JP2014088016A - Gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film endowed with an advanced gas barrier property without recourse to film thickness enlargement or multilayer lamination regardless of types of concomitantly selected substrates and enabling the manifestation of a stable gas barrier property.SOLUTION: The following [A] layer and [B] layer are configured in proper order contiguously on at least one side of a polymer substrate, whereas the [B] layer includes a layer constitution wherein a [Ba] layer, a [Bb] layer, a [Bc] layer are configured in proper order contiguously from the polymer substrate side, whereas the respective densities of the [Ba] layer and the [Bc] layer are each confined to a range of 2.0-9.0 g/cm, whereas the density of the [Bb] layer is 2.3-10.5 g/cmand higher than the density of either of the [Ba] layer and the [Bc] layer, whereas the thickness of the [Bb] layer is 0.2-20 nm: [A] layer: crosslinked resin layer having a pencil hardness of at least H and a surface free energy of 45 mN/m or below; [B] layer: gas barrier layer having a thickness of 10-2500 nm.

Description

  The present invention relates to a gas barrier film used for food and pharmaceutical packaging applications requiring high gas barrier properties and electronic member applications such as solar cells, electronic paper, and organic electroluminescence (EL) displays.

  Physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, etc. using inorganic materials (including inorganic oxides) such as aluminum oxide, silicon oxide, and magnesium oxide on the surface of the polymer substrate Method) or chemical vapor deposition (CVD) such as plasma enhanced chemical vapor deposition, thermal chemical vapor deposition, and photochemical vapor deposition, etc. The resulting gas barrier film 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 thin-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 using a compound that has been contained is used (Patent Document 1). Moreover, as a gas barrier property improving technique other than a film forming method such as a plasma CVD method, for the purpose of a smooth base material or a surface smoothing in which protrusions and irregularities that cause generation of pinholes and cracks that reduce the gas barrier property are reduced. A base material provided with an anchor coat layer is used (Patent Document 2). As another gas barrier property improvement technique other than the film formation method, cracks due to film stress can be obtained by alternately laminating an organic layer, which is an epoxy compound, and a silicon-based oxide layer formed by plasma CVD on the substrate. In addition, a gas barrier film having a multilayer laminated structure in which generation of defects is prevented (Patent Document 3).

JP-A-8-142252 (Claims) JP 2002-113826 A (Claims) JP 2003-341003 A (Claims)

  However, in the method of forming a gas barrier layer mainly composed of silicon oxide by plasma CVD, the formed gas barrier layer is a high-hardness layer. Due to the stress concentration, pinholes and cracks occurred, and there was a problem that high gas barrier properties could not be obtained.

  Moreover, although the method using the base material with an anchor coat for the purpose of smoothing or smoothing the surface of the base material for forming the gas barrier layer improves the gas barrier property by preventing the occurrence of pinholes and cracks, The base material and anchor coat undergo dimensional changes due to plasma emission heat and ion / radical collision when the gas barrier layer is formed, preventing the growth of atoms and particles that serve as the growth nuclei of the gas barrier layer film. There was a problem that the reproducibility of gas barrier properties was not stable.

In the method of forming a gas barrier layer in which an organic layer and an inorganic layer are alternately laminated, a high gas barrier property with a water vapor permeability of 1.0 × 10 ⁻³ g / (m ² · 24 hr · atm) or less is obtained. Therefore, it is necessary to form a thick film with several tens of layers, and cracks and defects are generated due to the stress of the gas barrier layer, so that there is a problem that the gas barrier property is greatly lowered.

  In view of the background of the prior art, the present invention provides a gas barrier film that enables high gas barrier properties and stable gas barrier properties to be developed without selecting a type of base material and without thickening or multilayer lamination. It is to be provided.

The present invention employs the following means in order to solve such problems. That is,
(1) The following [A] layer and [B] layer are arranged in contact in this order on at least one side of the polymer substrate, and the [B] layer is the [Ba] layer from the polymer substrate side, The [Bb] layer and the [Bc] layer are in contact with each other, and the [Ba] layer and the [Bc] layer have a density in the range of 2.0 to 9.0 g / cm ³ , respectively. The density of the [Bb] layer is 2.3 to 10.5 g / cm ³ and higher than the density of any of the [Ba] layer and the [Bc] layer, and the thickness of the [Bb] layer is 0. A gas barrier film having a thickness of 2 to 20 nm.
[A] layer: a crosslinked resin layer having a pencil hardness of H or more and a surface free energy of 45 mN / m or less [B] layer: a gas barrier layer having a thickness of 10 to 2500 nm (2) The density of the [Ba] layer is the above [ The gas barrier film according to (1), which is higher in density than the Bc] layer.
(3) The gas barrier film according to (1) or (2), wherein the density of the [Bb] layer is 0.1 to 4.0 g / cm ³ higher than the density of the [Ba] layer.
(4) The [Ba] layer and the [Bb] layer are mainly composed of a zinc (Zn) compound, and the [Bc] layer is composed of silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr). A compound containing at least one element selected from the group consisting of chromium (Cr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo) and tantalum (Ta), [Bb] The gas barrier film according to (1), wherein the density of the layer is 0.1 to 2.0 g / cm ³ higher than the density of the [Ba] layer.
(5) The density of the [Ba] layer is 3.9 to 4.6 g / cm ³ , the density of the [Bb] layer is 4.0 to 5.8 g / cm ³ , and the density of the [Bc] layer is 2 The gas barrier film according to the above (4), which is 0.0 to 5.5 g / cm ³ .
(6) The gas barrier film according to (5), wherein the [Bc] layer contains a silicon (Si) compound as a main component and has a density of 2.0 to 2.6 g / cm ³ .
(7) The [Bc] layer includes aluminum (Al), titanium (Ti), zirconium (Zr), chromium (Cr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo) and The gas barrier film according to (5), wherein a main component is a compound containing at least one element selected from the group consisting of tantalum (Ta), and the density is 3.5 to 5.5 g / cm ³ .
(8) The gas barrier film according to any one of (1) to (7), wherein the [Ba] layer is the following [Ba1] layer or [Ba2] layer.
[Ba1] layer: a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide [Ba2] layer: a layer composed of a coexisting phase of zinc sulfide and silicon dioxide (9) The [Ba] layer is the [Ba1] layer The composition is such that the zinc (Zn) atom concentration measured by ICP emission spectroscopy is 20 to 40 atom%, the silicon (Si) atom concentration is 5 to 20 atom%, and the aluminum (Al) atom concentration is 0.5. The gas barrier film according to the above (8), which has ˜5 atom% and an oxygen (O) atom concentration of 35 to 70 atom%.
(10) The [Ba] layer is the [Ba2] layer, and the composition is such that the molar fraction of zinc sulfide to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier film according to 1.
(11) The gas barrier film according to any one of (1) to (10), wherein the [A] layer has an average surface roughness Ra of 1 nm or less.
(12) The gas barrier film according to any one of (1) to (11), which has a transparent conductive layer on the surface of the [B] layer.
(13) The transparent conductive layer is any one of indium tin oxide (ITO), zinc oxide (ZnO), aluminum-containing zinc oxide (Al / ZnO), gallium-containing zinc oxide (Ga / ZnO), metal nanowires, and carbon nanotubes. The gas-barrier film in any one of said (1)-(12) containing these.
(14) A solar cell having the gas barrier film according to any one of (1) to (13).
(15) A display element having the gas barrier film according to any one of (1) to (13).

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

It is a schematic diagram which shows an example of the cross section of the gas barrier film of this invention. It is a schematic diagram which shows the outline of the winding-type sputtering apparatus for manufacturing the gas barrier film of this invention. It is a schematic diagram which shows the outline of the winding-type sputtering and chemical vapor deposition apparatus (sputtering and CVD apparatus) for manufacturing the gas barrier film of this invention. It is a schematic diagram which shows the outline of the winding-type sputtering and atomic layer deposition apparatus (sputtering and ALD apparatus) for manufacturing the gas barrier film of this invention.

[Gas barrier film]
The inventors have made extensive studies for the purpose of obtaining a gas barrier film having a good gas barrier property without selecting the type of substrate, and at least one side of the polymer substrate has a pencil hardness of H or more and a surface free. An [A] layer, which is a crosslinked resin layer having an energy of 45 mN / m or less, and a [B] layer (gas barrier layer) having a thickness of 10 to 2500 nm are disposed in this order, and the [B] layer is a polymer group. Including a layer structure in which the [Ba] layer, the [Bb] layer, and the [Bc] layer are disposed in contact with each other from the material side, and the densities of the [Ba] layer and the [Bc] layer are 2.0 to 9 respectively. in the range of .0g / cm ^3, the density of the [Bb] layer is higher than any of the density of said the 2.3~10.5g / cm ³ a and the [Ba] layer [Bc] layer, A gas barrier film having a thickness of 0.2 to 20 nm of the [Bb] layer. It was as Lum, is obtained by investigating the ability to solve the problem. Here, the [Ba] layer, [Bb] layer, and [Bc] layer constituting the [B] layer (gas barrier layer) in the present invention are specified in thickness and density by analysis of an X-ray reflectance method by a method described later. Is the layer to be played.

  FIG. 1 is a schematic cross-sectional view showing an example of the gas barrier film of the present invention. As shown in FIG. 1, the gas barrier film of the present invention comprises a crosslinked resin layer having a pencil hardness of H or more and a surface free energy of 45 mN / m or less as [A] layer 2 on the surface of the polymer substrate 1 [ B] A gas barrier layer having a thickness of 10 to 2500 nm is disposed in this order as the layer 3, and the [B] layer 3 includes the [Ba] layer 4 a and the [Bb] layer 4 b from the [A] layer 2 side. Bc] is a layer including a layer in which the layer 4c is disposed in this order. The example of FIG. 1 shows a case where the [B] layer (gas barrier layer) has a minimum configuration, and consists of a [Ba] layer 4a, a [Bb] layer 4b, and a [Bc] layer 4c. Although only the layer (gas barrier layer) is disposed in contact with the [A] layer 2, it is opposite to the [Ba] layer 4a on the polymer substrate 1 side or the [Bc] layer 4c with the [Bb] layer 4b. Other layers constituting the [B] layer on the side (consisting of any component of the [Ba] layer, [Bb] layer and [Bc] layer, but the density etc. are the [Ba] layer, [Bb] layer and A layer deviating from the definition of the [Bc] layer may be arranged.

Although details of each layer constituting the [B] layer will be described later, the [Ba] layer and the [Bc] layer have a density in the range of 2.0 to 9.0 g / cm ³ . Note that the densities of the [Ba] layer and the [Bc] layer may be the same or different. The [Bb] layer having a density of 2.3 to 10.5 g / cm ³ between the [Ba] layer and the [Bc] layer and having a density higher than any of the both is 0.2 to 20 nm. From the gas barrier film in which the [B] layer is a gas barrier layer composed of a single layer of the [Ba] layer or the [Bc] layer or a gas barrier layer composed of a combination of the two layers of the [Ba] layer and the [Bc] layer. It has been found that a gas barrier film having a higher gas barrier property against water vapor can be obtained.

