JP2013237264A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film high in gas barrier performance and reduced in the lowering of the gas barrier performance in a post-processing process.SOLUTION: A gas barrier film is formed by sequentially laminating the following [A] layer, [B] layer and [C] layer on at least a single face of a polymer base material. [A] layer: a first bridging resin layer whose pencil hardness is not lower than H and surface free energy is not higher than 45mN/m. [B] layer: a silicon-containing inorganic layer whose thickness is 10 to 1,000 nm. [C] layer: a second bridging resin layer whose pencil hardness is not lower than H and thickness is 0.05 to 10 μm.

Description

  TECHNICAL FIELD The present invention relates to a gas barrier film used for packaging for foods, pharmaceuticals, etc., and members for electronic devices such as solar cells, electronic paper, organic EL displays and lighting.

  On the surface of a polymer substrate, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, photochemical vapor deposition A gas barrier film formed by forming an inorganic substance (including inorganic oxide) such as aluminum oxide, silicon oxide, magnesium oxide by using a chemical vapor deposition method (CVD method) such as a growth method is water vapor or oxygen. It is used as a packaging material for foods and pharmaceuticals that needs to be blocked, and as a member for electronic devices such as solar cells, electronic paper, organic EL displays and lighting.

  As a gas barrier property improving technique, for example, a gas containing an organic silicon compound vapor and oxygen is used to form a main component of silicon oxide on a substrate by a plasma CVD method, and at least one of carbon, hydrogen, silicon and oxygen. A method of improving gas barrier properties while maintaining transparency by forming a contained compound is used (Patent Document 1).

  On the other hand, in post-processing using a gas barrier film, deterioration of gas barrier properties may be a problem due to generation of cracks and scratches in the gas barrier layer during film transport, printing, and lamination with other members. As a technique for improving this problem, for example, an inorganic oxide layer such as aluminum oxide or silicon oxide is formed on a substrate by vacuum deposition, and at least one of an acrylate group, a methacrylate group, and a vinyl group is further formed thereon. Suppressing gas barrier properties during post-processing by laminating an overcoat layer composed of a polymer containing a monomer containing silane coupling agent and at least one of acrylate, methacrylate and vinyl groups and a hydroxyl group Method is used. (Patent Document 2).

JP-A-8-142252 (Claims) JP-A-2005-186402 (Claims)

  The present invention makes it possible to achieve both high gas barrier properties that can withstand the use of electronic paper, organic EL displays, lighting applications, and the like, which have been difficult with the prior art, and suppression of gas barrier property deterioration due to conveyance or lamination processing during post-processing. Objective.

The present invention employs the following means in order to solve such problems. That is,
(1) A gas barrier film in which the following [A] layer, [B] layer, and [C] layer are laminated in this order on at least one surface of a polymer substrate.
[A] layer: a first crosslinked resin layer [B] having a pencil hardness of H or more and a surface free energy of 45 mN / m or less; a silicon-containing inorganic layer [C] layer having a thickness of 10 to 1000 nm; 2nd crosslinked resin layer (2) whose thickness is 0.05-10 micrometers which is more than H, The gas barrier film as described in said (1) whose thickness of the said [C] layer is 1-5 micrometers.
(3) The gas barrier film according to (1) or (2), wherein the [B] layer is constituted by a composition containing a zinc compound and a silicon oxide.
(4) The gas barrier film according to (3), wherein the [B] layer is one of the following [B1] layer and [B2] layer.
[B1] layer: a layer consisting of a coexisting phase of zinc oxide, silicon dioxide and aluminum oxide [B2] layer: a layer consisting of a coexisting phase of zinc sulfide and silicon dioxide (5) The [B] layer is a [B1] layer The [B1] layer has a zinc (Zn) atom concentration of 20 to 40 atom%, a silicon (Si) atom concentration of 5 to 20 atom%, and an aluminum (Al) atom concentration of 0. The gas barrier film according to (4) above, which is constituted by a composition having 5 to 5 atom% and an oxygen (O) atom concentration of 35 to 70 atom%.
(6) The [B] layer is a [B2] layer, and the [B2] layer has a composition in which the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier film as described in (4) above.
(7) The gas barrier film according to any one of (1) to (6), wherein the [A] layer has an average surface roughness Ra of 1.5 nm or less.
(8) A solar cell having the gas barrier film according to any one of (1) to (7).
(9) A display element having the gas barrier film according to any one of (1) to (7).

  It is possible to provide a gas barrier film having a high gas barrier property against water vapor, oxygen and the like, and having a small deterioration in gas barrier property due to post-processing such as transport and lamination with other members.

It is sectional drawing which showed an example of the gas barrier film of this invention. It is the schematic which shows typically the winding-type sputtering apparatus for manufacturing the gas barrier film of this invention. It is the schematic of a bending resistance test.

  The inventors have made it possible to achieve both high gas barrier properties that can withstand the use of electronic paper, organic EL displays, lighting applications, and the like, and suppression of gas barrier properties due to film transport during post-processing or lamination processing with other members. For the purpose of intensive studies, at least one surface of the polymer substrate has a first cross-linked resin layer having a specific pencil hardness and surface free energy, a silicon-containing inorganic layer having a specific thickness, and a specific pencil hardness and thickness. It has been clarified that the above-mentioned problems can be solved at once by arranging the second crosslinked resin layer in this order.

  FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention. In this example, the first cross-linked resin layer having a pencil hardness of H or more and a surface free energy of 45 mN / m or less as the [A] layer 2 and a thickness of 10 as the [B] layer 3 on one side of the polymer substrate 1. A silicon-containing inorganic layer having a thickness of ˜1000 nm and a second crosslinked resin layer having a pencil hardness of H or more and a thickness of 0.05 to 10 μm as the [C] layer 4 are laminated in this order. 2 to [C] layer 4 may be arranged on the other surface in the same order.

