JP6340843B2 - Gas barrier film - Google Patents

Description

  The present invention relates to a gas barrier film used for materials for foods and pharmaceuticals that require high gas barrier properties, and materials for electronic components such as solar cells, electronic paper, and organic electroluminescence (EL) displays.

  As a technique for improving the gas barrier property of the polymer film, 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 polymer substrate by a plasma CVD method, carbon, A technique for improving gas barrier properties while maintaining transparency by forming a layer of a compound containing at least one kind of hydrogen, silicon, and oxygen has been disclosed (Patent Document 1). Another technique for improving the gas barrier property is to form an organic layer containing an epoxy compound and a silicon-based oxide layer formed by a plasma CVD method on the substrate alternately, thereby causing cracks and defects due to film stress. Has disclosed a method of forming a gas barrier layer having a multi-layered structure in which the occurrence of gas is prevented (Patent Document 2).

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

  However, as disclosed in Patent Document 1, in the method of forming a gas barrier layer containing silicon oxide as a main component by the plasma CVD method, the gas barrier layer is formed under the influence of unevenness on the surface of the polymer base material that is the base of the gas barrier layer. There is a problem that defects are generated inside the gas barrier layer, and high gas barrier properties cannot be obtained stably.

In addition, in the method of Patent Document 2 for forming a gas barrier layer having a multilayer structure, in order to obtain a high gas barrier property with a water vapor permeability of 1.0 × 10 ⁻³ g / (m ² · 24 hr · atm) or less, several Ten layers need to be stacked to form a thick gas barrier layer, so cracking is likely to occur due to bending or external impact, film transport after gas barrier layer formation, handling, cutting, bonding, etc. in subsequent processes There has been a problem that the gas barrier property is greatly lowered during the processing of the above.

  In view of the background of such a conventional technique, the present invention can exhibit a high level of gas barrier properties without performing multilayer lamination, and can maintain a high level of gas barrier properties for film conveyance and processing in subsequent processes. It is intended to provide a gas barrier film.

The present invention employs the following means in order to solve such problems. That is,
(1) A first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) and a silicon compound as main components on at least one surface of the polymer substrate And a gas barrier layer disposed in contact with the polymer base material in this order. The first layer and the second layer have a film hardness of 0.5 GPa or more measured by a nanoindentation method. state, and are less 5.0 GPa, have an undercoat layer between the polymeric substrate and the first layer, a gas barrier to which the undercoat layer is characterized in that it comprises a polyurethane compound having an aromatic ring structure Sex film.
(2) The first layer includes at least one selected from the group consisting of aluminum (Al), silicon (Si), gallium (Ga), tin (Sn), and indium (In). The gas barrier film according to (1).
(3) The first layer is at least selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), gallium oxide (Ga ₂ O ₃ ), tin oxide (SnO ₂ ), and indium oxide (In ₂ O ₃ ). The gas barrier film according to any one of (1) and (2), comprising one.
(4) The second layer is mainly composed of a compound containing at least one selected from the group consisting of silicon carbide, silicon nitride, and silicon oxynitride. A gas barrier film according to claim 1.
( 5 ) The gas barrier film according to any one of (1) to ( 4 ), wherein the first layer is any one of the following [A] layer and [B] layer.
[A] layer: a layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide [B] layer: a layer consisting of a coexisting phase of zinc sulfide-silicon dioxide ( 6 ) The first layer is obtained by X-ray photoelectron spectroscopy. The measured zinc (Zn) atom concentration is 10 to 40 atom%, the silicon (Si) atom concentration is 5 to 20 atom%, the aluminum (Al) atom concentration is 0.5 to 4 atom%, and the oxygen (O) atom concentration is 50 to 50%. The gas barrier film according to any one of (1) to ( 5 ), which is 70 atom%.
( 7 ) The second layer has a silicon (Si) atom concentration of 25 to 45 atom% and an oxygen (O) atom concentration of 55 to 75 atom% measured by X-ray photoelectron spectroscopy. The gas barrier film according to any one of 6 ).