  The reason why such a remarkable effect can be obtained is estimated as follows. That is, the [Ba] layer is arranged under the [Bb] layer, so that the polymer film or [Ba] is formed by a thermal influence from an evaporation source, plasma, a heating source, or the like when the [Bb] layer is formed. It is possible to suppress the occurrence of cracks and defects in the [Bb] layer by causing the thermal dimensional change of the underlayer of the layer, and thus the [Bb] layer can be formed with high reproducibility and high density. Since the [Bb] layer is a layer having a higher density than the [Ba] layer, the [Bb] layer has a structure having a larger mass per unit volume and higher density than the [Ba] layer. Furthermore, by arranging the [Bc] layer on the [Bb] layer, it is possible to prevent the [Bb] layer from being reduced in density due to contamination by foreign matter or dust adhering from outside air. Further, the [B] layer is arranged on the [A] layer, so that the atoms and particles at the time of forming the layer are easily moved and diffused as described later, and a dense film quality is obtained. Therefore, if the [Ba] layer is disposed so as to be in contact with the [A] layer, the [Ba] layer surface is flatter and the number of defects is reduced, so that the [Bb] layer can be formed in a thin film with a high density. From this viewpoint, in order to obtain a higher gas barrier property against high water vapor, it is preferable to arrange the [Ba] layer so as to be in contact with the [A] layer and to form the [Ba] layer in a denser film quality.

  Note that the [B] layer (gas barrier layer) may be disposed on one side of the polymer substrate 1, or the stress balance on the side opposite to the [B] layer (gas barrier layer) side is disrupted on only one side, resulting in a gas barrier film. When warping or deformation occurs, a [B] layer (gas barrier layer) may be provided on both surfaces of the polymer substrate 1 for the purpose of stress adjustment.

  In addition, in the [B] layer used in the present invention, when the density of the [Ba] layer is higher than the density of the [Bc] layer, the [Bb] layer can be formed with higher reproducibility and improved gas barrier properties. Is preferable because it is possible.

  In the present invention, the thickness and density of the [Ba] layer, [Bb] layer, and [Bc] layer are measured by the X-ray reflectivity method (“Introduction to X-ray reflectivity” (edited by Kenji Sakurai) p. 51-78). Value.

  Specifically, first, X-rays are generated from an X-ray source, converted into a parallel beam by a multilayer mirror, and then the X-ray angle is limited through an entrance slit to be incident on a measurement sample. By making the incident angle of the X-rays to the sample enter at a shallow angle substantially parallel to the sample surface to be measured, a reflected beam of X-rays reflected and interfered with each layer and substrate interface of the sample is generated. The generated reflected beam is passed through the light receiving slit and limited to the required X-ray angle, and then incident on the detector to measure the X-ray intensity. Using this method, the X-ray intensity profile at each incident angle can be obtained by continuously changing the incident angle of X-rays.

  The analysis method of the number of layers, the thickness of each layer, and the density of each layer can be obtained by fitting measured data of the obtained X-ray intensity profile with respect to the incident angle of X-rays to the Parratt's theoretical formula by the nonlinear least square method. In the fitting, arbitrary initial values are set for the parameters of the number of layers, the thickness of each layer, and the density of each layer, so that the standard deviation of the residual between the X-ray intensity profile and the measured data obtained from the set configuration is minimized. Determine the final parameters. In the present invention, fitting is performed until the number of stacked layers is the minimum and the standard deviation of the residual is 3.0% or less, and parameters of the number of layers, the thickness of each layer, and the density of each layer are determined. As the initial value of each parameter used for fitting, the number of layers and the thickness of each layer are values obtained from TEM cross-sectional observation of the measurement sample. The density of each layer is 2 minutes for each layer specified by TEM cross-sectional observation. The value obtained from the element ratio obtained by the XPS analysis at the position of 1 is used. In the embodiment of the present application, fitting is performed by Rigaku Global Fit, which is analysis software of the apparatus used for X-ray reflection measurement (Rigaku SmartLab). In this analysis software, since the number of layers is fixed, fitting is performed based on the set number of layers (assumed to be n layers). In the configuration, the layer with the highest theoretical density is divided equally, and fitting is performed with the configuration in which one layer is added (n + 1 layer), and this is continued until the standard deviation of the residual is 3.0% or less. However, it may be obtained by setting in the same way according to the analysis software.

  In the present invention, since the number of [B] layers (gas barrier layers) is determined by the method described above, the total number of layers forming the [B] layers (gas barrier layers) obtained from the TEM cross-sectional observation and The total number of layers forming the [B] layer (gas barrier layer) determined by the X-ray reflectivity method of the invention may be different. As an aspect of the present invention, for example, even when it is determined that the total number of layers is 1 or 2 by TEM cross-sectional observation, the number of layers determined by the X-ray reflectivity method is 3 as shown in FIG. It suffices that the density and thickness of the [Ba] layer, [Bb] layer, and [Bc] layer coincide with the previous regulations. When the total number of layers obtained by the X-ray reflectivity method is 4 or more, there is at least one adjacent three layer composed of a [Ba] layer, a [Bb] layer, and a [Bc] layer that meets the above definition. It only has to be included. For example, when the total number of layers obtained by the X-ray reflectivity method is 4, 3 layers whose density and thickness apply to the above definition may be adjacent to the base material, and included in the 3 layers on the surface side It may be. When the total number of layers obtained by the X-ray reflectivity method is 5 or more, there is at least one adjacent 3 layer that matches the definition of the [Ba] layer, [Bb] layer, and [Bc] layer of the present invention. It only has to be included.

  The thickness of the [B] layer (gas barrier layer) used in the present invention is preferably 10 nm or more, and more preferably 50 nm or more. In the case of the three-layer configuration of the [Ba] layer, [Bb] layer, and [Bc] layer, which is the minimum configuration as the [B] layer (gas barrier layer) of the present invention, the thickness is less than 10 nm. This is because there are places where gas barrier properties cannot be sufficiently secured, and problems such as variations in gas barrier properties within the polymer substrate surface may occur. Moreover, 2500 nm or less is preferable and 1000 nm or less is more preferable. If the thickness of the gas barrier layer is greater than 2500 nm, the stress remaining in the layer increases, so that the gas barrier layer is liable to be cracked by bending or external impact, and the gas barrier property may decrease with use. It is. For this reason, the [B] layer (gas barrier layer) used in the present invention preferably has a thickness of 10 to 2500 nm.

[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.

  In addition, the organic polymer that can be suitably used for the polymer substrate in the present invention is an organic polymer whose basic skeleton is linear as listed above (here, linear is branched). Even if it is, it indicates that it does not have a network structure: hereinafter, an organic polymer having a basic skeleton is abbreviated as a linear organic polymer). Even if a cross-linking agent having two or more functional groups in the molecule is added and reacted or irradiated with radiation to form a cross-link, the number average molecular weight is 5000 to 20000. It is defined as an organic polymer. In such a case, the linear organic polymer preferably has a pencil hardness of F or less.

  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. The polymer substrate surface on the side where the crosslinked resin layer and the gas barrier layer are formed is subjected to pretreatment such as corona treatment, ion bombardment treatment, solvent treatment, and roughening treatment in order to improve adhesion. It doesn't matter. In addition, a coating layer of an organic material, an inorganic material, or a mixture thereof may be applied to the opposite surface on the side on which the cross-linked resin layer and the gas barrier layer are formed for the purpose of improving the slipping property when winding the film. .

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

[Crosslinked resin layer]
Next, the [A] layer, which is a cross-linked resin 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.

  The thickness of the [A] layer used in the present invention is preferably 0.5 μm or more and 10 μm or less. When the thickness of the [A] layer is less than 0.5 μm, the film quality of the [B] layer is not uniform due to the unevenness of the polymer base material, so that the gas barrier property may be lowered. When the thickness of the [A] layer is greater than 10 μm, the residual stress in the [A] layer increases, causing the polymer substrate to warp and cracks in the [B] layer, resulting in a decrease in gas barrier properties. There is. Therefore, the thickness of the [A] layer is preferably 0.5 μm or more and 10 μm or less, and more preferably 1 μm or more and 5 μm or less from the viewpoint of ensuring flexibility. 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 contribution of the pencil hardness of the [A] layer to the effect that enables stable gas barrier properties to be expressed is that the pencil hardness of the [A] layer is H or more, whereby the polymer substrate has heat resistance and Because dimensional stability can be imparted, when the [B] layer is formed, damage caused by collision of plasma emission heat, ions, and radicals can be prevented, and as a result, reproducibility of gas barrier properties can be stabilized. I guess. Therefore, the pencil hardness of the [A] layer is preferably H or higher, more preferably 2H or higher. On the other hand, when the upper limit of 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 gas barrier layer. Therefore, it is preferable that it is 5H or less (pencil hardness is (soft) 10B-B, HB, F, H-9H (hard)).

  The pencil hardness test of the [A] layer in the present invention is carried out 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. [A] When an inorganic layer or a resin layer is laminated on the surface of the layer [A], it is possible to evaluate the pencil hardness by performing a pencil hardness test after removing the layer by ion etching or chemical treatment as necessary. it can.

  Further, in the present invention, the contribution of the surface free energy of the [A] layer to the effect of dramatically improving the gas barrier property is that when the [B] layer is formed by setting the surface free energy to 45 mN / m or less. In the initial growth process of the gas barrier compound, the atoms and particles that are the growth nuclei of the film are likely to move and diffuse, so the film quality near the [B] layer becomes dense, and as a result, the entire layer has a dense structure. It is speculated that the improvement is to suppress the permeation of oxygen and water vapor. Therefore, the surface free energy of the [A] layer is preferably 45 mN / m or less, more preferably 40 mN / m or less. In addition, the surface free energy is preferably 10 mN / m or more. When the surface free energy is less than 10 mN / m, the adhesiveness between the crosslinked resin layer and the inorganic layer is lowered, and a dense structure of the inorganic layer may not be formed.

  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 inorganic layer and the resin layer are laminated | stacked on the [A] layer surface, in the gas barrier film of this invention, the contact angle of said 4 types of measurement liquids is [A] layer thickness of [A] layer. It measures after grind | polishing by ion etching or a chemical | medical solution process in 30 to 70% of range. [A] The layer is located between the gas barrier layer and the polymer base material layer, and after removing any layer by ion etching or chemical treatment as necessary, the above-described measurement method is performed. The pencil hardness and surface free energy can be evaluated.

  When the average surface roughness Ra of the surface of the [A] layer in the present invention (the boundary surface with the [B] layer in the gas barrier film) is 1 nm or less, the occurrence of pinholes and cracks in the [B] layer to be laminated is further increased. Since it can reduce, the reproducibility of gas barrier property improves, and it is preferable. When the average surface roughness Ra of the surface of the [A] layer is larger than 1 nm, in the convex portion, pinholes are likely to occur after the lamination of the [B] layer, and cracks are generated in a portion with more unevenness. In some cases, the reproducibility of gas barrier properties may be reduced. Therefore, in the present invention, the average surface roughness Ra of the surface of the [A] layer is preferably 1 nm or less, from the viewpoint of suppressing the occurrence of fine defects such as microcracks during bending and improving flexibility. More preferably, it is 0.6 nm or less. [A] The average surface roughness Ra of the surface of the layer is preferably as low as possible, and as close to 0 nm as possible.

  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 and a resin layer are 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 crosslinked resin layer in the present invention include acrylic, urethane-based, organic silicate compounds, silicone-based crosslinked resins, and the like. Among these, a thermosetting acrylic resin and an actinic ray curable acrylic resin are preferable from the viewpoint of durability of plasma heat and pencil hardness.