[Polymer substrate]
The material of the polymer substrate used in the present invention is not particularly limited as long as it has a film form, but is preferably an organic polymer because it has flexibility necessary for a gas barrier film. Examples of the organic polymer that can be suitably used in the present invention include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polystyrenes, polyvinyl alcohol, and ethylene vinyl acetate copolymers. Various polymers such as saponified products, polyacrylonitrile, polyacetal and the like can be mentioned. Among these, it is preferable to contain polyethylene terephthalate. The organic polymer may be either a homopolymer or a copolymer, one kind of organic polymer may be used, or a plurality of kinds of organic polymers may be blended.

  As a form of the polymer substrate, a single layer film or a film having two or more layers, for example, a film formed by a co-extrusion method may be used. As the type of film, a film stretched in a uniaxial direction or a biaxial direction may be used. In order to improve adhesion, the surface of the polymer base material forming the first crosslinked resin layer is treated with corona treatment, ion bombardment treatment, solvent treatment, surface roughening treatment, and organic or inorganic matter or a mixture thereof. A pretreatment such as a formation treatment of the anchor coat layer to be configured may be performed. In the case where the [A] layer to the [C] layer are arranged on one side of the polymer base material, the surface on the opposite side of the polymer base material from the [A] layer to the [C] layer forming side. For the purpose of improving the slipperiness at the time of winding the film, a coating layer of an organic material, an inorganic material, or a mixture thereof may be disposed.

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

[A] Layer The first crosslinked resin layer (hereinafter also referred to as “[A] layer”) having a pencil hardness of H or more and a surface free energy of 45 mN / m or less will be described in detail.

  By forming the [A] layer on at least one surface of the polymer substrate and laminating the [B] layer, which is a silicon-containing inorganic layer, on the [A] layer, the gas barrier property is dramatically improved and stabilized. It has been found that gas barrier properties can be expressed.

  The thickness of the [A] layer used in the present invention is preferably 0.5 μm or more and 10 μm or less. If the thickness of the layer is less than 0.5 μm, the film quality of the [B] layer is not uniform due to the influence of the unevenness of the polymer substrate, so that the gas barrier property may be lowered. If the thickness of the layer is greater than 10 μm, the stress remaining in the [A] layer increases and the polymer base material warps and cracks are generated in the [B] layer, so that the gas barrier property may be lowered. is there. Furthermore, from a viewpoint of ensuring flexibility, 1 μm or more and 5 μm or less are more preferable.

  The thickness of the [A] layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

  In the present invention, the mechanism by which the pencil hardness of the [A] layer contributes to the stable gas barrier property is not clear, but by making the pencil hardness of the [A] layer equal to or higher than a specific hardness, the polymer Since heat resistance and dimensional stability can be imparted to the base material, it is possible to prevent damage caused by collision of plasma emission heat, ions, and radicals when forming a silicon-containing inorganic layer, resulting in gas barrier properties. It is assumed that the reproducibility is stable. The pencil hardness of the [A] layer that exhibits this effect is H or higher, and preferably 2H or higher. On the other hand, when the pencil hardness of the [A] layer exceeds 5H, the flexibility is lowered, which may cause a decrease in gas barrier properties due to cracks in handling and post-processing after forming the silicon-containing inorganic layer. Therefore, it is preferable that it is 5H or less. (The pencil hardness is (soft) 10B to B, HB, F, H to 9H (hard), and the one on the right side of the rank indicates that the hardness is high).

  The pencil hardness test of the [A] layer is performed according to JIS K5600 (1999). The test is performed under a load of 0.5 kg using pencils having different hardnesses, and the determination is made based on the presence or absence of scratches.

  In addition, although the mechanism by which the surface free energy of the [A] layer contributes to improving the gas barrier property is not clear in the present invention, the [B] layer is formed by setting the surface free energy to a specific value or less. During the initial growth process of the silicon-containing inorganic compound, the atoms and particles that are the growth nuclei of the film are likely to move and diffuse, so the quality of the film near the [B] layer becomes denser. As a result, the entire layer becomes dense. It is estimated that the structure is improved and the permeation of water vapor and oxygen is suppressed. The surface free energy of the [A] layer exhibiting such effects is 45 mN / m or less, preferably 40 mN / m or less.

  The surface free energy of the [A] layer in the present invention is obtained by using four types of measurement liquids (water, formamide, ethylene glycol, methylene iodide) with known components (dispersion force, polar force, hydrogen bonding force), The contact angle of each measurement solution is measured, and each component can be calculated using the following formula (1) introduced from the extended Fowkes formula and Young's formula.

In addition, when the [B] layer and the [C] layer are laminated on the surface of the [A] layer, the [B] layer and the [C] layer are removed by ion etching, chemical treatment, or the like, and then described above. Pencil hardness and surface free energy can be evaluated by performing the measurement method.

  Generation of pinholes and cracks in the [B] layer to be laminated when the average surface roughness Ra of the surface of the [A] layer in the present invention (in the gas barrier film, the boundary surface with the [B] layer) is 1.5 nm or less. Since the reproducibility of gas barrier properties is improved, it is preferable. When the average surface roughness Ra of the surface of the [A] layer is larger than 1.5 nm, pinholes are likely to occur after the lamination of the [B] layer in the convex portions, and cracks are generated in the portions with many irregularities. For this reason, the reproducibility of gas barrier properties may be reduced. The average surface roughness Ra of the surface of the [A] layer is more preferably 1 nm or less from the viewpoint of suppressing generation of fine defects such as microcracks during bending and improving flexibility.

  The average surface roughness Ra of the [A] layer in the present invention can be measured using an atomic force microscope. In addition, when an inorganic layer or a resin layer is laminated on the surface of the [A] layer, the X-ray reflectivity method (“X-ray reflectivity introduction” (edited by Kenji Sakurai) Kodansha p.51-78, 2009) is used. The value obtained in this manner is defined as the average surface roughness Ra of the [A] layer.

  The material of the [A] layer used in the present invention is not particularly limited as long as the pencil hardness is H or more and the surface free energy is 45 mN / m or less, and various cross-linked resins can be used. The cross-linked resin here is defined as having one or more cross-linking points per 20000 number average molecular weight. Examples of the crosslinked resin that can be applied to the first crosslinked resin layer in the present invention include acrylic, urethane, organic silicate compounds, silicone-based crosslinked resins, and the like. Among these, from the viewpoint of durability of plasma heat and pencil hardness, it is preferable to use a thermosetting acrylic resin and / or an actinic radiation curable acrylic resin as the cross-linking resin.

