for the photopolymerization initiator is not particularly limited as long as the gas barrier property and the bending resistance of the gas barrier film of the present invention can be maintained. Examples of the photopolymerization initiator that can be suitably used in the present invention include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl-ketone, and 2-hydroxy-2- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- { 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthio Phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 Alkylphenone photopolymerization initiators such as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6 -Acylphosphine oxide photopolymerization initiators such as trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -Titanocene photopolymerization initiators such as bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 1,2-octanedione, 1- [4- (phenylthio)-, And 2- (0-benzoyloxime)] and the like photopolymerization initiators having an oxime ester structure.

  Among these, from the viewpoint of curability and surface protection performance, 1-hydroxy-cyclohexylphenyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2,4,6 A photopolymerization initiator selected from trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.

  Although content of a photoinitiator is not specifically limited, From a viewpoint of sclerosis | hardenability and surface protection performance, it is preferable that it is the range of 0.01-10 mass% in the total amount of 100 mass% of a polymeric component, 0 More preferably, it is in the range of 1 to 5% by mass.

  Examples of the organosilicon compound include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanate propyl triethoxysilane, and the like.

  Among these, from the viewpoint of curability and polymerization activity by irradiation with active energy rays, selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. At least one organosilicon compound is preferred. Moreover, these may be used by a single composition, and may mix and use two or more components.

  The content of the organosilicon compound is not particularly limited, but from the viewpoint of curability and surface protection performance, it is preferably in the range of 0.01 to 10% by mass in 100% by mass of the total amount of polymerizable components. A range of 1 to 5% by mass is more preferable.

  As the inorganic silicon compound, silica particles are preferable from the viewpoint of surface protection performance and transparency, and the primary particle diameter of the silica particles is preferably in the range of 1 to 300 nm, and more preferably in the range of 5 to 80 nm. . In addition, the primary particle diameter here refers to the particle diameter d calculated | required by applying the specific surface area s calculated | required by the gas adsorption method to following formula (1).

  The thickness of the undercoat layer is preferably from 200 nm to 4,000 nm, more preferably from 300 nm to 2,000 nm, still more preferably from 500 nm to 1,000 nm. If the thickness of the undercoat layer is thinner than 200 nm, the adverse effects of defects such as protrusions and scratches present on the polymer film substrate may not be suppressed. When the thickness of the undercoat layer is greater than 4,000 nm, the smoothness of the undercoat layer is reduced, and the uneven shape of the surface of the first layer laminated on the undercoat layer is increased, and gaps are formed between the sputtered particles to be laminated. Therefore, the film quality is less likely to be dense, and the effect of improving gas barrier properties may be difficult to obtain. Here, the thickness of the undercoat layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

  The center surface average roughness SRa of the undercoat layer is preferably 10 nm or less. When SRa is 10 nm or less, it is easy to form a homogeneous first layer on the undercoat layer, and it is preferable because repeated reproducibility of gas barrier properties is improved. When SRa on the surface of the undercoat layer is larger than 10 nm, the uneven shape on the surface of the first layer on the undercoat layer also increases, and a gap is formed between the laminated first layer particles, so that the film quality is difficult to be dense, The effect of improving the gas barrier property may be difficult to obtain, and cracks due to stress concentration are likely to occur in portions where there are many irregularities, which may cause a decrease in the reproducibility of the gas barrier property. Therefore, in the present invention, the SRa of the undercoat layer is preferably 10 nm or less, more preferably 7 nm or less.

  SRa of the undercoat layer in the present invention can be measured using a three-dimensional surface roughness measuring machine.

  When applying an undercoat layer to the gas barrier film of the present invention, as a coating means for applying a coating liquid containing a resin for forming the undercoat layer, first, a polyurethane compound having an aromatic ring structure is included on a polymer film substrate. Adjust the solid content concentration so that the thickness after drying the paint becomes the desired thickness, for example, apply by reverse coating method, gravure coating method, rod coating method, bar coating method, die coating method, spray coating method, spin coating method, etc. It is preferable to do. Moreover, in this invention, it is preferable to dilute the coating material containing the polyurethane compound which has an aromatic ring structure using an organic solvent from a viewpoint of coating suitability.