  Preferred examples of the thermosetting acrylic resin and the actinic ray curable acrylic resin include those containing a polyfunctional acrylate, an acrylic oligomer, and a reactive diluent, and other photoinitiators and photosensitizers as necessary. An agent, a thermal polymerization initiator or a modifier may be added.

  Examples of the polyfunctional acrylate suitably used for the acrylic resin described above include compounds having 3 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 may include a modified polymer of 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.

  The reactive diluent has a function of a solvent in the coating process as a coating medium, and has a group that itself reacts with a monofunctional or polyfunctional acrylic oligomer. It will be.

  In particular, in the case of cross-linking with ultraviolet rays, since light energy is small, a photopolymerization initiator and / or a photosensitizer should be added for the purpose of conversion of light energy and promotion of reaction, as will be described in detail later. Is preferred.

  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 this ratio is larger than 90% by mass, the curing shrinkage is large and the polymer base material may be warped. In such a case, cracks occur in the gas barrier layer, and problems such as deterioration in gas barrier properties occur. There is. 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 benzoylfomate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2,2-dimethoxy Carbonyl compounds such as 2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthiura Examples thereof include sulfur compounds such as mudisulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone, and peroxide compounds such as benzoyl peroxide and 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, and remains as an unreacted product during polymerization and does not affect the gas barrier property. 05-5 mass parts is preferable.

  The coating liquid containing the resin forming the [A] cross-linked resin layer used in the present invention loses the effect of the present invention for the purpose of improving workability during coating and controlling the coating film thickness. In such a range, it is preferable to add an organic solvent. 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 a resin that forms the crosslinked resin layer of the [A] layer used in the present invention includes inorganic substances such as silica, alumina, and zinc oxide for the purpose of improving adhesion with the [B] layer. It is preferable to blend particles. Among these, silica-based inorganic particles that adhere strongly to the gas barrier 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.

  In the present invention, various additives can be blended as necessary within the range where 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 of 0.5 μm or more and 10 μm or less, which is the thickness of the [A] layer in the present invention.

  The active rays used when the [A] layer is crosslinked include ultraviolet rays, electron beams, radiation (α rays, β rays, γ rays), and ultraviolet rays are preferred as a practically simple method. The heat source used for crosslinking by heat includes a steam heater, an electric heater, an infrared heater and the like, and an infrared heater is preferable from the viewpoint of temperature control stability.

[[Ba] layer]
The [Ba] layer is arranged closest to the polymer substrate in the [B] layer. The material of the [Ba] layer used in the present invention is, for example, an oxide containing at least one element selected from the group consisting of Zn, Si, Al, Ti, Zr, Sn, In, Nb, Mo, and Ta. Oxide, nitride, oxynitride, sulfide, or a mixture thereof. Since a high gas barrier property and flexible layer can be obtained, a zinc compound containing zinc oxide, nitride, oxynitride, or sulfide as a main component is preferably used. Here, the main component means 60% by mass or more of the entire [Ba] layer, and preferably 80% by mass or more. The compound as the main component is identified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later. The composition ratio of each element constituting the compound may be a composition ratio slightly deviated from the stoichiometric ratio depending on the conditions for forming the [Ba] layer, but the composition ratio is an integer. (Hereinafter the same).

  For example, a layer having a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide (hereinafter abbreviated as [Ba1] layer) or a layer having a coexisting phase of zinc sulfide and silicon dioxide (hereinafter referred to as [ (Abbreviated as “Ba2] layer” is preferably used (detailed explanation of each of the [Ba1] layer and the [Ba2] layer will be given later).

  The thickness and density of the [Ba] layer used in the present invention are values measured by the X-ray reflectivity method described above.

  The thickness of the [Ba] layer used in the present invention is preferably 10 nm or more, and more preferably 100 nm or more. When the thickness of the layer is less than 10 nm, there may be a portion where the gas barrier property cannot be sufficiently secured, and there may be a problem that the gas barrier property varies in the plane of the gas barrier film. Further, the thickness of the [Ba] layer is preferably 1000 nm or less, and more preferably 500 nm or less. When the thickness of the layer is greater than 1000 nm, the stress remaining in the layer increases, so that cracks are likely to occur in the [Ba] layer due to bending or external impact, and the gas barrier properties may decrease with use. .

The density of the [Ba] layer measured by the X-ray reflectivity method is in the range of 2.0 to 9.0 g / cm ³ . When the density of the [Ba] layer is smaller than 2.0 g / cm ³ , the particle size of the inorganic compound forming the [Ba] layer is increased, so that void portions and defect portions are relatively increased but stable. As a result, sufficient gas barrier properties may not be obtained. If the density of the [Ba] layer is greater than 9.0 g / cm ³ , the particle size of the inorganic compound forming the [Ba] layer is reduced, resulting in an excessively dense film quality. In some cases, cracks are likely to occur. Therefore, the density of the [Ba] layer is 2.0 to 9.0 g / cm ³ , preferably 2.8 to 9.0 g / cm ³ , and 3.5 to 7.0 g / cm ^3. A range of ³ is more preferred.

  The method for forming the [Ba] 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 capable of forming the [Ba] layer easily and inexpensively.

  As an example of forming the [Ba] layer by sputtering, a mixed firing in which a [Ba] layer is formed on the surface of the polymer substrate 5 using a winding type sputtering apparatus having a structure shown in FIG. 2A. There is a method in which a sputter target of a binder is placed on the sputter electrode 18 and sputtering is performed with argon gas and oxygen gas to provide a [Ba] layer.

Specific operations for forming the [Ba1] layer described later as the [Ba] layer are, for example, as follows. First, unwinding is performed in a winding chamber 7 of a winding-type sputtering apparatus 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 18. The polymer base material 5 is set on the roll 8 so that the surface on which the [Ba1] layer is provided faces the sputter electrode 18, unwinds, and passes through the guide rolls 9, 10, 11 with tap water at 15 ° C. Pass through the cooling drum 12 adjusted to. Argon gas and oxygen gas are introduced with a partial pressure of oxygen gas of 10% so that the degree of vacuum 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. To form a [Ba1] layer on the surface of the polymer substrate 5. Thickness can be adjusted with the conveyance speed of a polymer base material.

[[Bb layer]]
The [Bb] layer is a layer having a higher density and a thickness of 0.2 to 20 nm than any of the [Ba] layer and the [Bc] layer, and is in contact with the [Ba] layer and the [Bc] layer. Be placed. By disposing the [Bb] layer so as to be in contact with the [Ba] layer and the [Bc] layer, the gas barrier property can be remarkably improved while ensuring the flexibility of the gas barrier layer. The material of the [Bb] layer used in the present invention is, for example, at least one selected from the group consisting of Zn, Si, Al, Ti, Zr, Sn, In, Nb, Mo, Y, W, Hf, and Ta. Examples thereof include oxides, nitrides, oxynitrides, sulfides, mixtures thereof, and the like containing seed elements. Among these, it is preferable to apply a composition containing an element having a large atomic weight and a high density as an element that is easily moved and diffused in the initial growth stage during layer formation. The composition of the [Bb] layer is determined by quantitative analysis of the amount of atoms of each element using X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc. alone or in combination. Can know.

The thickness and density of the [Bb] layer are values measured by the X-ray reflectivity method described above. The density of the [Bb] layer measured by the X-ray reflectivity method is in the range of 2.3 to 10.5 g / cm ³ . When the density of the [Bb] layer is smaller than 2.3 g / cm ³ , the particle size of the inorganic compound forming the [Bb] layer is increased, so that the gas barrier property improving effect is reduced. If the density of the [Bb] layer is greater than 10.5 g / cm ^{3, the} entire [Bb] layer becomes excessively dense and the flexibility decreases, so that the lower density [Ba] and [Bc] layers Even if it is sandwiched between the films, the flexibility of the gas barrier film against mechanical bending is lowered. Thus, the density of [Bb] layer is in the range of 2.3~10.5g / cm ^3, preferably in the range of ^{2.9~10.5g / cm 3, 4.0~7.0g / cm} 3 The range of is more preferable.

Moreover, it is preferable that the density of the [Bb] layer measured by the X-ray reflectivity method is 0.1 to 4.0 g / cm ³ higher than the density of the [Ba] layer. When the density difference obtained by subtracting the density of the [Ba] layer from the density of the [Bb] layer is smaller than 0.1 g / cm ³ , the effect of disposing a high-density layer between the [Ba] layer and the [Bc] layer Therefore, the gas barrier property improvement effect may be small. In addition, when the difference in density obtained by subtracting the density of the [Ba] layer from the density of the [Bb] layer is larger than 4.0 g / cm ³ , the particle size of the inorganic compound in the [Bb] layer is small, and an excessively dense film quality is obtained. Therefore, cracks are likely to occur against heat and external stress. Accordingly, the density of the [Bb] layer is preferably 0.1 to 4.0 g / cm ³ higher than the density of the [Ba] layer, and more preferably 0.4 to 2.0 g / cm ³ higher.

  The thickness of the [Bb] layer used in the present invention is in the range of 0.2 to 20 nm. If the thickness of the [Bb] layer is thinner than 0.2 nm, the effect of improving the gas barrier property of the [Bb] layer may not be obtained, and there may be a problem that the gas barrier property varies within the surface of the polymer substrate. . In addition, when the thickness of the [Bb] layer is greater than 20 nm, the flatness of the surface of the [Bb] layer is reduced due to the growth of inorganic compound particles in the [Bb] layer. In the initial stage of growth, atoms and particles that are the growth nuclei of the film are difficult to move and diffuse, the film quality near the [Bb] layer cannot be densified, and a sufficient gas barrier property improving effect may not be obtained. Therefore, the thickness of the [Bb] layer is in the range of 0.2 to 20 nm, and preferably in the range of 2 to 10 nm.

  The formation method of the [Bb] layer used in the present invention is not particularly limited. For example, the [Bb] layer may be formed by using a material having a relatively high density by a vacuum deposition method, a sputtering method, an ion plating method, or the like. However, as a method of forming a higher density layer using the same material, the surface of the [Ba] layer is treated with a reactive gas plasma such as oxygen gas or carbon dioxide gas or an ion beam while the [Bb] layer is formed. A plasma assisted vapor deposition method, a plasma assisted sputtering method, an ion beam assisted vapor deposition method, an ion beam assisted sputtering method, an ion beam assisted ion plating method, an ion beam assisted CVD method, or the like may be used.

  In addition, when the [Bb] layer is formed, the surface of the [Ba] layer may be subjected to pretreatment such as corona treatment, ion bombardment treatment, solvent treatment, and roughening treatment.

  As an example of forming the [Bb] layer by sputtering, a winding type sputtering apparatus having a structure shown in FIG. 2A is used, and the surface of the polymer substrate 5 (the surface on which the [Ba1] layer is formed). A method of providing a [Bb] layer by placing a sputtering target of a mixed sintered material on which a [Bb] layer is formed on the sputtering electrode 18 and performing sputtering with an argon gas plasma.