  The thermosetting acrylic resin and / or the actinic radiation curable acrylic resin includes a polyfunctional acrylate, an acrylic oligomer and / or a reactive diluent, and, if necessary, a photoinitiator, a light A sensitizer, a thermal polymerization initiator or a modifier may be added.

  The polyfunctional acrylate suitably used for the acrylic resin described above refers to a compound having three or more (meth) acryloyloxy groups in one molecule. Examples of such compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and trimethylolpropane tri (meth) acrylate. These polyfunctional acrylates can be used alone or in combination of two or more. In the present invention, the polyfunctional acrylate includes a modified polymer of the polyfunctional acrylate.

  The acrylic oligomer has a number average molecular weight of 100 to 5000 and has at least one reactive acrylic group bonded in the molecule. Examples of the skeleton include polyacrylic resins, polyester resins, polyurethane resins, polyepoxy resins, and polyether resins. The skeleton may be a rigid skeleton such as melamine or isocyanuric acid.

  A reactive diluent is a coating agent component having a group that reacts with a monofunctional or polyfunctional acrylic oligomer as well as serving as a solvent in the coating process as a coating medium. It will be.

  In particular, in the case of crosslinking by ultraviolet rays, since the light energy is small, it is preferable to add a photopolymerization initiator and / or a photosensitizer in order to convert the light energy and accelerate the reaction. Details of the photopolymerization initiator and the photosensitizer will be described later.

  The use ratio of the polyfunctional acrylate in the blending of the material of the [A] layer used in the present invention is preferably 20 to 90% by mass with respect to the total amount of the [A] layer, from the viewpoint of making the pencil hardness H or more. Preferably it is 40-70 mass%. When the ratio is larger than 90% by mass, the curing shrinkage is large and the polymer substrate may be warped. In such a case, cracks are generated in the silicon-containing inorganic layer, and the gas barrier property is lowered. May occur. Moreover, when the ratio of a monomer becomes smaller than 20 mass%, the adhesive strength of a base material and an [A] layer falls, and problems, such as peeling, may generate | occur | produce.

  As a method of crosslinking the [A] layer in the present invention, it is preferable to add a photopolymerization initiator when applying curing by light. Examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4. '-Bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy Carbonyl compounds such as 2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiu Arm disulfide, thioxanthone, 2-chlorothioxanthone, sulfur compounds such as 2-methyl thioxanthone, benzoyl peroxide, etc. peroxide compounds such as di -t- butyl peroxide.

  The amount of the photopolymerization initiator used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable composition, remains as an unreacted product during polymerization, and has a small influence on gas barrier properties. 0.05 to 5 parts by mass is preferable.

  The coating liquid containing the resin that forms the first cross-linked resin layer of the [A] layer used in the present invention (hereinafter sometimes referred to as “[A] layer forming coating liquid”) For the purpose of improving the properties and controlling the coating film thickness, it is preferable to add an organic solvent as long as the effects of the present invention are not impaired. A preferred range for blending the organic solvent is 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less.

  Examples of the organic solvent include alcohol solvents such as methanol, ethanol and isopropyl alcohol, acetate solvents such as methyl acetate, ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene. Etc. can be used. These solvents may be used alone or in combination of two or more.

  In addition, the coating liquid containing the resin forming the [A] layer used in the present invention is blended with inorganic particles such as silica, alumina and zinc oxide for the purpose of improving the adhesion to the [B] layer. It is preferable. Among these, silica-based inorganic particles that strongly adhere to the silicon-containing inorganic layer are preferable, and silica-based inorganic particles obtained by hydrolysis with a silane compound or the like are more preferable. A preferred range for blending the inorganic particles is 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less.

  [A] Various additives can be blended in the layer-forming coating liquid as needed, as long as the effects of the present invention are not impaired. For example, stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, surfactants, leveling agents, antistatic agents, and the like can be used.

  As a method of setting the surface free energy of the [A] layer used in the present invention to 45 mN / m or less, dimethylpolysiloxane, as long as the adhesion and gas barrier properties between the [A] layer and the [B] layer are not lowered, Examples thereof include a method of adding a silicone having a low surface tension such as methylphenylpolysiloxane or a monomer having a long-chain alkyl group such as n-stearyl acrylate which is lipophilic.

  [A] As a means for applying a coating liquid comprising a resin forming the layer, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, a spray coating method, or the like can be used. Among these, a gravure coating method is preferable as a method suitable for coating with a preferable thickness of the [A] layer of 0.5 μm or more and 10 μm or less.

  [A] When an active ray curable acrylic resin is used as the cross-linking resin constituting the layer, the active rays used for cross-linking include ultraviolet rays, electron beams, radiation (α rays, β rays, γ rays) and the like. Although it can be mentioned, ultraviolet rays are preferable because they can be used simply and practically. In addition, when a thermosetting acrylic resin is used as the cross-linking resin constituting the [A] layer, the heat source used for cross-linking includes a steam heater, an electric heater, an infrared heater, etc. From the viewpoint, an infrared heater is preferable.

[B] Layer A silicon-containing inorganic layer having a thickness of 10 to 1000 nm (hereinafter sometimes referred to as “[B] layer”) will be described in detail. The silicon-containing inorganic layer is known as a so-called gas barrier layer. In the present invention, the [B] layer is disposed on the first cross-linked resin layer which is the [A] layer and has a pencil hardness of H or more and a surface free energy of 45 mN / m or less. It has been found that gas barrier properties can be dramatically improved by laminating the [B] layer on the [A] layer.

In the present invention, the material suitably used for the [B] layer is preferably silicon dioxide having an amorphous and dense film quality and excellent gas barrier properties. “Silicon dioxide” may be referred to as “SiO ₂ ”. Also, silicon (SiO ₂₎ dioxide, the generation time conditions, said that deviates slightly from the composition formula of silicon and oxygen composition ratio (SiO~SiO ₂₎ although it is possible to produce, in this specification It will be expressed as silicon dioxide or SiO ₂ .