  Specifically, the solid content concentration is diluted to 10% by mass or less using a hydrocarbon solvent such as xylene, toluene, methylcyclohexane, pentane, hexane or the like, or an ether solvent such as dibutyl ether, ethyl butyl ether or tetrahydrofuran. Are preferably used. These solvents may be used alone or in combination of two or more. Moreover, various additives can be mix | blended with the coating material which forms an undercoat layer as needed. For example, a catalyst, an antioxidant, a light stabilizer, a stabilizer such as an ultraviolet absorber, a surfactant, a leveling agent, an antistatic agent, or the like can be used.

  Subsequently, it is preferable to dry the coating film after application | coating and to remove a dilution solvent. Here, there is no restriction | limiting in particular as a heat source used for drying, Arbitrary heat sources, such as a steam heater, an electric heater, and an infrared heater, can be used. In order to improve gas barrier properties, the heating temperature is preferably 50 to 150 ° C. The heat treatment time is preferably several seconds to 1 hour. Furthermore, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Moreover, you may heat-process, adjusting humidity in the range of 20 to 90% RH by relative humidity during a drying process. The heat treatment may be performed in the air or while enclosing an inert gas.

  Next, it is preferable to form an undercoat layer by subjecting the coating film containing a polyurethane compound having an aromatic ring structure after drying to an active energy ray irradiation treatment to crosslink the coating film.

  The active energy ray applied in such a case is not particularly limited as long as the undercoat layer can be cured, but it is preferable to use ultraviolet treatment from the viewpoint of versatility and efficiency. As the ultraviolet ray generation source, a known source such as a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp or the like can be used. Moreover, it is preferable to use an active energy ray in inert gas atmosphere, such as nitrogen and argon, from a viewpoint of hardening efficiency. The ultraviolet treatment may be performed under atmospheric pressure or reduced pressure, but in the present invention, the ultraviolet treatment is preferably performed under atmospheric pressure from the viewpoint of versatility and production efficiency. The oxygen concentration during the ultraviolet treatment is preferably 1.0% or less, more preferably 0.5% or less, from the viewpoint of controlling the degree of crosslinking of the undercoat layer. The relative humidity may be arbitrary.

  As the ultraviolet ray generation source, a known source such as a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp or the like can be used.

Preferably the integrated light quantity of ultraviolet irradiation is ^{0.1~1.0J / cm 2, 0.2~0.6J / cm} 2 is more preferable. It is preferable that the integrated light amount is 0.1 J / cm ² or more because a desired degree of crosslinking of the undercoat layer can be obtained. Moreover, it is preferable if the integrated light quantity is 1.0 J / cm ² or less because damage to the polymer film substrate can be reduced.

[Other layers]
On the outermost surface of the gas barrier film of the present invention, a hard coat layer may be formed for the purpose of improving scratch resistance as long as the gas barrier property does not deteriorate, or a film made of an organic polymer compound is laminated. It is good also as a laminated structure. The outermost surface here refers to the surface of the second layer not in contact with the first layer after being laminated in this order so that the first layer and the second layer are in contact with each other on the polymer film substrate. Say.

[Usage]
Since the gas barrier film of the present invention has a high gas barrier property, it can be used in various electronic devices. For example, it can be suitably used for an electronic device such as a back sheet of a solar cell or a flexible circuit board. Moreover, it can utilize suitably for a packaging film of foodstuffs, an electronic component, etc. besides an electronic device taking advantage of high gas barrier property.

  Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.

[Evaluation method]
First, an evaluation method in each example and comparative example will be described. The number of evaluation n was n = 5 and the average value was obtained unless otherwise specified.

(1) Layer thickness Samples for cross-sectional observation were obtained by the FIB method using a micro-sampling system (FB-2000A manufactured by Hitachi, Ltd.) (specifically, “Polymer Surface Processing” (by Atsushi Iwamori) p) .118-119)). Using a transmission electron microscope (H-9000UHRII, manufactured by Hitachi, Ltd.), the cross section of the observation sample was observed at an acceleration voltage of 300 kV, and the thicknesses of the first layer, the second layer, and the undercoat layer were measured.

(2) Water vapor permeability (g / (m ² · 24 hr · atm))
Measurement was performed using a water vapor transmission rate measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox, England, under conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 50 cm 2. The number of evaluation n was set to 2 for each level, the number of measurements was 10 for each specimen, and the average value was the water vapor permeability (g / (m ² · 24 hr · atm)). Moreover, the value below 2.0 * 10 < ^-4 > (g / (m < ² > 24hr * atm)) which is the measurement limit lower limit of the water vapor transmission rate of this apparatus was described as 2.0 * 10 < ^-4 > or less. .