As the [Bb] layer, for example, a specific operation in the case of forming a layer made of tantalum pentoxide is as follows. First, in the winding chamber 7 of a winding type sputtering apparatus in which a sputtering target obtained by sintering tantalum pentoxide is installed on the sputtering electrode 18, the polymer base material 5 is provided on the winding roll 8 with the [Ba1] layer. The surface is set so as to face the sputter electrode 18, unwound, and passed through the cooling drum 12 adjusted to 15 ° C. with tap water through the guide rolls 9, 10 and 11. Argon gas is introduced so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and an applied power of 500 W is applied by a high frequency power source to generate argon gas plasma, and the [Ba] layer of the polymer substrate 5 is formed by sputtering. A [Bb] layer is formed thereon. Thickness can be adjusted with the conveyance speed of a polymer base material.

[[Bc] layer]
The [Bc] layer is a layer having a density in the range of 2.0 to 9.0 g / cm ³ positioned on the [Bb] layer. The density of the [Bc] layer may be the same as or different from the density of the [Ba] layer within the above range, but the density of the [Ba] layer is higher than the density of the [Bc] layer. Is preferable as described above.

  The material of the [Bc] layer used in the present invention is, for example, at least one element selected from the group consisting of Zn, Si, Al, Ti, Zr, Cr, Sn, In, Nb, Mo, and Ta. Oxides, nitrides, oxynitrides, sulfides, mixtures thereof, and the like containing A silicon compound mainly composed of silicon oxide, nitride, or oxynitride is preferably used because of its high gas barrier property and high densification effect due to surface flattening of the [Bb] layer. Here, the main component means 60% by mass or more of the entire [Bc] layer, and preferably 80% by mass or more. The compound as the main component is identified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later. The composition ratio of each element constituting the compound may be a composition ratio slightly deviating from the stoichiometric ratio depending on the conditions for forming the [Bc] layer, but the composition ratio is an integer. It treats as a compound which has a compositional formula represented by these.

  The composition of the [Bc] layer preferably includes an oxide of silicon having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0. When the ratio of the number of silicon atoms to oxygen atoms is larger than 2.0, the amount of oxygen atoms contained is increased, so that void portions and defect portions increase, and a predetermined gas barrier property may not be obtained. On the other hand, when the atomic ratio of silicon atoms to oxygen atoms is smaller than 1.5, oxygen atoms are reduced to obtain a dense film quality, but flexibility may be lowered. More preferably, it is the range of 1.4-1.8.

  The composition analysis of the [Bc] layer can quantitatively analyze the atomic weight of each element using X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopy, and Rutherford backscattering method according to the composition. When another layer is disposed on the [Bc] layer, the thickness obtained by the X-ray reflectance method can be removed by ion etching or chemical treatment and then analyzed.

  The thickness and density of the [Bc] layer used in the present invention can be measured by the X-ray reflectivity method described above.

  The thickness of the [Bc] layer used in the present invention is preferably 10 nm or more, and more preferably 100 nm or more. When the thickness of the layer is less than 10 nm, there may be a portion where the gas barrier property cannot be sufficiently secured, and there may be a problem that the gas barrier property varies in the plane of the gas barrier film. Further, the thickness of the [Bc] layer is preferably 1000 nm or less, and more preferably 500 nm or less. When the thickness of the layer is greater than 1000 nm, the stress remaining in the layer increases, so that the [Bc] layer is likely to crack due to bending or external impact, and the gas barrier property may decrease with use. .

The density of the [Bc] layer measured by the X-ray reflectivity method is in the range of 2.0 to 9.0 g / cm ³ . When the density of the [Bc] layer is smaller than 2.0 g / cm ³ , the particle size of the inorganic compound forming the [Bc] layer is increased, so that voids and defects are increased, and sufficient gas barrier properties are obtained. It becomes impossible. When the density of the [Bc] layer is higher than 9.0 g / cm ³ , the mass per unit volume of the [Bc] layer increases, so that it becomes a growth nucleus of the film due to the effect of planarizing the surface of the [Bb] layer. Since the surface movement and diffusion of atoms and particles are difficult, the film quality in the vicinity of the [Bb] layer cannot be densified, and a sufficient gas barrier property improvement effect may not be obtained. Thus, the density of [Bc] layer is in the range of 2.0~9.0g / cm ^3, preferably in the range of ^{2.0~6.0g / cm 3, 2.0~2.6g / cm} 3 The range of is more preferable.

  The method for forming the [Bc] layer used in the present invention is not particularly limited, and can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

  As an example of forming the [Bc] layer by sputtering, a winding type sputtering apparatus having a structure shown in FIG. 2A is used, and the surface of the polymer substrate 5 (the surface on which the [Bb] layer is formed). A method of providing a [Bc] layer by placing a sputtering target of a mixed sintered material on which a [Bc] layer is formed on the sputter electrode 18 and performing sputtering by argon gas plasma can be mentioned.

As the [Bc] layer, for example, a specific operation for forming a layer made of aluminum oxide is as follows. First, the [Bb] layer was provided on the unwinding roll 8 in the winding chamber 7 of a winding-type sputtering apparatus in which a sputtering target in which aluminum oxide was sintered was installed on the sputtering electrode 18. It is set so that the surface faces the sputter electrode 18, unwinds, and passes through a cooling drum 12 adjusted to 15 ° C. with tap water through guide rolls 9, 10, and 11. Argon gas is introduced so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and an applied power of 500 W is applied by a high frequency power source to generate argon gas plasma, and the [Ba] layer of the polymer substrate 5 is formed by sputtering. A [Bb] layer is formed thereon. Thickness can be adjusted with the conveyance speed of a polymer base material.

[[Ba] layer and [Bb] layer containing zinc compound as main component]
So far, the [Ba] layer, [Bb] layer, and [Bc] layer have been described separately. Preferred combinations of the [Ba] layer, [Bb] layer, and [Bc] layer will be described below.

In the gas barrier layer, the [Ba] layer and the [Bb] layer are mainly composed of a zinc (Zn) compound, and the [Bc] layer is composed of silicon (Si), aluminum (Al), titanium (Ti), zirconium ( The main component is a compound containing at least one element selected from the group consisting of Zr) and chromium (Cr), and the density of the [Bb] layer is 0.1 to 2.0 g from the density of the [Ba] layer. A high / cm ³ is preferable because the gas barrier properties are further improved.

The reason why the effect can be obtained more in this aspect is estimated as follows. That is, the [Ba] layer and the [Bb] layer are layers mainly composed of a zinc compound, and the [Bb] layer has a density higher than that of the [Ba] layer, although it is a material mainly composed of a zinc compound similar to the [Ba] layer. 0.1 to 2.0 g / cm ³ high. This indicates that the [Bb] layer has a dense structure in which the defect portion of the material of the layer mainly composed of the zinc compound is filled with other elements, and the gas barrier property is further increased due to such a structure. Estimated to be improved.

  A preferred production method for obtaining the layer structure of the above embodiment will be described. First, a first layer forming stage in which a layer mainly composed of a zinc compound is formed on a polymer substrate, and then silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr) and chromium ( A gas barrier layer is formed through a second layer forming step of forming a layer mainly composed of a compound containing at least one element selected from the group consisting of Cr). The layer formed in the first layer forming stage is a layer that becomes the [Ba] layer and the [Bb] layer after the second layer forming stage, and the [Bc] layer is formed in the second layer forming stage. At the same time, the layered region on the surface on the [Bc] layer side of the layer formed in the first layer forming stage is converted into the [Bb] layer. From this point of view, the layer formed in the first layer formation step in this embodiment and before the surface layered region is converted to the [Bb] layer is referred to as a “first layer”, and the second layer This will be described separately from the “layer derived from the first layer formation stage”, which is a general term for the [Ba] layer and the [Bb] layer after the layer formation stage.

  Since the first layer is a layer having a relatively low hardness mainly composed of a zinc compound, silicon (Si), aluminum (Al), titanium, which are the main components of the second layer, in the second layer formation stage. Particles of a compound containing at least one element selected from the group consisting of (Ti), zirconium (Zr), and chromium (Cr) are injected into and mixed with the layered region on the surface of the first layer. The [Bb] layer in which other elements are efficiently filled in the defect portion existing on the surface of the substrate can be converted into the [Bb] layer. On top of this, a dense [Bb] layer having a high density is arranged, and the presence of such a [Bb] layer is considered to further improve the gas barrier properties. In such a second layer formation step, the main component of the second layer is a compound containing an element having a small atomic radius in order to efficiently fill a particle that forms a thin film with defects on the surface of the first layer. Of these, compounds containing silicon atoms are preferred.

  The first layer forming step and the second layer forming step are for explaining a preferable method for producing the [Ba] layer, [Bb] layer, and [Bc] layer. The [Ba] layer, [Bb] It goes without saying that the boundary between the layer and the [Bc] layer is specified by the X-ray reflectivity analysis as described above.

  Hereinafter, the layer derived from the first layer formation stage ([Ba] layer and [Bb] layer) and the layer formed in the second layer formation stage ([Bc] layer) will be sequentially described.

[Layers derived from the first layer formation stage ([Ba] layer and [Bb] layer)]
As a result of the inventors' investigation, silicon (Si), aluminum (Al), titanium (Ti), and the like under specific conditions as the second layer formation stage on the first layer mainly composed of the zinc compound. It is possible to dramatically improve the gas barrier property by forming a layer mainly composed of a compound containing at least one element selected from the group consisting of zirconium (Zr) and chromium (Cr). I found it. Here, the main component means 60% by mass or more of the layer, and preferably 80% by mass or more (the same shall apply hereinafter). The zinc compound in the present invention is a composition in which the composition ratio of each element whose components are specified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later, is expressed as an integer. Treated as a compound having the formula. For example, depending on the conditions at the time of generation, even when ZnS, ZnO or the like has a composition ratio slightly deviated from the stoichiometric ratio, it is treated as ZnS, ZnO, and the above-described mass content is calculated.

  The method applied to the first layer forming step is not particularly limited, and for example, a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like can be applied. Among these methods, the sputtering method is preferable as a method capable of performing the first layer forming step easily and inexpensively.

  In such a preferred embodiment, the [Bb] layer preferably has a thickness of 0.2 to 20 nm. When the thickness is smaller than 0.2 nm, there are cases where voids and defects are present, so that it is difficult to improve gas barrier properties. Further, when the thickness is larger than 20 nm, the particles constituting the [Bb] layer grow and the particle size increases, so that the formation of a defective portion is formed inside the film by inhibiting the formation of the second layer, and the gas barrier property is increased. Problems such as degradation may occur. Therefore, the thickness of the [Bb] layer is preferably 0.2 to 20 nm, and more preferably 2 to 10 nm.

In such a preferred embodiment, the density of the [Bb] layer is preferably 0.1 to 2.0 g / cm ³ higher than the density of the [Ba] layer. If the difference from the density of the [Ba] layer is less than 0.1 g / cm ³ , silicon (Si), aluminum (Al), titanium (Ti), zirconium ( Since the compound containing at least one element selected from the group consisting of Zr) and chromium (Cr) may not be sufficiently filled, the improvement in gas barrier properties may be reduced. Also, if the difference from the density of the [Ba] layer is larger than 2.0 g / cm ³ , the film quality of the [Bb] layer becomes excessively dense and the flexibility is lowered. In some cases, cracks occur and problems such as gas barrier properties decrease. Accordingly, the density of the [Bb] layer is preferably 0.1 to 2.0 g / cm ³ higher than the density of the [Ba] layer, and more preferably 0.2 to 1.0 g / cm ³ higher.