  The reason why the effect of the present invention can be obtained by laminating the [B] layer on the [A] layer is considered as follows. That is, since the [A] layer is the first crosslinked resin layer having a pencil hardness of H or higher, the heat resistance and thermal dimensionality of the polymer base material are improved. Then, by forming a silicon dioxide layer on the [A] layer, the silicon dioxide layer is formed as compared to forming the silicon dioxide layer directly on the polymer substrate. Since the polymer substrate can be prevented from being damaged by plasma ions and radicals, a stable and dense silicon dioxide layer can be formed. Furthermore, since the surface free energy of the [A] layer is in the range of 45 mN / m or less, the sputtered particles of the silicon dioxide layer on the surface of the polymer base material are more likely to diffuse, which is closer to the surface of the polymer base material than before. It is presumed that the gas barrier properties can be improved because the film quality becomes finer and denser.

[B] If the layer contains silicon oxide, oxide, nitride, sulfide, or a mixture of elements such as Zn, Al, Ti, Zr, Sn, In, Nb, Mo, Ta, etc. May be included. Especially, it is preferable that it is comprised by the composition containing a zinc compound and a silicon oxide. Among those composed of such a composition, a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide (hereinafter also referred to as “[B1] layer”) or [B2] A layer composed of a coexisting phase of zinc sulfide and silicon dioxide (hereinafter sometimes referred to as “[B2] layer”) is preferably used. (Detailed explanation of each of the [B1] layer and the [B2] layer will be given later.)
The thickness of the [B] layer used for this invention is 10 nm or more and 1000 nm or less as the thickness of the layer which expresses gas barrier property. When the thickness of the layer is less than 10 nm, there may be a portion where sufficient gas barrier properties cannot be ensured, resulting in problems such as variations in gas barrier properties within the polymer substrate surface. In addition, when the thickness of the layer is greater than 1000 nm, the stress remaining in the layer increases, so that the [B] layer is liable to be cracked by bending or external impact, and the gas barrier property decreases with use. There is. 100 nm or more and 500 nm or less are preferable from a viewpoint of ensuring a softness | flexibility. [B] The thickness of the layer can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).

  The method for forming the [B] layer is not particularly limited, and can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like. Among these methods, the sputtering method is preferable as a method for forming the [B] layer easily and inexpensively.

[B1] Layer Next, as the [B1] layer suitably used as the silicon-containing inorganic layer in the present invention, a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide will be described in detail. The “coexisting phase of zinc oxide-silicon dioxide-aluminum oxide” is sometimes referred to as “ZnO—SiO ₂ —Al ₂ O ₃ ”. In addition, silicon dioxide (SiO ₂ ) is described as silicon dioxide or SiO ₂ regardless of a slight deviation from the composition ratio of silicon and oxygen. However, zinc oxide and aluminum oxide also have such a composition. The deviation from the chemical formula of the ratio is handled in the same way. That is, in this specification, it will be expressed as zinc oxide or ZnO, aluminum oxide or Al ₂ O ₃ regardless of the difference in composition ratio depending on the conditions during generation.

  The reason why the gas barrier property is improved by applying the [B1] layer in the gas barrier film of the present invention is that, in the coexisting phase of zinc oxide-silicon dioxide-aluminum oxide, the crystalline component contained in zinc oxide and silicon dioxide Presuming that by coexisting with the amorphous component, crystal growth of zinc oxide, which tends to generate microcrystals, is suppressed and the particle size is reduced, so that the layer is densified and the permeation of oxygen and water vapor is suppressed. Yes.

  In addition, it is considered that the coexistence of aluminum oxide can suppress the crystal growth more than the coexistence of zinc oxide and silicon dioxide, so that it is possible to suppress the decrease in gas barrier properties due to the generation of cracks. .

  The composition of the [B1] layer can be measured by ICP emission spectroscopy as described later. The Zn atom concentration measured by ICP emission spectroscopy is 20 to 40 atom%, the Si atom concentration is 5 to 20 atom%, the Al atom concentration is 0.5 to 5 atom%, and the O atom concentration is 35 to 70 atom%. preferable. When the Zn atom concentration is higher than 40 atom% or the Si atom concentration is lower than 5 atom%, the oxide that suppresses the crystal growth of zinc oxide is insufficient, so that voids and defects are increased, and sufficient gas barrier properties are obtained. It may not be obtained. When the Zn atom concentration is lower than 20 atom% or the Si atom concentration is higher than 20 atom%, the amorphous component of silicon dioxide inside the layer may increase and the flexibility of the layer may be lowered. Further, when the Al atom concentration is higher than 5 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that the pencil hardness of the film increases, and cracks are likely to occur due to heat and external stress. is there. When the Al atom concentration is less than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved and flexibility may be lowered. Further, when the O atom concentration is higher than 70 atom%, the amount of defects in the [A] layer increases, so that a predetermined gas barrier property may not be obtained. If the O atom concentration is less than 35 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, it is more preferable that the Zn atom concentration is 25 to 35 atom%, the Si atom concentration is 10 to 15 atom%, the Al atom concentration is 1 to 3 atom%, and the O atom concentration is 50 to 64 atom%.

  The component contained in the [B1] layer is 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, Al, Ti, Zr, Sn, In, Nb, Mo, A metal oxide formed of Ta, Pd, or the like may be included. Here, the main component means 60% by mass or more of the composition of the [B1] layer, and preferably 80% by mass or more.

  The composition of the [B1] layer is formed with the same composition as the mixed sintered material used at the time of forming the layer. Therefore, by using a mixed sintered material having a composition that matches the composition of the target layer [B1 It is possible to adjust the composition of the layer.

The composition analysis of the [B1] layer uses ICP emission spectroscopy to quantitatively analyze each element of zinc, silicon, and aluminum, and determine the composition ratio of zinc oxide, silicon dioxide, aluminum oxide, and the inorganic oxide contained. I can know. The oxygen atoms are calculated on the assumption that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis.