(3) Composition analysis of the first layer The composition analysis of the first layer was performed by X-ray photoelectron spectroscopy (XPS method).
After removing the outermost layer by etching about 5 nm by sputter etching using argon ions, the content ratio of each element was measured. It was assumed that there was no composition gradient in the first layer, and the composition ratio at this measurement point was the composition ratio of the first layer.
The measurement conditions of the XPS method were as follows.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
Excitation X-ray: monochromic AlKα
・ X-ray output: 300W
-X-ray diameter: 800 μm
-Photoelectron escape angle: 45 °
Ar ion etching: 2.0 kV, 10 mPa.

(4) Total light transmittance Based on JIS K7361: 1997, it measured using turbidimeter NDH2000 (made by Nippon Denshoku Industries Co., Ltd.). The measurement was performed on three films cut into a size of 50 mm in length and 50 mm in width, the number of measurements was 5 times for each sample, and the average value of 15 times in total was the total light transmittance.

(5) Haze Based on JIS K7136: 2000, the haze was measured using a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement was performed on three films cut to a size of 50 mm in length and 50 mm in width, the number of measurements was 5 times for each sample, and the average value of 15 measurements in total was taken as the haze value.

(6) Evaluation of Adhesiveness between First Layer and Second Layer After storing at high temperature and high humidity under the following conditions, a cross-cut tape peeling test was performed according to JIS K5600-5-6: 1999. First, a total of 100 notches of 1 mm × 1 mm in 10 mm × 10 mm were formed on the surface on the side where the second layer was formed as a test surface. Subsequently, it was affixed to the surface of the test surface using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), brought into close contact with the abdomen of the finger, and then peeled by pulling in the 90 ° direction. In the judgment, the case where the number of squares not to be peeled out of 100 squares was 90 squares or more was judged as “◯” and judged to have adhesion. The case of less than 90 squares was judged as “x”, indicating no adhesion.
<High temperature and high humidity storage conditions>
・ Equipment used: ESPEC CO., LTD. Environmental tester (model: PR-2KTH)
・ Temperature: 85 ℃
・ Humidity: 85% RH
-Storage time: 500 hours.

(7) Acid resistance evaluation A sulfuric acid aqueous solution produced at a concentration of 2.5 mol / L (5 N) was dropped into the surface on the side on which the first layer or the second layer was formed within a diameter of 10 mm, and the temperature was 25 ° C. The sample was left for 10 minutes in an environment with a humidity of 50% RH. After standing, the appearance of the portion where the sulfuric acid aqueous solution was dropped was visually observed. A case where no change in the appearance was visually observed was determined as “◯”, and a case where a change such as dissolution, coloring, or swelling was observed was determined as “X”.

(8) Measurement of the proportion of (a1) to (a3) in the copolymer The proportion of (a1) to (a3) in the copolymer (A) is first determined with hexafluoroisopanol (HFIP) on the substrate. A certain polyethylene terephthalate is melt | dissolved and a 1st layer and a 2nd layer are fractionated. Next, the fraction of (a1) to (a3) is quantified by conducting solid state NMR analysis of the collected second layer. Table 2 shows the ratio of (a1) to (a3) measured by solid-state NMR.

(9) Evaluation of water vapor permeability after flat wear test After performing a flat wear test under the following conditions, the water vapor permeability was measured by the method described in Evaluation Method (2). First, a cotton canvas was attached as a friction cloth to the surface of the friction element of the flat wear tester, and the first layer or second layer forming surface of the test sample was worn back and forth 100 times with a load of 1,000 g. Next, the water vapor permeability of the worn position was measured by the method described in Evaluation Method (2). The number of evaluation n was set to 2 for each level, the number of measurements was 10 for each specimen, and the average value was the water vapor permeability (g / (m ² · 24 hr · atm)).
<Plane wear test conditions>
-Equipment used: Plane abrasion tester manufactured by Taiei Kagaku Seisakusho Co., Ltd. (model: PA-300A)
・ Friction material: Aluminum ・ Friction surface shape: 20mm × 20mm
・ Friction cloth: Cotton canvas ・ Stage material: Stainless steel ・ Friction stroke: 30 mm
・ Rubber reciprocating speed: 60 times / min ・ Test load: 1,000 g
-Number of friction reciprocations: 100 times.