  If the first layer contains a zinc compound as a main component, oxides, nitrides, sulfides, or the like of elements such as Si, Al, Ti, Zr, Sn, In, Nb, Mo, Ta, etc. May be included. For example, a layer having a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide (hereinafter abbreviated as [Ba1] layer) or a layer having a coexisting phase of zinc sulfide and silicon dioxide (hereinafter referred to as [ (Abbreviated as “Ba2] layer” is preferably used (detailed explanation of each of the [Ba1] layer and the [Ba2] layer will be given later).

The density of the first layer and the [Ba] layer is preferably in the range of 3.9 to 4.6 g / cm ³ . When the density of the [Ba] layer is smaller than 3.9 g / cm ³ , the denseness of the film quality of the [Ba] layer is reduced, and voids and defects are increased, so that sufficient gas barrier properties cannot be obtained. There is. If the density of the [Ba] layer is larger than 4.6 g / cm ³ , the [Ba] layer has an excessively dense film quality, so that cracks are likely to occur due to heat and external stress. Thus, the density of [Ba] layer is preferably in the range of 3.9~4.6g / cm ^3, a range of 4.0~4.5g / cm ³ is more preferable.

The density of the [Bb] layer measured by the X-ray reflectance method is preferably 4.0 g / cm ³ or more, more preferably 4.4 g / cm ³ or more, and 4.5 g / cm ^3. The above is more preferable. When the density of the [Bb] layer is 4.0 g / cm ³ or more, silicon (Si), aluminum (Al), titanium (Ti) to void portions and defect portions existing on the surface of the first layer, Since the filling of the compound containing at least one element selected from the group consisting of zirconium (Zr) and chromium (Cr) further progresses and the denseness of the film quality of the [Bb] layer further improves, This is because an improvement effect can be obtained. On the other hand, the density of the [Bb] layer measured by the X-ray reflectivity method is preferably 5.8 g / cm ³ or less, more preferably 5.5 g / cm ³ or less, and 4.8 g / cm ^3. More preferably, it is more preferably 4.7 g / cm ³ or less. When the density of the [Bb] layer is 5.8 g / cm ³ or less, it is possible to suppress the [Bb] layer from becoming an excessively dense film quality, so that cracks are generated when the second layer is formed. Is suppressed. Thus, the density of [Bb] layer is preferably in the range of 4.0~5.8g / cm ^3, more preferably in the range of 4.0~5.5g / cm ^3, 4.4 more preferably in the range of ~4.8g / cm ^3, particularly preferably in the range of 4.4~4.7g / cm ^3.

  Examples of the case where the first layer is formed by sputtering include a winding type sputtering apparatus having the structure shown in FIG. 2A used in the description of the method for providing the [Ba] layer, and a second layer described later. The winding type sputtering / chemical vapor deposition apparatus having the structure shown in FIG. 2B used in the forming stage <1>, and the winding type having the structure shown in FIG. 2C used in the second layer forming stage <2> described later. Using a sputtering / atomic layer deposition apparatus or the like, a sputter target of a mixed sintered material that forms the first layer on the surface of the polymer substrate 5 is placed on the sputter electrode 18, and sputtering with argon gas and oxygen gas is performed. The method of implementing and providing a 1st layer is mentioned.

[Second Layer Formation Stage <1>]
In a preferred embodiment of the present invention, the layer formed on the first layer in the second layer formation step is silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), chromium (Cr ), Tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), and tantalum (Ta). Of these, the case where a silicon (Si) compound is the main component will be described first. In this section, the layer formed on the first layer in the second layer formation stage is referred to as a [Bc] layer. As described above, when the processing of the second layer formation stage is performed on the first layer under specific conditions, the layered region adjacent to the [Bc] layer of the first layer becomes dense and dense. It is converted into a [Bb] layer, and the gas barrier property can be remarkably improved. The silicon compound in the present invention is a composition in which the composition ratio of each element whose components are specified by X-ray photoelectron spectroscopy (XPS method), ICP emission spectroscopic analysis, Rutherford backscattering method, etc., which will be described later, is expressed as an integer. Treated as a compound having the formula. For example, silicon dioxide (SiO _2), by 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, even in such a case The mass content is calculated as SiO ₂ .

  In such a preferred embodiment, the composition of the [Bc] layer preferably includes an oxide of silicon in which the atomic ratio of oxygen atoms to silicon atoms is 1.5 to 2.0. When the ratio of the number of oxygen atoms to silicon atoms is larger than 2.0, the amount of oxygen atoms contained increases, so that void portions and defect portions increase, and a predetermined gas barrier property may not be obtained. On the other hand, when the atomic ratio of oxygen atoms to silicon atoms is smaller than 1.5, oxygen atoms are reduced to obtain a dense film quality, but flexibility may be lowered. More preferably, it is the range of 1.7-1.9.

  The thickness and density of the [Bc] layer used in the preferred embodiment of the present invention can also be measured by the X-ray reflectivity method as described above.

  Also in this preferred embodiment, the range of the thickness of the [Bc] layer is the same as described above.

In such a preferred embodiment, the density of the [Bc] layer measured by the X-ray reflectance method is preferably in the range of 2.0 to 2.6 g / cm ³ . When the density of the [Bc] layer is smaller than 2.0 g / cm ³ , the denseness of the film quality of the [Bc] layer is lowered, and voids and defects are increased, so that sufficient gas barrier properties cannot be obtained. There is. When the density of the [Bc] layer is larger than 2.6 g / cm ³ , the [Bc] layer has an excessively dense film quality, so that cracks are likely to occur due to heat or external stress. Thus, the density of [Bc] layer is preferably in the range of 2.0~2.6g / cm ^3, a range of 2.3~2.5g / cm ³ is more preferable.

  The method applied to the second layer formation stage is not particularly limited, and can be formed by, for example, vacuum deposition, sputtering, ion plating, chemical vapor deposition, CVD (abbreviated as CVD), or the like. However, as a condition to be applied to the second layer formation stage, the defects present in the layered region on the surface of the first layer are efficiently filled with particles and converted to the [Bb] layer, so that the melting point is lower. It is preferable to use the above evaporation material, to perform evaporation under a reduced pressure condition, or to set the energy for activation high.

  In the case of the sputtering method, in addition to filling the particles constituting the [Bb] layer into the defects present in the layered region on the surface of the first layer, the surface diffusion of the particles forming the second layer causes the denseness. In order to form the second layer having a good film quality, the second layer is formed while assisting the surface of the first layer with a plasma of a reactive gas such as oxygen gas or carbon dioxide gas, in addition to the plasma for sputtering the target material. A plasma assisted sputtering method is preferable. In the case of the CVD method, it is preferable to activate a monomer gas of a silicon-based organic compound with high-intensity plasma and form a dense silicon-based thin film layer by a polymerization reaction. Among these methods, the method applied to the second layer forming stage used in the present invention can efficiently fill the defects on the surface of the first layer and dramatically improve the gas barrier property. A CVD method in which a monomer gas of an organic organic compound is activated by high-intensity plasma and a dense silicon-based thin film layer is formed by a polymerization reaction is more preferable. When forming the second layer by the CVD method, it is preferable to use a winding type sputtering / chemical vapor deposition apparatus having a structure shown in FIG. 2B.

  The silicon-based organic compound is a compound containing silicon in the molecule, for example, silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, propoxysilane, Dipropoxysilane, tripropoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyldisiloxane, hexamethyldisiloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, Hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, undecamethylcyclohexasiloxane, dimethyl Silazane, trimethyldisilazane, tetramethyldisilazane, hexamethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasiloxane silazane, such undecapeptide methyl cyclohexasilane La disilazane and the like. Among these, hexamethyldisiloxane and tetraethoxysilane are preferable from the viewpoint of handling.

[Second layer forming step <2>]
In a preferred embodiment of the present invention, silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), chromium (Cr), formed on the first layer in the second layer forming step, Of the layers mainly composed of a compound containing at least one element selected from the group consisting of tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), and tantalum (Ta), Al, Ti The case where a main component is a compound containing at least one element selected from the group consisting of Zr, Cr, Sn, In, Nb, Mo and Ta will be described. The layer formed on the first layer in the second layer formation step is referred to as a [Bc] layer in this section as in the previous section. As described above, when the processing of the second layer formation stage is performed on the first layer under specific conditions, the layered region adjacent to the [Bc] layer of the first layer becomes dense and dense. It is converted into a [Bb] layer, and the gas barrier property can be remarkably improved. The compound containing at least one element selected from the group consisting of Al, Ti, Zr, Cr, Sn, In, Nb, Mo and Ta in the present invention is an X-ray photoelectron spectroscopy (XPS method) described later. , ICP emission spectroscopic analysis, Rutherford backscattering method and the like are treated as compounds having a composition formula in which the composition ratio of each element specified by an integer is represented by an integer. For example, titanium dioxide (TiO _2), by the generation time of the condition, those slightly deviated from the composition ratio of titanium and oxygen on the left formula (TiO~TiO ₂₎ although it is possible to produce, even in such a case The above-described mass content is calculated as TiO ₂ .

  In such a preferred embodiment, the [Bc] layer is an oxide, nitride, oxynitride containing at least one metal element selected from the group consisting of Al, Ti, Zr, Cr, Sn, In, Nb, Mo, and Ta. Preferably, the compound is at least one compound. Metal oxide containing at least one element selected from the group consisting of Al, Ti, Zr, Cr, Sn, In, Nb, Mo and Ta from the viewpoint of flexibility and durability against bending and external impact Are preferably used.

  In the composition of the metal oxide constituting the [Bc] layer, the atomic ratio of oxygen atoms to metal atoms is preferably 1.0 to 2.0. When the atomic ratio of oxygen atoms to metal atoms is larger than 2.0, the amount of oxygen atoms contained increases, so that void portions and defect portions increase and predetermined gas barrier properties may not be obtained. On the other hand, when the atomic ratio of oxygen atoms to metal atoms is smaller than 1.0, oxygen atoms decrease and the film quality becomes dense, but flexibility may decrease. More preferably, it is the range of 1.3-1.8.

  The thickness and density of the [Bc] layer used in the preferred embodiment of the present invention can also be measured by the X-ray reflectivity method described above.

  Also in this preferred embodiment, the range of the thickness of the [Bc] layer is the same as described above.

In such a preferred embodiment, the density of the [Bc] layer measured by the X-ray reflectance method is preferably in the range of 3.5 to 5.5 g / cm ³ . When the density of the [Bc] layer is smaller than 3.5 g / cm ³ , the denseness of the film quality of the [Bc] layer is lowered, and voids and defects are increased, so that sufficient gas barrier properties cannot be obtained. There is. When the density of the [Bc] layer is larger than 5.5 g / cm ³ , the [Bc] layer has an excessively dense film quality, so that cracks are likely to occur due to heat and external stress. Thus, the density of [Bc] layer is preferably in the range of 3.5~5.5g / cm ^3, a range of 4.0~5.0g / cm ³ is more preferable.

  The method applied to the second layer formation stage is not particularly limited, and can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, an atomic layer deposition method (abbreviated as ALD method), etc. As a condition to be applied to the layer formation step of 2, the polymer base material is heated at a high temperature in order to efficiently fill the defects existing in the layered region of the surface of the first layer with particles and convert them into the [Bb] layer. The particles constituting the [Bb] layer are heated by heating, using a lower melting point evaporation material, evaporating under reduced pressure conditions, or activating the surface of the first layer with ions or radicals. A method of facilitating surface diffusion is preferred.