  When the [C] layer is laminated on the surface of the [B1] layer, ICP emission spectroscopic analysis can be performed after removing the [C] layer by ion etching or chemical treatment.

  The method for forming the [B1] layer on the polymer substrate is not particularly limited, and a vacuum deposition method, a sputtering method, an ion plating method, etc. using a mixed sintered material of zinc oxide, silicon dioxide and aluminum oxide, etc. Can be formed. 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 [B1] layer forming method used in 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.

[B2] Layer Next, as the [B2] layer, a layer composed of a coexisting phase of zinc sulfide and silicon dioxide will be described in detail. The “zinc sulfide-silicon dioxide coexisting phase” is sometimes referred to as “ZnS—SiO ₂ ”. In addition, silicon dioxide (SiO ₂ ) is described as silicon dioxide or SiO ₂ regardless of a slight deviation from the composition ratio of silicon and oxygen. The same treatment will be applied to deviations from. That is, in this specification, it will be expressed as zinc sulfide or ZnS regardless of the difference in composition ratio depending on the conditions during generation.

  The reason why the gas barrier property is improved by applying the [B2] layer in the gas barrier film of the present invention is that the crystalline component contained in the zinc sulfide and the amorphous component of silicon dioxide in the zinc sulfide-silicon dioxide coexisting phase. It is presumed that the crystal growth of zinc sulfide, which tends to generate microcrystals, is suppressed and the particle size is reduced, so that the layer is densified and the permeation of oxygen and water vapor is suppressed. In addition, the zinc sulfide-silicon dioxide coexisting phase containing zinc sulfide with suppressed crystal growth is more flexible than a layer formed only of inorganic oxides or metal oxides. On the other hand, since cracks are unlikely to occur, it is considered that application of the [B2] layer can suppress a decrease in gas barrier properties due to generation of cracks.

  The composition of the [B2] layer is preferably such that the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. If the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is greater than 0.9, there will be insufficient oxide that suppresses crystal growth of zinc sulfide, resulting in an increase in voids and defects, resulting in a predetermined gas barrier property. May not be obtained. Further, when the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is less than 0.7, the amorphous component of silicon dioxide inside the [B2] layer increases and the flexibility of the layer decreases, The flexibility of the gas barrier film with respect to mechanical bending may be reduced. More preferably, it is the range of 0.75-0.85.

  The components contained in the [B2] layer are not particularly limited as long as zinc sulfide and silicon dioxide are in the above composition and are the main components. For example, Al, Ti, Zr, Sn, In, Nb, Mo, Ta, Pd Or a metal oxide such as Here, the main component means 60% by mass or more of the composition of the [B2] layer, and preferably 80% by mass or more.

  Since the composition of the [B2] layer is formed with the same composition as the mixed sintered material used at the time of forming the layer, the composition of the [B2] layer can be changed by using a mixed sintered material having a composition suitable for the purpose. It is possible to adjust.

  The composition analysis of the [B2] layer is based on ICP emission spectroscopic analysis. First, the composition ratio of zinc and silicon is obtained. Based on this value, each element is quantitatively analyzed by using Rutherford backscattering method, and zinc sulfide and silicon dioxide are analyzed. And the composition ratio of other inorganic oxides contained. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis. In Rutherford backscattering method, a charged particle accelerated by a high voltage is irradiated on a sample, and the number of charged particles bounced from the sample and the element are identified and quantified from the energy, and the composition ratio of each element can be known. Since the [B2] layer is a composite layer of sulfide and oxide, analysis by Rutherford backscattering method capable of analyzing the composition ratio of sulfur and oxygen is performed.

  When the [C] layer is laminated on the surface of the [B2] layer, the [C] layer is removed by ion etching or chemical treatment, and then analyzed by ICP emission spectroscopic analysis and Rutherford backscattering method. Can do.

  The method for forming the [B2] layer on the transparent polymer substrate is not particularly limited, and it is formed by using a mixed sintered material of zinc sulfide and silicon dioxide by a vacuum deposition method, a sputtering method, an ion plating method, or the like. can do. When a single material of zinc sulfide and silicon dioxide is used, it can be formed by simultaneously forming films of zinc sulfide and silicon dioxide from different vapor deposition sources or sputtering electrodes, and mixing them to obtain a desired composition. Among these methods, the [B2] layer forming method used in 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.

[C] Layer The details of the second crosslinked resin layer (hereinafter also referred to as “[C] layer”) having a pencil hardness of H or more and a thickness of 0.05 to 10 μm will be described. By disposing the [C] layer on the [B] layer, it is possible to suppress a decrease in gas barrier properties due to conveyance during post-processing, lamination processing with other members, and the like, and gas barrier properties such as a flex resistance test described later. Even when the film was repeatedly bent, it was found that the gas barrier property could be prevented from lowering. Specifically, it functions as a surface protective layer for the [B] layer and has a structure in which the silicon-containing inorganic layer [B] is sandwiched between the polymer substrate and the [C] layer in tests such as bending resistance. By doing so, it is presumed that the tensile stress and the compressive stress when the gas barrier film is bent can be balanced, and as a result, the stress applied to the [B] layer can be reduced.

  The thickness of the [C] layer is 0.05 μm or more and 10 μm or less. If the thickness of the layer is less than 0.05 μm, the [B] layer may be cracked or scratched due to various stresses caused by post-processing, and the gas barrier property may be lowered. If the thickness of the layer is greater than 10 μm, the stress remaining in the [A] layer increases and the polymer base material warps and cracks are generated in the [B] layer, so that the gas barrier property may be lowered. is there. In addition, the production efficiency may decrease with these. From the viewpoint of ensuring flexibility, the thickness of the [C] layer is more preferably 1 μm or more and 5 μm or less. The thickness of the [C] layer can be measured from a cross-sectional observation image by a transmission electron microscope (TEM).