[Production of copolymer]
Copolymers used in the following examples and comparative examples are blended in the proportions (mass ratio) shown in Table 1 for monomers of methyl methacrylate (MMA), acrylonitrile (AN) and 2-hydroxyethyl methacrylate (2-HEMA). And obtained by copolymerization by a known technique. The obtained copolymer was dissolved in a mixed solvent of propyl acetate, propylene glycol monomethyl ether and n-propyl alcohol to obtain copolymers a to k having a solid content concentration of 30% by mass. Table 1 shows the mixing ratio of the monomers of each copolymer and the appearance of the obtained paint.

Example 1
(Formation of the first layer)
As the polymer film substrate 1, a polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used.

Using a single wafer type sputtering apparatus (hereinafter abbreviated as a sputtering apparatus) 4 shown in FIG. 3, a sputter target that is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide is installed on the sputtering electrode 5, Sputtering with argon gas and oxygen gas was performed, and a ZnO—SiO ₂ —Al ₂ O ₃ layer was provided as a first layer on the surface of the polymer film substrate 1 placed on the substrate holder 6 with a target thickness of 50 nm. .

The specific operation is as follows. First, in a film forming chamber 7 of a sputtering apparatus 4 in which a sputtering target sintered with a composition mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 is installed on the sputtering electrode 5, the length is 110 mm and the width The 110 mm-thick polymer film substrate 1 is placed on the substrate holder 6 so that the surface on which the first layer is provided faces the sputter electrode 5 and is evacuated to a vacuum degree of 1.0 × 10 ⁻³ Pa or less. It was. Next, argon gas and oxygen gas were introduced at an oxygen gas partial pressure of 10% so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an input power of 1,500 W was applied by a DC pulse power source, whereby argon / oxygen gas was applied. Plasma was generated and a ZnO—SiO ₂ —Al ₂ O ₃ layer was formed on the surface of the polymer film substrate 1 by sputtering. The thickness was adjusted by the film formation time.

  As for the composition of this first layer, the Zn atom concentration was 27.8 atom%, the Si atom concentration was 12.6 atom%, the Al atom concentration was 1.6 atom%, and the O atom concentration was 58.0 atom%.

(Second layer coating solution)
3.8 parts by mass of silane compound KBE-903 (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., 0.9 parts by mass of pure water and 20.3 parts by mass of acetone are blended, and 30 ° C. using a stirrer. A hydrolyzate of a silane compound having a solid content concentration of 15% by mass that was hydrolyzed by stirring for 120 minutes was obtained.

  Next, 10.0 parts by mass of copolymer a, 4.9 parts by mass of a curing agent mainly composed of xylene diisocyanate manufactured by DIC Corporation, 25.4 parts by mass of methyl ethyl ketone, 5- (2,5-di Oxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride methylethylketone diluent (10% by mass) 3.0 parts by mass, silane compound hydrolyzate 1.63 parts by mass Was stirred for 30 minutes to prepare a second layer coating solution 1 having a solid content of 15% by mass.

(Formation of the second layer)
On the first layer, the coating liquid 1 was applied using a wire bar, dried at 100 ° C. for 30 seconds, and the second layer was provided so that the thickness after drying was 1,000 nm.

  About the obtained gas-barrier film, evaluation of (1)-(9) was implemented. The results are shown in Tables 2 and 3.

(Example 2)
(Synthesis of polyurethane compounds having an aromatic ring structure)
In a 5-liter four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 3000A) and 710 parts by mass of ethyl acetate are added, and the internal temperature becomes 60 ° C. So warmed. As a synthesis catalyst, 0.2 part by mass of di-n-butyltin dilaurate was added, and 200 parts by mass of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. Reaction was continued for 2 hours after completion | finish of dripping, and 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries Ltd.) was dripped over 1 hour continuously. The reaction was continued for 5 hours after the dropwise addition to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.

(Formation of undercoat layer)
As the polymer film substrate 1, a polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used.
As a coating liquid for forming an undercoat layer, 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), 1-hydroxy-cyclohexylphenyl- 5 parts by weight of ketone (manufactured by BASF Japan, trade name: IRGACURE 184), 3 parts by weight of 3-methacryloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Silicone, trade name: KBM-503), and 170 parts by weight of ethyl acetate Parts, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone were added to prepare a coating solution. Next, the coating liquid was applied on a polymer film substrate with a micro gravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to ultraviolet treatment under the following conditions. An undercoat layer having a thickness of 1,000 nm was provided.