  In the case of the sputtering method, the first layer is separated from the plasma for sputtering the target material in order to efficiently fill the particles constituting the [Bb] layer into the defects present in the layered region on the surface of the first layer. A plasma-assisted sputtering method is preferred in which the second layer is formed while assisting the surface of the substrate with a reactive gas plasma such as oxygen gas or carbon dioxide gas. In the case of the ALD method, the first source gas containing at least one element selected from the group consisting of Al, Ti, Zr, Cr, Sn, In, Nb, Mo, and Ta and a chemical reaction with the first source gas The [Bc] source gas is used, and the single atom of the particles constituting the [Bb] layer facilitates surface diffusion on the surface of the first layer. Can be preferably applied alternately and repeatedly to advance the conversion into a dense [Bb] layer. Among these methods, the [Bc] layer forming method used in the present invention is at least one selected from the group consisting of Al, Ti, Zr, Cr, Sn, In, Nb, Mo, and Ta at a high temperature. A monomer gas containing an element is chemisorbed onto the first layer, and by a chemical reaction, defects on the surface of the first layer are efficiently filled at the monoatomic level, forming a dense metal oxide layer, and jumping In particular, the ALD method that can improve the gas barrier property is more preferable. When forming the second layer by the ALD method, it is preferable to use a winding-type sputtering / atomic layer deposition apparatus having a structure shown in FIG. 2C.

Examples of the first source gas used in the ALD method include trimethylaluminum, triethylaluminum, trichloroaluminum, dimethylaluminum hydride and the like when Al is included. When Ti is contained, tetrakis (dimethylamino) titanium (TDMAT), tetrakis (diethylamino) titanium (TDEAT), tetrakis (dialkylamino) titanium (TEMAT) and the like can be mentioned. In the case of containing Zr, examples thereof include zirconium terributoxide (Zr (OtBu) ₄ ), zirconium tetrakis, and tetra t-butoxyzirconium. When Cr is contained, trisacetylacetonatochrome and the like can be mentioned. [Bc] Examples of the source gas include water vapor-containing gas, oxygen gas, and ozone-containing gas.

[Layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide]
Next, details of a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide (hereinafter sometimes referred to as [Ba1] layer) that is preferably used as the [Ba] layer of the present invention will be described. The “coexisting phase of zinc oxide-silicon dioxide-aluminum oxide” may be abbreviated as “ZnO—SiO ₂ —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, in this specification It will be expressed as silicon dioxide or SiO ₂ and will be treated as its composition. Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc oxide and aluminum oxide. In this specification, zinc oxide or ZnO is used regardless of the deviation of the composition ratio depending on the conditions at the time of production. These are expressed as aluminum oxide or Al ₂ O ₃ and are treated as their compositions.

  The reason why the gas barrier property is improved by applying the [Ba1] 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, the coexistence of aluminum oxide can suppress the crystal growth more than the coexistence of zinc oxide and silicon dioxide, so it is considered that the gas barrier property deterioration due to the generation of cracks can be suppressed. It is done.

  The composition of the [Ba1] 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. On the other hand, when the Al atom concentration is higher than 5 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that cracks are likely to occur due to heat and external stress. When the Al atom concentration is less than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, the bonding force between the particles forming the layer cannot be improved, and the flexibility may be lowered. Further, when the O atom concentration is higher than 70 atom%, the amount of defects in the [Ba1] 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 [Ba1] 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 [Ba1] layer, and preferably 80% by mass or more.

  The composition of the [Ba1] 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, [Ba1] It is possible to adjust the composition of the layer.

The composition analysis of the [Ba1] 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 contained inorganic oxide. 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 an inorganic layer or a resin layer is disposed on the [Ba] layer, ICP emission spectroscopic analysis can be performed after removing the thickness obtained by the X-ray reflectance method by ion etching or chemical treatment.

  The method for forming the [Ba1] layer on the polymer substrate (or on the layer provided on the polymer substrate) is not particularly limited, and a mixed sintered material of zinc oxide, silicon dioxide and aluminum oxide is used. Then, it can be formed by a vacuum deposition method, a sputtering method, an ion plating method or the like. 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 [Ba1] 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.

[Layer consisting of a coexisting phase of zinc sulfide and silicon dioxide]
Next, the details of the layer composed of a coexisting phase of zinc sulfide and silicon dioxide (hereinafter sometimes referred to as the [Ba2] layer) that is preferably used as the [Ba] layer of the present invention will be described. The “zinc sulfide-silicon dioxide coexisting phase” is sometimes abbreviated as “ZnS—SiO ₂ ”. Further, silicon dioxide (SiO _2), depending on the conditions at the time of generation, those slightly deviated from the composition ratio of silicon and oxygen on the left formula (SiO~SiO ₂₎ although it is possible to produce, in the present specification Is expressed as silicon dioxide or SiO ₂ and is treated as its composition. Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc sulfide, and in this specification, it is expressed as zinc sulfide or ZnS regardless of the deviation of the composition ratio depending on the conditions at the time of formation. It will be treated as a composition.

  The reason why the gas barrier property is improved by applying the [Ba2] layer in the gas barrier film of the present invention is that, in the zinc sulfide-silicon dioxide coexisting phase, the crystalline component contained in zinc sulfide and the amorphous component of silicon dioxide 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, and is resistant to heat and external stress. Since cracks are unlikely to occur, it is considered that application of such a [Ba2] layer can suppress a decrease in gas barrier properties due to generation of cracks.

  The composition of the [Ba2] 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. In addition, 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 [Ba2] 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 [Ba2] 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 [Ba2] layer, and preferably 80% by mass or more.

  Since the composition of the [Ba2] layer is formed with the same composition as the mixed sintered material used at the time of forming the layer, the composition of the [Ba2] layer can be changed by using a mixed sintered material having a composition suitable for the purpose. It is possible to adjust.

  In the composition analysis of the [Ba2] layer, first, the composition ratio of zinc and silicon is obtained by ICP emission spectroscopic analysis. Based on this value, each element is quantitatively analyzed by using Rutherford backscattering method, and zinc sulfide and silicon dioxide and The composition ratio of other inorganic oxides contained can be known. 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 [Ba2] 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 another layer is arranged on the [Ba2] layer, the thickness obtained by the X-ray reflectance method 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 [Ba2] layer on the polymer substrate (or on the layer provided on the polymer substrate) is not particularly limited, and a vacuum is obtained using a mixed sintered material of zinc sulfide and silicon dioxide. It can be formed by vapor deposition, sputtering, ion plating, or the like. 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 [Ba2] 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.

[Transparent conductive layer]
Since the gas barrier film of the present invention has excellent gas barrier properties such as oxygen and water vapor, it is mainly used for packaging materials such as foods and pharmaceuticals, display elements such as electronic paper and organic EL television, and electronic devices such as solar cells. It can be used as a member. That is, by providing a transparent conductive layer on the surface of the [B] layer and sealing the display element and the electronic device, it is possible to impart high durability with little change in electrical resistance due to oxygen and water vapor from the outside. it can.

  Examples of the transparent conductive layer used in the present invention include indium tin oxide (ITO), zinc oxide (ZnO), aluminum-containing zinc oxide (Al / ZnO), gallium-containing zinc oxide (Ga / ZnO), metal nanowires and A layer containing any of the carbon nanotubes is preferable. As a thickness of a transparent conductive layer, the range of 0.1-500 nm is preferable, and 5-300 nm is more preferable as a range with favorable transparency.

  The methods for forming the transparent conductive layer include dry coating methods such as vacuum deposition, EB deposition and sputter deposition, casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, and screen. General methods such as wet coating methods such as printing, mold coating, printing transfer, and ink jet can be listed.

  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) Thickness of [A] layer and [B] layer A sample for cross-sectional observation is used by a FIB method (specifically, “polymer surface processing”) using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.). Gaku "(written by Iwamori Satoshi) 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 [A] layer and the [B] layer were measured. In observing each level of the sample, the thickness was measured at five boundary positions obtained by dividing the visual field into six equal parts in the plane direction of the layer, and the average of the five points was obtained. The interface of the substrate and the [B] layer, [A] layer and [B] layer was judged by a cross-sectional observation photograph using a transmission electron microscope.

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

(3) Surface Free Energy [A] Four types of measurement liquids (water, formamide, ethylene glycol, methylene iodide) whose surface free energy and its components (dispersion force, polarity force, hydrogen bonding force) are known on the surface of the layer [A] 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%. For each measurement solution, measure the contact angle with n = 5, obtain the average value, and substitute this value into the following formula (1) introduced from the extended Fowkes formula and Young formula to calculate each component did.

(4) Average surface roughness Ra
Using an atomic force microscope, the surface of the crosslinked resin layer as the [A] 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) Thickness and density of [Ba] layer, [Bb] layer, [Bc] layer (5-1) Cross-sectional observation by TEM Microsampling system (FB-2000A manufactured by Hitachi, Ltd.) was used for the cross-sectional observation sample. It was prepared by the FIB method (specifically, based on the method described in “Polymer surface processing” (written by Iwamori Satoshi) 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 number of layers and the thickness of each layer were measured by TEM observation used as initial values.
(5-2) Fitting of thickness and density of each layer by X-ray reflectance method The thickness and density of the [Ba] layer, [Bb] layer, and [Bc] layer were measured by the X-ray reflectance method. That is, X-rays are irradiated from the oblique direction to the gas barrier layer ([Ba] layer, [Bb] layer, [Bc] layer) disposed on the polymer substrate, and the total reflection X-ray intensity with respect to the incident X-ray intensity. The X-ray intensity profile of the obtained reflected wave was obtained by measuring the dependency of the incident angle on the surface of the gas barrier layer. The X-ray intensity profile described in the text with the initial value of the density calculated from the layer data specified by the cross-sectional observation of (5-1) and the composition information obtained by the evaluation of (6) to (8) Using the fitting method, the thickness and density of each region were determined.
The measurement conditions were as follows.
・ Apparatus: Rigaku SmartLab
-Analysis software: Rigaku Global Fit ver. 1.3.2
・ Measurement range (angle formed by the sample surface): 0 to 8.0 °, 0.001 ° step ・ Incoming slit size: 0.05 mm × 10.0 mm
-Light receiving slit size: 0.15 mm x 20.0 mm.

(6) Composition of [Ba1] layer It was performed by ICP emission spectroscopic analysis (manufactured by SII Nanotechnology, Inc., SPS4000). The contents of zinc atom, silicon atom, and aluminum atom in the sample were measured and converted to the atomic ratio. The oxygen atoms were calculated values based 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.

(7) Composition of [Ba2] layer ICP emission spectroscopic analysis (manufactured by SII NanoTechnology Co., Ltd., SPS4000) was performed, and Rutherford backscattering method (Nisshin High Voltage Co., Ltd. AN) -2500), each element was quantitatively analyzed to determine the composition ratio of zinc sulfide and silicon dioxide.

(8) Composition of [Bb] layer and [Bc] layer By using X-ray photoelectron spectroscopy (XPS method), the atomic number ratio of contained metal or nonmetal atom to oxygen atom is measured, and if necessary, the above The measurement of (3) or (4) was also used.
The measurement conditions were as follows.
・ Device: Quantera SXM (manufactured by PHI)
Excitation X-ray: monochromic AlKα1,2
・ X-ray diameter 100μm
-Photoelectron escape angle: 10 °.