  In the present invention, the contribution of the pencil hardness of the [C] layer to the effect that enables stable gas barrier properties to be achieved is that the pencil hardness of the [C] layer is H or more, thereby being resistant to various stresses applied during post-processing. Is estimated to improve. Therefore, the pencil hardness of the [C] layer is H or higher, and preferably 2H or higher. On the other hand, if the pencil hardness of the [C] layer exceeds 5H, the flexibility is lowered, which may cause a decrease in gas barrier properties due to cracks in handling and post-processing after forming the silicon-containing inorganic layer. Therefore, it is preferable that it is 5H or less.

  The pencil hardness test of the [C] layer is performed according to JIS K5600 (1999). The test is performed under a load of 0.5 kg using pencils having different hardnesses, and the determination is made based on the presence or absence of scratches.

  The material of the [C] layer used in the present invention is not particularly limited as long as the pencil hardness is H or more and the thickness is 0.05 μm to 10 μm, and various cross-linked resins can be used. Specifically, the same cross-linked resin and coating means as those in the [A] layer can be used.

[Usage]
Since the gas barrier film of the present invention has excellent gas barrier properties such as water vapor and oxygen, it can be used for display elements such as solar cells and organic EL displays. For example, in an organic thin-film solar cell, an organic thin-film solar cell with a small reduction in power generation performance can be provided by sandwiching the light-emitting layer from one side or both sides with the gas barrier film of the present invention. In addition, in the organic EL display, an organic EL display with a small decrease in light emission characteristics can be provided by sandwiching the light emitting layer from one side or both sides with the gas barrier film of the present invention.

  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 microsampling system (Hitachi FB-2000A) (specifically, “Polymer Surface Processing” (by Satoshi Iwamori) p. 118-119). (Based on the method described in 1). Using a transmission electron microscope (Hitachi H-9000UHRII), the cross section of the observation sample was observed at an acceleration voltage of 300 kV, and the [A] layer or [A ′] layer (hereinafter referred to as “first layer”), [ The thicknesses of the B] layer or the [B ′] layer (hereinafter referred to as “second layer”), the [C] layer or the [C ′] layer (hereinafter referred to as “third layer”) were measured. The interface between the base material and the first layer, the first layer and the second layer, the second layer and the third layer was judged by a cross-sectional observation photograph using a transmission electron microscope.

(2) Pencil hardness test The pencil hardness of the surface of the first layer and the third layer is measured according to JIS K5600-5-4 (1999) using a pencil hardness tester HEIDON-14 (Shinto Kagaku Co., Ltd.). Then, the pencil hardness was measured at n = 1.

(3) Surface free energy For the surface of the first layer, four types of measurement liquids (water, formamide, ethylene glycol, methylene iodide) whose surface free energy and its components (dispersing force, polar force, hydrogen bonding force) are known are known. The contact angle of each liquid on the laminated film was measured with a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.) under the conditions of a temperature of 23 ° C. and a relative humidity of 65%. The average value of 5 pieces was used for the measurement. Each component was calculated from this value using the following formula (1) introduced from the extended Fowkes formula and Young's formula.

(4) Average surface roughness Ra
Using an atomic force microscope, the surface of the first layer was measured under the following conditions.
System: NanoScopeIII / MMAFM (manufactured by Digital Instruments)
Scanner: AS-130 (J-Scanner)
Probe: NCH-W type, single crystal silicon (manufactured by Nanoworld)
Scanning mode: Tapping mode Scanning range: 10 μm × 10 μm
Scanning speed: 0.5Hz
Measurement environment: temperature 23 ° C., relative humidity 65%, in air.

(5) Water vapor transmission rate (g / (m ² · 24h))
The measurement was performed using a water vapor transmission rate measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox, UK, under conditions of a temperature of 40 ° C., a relative humidity of 90%, and a measurement area of 50 cm ² . The number of samples was 2 samples per level, the number of measurements was 5 for each sample, and the average value of the 10 points obtained was the water vapor transmission rate (g / (m ² · 24 h)).
(6) Bending resistance As shown in FIG. 3, the gas barrier film is sampled to 100 mm × 140 mm, and the first to third layers (including the case where some layers are omitted) of this sample are formed. A metal cylinder 19 having a diameter of 5 mm is fixed to the central portion on the side of the surface 20, and the holding angle from the cylinder holding angle of 0 ° (the sample is flat) to the cylinder is 180 ° (cylinder) along the cylinder. After performing 100 bending operations within the range of (folded state), water vapor permeability was evaluated by the method shown in (5). The number of measurements was 5 for each specimen, and the average value of the 10 points obtained was taken as the water vapor transmission rate after the flex resistance test.

(7) Composition of [B1] layer The analysis of the composition of the [B1] layer described later was performed by ICP emission spectroscopic analysis (SPS4000, manufactured by SII Nanotechnology). The sample was thermally decomposed with nitric acid and sulfuric acid, heated and dissolved with dilute nitric acid, and filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom, a silicon atom, and an aluminum atom was measured, and it converted into atomic ratio. The oxygen atoms were calculated values assuming that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively.

(8) Composition of the [B2] layer The analysis of the composition of the [B2] layer described later was performed by ICP emission spectroscopic analysis (SII Nanotechnology, SPS4000) and Rutherford backscattering method (AN manufactured by Nisshin High Voltage Co., Ltd.). -2500). The sample was thermally decomposed with nitric acid and sulfuric acid, heated and dissolved with dilute nitric acid, and filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom and a silicon atom was measured. Next, based on this value, further using Rutherford backscattering method (AN-2500 manufactured by Nissin High Voltage Co., Ltd.), quantitative analysis of zinc atom, silicon atom, sulfur atom, oxygen atom and zinc sulfide The composition ratio of silicon dioxide was determined.

(9) Composition of [B′3] layer By using X-ray photoelectron spectroscopy (XPS method), the atomic ratio of oxygen atoms to aluminum atoms (O / Al ratio) was measured. The measurement conditions were as follows.
・ Device: Quantera SXM (manufactured by PHI)
Excitation X-ray: monochromic AlKα1,2
X-ray diameter 100 μm Photoelectron escape angle: 10 °

[Formation of second layer]
([B1] layer)
A sputter target, which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide, is placed on the sputter electrode 13 using a winding type sputtering apparatus having the structure shown in FIG. Sputtering is performed on the surface of the polymer substrate 5 on the side of the sputter electrode 13 (on the first layer when the first layer is formed, or on the polymer group when the first layer is not formed). [B1] layer was provided on the material. (The material of the [B1] layer is referred to as “B1”).