Ultraviolet ray processing apparatus: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: N ₂ (nitrogen inert BOX)
Ultraviolet light source: Microwave type electrodeless lamp Integrated light quantity: 400 mJ / cm ²
Sample temperature control: room temperature.

Next, a 50 nm thick ZnO—SiO ₂ —Al ₂ O ₃ layer was provided as a first layer on the undercoat layer in the same manner as in Example 1. Furthermore, a second layer having a thickness of 1,000 nm was formed on the first layer in the same manner as in Example 1, to obtain a gas barrier film.

  About the obtained gas-barrier film, evaluation of (1)-(9) was implemented. The results are shown in Tables 2 and 3.

(Example 3)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer b was used in place of the copolymer a.

Example 4
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer c was used in place of the copolymer a.

(Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer d was used instead of the copolymer a.

(Example 6)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer e was used instead of the copolymer a.

(Example 7)
(Formation of undercoat layer)
As the polymer film substrate 1, a polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used. An undercoat layer having a thickness of 1,000 nm was provided on the polymer film substrate 1 in the same manner as in Example 2.

(Formation of the first layer)
A single wafer type sputtering apparatus (hereinafter abbreviated as a sputtering apparatus) 4 shown in FIG. 3 is used, and a sputtering target, which is a mixed sintered material formed of zinc oxide and silicon dioxide, is placed on the sputtering electrode 5, and argon gas and Sputtering with oxygen gas was performed, and a ZnO—SiO ₂ layer was provided as a first layer on the surface of the undercoat layer with a target thickness of 50 nm.

The specific operation is as follows. First, in the film forming chamber 7 of the sputtering apparatus 4 in which a sputtering target sintered at a composition ratio of zinc oxide / silicon dioxide of 80/20 is installed on the sputtering electrode 5, the polymer having a length of 110 mm and a width of 110 mm is provided. The film base 1 was placed on the substrate holder 6 so that the surface on the side where the first layer is provided faces the sputter electrode 5, and evacuated to a vacuum degree of 1.0 × 10 ⁻³ Pa or less. Next, argon gas and oxygen gas are introduced at an oxygen gas partial pressure of 10% so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and an input power of 1,000 W is applied by a high-frequency power source, whereby argon / oxygen gas plasma And a ZnO—SiO ₂ layer was formed on the surface of the undercoat layer by sputtering. The thickness was adjusted by the film formation time.

  The composition of the first layer was such that the Zn atom concentration was 30.5 atom%, the Si atom concentration was 12.6 atom%, and the O atom concentration was 56.9 atom%.

  Next, a second layer having a thickness of 1,000 nm was formed on the first layer in the same manner as in Example 2 except that the copolymer b was used in place of the copolymer a to obtain a gas barrier film. .

(Example 8)
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the first layer was 100 nm.

Example 9
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the first layer was 200 nm.

(Example 10)
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the first layer was 300 nm.

(Example 11)
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the second layer was 300 nm.

(Example 12)
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the second layer was 200 nm.

(Comparative Example 1)
A gas barrier film was obtained in the same manner as in Example 1 except that the second layer was not formed.

(Comparative Example 2)
A gas barrier film was obtained in the same manner as in Example 2 except that the second layer was not formed.

(Comparative Example 3)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer f was used instead of the copolymer a.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer g was used in place of the copolymer a.

(Comparative Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer h was used in place of the copolymer a.

(Comparative Example 6)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer i was used in place of the copolymer a.

(Comparative Example 7)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer j was used in place of the copolymer a.

(Comparative Example 8)
A gas barrier film was obtained in the same manner as in Example 2 except that the copolymer k was used in place of the copolymer a.

(Comparative Example 9)
Implemented except that 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride methyl ethyl ketone diluent is not used for the second layer coating solution In the same manner as in Example 3, a gas barrier film was obtained.

(Comparative Example 10)
In Example 7, a gas barrier film was prepared in the same manner as in Example 7 except that a sputtering target composed of zinc oxide having a purity of 99.99% by mass was used as the first layer and the ZnO layer was provided to a thickness of 50 nm. Got. The composition of the first layer was such that the Zn atom concentration was 45.2 atom% and the O atom concentration was 54.8 atom%.