  A gas barrier film having a high gas barrier property against water vapor and excellent in bending resistance can be provided.

It is sectional drawing which showed an example of the gas barrier film of this invention. It is sectional drawing which showed an example of the gas barrier film of this invention. It is an example of the load-pushing depth diagram obtained by the nanoindentation method. It is the schematic of a bending resistance test. It is the schematic which shows typically the winding-type sputtering chemical vapor deposition apparatus for manufacturing the gas barrier film of this invention.

[Gas barrier film]
The gas barrier film of the present invention includes a first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) on at least one surface of the polymer substrate. A gas barrier layer disposed in this order from a polymer substrate in contact with a second layer containing a silicon compound as a main component, the first layer and the second layer having a film hardness in a specific range; It is a gas barrier film. Note that “first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ )” is simply referred to as “first layer” and “silicon compound. The “including second layer” may be simply abbreviated as “second layer”.

FIG. 1 shows a cross-sectional view of an example of the gas barrier film of the present invention. The gas barrier film of the present invention has a gas barrier layer 2 on one surface of a polymer substrate 1, and the gas barrier layer 2 contains zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ). The first layer 2a containing the compound containing the main component and the second layer 2b containing the silicon compound are arranged in this order from the polymer substrate 1. The gas barrier layer 2 has a second layer 2b containing a silicon compound in contact with a first layer 2a mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ). As a result, defects such as pinholes and cracks on the surface of the first layer are filled with the silicon compound contained in the second layer, and a high gas barrier property and adhesion are obtained.

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

  In addition, since the first layer and the second layer have flexibility of the entire gas barrier layer by setting the film hardness measured by the nanoindentation method to 0.5 GPa or more and 5.0 GPa or less, from the bending or the outside Due to this impact, cracks and defects are unlikely to occur, and a gas barrier film capable of maintaining high gas barrier properties can be obtained.

  The nanoindentation method is a method in which an indenter is slightly vibrated during an indentation test, and an initial gradient at the time of indenter unloading is continuously calculated corresponding to a continuous change in the indentation depth. Specifically, it is calculated by the measurement method shown below.

  As a method of calculating the hardness of the film, a load-indentation depth diagram (FIG. 3) is obtained by performing an indentation load / unloading test using a triangular pyramid indenter (Berkovich indenter) on a stationary sample surface. To do. The hardness H at the maximum load is obtained by H = P / A using the projected area A of the remaining indentation after the elastic deformation is restored after the load P and the pressing.

Here, the projected area A of the indentation is obtained from A = ηκh _c ² . η is a correction coefficient for the indenter tip shape, κ is a constant obtained from the geometric shape of the indenter, and in the case of Berkovich indenter, κ = 24.56 was used. Further, h _c is an effective contact depth, and is obtained by h _c = h−ε {P / (dP / dh)}. h is the total displacement of the measured contact depth, and dP / dh is the initial gradient at the time of unloading in the obtained load-pushing depth diagram. ε is a constant for determining the geometric shape of the indenter, and in the case of the Berkovich indenter, ε = 0.75.

From the above, the hardness H at the maximum load at the maximum load P _max can be calculated by H = P _max / ηκh _c ² .

dP / dh can be calculated using a continuous stiffness measurement method. In the continuous stiffness measurement method, the indenter is microvibrated during the indentation test, the response amplitude and phase difference with respect to the vibration are acquired as a function of time, and dP / dh is continuously measured corresponding to the continuous change of the indentation depth. It is a method to calculate. By this method, the film hardness in the depth direction of the thin film can be continuously measured.
In addition, when an inorganic layer or a resin layer is laminated on the layer whose film hardness is to be measured, the thickness of the inorganic layer or the resin layer is removed by ion etching or chemical treatment, and then the film hardness is measured by a nanoindentation method. Can be measured.