The specific operation is as follows. First, in a winding chamber 7 of a winding type sputtering apparatus 6 in which a sputtering target sintered with a composition ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 is installed on the sputtering electrode 13, The polymer base material 5 is set on the delivery roll 8 so that the surface on which the [B1] layer is provided faces the sputter electrode 13 and unwinds, and the cooling drum is passed through the delivery-side guide rolls 9, 10, 11. 12 was passed. Argon gas and oxygen gas are introduced at a partial pressure of oxygen of 10% so that the degree of decompression is 2 × 10 ⁻¹ Pa, and an argon / oxygen gas plasma is generated by applying an input power of 4000 W from a DC power source, and sputtering is performed. Thus, a [B1] layer was formed on the surface of the polymer substrate 5. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll 17 via the winding side guide rolls 14, 15, and 16.

([B2] layer)
A sputter target, which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide, is placed on the sputter electrode 13 using a winding type sputtering apparatus having the structure shown in FIG. Sputtering is performed on the surface of the polymer substrate 5 on the side of the sputter electrode 13 (on the first layer when the first layer is formed, or on the polymer group when the first layer is not formed). [B2] layer was provided on the material. (The material of the [B2] layer provided in this example is referred to as “B2”).

The specific operation is as follows. First, in the winding chamber 7 of the winding type sputtering apparatus 6 in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar composition ratio of 80/20 is installed on the sputtering electrode 13, The polymer substrate 5 was set and unwound so that the surface on which the [B2] layer is provided faces the sputter electrode 13, and passed through the cooling drum 12 through the unwinding side guide rolls 9, 10 and 11. Argon gas was introduced so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an applied power of 500 W was applied by a high-frequency power source to generate argon gas plasma. By sputtering, the surface of the polymer substrate 5 was [ B2] layer was formed. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll 17 via the winding side guide rolls 14, 15, and 16.

([B'3] layer: second layer that is not [B] layer)
Using a winding type sputtering apparatus having the structure shown in FIG. 2, a sputtering target, which is a sintered material of aluminum oxide, is placed on the sputtering electrode 13, and sputtering is performed using argon gas and oxygen gas. [B3] layer (on the first layer when the first layer is formed, or on the polymer substrate when the first layer is not formed) A second layer that is not the [B] layer was provided. (The material of the [B′3] layer provided in this example is referred to as “B′3”).

The specific operation is as follows. First, in a winding chamber 7 of a winding type sputtering apparatus 6 in which a sputtering target sintered with a sputtering electrode 13 having an atomic ratio of oxygen atoms to aluminum atoms (O / Al ratio) of 1.5 is installed. The polymer base material 5 was set on the unwinding roll 8 and unwound and passed through the cooling drum 12 through unwinding side guide rolls 9, 10, and 11. Argon gas was introduced so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an applied power of 500 W was applied by a high-frequency power source to generate argon gas plasma. By sputtering, the surface of the polymer substrate 5 was [ B′3] layer was formed. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll 17 via the winding side guide rolls 14, 15, and 16.

Example 1
A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 100 μm was used as the polymer substrate.

[A] layer was formed as the 1st layer. [A] A coating liquid 1 was prepared by diluting 100 parts by mass of urethane acrylate (Forseed 420C manufactured by China Paint Co., Ltd.) with 70 parts by mass of toluene as a coating liquid for layer formation. Next, the coating liquid 1 is applied to one side of the polymer substrate with a micro gravure coater (gravure wire number 200UR, gravure rotation ratio 100%), dried at 60 ° C. for 1 minute, and then irradiated with ultraviolet rays at 1 J / cm ² and cured. Then, an [A] layer having a thickness of 3 μm was provided (the material of the [A] layer provided in this example is referred to as “A1”).

  A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the [A] layer was formed, and the pencil hardness test, surface free energy, and average surface roughness of the [A] layer were evaluated. The results are shown in Table 1.

  Next, a [B1] layer having a thickness of 100 nm was formed on the [A] layer. As for the composition of the [B1] layer, the Zn atom concentration was 27.5 atom%, the Si atom concentration was 13.1 atom%, the Al atom concentration was 2.3 atom%, and the O atom concentration was 57.1 atom%.

[C] layer was provided on the [B1] layer in the following procedure. A coating liquid 1 was prepared by diluting 100 parts by mass of urethane acrylate (Forseed 420C manufactured by China Paint Co., Ltd.) with 70 parts by mass of toluene. Next, the coating liquid 1 is applied to one side of the polymer substrate with a micro gravure coater (gravure wire number 300UR, gravure rotation ratio 100%), dried at 60 ° C. for 1 minute, and then irradiated with ultraviolet rays at 1 J / cm ² and cured. Then, a [C] layer having a thickness of 1 μm was provided. (The material of the [C] layer provided in this example is described as “C1”).

  A test piece having a length of 100 mm and a width of 100 mm was cut out from the obtained gas barrier film, and a pencil hardness test and an evaluation of water vapor permeability were performed. The results are shown in Table 1.

(Example 2)
[A] layer was formed as the 1st layer. [A] As a coating solution for forming a layer, 0.2 parts by mass of silicone oil (SH 190 manufactured by Toray Dow Corning Co., Ltd.) is added to 100 parts by mass of polyester acrylate (FOP-1740 manufactured by Nippon Kayaku Co., Ltd.). Then, a coating liquid 2 diluted with 50 parts by mass of toluene and 50 parts by mass of MEK is prepared, and the coating liquid 2 is applied with a micro gravure coater (gravure wire number 300UR, gravure rotation ratio 100%) and dried at 60 ° C. for 1 minute. Thereafter, ultraviolet rays were irradiated at 1 J / cm ² and cured to provide a 3 μm thick [A] layer (the material of the [A] layer provided in this example is referred to as “A2”), and thereafter the [C] layer was thickened. A gas barrier film was obtained in the same manner as in Example 1 except that the thickness was 3 μm.