(9) Water vapor permeability (g / (m ² · 24 hr · atm))
Measurement was carried out 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. .

[Method for Forming [Ba] Layer, [Bb] Layer, and [Bc] Layer in Examples 1 and 2]
(Formation of [Ba1] layer)
A sputter target that is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide on the surface of the polymer substrate 5 is used as the sputter electrode 18 by using a winding type sputtering apparatus having the structure shown in FIG. 2A. Then, sputtering with argon gas and oxygen gas was performed to provide a [Ba1] layer.

The specific operation is as follows. First, unwinding is performed in a winding chamber 7 of a winding-type sputtering apparatus 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 18. The polymer base material 5 is set on the roll 8 so that the surface on which the [Ba1] layer is provided faces the sputter electrode 18, unwinds, and passes through the guide rolls 9, 10, 11 with tap water at 15 ° C. It was passed through a cooling drum 12 adjusted to the above. Argon gas and oxygen gas are introduced with a partial pressure of oxygen gas of 10% so that the degree of vacuum 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 [Ba1] layer was formed on the surface of the polymer substrate 5. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

(Formation of [Bb] layer)
Using a winding type sputtering apparatus having the structure shown in FIG. 2A, a sputter target formed of tantalum pentoxide is sputtered on the surface of the polymer substrate 5 (the surface on which the [Ba1] layer is formed). And sputtering with argon gas plasma was performed to provide a [Bb] layer.

The specific operation is as follows. First, in the winding chamber 7 of a winding type sputtering apparatus in which a sputtering target obtained by sintering tantalum pentoxide is installed on the sputtering electrode 18, the polymer base material 5 is set on the winding roll 8 and unwinding. It passed through the cooling drum 12 adjusted to 15 degreeC with the tap water through the guide rolls 9, 10, and 11. Argon gas was introduced so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an application power of 500 W was applied by a high frequency power source to generate argon gas plasma, which was then sputtered onto the surface of the polymer substrate 5 by sputtering. Bb] layer was formed. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

(Formation of [Bc] layer)
A sputter target made of aluminum oxide is applied to the sputter electrode 18 on the surface of the polymer substrate 5 (the surface on which the [Bb] layer is formed) by using a winding type sputtering apparatus having the structure shown in FIG. 2A. Then, sputtering with argon gas plasma was performed to provide a [Bc] layer.

The specific operation is as follows. First, in the winding chamber 7 of a winding type sputtering apparatus in which a sputtering target obtained by sintering aluminum oxide is installed on the sputtering electrode 18, the polymer base material 5 is set on the winding roll 8, unwinding, and guiding It passed through the cooling drum 12 adjusted to 15 degreeC with the tap water through the rolls 9,10,11. Argon gas was introduced so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an application power of 500 W was applied by a high frequency power source to generate argon gas plasma, which was then sputtered onto the surface of the polymer substrate 5 by sputtering. Bc] layer was formed. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

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] 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 (denoted as A1) having a thickness of 3 μm was provided.

  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.

  On the [A] layer, the [Ba1] layer was provided with a target thickness of 100 nm. Next, one [Bb] layer is laminated on the [Ba1] layer with a thickness of 15 nm as a target, and one [Bc] layer is laminated on the [Bb] layer with a thickness of 100 nm as a target. Obtained. The composition of the [Ba] layer was such that 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%. In the composition of the [Bb] layer, the atomic ratio of oxygen atoms to tantalum atoms was 2.5. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to aluminum atoms was 1.3.

  Next, 100 mm long and 140 mm wide test pieces were cut out from the obtained gas barrier film, and the film thickness and density of each layer were evaluated by the X-ray reflectivity method, and the water vapor permeability was evaluated. The results are shown in Table 1.

(Example 2)
[A] As a coating liquid for forming a layer, instead of urethane acrylate, 100 parts by mass of polyester acrylate (Nippon Kayaku Co., Ltd. FOP-1740) and silicone oil (Toray Dow Corning Co., Ltd. SH190) 0 Add 2 parts by weight, prepare a coating liquid 2 diluted with 50 parts by weight of toluene and 50 parts by weight of MEK, and apply the coating liquid 2 with a microgravure coater (gravure wire number 200UR, gravure rotation ratio 100%). After drying at 60 ° C. for 1 minute, a gas barrier film was obtained in the same manner as in Example 1 except that ultraviolet rays were irradiated at 1 J / cm ² and cured to provide a 5 μm thick [A] layer (denoted as A2).

[Method for Forming [Ba] Layer, [Bb] Layer, and [Bc] Layer in Examples 3 to 8]
(Formation of the first layer)
Formation of the first layer (hereinafter referred to as the first layer-1) when the [Ba] layer is the [Ba1] layer (winding type sputtering / chemical vapor deposition apparatus having the structure shown in FIG. 2B) (Hereinafter abbreviated as sputtering / CVD apparatus), a sputtering target, which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide, is placed on the sputtering electrode 18 on the surface of the polymer substrate 5, and argon Sputtering with gas and oxygen gas was performed to provide the first layer-1.

The specific operation is as follows. First, in a winding chamber 7 of a sputtering / CVD apparatus 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 18, an unwinding roll 8 is set so that the surface on which the first layer-1 is provided faces the sputter electrode 18, unwinds, and 15 with tap water through the guide rolls 9, 10, 11. It passed through a cooling drum 12 adjusted to ° C. Argon gas and oxygen gas are introduced with a partial pressure of oxygen gas of 10% so that the degree of vacuum 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, the first layer-1 was formed on the surface of the polymer substrate 5. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

Formation of first layer (hereinafter referred to as first layer-2) when [Ba] layer is [Ba2] layer Using a sputtering / CVD apparatus having the structure shown in FIG. On the surface 5, a sputtering target, which is a mixed sintered material formed of zinc sulfide and silicon dioxide, was placed on the sputtering electrode 18, and sputtering with argon gas plasma was performed to provide the first layer-2.

The specific operation is as follows. First, in the winding chamber 7 of a sputtering / CVD apparatus in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar composition ratio of 80/20 is installed on the sputtering electrode 18, the polymer is placed on the winding roll 8. The substrate 5 was set, unwound, and passed through a cooling drum 12 adjusted to 15 ° C. with tap water through 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, which was then formed on the surface of the polymer substrate 5 by sputtering. 1 layer-2 was formed. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

(Formation of second layer)
Using a sputtering / CVD apparatus having the structure shown in FIG. 2B, hexamethyldisiloxane is used as a raw material on the surface of the polymer substrate 5 (the surface on which the first layer-1 or the first layer-2 is formed). Chemical vapor deposition was performed to provide a second layer.

The specific operation is as follows. In the winding chamber 7 of the sputtering / CVD apparatus, the polymer substrate 5 was set on the unwinding roll 8, unwound, and passed through the cooling drum 12 through the guide rolls 9, 10, and 11. Oxygen gas 0.5 L / min and hexamethyldisiloxane 70 ml / min are introduced so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and plasma is generated by applying an input power of 3000 W from the high frequency power source to the CVD electrode 19. Then, a second layer was formed on the surface of the polymer substrate 5 by CVD. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

(Example 3)
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] 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 (denoted as A1) having a thickness of 3 μm was provided.

  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, the first layer-1 was provided on the [A] layer with a target thickness of 100 nm. Further, a second layer was formed on the first layer-1 with a target thickness of 100 nm to obtain a gas barrier film. In the obtained gas barrier film, the layered region on the second layer side of the first layer-1 is converted to the [Bb] layer, and the [Ba] layer, [Bb] layer, and [Bc] layer are converted. It was confirmed that a gas barrier layer made of The [Ba] layer is the [Ba1] layer, and the composition thereof is such that the Zn atom concentration is 27.5 atom%, the Si atom concentration is 13.1 atom%, the Al atom concentration is 2.3 atom%, and the O atom concentration is 57.1 atom. %Met. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 1.7.

  Next, a test piece having a length of 100 mm and a width of 140 mm was cut out from the obtained gas barrier film, and evaluation of thickness and density of each layer and evaluation of water vapor permeability were performed by an X-ray reflectivity method. The results are shown in Table 1. In addition, the initial value of the thickness of each layer used for the analysis of the X-ray reflectivity method is a value obtained from a cross-sectional observation photograph using a transmission electron microscope, and the initial value of the density of each layer is the center of the thickness of each layer. The value calculated from the composition obtained by the composition analysis of the part was used.

(Example 4)
[A] As a coating liquid for forming a layer, instead of urethane acrylate, 100 parts by mass of polyester acrylate (Nippon Kayaku Co., Ltd. FOP-1740) and silicone oil (Toray Dow Corning Co., Ltd. SH190) 0 Add 2 parts by weight, prepare a coating liquid 2 diluted with 50 parts by weight of toluene and 50 parts by weight of MEK, and apply the coating liquid 2 with a microgravure coater (gravure wire number 200UR, gravure rotation ratio 100%). After drying at 60 ° C. for 1 minute, a gas barrier film was obtained in the same manner as in Example 3 except that ultraviolet rays were irradiated at 1 J / cm ² and cured to provide a 5 μm thick [A] layer (denoted as A2).

(Example 5)
A gas barrier film was obtained in the same manner as in Example 4 except that the second layer was formed by raising the input power of the high frequency power source to 5000 W. In the composition of the second layer, the atomic ratio of oxygen atoms to silicon atoms was 1.9.

(Example 6)
A gas barrier film was obtained in the same manner as in Example 4 except that the [Ba] layer was provided to have a thickness of 300 nm.

(Example 7)
A gas barrier film was obtained in the same manner as in Example 3 except that the first layer-2 was formed instead of the first layer-1.

(Example 8)
A gas barrier film was obtained in the same manner as in Example 4 except that the first layer-2 was formed instead of the first layer-1.

[Method for Forming [Ba] Layer, [Bb] Layer, and [Bc] Layer in Examples 9 and 10]
(Formation of the first layer)
Formation of the first layer (hereinafter referred to as the first layer-1) when the [Ba] layer is the [Ba1] layer (hereinafter referred to as the winding type sputtering / atomic layer deposition apparatus having the structure shown in FIG. 2C) A sputter target, which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide, on the surface of the polymer base material 5 on the surface of the polymer base material 5 and placed on the sputter electrode 18. Then, sputtering with oxygen gas was performed to provide the first layer-1.

The specific operation is as follows. First, in the winding chamber 7 of a sputtering / ALD apparatus 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 18, a winding roll 8 is set so that the surface on which the first layer-1 is provided faces the sputter electrode 18, unwinds, and 15 with tap water through the guide rolls 9, 10, 11. It passed through a cooling drum 12 adjusted to ° C. Argon gas and oxygen gas were introduced with a partial pressure of oxygen gas of 10% so that the degree of vacuum in the sputtering chamber 22 was 2 × 10 ⁻¹ Pa, and an argon / oxygen gas plasma was generated by applying an input power of 4000 W from a DC power source. The first layer-1 was formed on the surface of the polymer substrate 5 by sputtering. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

Formation of the first layer (hereinafter referred to as the first layer-2) when the [Ba] layer is the [Ba2] layer Using a sputtering / ALD apparatus having the structure shown in FIG. On the surface 5, a sputtering target, which is a mixed sintered material formed of zinc sulfide and silicon dioxide, was placed on the sputtering electrode 18, and sputtering with argon gas plasma was performed to provide the first layer-2.