(Comparative Example 11)
In Example 7, a sputtering target made of aluminum oxide having a purity of 99.99% by mass was used as the first layer, and the Al ₂ O ₃ layer was provided so as to have a thickness of 50 nm. A gas barrier film was obtained. The composition of the first layer was an Al atom concentration of 37.5 atom% and an O atom concentration of 62.5 atom%.

(Comparative Example 12)
In Example 7, gas barrier properties were used in the same manner as in Example 7 except that a sputtering target composed of silicon dioxide having a purity of 99.99% by mass was used as the _first layer and the SiO ₂ layer was provided to a thickness of 50 nm. A film was obtained. The composition of the first layer was such that the Si atom concentration was 35.3 atom% and the O atom concentration was 64.7 atom%.

(Comparative Example 13)
In Example 7, gas barrier properties were used in the same manner as in Example 7 except that a sputtering target composed of titanium dioxide having a purity of 99.99% by mass was used as the _first layer and the TiO ₂ layer was provided to a thickness of 50 nm. A film was obtained. The composition of the first layer was a Ti atom concentration of 31.4 atom% and an O atom concentration of 68.6 atom%.

(Comparative Example 14)
In Example 7, a sputtering target sintered with an aluminum oxide / silicon dioxide composition mass ratio of 50/50 was used as the _first layer, and an Al ₂ O ₃ —SiO ₂ layer was provided to a thickness of 50 nm. Except for this, a gas barrier film was obtained in the same manner as in Example 7. The composition of the first layer was such that the Al atom concentration was 22.3 atom%, the Si atom concentration was 16.0 atom%, and the O atom concentration was 61.7 atom%.

(Comparative Example 15)
A gas barrier film was obtained in the same manner as in Comparative Example 2 except that the thickness of the first layer was 100 nm.

(Comparative Example 16)
A gas barrier film was obtained in the same manner as in Comparative Example 2 except that the thickness of the first layer was 200 nm.

(Comparative Example 17)
A gas barrier film was obtained in the same manner as in Comparative Example 2 except that the thickness of the first layer was 300 nm.

  Since the gas barrier film of the present invention is excellent in gas barrier properties against oxygen gas, water vapor, etc., it can be usefully used, for example, as a packaging material for foods, pharmaceuticals, etc., and as a member for electronic devices such as thin televisions and solar cells. However, the application is not limited to these.

DESCRIPTION OF SYMBOLS 1 Polymer film base material 2 Gas barrier layer 2a 1st layer 2b containing zinc oxide and silicon dioxide 2nd layer containing (A)-(C) 3 Undercoat layer 4 Single wafer type sputtering apparatus 5 Sputtering electrode 6 Substrate holder 7 Deposition chamber

Claims (5)

On at least one surface of the polymer film substrate, a first layer containing zinc oxide and silicon dioxide and a second layer containing the following (A) to (C) were disposed in this order from the polymer film substrate. A gas barrier film characterized by that.
(A) having at least one unsaturated compound (a1) selected from the group consisting of unsaturated carboxylic acid ester, styrene, unsaturated carboxylic acid, unsaturated hydrocarbon and vinyl ester, unsaturated nitrile (a2) and hydroxyl group Copolymer (a1): a copolymer having at least three components as a monomer and an unsaturated compound (a3), wherein the proportion of (a1) to (a3) in the copolymer is as follows: a2): (a3) = 20-40% by mass: 10-30% by mass: 30-70% by mass
(B) Compound having isocyanate group (C) Compound having two or more carboxylic acid groups or one or more carboxylic anhydride groups The gas barrier film according to claim 1, further comprising an undercoat layer between the polymer film substrate and the first layer, wherein the undercoat layer includes a polyurethane compound having an aromatic ring structure. . 3. The first layer according to claim 1, wherein the first layer includes at least one selected from the group consisting of aluminum (Al), gallium (Ga), tin (Sn), and indium (In). The gas barrier film according to 1. The first layer includes aluminum (Al), and the first layer has a zinc (Zn) atom concentration of 10 to 35 atom% and a silicon (Si) atom concentration of 5 to 25 atom% as measured by X-ray photoelectron spectroscopy. The gas barrier film according to any one of claims 1 to 3, wherein the aluminum (Al) atom concentration is 1 to 7 atom% and the oxygen (O) atom concentration is 50 to 70 atom%. The gas barrier film according to claim 1, wherein the second layer has a thickness of 0.1 μm or more.

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