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

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

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

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

[First layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ )]
The gas barrier film of the present invention has a high gas barrier property because the gas barrier layer has a first layer whose main component is a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ). Can be expressed. The reason why the gas barrier property is improved by applying the first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) is that zinc oxide and / or Alternatively, the coexistence of the crystalline component contained in zinc sulfide and the vitreous component of silicon dioxide suppresses the crystal growth of zinc oxide and / or zinc sulfide, which tends to form microcrystals, and is a layer having a large amorphous structure. Thus, it is speculated that the permeation of water vapor is suppressed because the dense layer has a small particle size. In addition, zinc oxide and zinc sulfide have low hardness physical properties compared to other metal oxides and nitrides such as aluminum oxide, titanium oxide, and zirconium oxide. By having a layer with a structure, it does not have a grain boundary peculiar to the crystal structure, so it becomes a flexible layer that is not easily cracked by heat and external stress, and it is considered that the gas barrier property can be prevented from lowering. .

The gas barrier film of the present invention has a film hardness of 0.5 GPa or more of the first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ). It is preferably within a range of 0.0 GPa or less. If the film hardness of the first layer is less than 0.5 GPa, the mechanical strength of the film is weak, so cracks occur in the first layer due to bending, contact with the second layer surface, and friction during film transport and handling. In addition, gas barrier properties may be reduced. In addition, when the film hardness of the first layer is higher than 5.0 GPa, the first layer cannot follow bending and deformation, so that cracks may occur and gas barrier properties may be lowered. Therefore, it is preferable that the film hardness of the first layer, which is difficult to be damaged by an external impact and has a bending resistance against bending or deformation, is in a range of 0.5 GPa or more and 5.0 GPa or less. Is more preferably 1.0 GPa or more and 3.0 GPa or less.

In the present invention, the first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) is composed of zinc oxide and / or zinc sulfide and silicon dioxide (SiO _2). ), Aluminum (Al), gallium (Ga), titanium (Ti), zirconium (Zr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo) and tantalum ( It may contain at least one selected from the group consisting of Ta). Further, oxides, nitrides, sulfides, or mixtures of these elements may be included. For example, as a first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) capable of obtaining high gas barrier properties, a layer composed of the following coexisting phases is used. Preferably used.
[A] layer: layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide [B] layer: layer consisting of a coexisting phase of zinc sulfide and silicon dioxide Details of the layer consisting of this coexisting phase will be described later.

  The thickness of the first layer used in the present invention is preferably 10 nm or more and 500 nm or less as the thickness of the layer that achieves both gas barrier properties and flexibility. 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 the gas barrier property may vary in the polymer substrate surface. In addition, when the thickness of the layer is greater than 500 nm, the stress remaining in the layer increases, so that cracks are likely to occur in the first layer due to bending or external impact, and the gas barrier properties may decrease with use. is there. Therefore, the thickness of the first layer is preferably 10 nm or more and 500 nm or less, and more preferably 100 nm or more and 300 nm or less from the viewpoint of ensuring flexibility. The thickness of the first layer can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).

  The center layer average roughness SRa of the first layer used in the present invention is preferably 10 nm or less. When SRa is larger than 10 nm, the uneven shape on the surface of the first layer becomes large, and a gap is formed between the sputtered particles to be laminated. May be difficult to obtain. Further, when SRa is larger than 10 nm, the film quality of the second layer containing the silicon compound laminated on the first layer is not uniform, so that the gas barrier property may be lowered. Accordingly, the SRa of the first layer is preferably 10 nm or less, more preferably 7 nm or less.

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

  In the present invention, the method for forming the first layer is not particularly limited. For example, the first layer can be formed by a vacuum deposition method, a sputtering method, an ion plating method, or the like. In order to form in the range of 0.5 GPa or more and 5.0 GPa or less, a method of forming the first layer in a state where the temperature of the surface on which the first layer is formed is controlled at 50 ° C. or more and 150 ° C. or less is preferable.