The specific operation is as follows. First, in the winding chamber 7 of the sputtering / ALD apparatus in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar composition ratio of 80/20 is installed on the sputtering electrode 18, the polymer is placed on the winding roll 8. The substrate 5 was set, unwound, and passed through a cooling drum 12 adjusted to 15 ° C. with tap water through guide rolls 9, 10 and 11. Argon gas is introduced so that the degree of vacuum of the sputtering chamber 22 is 2 × 10 ⁻¹ Pa, and an applied power of 500 W is applied by a high frequency power source to generate argon gas plasma. A first layer-2 was formed on the surface. The thickness was adjusted by the conveyance speed of the polymer substrate. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

(Formation of second layer)
Using a sputtering / ALD apparatus having the structure shown in FIG. 2C, an atomic layer deposition method is used on the surface of the polymer substrate 5 (the surface on which the first layer-1 or the first layer-2 is formed). A second layer made of aluminum oxide was provided.

The specific operation is as follows. In the winding chamber 7 of the sputtering / ALD apparatus, the polymer base material 5 is set on the unwinding roll 8, unwinded, and adjusted to 90 ° C. with a heating medium via the guide rolls 9, 10, 11. And passed through a cooling drum 12. Trimethylaluminum gas is introduced so that the vacuum degree of the first source gas supply chamber 23 is 5 × 10 ¹ Pa, and water vapor is introduced so that the degree of vacuum of the second source gas supply chamber 24 is 5 × 10 ¹ Pa. A second layer was formed on the surface of the polymer substrate 5 by passing the polymer substrate 5 through the first source gas supply chamber 23 and the second source gas supply chamber 24 in this order. Then, it wound up on the winding roll 16 through the guide rolls 13, 14, and 15.

Example 9
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] 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 (denoted as A1) having a thickness of 3 μm was provided.

  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, the first layer-1 was provided on the [Ba] layer with a target thickness of 100 nm.

  A second layer was formed on the first layer-1 with a thickness of 50 nm as a target to obtain a gas barrier film. The thickness was adjusted by repeatedly forming the film in the order of the first source gas supply chamber 23 and the second source gas supply chamber 24. In the obtained gas barrier film, the layered region on the second layer side of the first layer-1 is converted to the [B] layer, and the [Ba] layer, [Bb] layer, and [Bc] layer are converted. It was confirmed that a gas barrier layer made of The [Ba] layer is the [Ba1] layer, and the composition thereof is such that the Zn atom concentration is 27.5 atom%, the Si atom concentration is 13.1 atom%, the Al atom concentration is 2.3 atom%, and the O atom concentration is 57.1 atom. %Met. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to aluminum atoms was 1.3.

  A test piece having a length of 100 mm and a width of 140 mm was cut out from the obtained gas barrier film, and evaluation of the thickness and density of each layer and evaluation of water vapor permeability were performed by an X-ray reflectivity method. The results are shown in Table 3. In addition, the initial value of the thickness of each layer used for the analysis of the X-ray reflectivity method is a value obtained from a cross-sectional observation photograph using a transmission electron microscope, and the initial value of the density of each layer is the center of the thickness of each layer. The value calculated from the composition obtained by the composition analysis of the part was used.

(Example 10)
A gas barrier film was obtained in the same manner as in Example 9 except that the first layer-2 was formed instead of the first layer-1. The [Ba] layer was the [Ba2] layer, and the composition had a molar fraction of zinc sulfide of 0.85.

(Example 11)
A gas barrier film was obtained in the same manner as in Example 2 except that the sputtering target at the time of forming the [Bb] layer was changed to tin oxide and the sputtering target at the time of forming the [Bc] layer was changed to silicon dioxide. In the composition of the [Bb] layer, the atomic ratio of oxygen atoms to tin atoms was 1.9. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 2.1.

(Example 12)
A gas barrier film was obtained in the same manner as in Example 2 except that the sputtering target at the time of forming the [Bb] layer was changed to niobium pentoxide and the sputtering target at the time of forming the [Bc] layer was changed to silicon dioxide. . In the composition of the [Bb] layer, the atomic ratio of oxygen atoms to niobium atoms was 2.2. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 2.1.

(Comparative Example 1)
A polyethylene terephthalate film ("Lumirror" (registered trademark) U35 manufactured by Toray Industries, Inc.) is used as the polymer substrate, and without forming the [A] layer, the [Ba] layer, [ A gas barrier film was obtained in the same manner as in Example 3 except that the Bb] layer and the [Bc] layer were formed.

(Comparative Example 2)
A polyethylene naphthalate film (Q65FA manufactured by Teijin Limited) is used as the polymer substrate, and the [Ba] layer, [Bb] layer, [Bc] are formed directly on the surface of the polymer substrate without forming the [A] layer. A gas barrier film was obtained in the same manner as in Example 3 except that the layer was formed.

(Comparative Example 3)
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] 10 parts by mass of “Sepoljon” (registered trademark) VH100 manufactured by Sumitomo Seika Co., Ltd., which is a coating agent in which an EVOH-based resin is dispersed in water, instead of urethane acrylate, is used as a coating liquid for layer formation. (Solid content concentration: 15% by mass) Weighed out, added 1.9 parts by mass of water and 0.6 parts by mass of isopropanol as a diluent solvent, and stirred for 30 minutes to prepare coating solution 3 having a solid content concentration of 12%. . Next, the coating liquid 3 was applied to one side of the polymer substrate with a micro gravure coater (gravure wire number 200UR, gravure rotation ratio 100%), dried and cured at 120 ° C. for 40 seconds, and a thickness of 1 μm [A] A gas barrier film was obtained in the same manner as in Example 3 except that a layer (referred to as A3) was provided.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Example 4 except that the second layer was formed by reducing the input power of the high-frequency power source to 500 W. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 1.5.

(Comparative Example 5)
Before the formation of the second layer, oxygen gas 0.5 L / min is introduced into the surface treatment electrode 17 and an applied power of 2000 W is applied by a DC power source to generate oxygen gas plasma. Example 1 except that the surface layer of 1 was etched and then formed on the etched surface of the first layer-1 by reducing the input power of the high-frequency power supply during the formation of the second layer to 500 W In the same manner as in Example 4, a gas barrier film was obtained. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 1.4.

(Comparative Example 6)
A gas barrier film was obtained in the same manner as in Example 4 except that the input power of the high-frequency power source during the formation of the second layer was increased to 5000 W, the conveying speed of the polymer substrate was decreased, and the polymer layer was formed longer. In the composition of the [Bc] layer, the atomic ratio of oxygen atoms to silicon atoms was 1.9.

(Comparative Example 7)
A gas barrier film was obtained in the same manner as in Example 2 except that the [Bb] layer was not formed.

(Comparative Example 8)
A gas barrier film was obtained in the same manner as in Example 11 except that the [Bc] layer was not formed.

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

DESCRIPTION OF SYMBOLS 1 Polymer base material 2 [A] layer 3 [B] layer 4a [Ba] layer 4b [Bb] layer 4c [Bc] layer 5 Polymer base material 6 Conveying direction 7 Winding chamber 8 Unwinding rolls 9, 10, DESCRIPTION OF SYMBOLS 11 Unwinding side guide roll 12 Cooling drum 13, 14, 15 Winding side guide roll 16 Winding roll 17 Surface treatment electrode 18 Sputter electrode 19 CVD electrode 20 1st source gas supply nozzle 21 2nd source gas supply nozzle 22 Sputter Chamber 23 First source gas supply chamber 24 Second source gas supply chamber

Claims (15)

The following [A] layer and [B] layer are arranged in contact in this order on at least one side of the polymer substrate,
The [B] layer includes a layer structure in which the [Ba] layer, the [Bb] layer, and the [Bc] layer are arranged in contact with each other from the polymer substrate side, and the [Ba] layer and the [Bc] layer The density is in the range of 2.0 to 9.0 g / cm ³ , the density of the [Bb] layer is 2.3 to 10.5 g / cm ³ , and the [Ba] layer and the [Bc] A gas barrier film having a density higher than any of the layers and a thickness of the [Bb] layer of 0.2 to 20 nm.
[A] layer: a crosslinked resin layer having a pencil hardness of H or more and a surface free energy of 45 mN / m or less [B] layer: a gas barrier layer having a thickness of 10 to 2500 nm   The gas barrier film according to claim 1, wherein the density of the [Ba] layer is higher than the density of the [Bc] layer. The gas barrier film according to claim 1 or 2, wherein the density of the [Bb] layer is 0.1 to 4.0 g / cm ³ higher than the density of the [Ba] layer. The [Ba] layer and the [Bb] layer are mainly composed of a zinc (Zn) compound, and the [Bc] layer is composed of silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), chromium ( [Bb] containing as a main component a compound containing at least one element selected from the group consisting of Cr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), and tantalum (Ta). The gas barrier film according to claim 1, wherein the density of the layer is 0.1 to 2.0 g / cm ³ higher than the density of the [Ba] layer. The density of the [Ba] layer is 3.9 to 4.6 g / cm ³ , the density of the [Bb] layer is 4.0 to 5.8 g / cm ³ , and the density of the [Bc] layer is 2.0 to The gas barrier film according to claim 4, which is 5.5 g / cm ³ . The gas barrier film according to claim 5, wherein the [Bc] layer contains a silicon (Si) compound as a main component and has a density of 2.0 to 2.6 g / cm ³ . The [Bc] layer includes aluminum (Al), titanium (Ti), zirconium (Zr), chromium (Cr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), and tantalum (Ta). 6. The gas barrier film according to claim 5, wherein the gas barrier film has a compound containing at least one element selected from the group consisting of a main component and a density of 3.5 to 5.5 g / cm ³ . The gas barrier film according to any one of claims 1 to 7, wherein the [Ba] layer is the following [Ba1] layer or [Ba2] layer.
[Ba1] layer: a layer composed of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide [Ba2] layer: a layer composed of a coexisting phase of zinc sulfide and silicon dioxide   The [Ba] layer is the [Ba1] layer, and its composition is such that the zinc (Zn) atom concentration is 20 to 40 atom% and the silicon (Si) atom concentration is 5 to 20 atom as measured by ICP emission spectroscopy. The gas barrier film according to claim 8, having an aluminum (Al) atom concentration of 0.5 to 5 atom% and an oxygen (O) atom concentration of 35 to 70 atom%.   The gas barrier according to claim 8, wherein the [Ba] layer is the [Ba2] layer, and the composition thereof is such that the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. Sex film.   The gas barrier film according to any one of claims 1 to 10, wherein the average surface roughness Ra of the [A] layer is 1 nm or less.   The gas barrier film according to claim 1, further comprising a transparent conductive layer on the surface of the [B] layer.   The transparent conductive layer includes any one of indium tin oxide (ITO), zinc oxide (ZnO), aluminum-containing zinc oxide (Al / ZnO), gallium-containing zinc oxide (Ga / ZnO), metal nanowires, and carbon nanotubes. The gas barrier film according to any one of claims 1 to 12.   The solar cell which has a gas barrier film in any one of Claims 1-13.   A display element having the gas barrier film according to claim 1.

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