(Example 3)
In the same manner as in Example 1, the [A] layer was provided. Next, instead of the [B1] layer, a [B2] layer was provided to a thickness of 200 nm. The composition of the [B2] layer had a zinc sulfide molar fraction of 0.80.

The [C] layer was provided on the [B2] layer in the following procedure. 0.2 parts by mass of silicone oil (SH190 manufactured by Toray Dow Corning Co., Ltd.) is added to 100 parts by mass of polyester acrylate (Nippon Kayaku Co., Ltd. FOP-1740), and diluted with 100 parts by mass of toluene and 100 parts by mass of MEK. The coating liquid 2 was prepared, and the coating liquid 2 was applied with a microgravure coater (gravure wire number 300UR, gravure rotation ratio 100%), dried at 60 ° C. for 1 minute, and then irradiated with ultraviolet rays at 1 J / cm ² to be cured. A [C] layer having a thickness of 1 μm was provided. (The material of the [C] layer provided in this example is described as “C2”).

Example 4
A gas barrier film was obtained in the same manner as in Example 3 except that A2 was used as the material for the [A] layer and the thickness of the [C] layer was 3 μm.

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

(Comparative Example 2)
A gas barrier film was obtained in the same manner as in Example 1 except that the third layer was provided on the [B1] layer by the following procedure. Weigh out 10 parts by mass (solid content concentration: 15% by mass) of “Sepoljon” (registered trademark) VH100, manufactured by Sumitomo Seika Co., Ltd., which is a coating agent in which an ethylene / vinyl alcohol copolymer resin is dispersed in water. 1.9 parts by mass of water and 0.6 parts by mass of isopropanol were added, and the coating liquid 3 having a solid content concentration of 12% by mass was prepared by stirring for 30 minutes. Next, it apply | coated using the wire bar, it was made to dry at the temperature of 120 degreeC for 40 second, and the 3rd layer of thickness 1 micrometer was provided. (The material of the third layer provided in this example is described as “C′3”).

(Comparative Example 3)
[A] A gas barrier film was obtained in the same manner as in Example 1 except that the layer was not formed.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Example 1 except that the first layer was provided by the following procedure. 10 parts by mass (solid content concentration: 15% by mass) of “Sepoljon” (registered trademark) VH100 manufactured by Sumitomo Seika Co., Ltd., which is a coating agent in which an ethylene / vinyl alcohol copolymer resin is dispersed in water, is used as a diluent solvent. 1.9 parts by mass of water and 0.6 parts by mass of isopropanol were added, and the coating liquid 3 having a solid content concentration of 12% by mass was prepared by stirring for 30 minutes. Next, it apply | coated using the wire bar, it was made to dry for 40 second at the temperature of 120 degreeC, and the 1st layer of thickness 3 micrometers was provided. (The material of the first layer provided in this example is indicated as “A′3”).
(Comparative Example 5)
A gas barrier film was obtained in the same manner as in Example 1 except that the thickness of the second layer was 1200 nm.
(Comparative Example 6)
A gas barrier film was obtained in the same manner as in Example 3 except that the thickness of the second layer was 1200 nm.
(Comparative Example 7)
A gas barrier film was obtained in the same manner as in Example 1 except that a [B′3] layer having a thickness of 100 nm was provided as the second layer. Regarding the composition of the Al ₂ O ₃ layer, the atomic ratio of oxygen atoms to aluminum atoms (O / Al ratio) was 1.65.

  Since the gas barrier film of the present invention is excellent in gas barrier properties that block gas such as water vapor and oxygen, for example, packaging materials such as foods and pharmaceuticals, and electronic devices such as solar cells, electronic paper, organic EL displays and lighting Although it can be usefully used as a member, the application is not limited thereto.

DESCRIPTION OF SYMBOLS 1 Polymer base material 2 [A] layer 3 [B] layer 4 [C] layer 5 Polymer base material 6 Winding-type sputtering apparatus 7 Winding chamber 8 Unwinding roll 9, 10, 11 Unwinding side guide roll 12 Cooling drum 13 Sputter electrodes 14, 15, 16 Winding side guide roll 17 Winding roll 18 Gas barrier film 19 Metal cylinder 20 Surface on which the first to third layers are formed

Claims (9)

A gas barrier film in which the following [A] layer, [B] layer, and [C] layer are laminated in this order on at least one surface of a polymer substrate.
[A] layer: a first crosslinked resin layer [B] having a pencil hardness of H or more and a surface free energy of 45 mN / m or less; a silicon-containing inorganic layer [C] layer having a thickness of 10 to 1000 nm; Second crosslinked resin layer having a thickness of H or more and a thickness of 0.05 to 10 μm The gas barrier film according to claim 1, wherein the [C] layer has a thickness of 1 to 5 μm. The gas barrier film according to claim 1 or 2, wherein the [B] layer is composed of a composition containing a zinc compound and a silicon oxide. The gas barrier film according to claim 3, wherein the [B] layer is any one of the following [B1] layer and [B2] layer.
[B1] layer: a layer composed of a coexisting phase of zinc oxide, silicon dioxide and aluminum oxide [B2] layer: a layer composed of a coexisting phase of zinc sulfide and silicon dioxide The [B] layer is a [B1] layer, and the [B1] layer has a zinc (Zn) atom concentration of 20 to 40 atom% and a silicon (Si) atom concentration of 5 to 5 as measured by ICP emission spectroscopy. 5. The gas barrier film according to claim 4, wherein the gas barrier film has a composition of 20 atom%, an aluminum (Al) atom concentration of 0.5 to 5 atom%, and an oxygen (O) atom concentration of 35 to 70 atom%. The [B] layer is a [B2] layer, and the [B2] layer has a composition in which the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier film according to claim 4. The gas barrier film according to claim 1, wherein an average surface roughness Ra of the [A] layer is 1.5 nm or less. The solar cell which has a gas barrier film in any one of Claims 1-7. A display element having the gas barrier film according to claim 1.

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