[[A] layer: a layer comprising a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide]
The [A] layer that is suitably used as the first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) in the present invention will be described in detail. 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 silicon dioxide or SiO ₂ It shall be written as Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc oxide and aluminum oxide. Regardless of the deviation of the composition ratio depending on the conditions at the time of production, zinc oxide or ZnO, aluminum oxide or Al, respectively. _It shall be expressed as ₂ O ₃ .

  The reason why the gas barrier property is improved by applying the [A] layer as the first layer of the gas barrier layer in the gas barrier film of the present invention is that the layer containing zinc oxide and silicon dioxide further coexists with aluminum oxide. The crystal growth can be further suppressed as compared with the case where only zinc oxide and silicon dioxide coexist, and it is considered that the gas barrier property deterioration due to the generation of cracks can be suppressed.

  The composition of the [A] layer can be obtained by measuring by X-ray photoelectron spectroscopy (XPS method) as described later. Here, the composition of the [A] layer in the present invention is represented by the atomic concentration ratio of each element measured by the XPS method at the position where the thickness of the [A] layer becomes 1/2. In addition, the thickness of the [A] layer is a thickness obtained by cross-sectional observation with a transmission electron microscope (TEM) as described above. Zinc (Zn) atom concentration measured by X-ray photoelectron spectroscopy is 10 to 40 atom%, silicon (Si) atom concentration is 5 to 20 atom%, aluminum (Al) atom concentration is 1 to 4 atom%, and oxygen (O) atom. The concentration is preferably 50 to 70 atom%.

  When the zinc (Zn) atom concentration is higher than 40 atom% or the silicon (Si) atom concentration is lower than 5 atom%, the silicon dioxide and / or aluminum oxide that suppresses the crystal growth of zinc oxide is insufficient. Defects may increase and sufficient gas barrier properties may not be obtained. When the zinc (Zn) atom concentration is lower than 10 atom% or the silicon (Si) atom concentration is higher than 20 atom%, silicon dioxide having a higher physical property than zinc oxide increases and the flexibility of the layer decreases. There is a case. Further, when the aluminum (Al) atomic concentration is higher than 4 atom%, aluminum oxide having higher hardness than zinc oxide and silicon dioxide increases, and cracks are likely to occur due to heat and external stress. When the aluminum (Al) atomic concentration is smaller than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved. May decrease. In addition, when the oxygen (O) atom concentration is higher than 70 atom%, the amount of defects in the first layer increases, so that a desired gas barrier property may not be obtained. When the oxygen (O) atom concentration is less than 45 atom%, the oxidation state of zinc, silicon, and aluminum becomes insufficient, crystal growth cannot be suppressed, and the particle diameter becomes large, so that the gas barrier property may be lowered. From this viewpoint, the zinc (Zn) atom concentration is 10 to 40 atom%, the silicon (Si) atom concentration is 5 to 20 atom%, the aluminum (Al) atom concentration is 0.5 to 4 atom%, and the oxygen (O) atom concentration is 50. More preferably, it is -70 atom%.

  The component contained in the [A] layer is not particularly limited as long as zinc oxide, silicon dioxide and aluminum oxide are in the above composition and are main components. For example, aluminum (Al), titanium (Ti), zirconium (Zr) Further, a metal oxide formed of tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd), or the like may be included. Here, the main component means 50% by mass or more of the composition of the first layer, preferably 60% by mass or more, and more preferably 80% by mass or more.

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

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

  [A] When an inorganic layer or a resin layer is laminated on the layer, after removing the thickness of the inorganic layer or the resin layer measured by cross-sectional observation with a transmission electron microscope by ion etching or chemical treatment, [A] The layer can be removed by argon ion etching to a position where the thickness of the layer becomes ½, and analyzed by X-ray photoelectron spectroscopy.

  The method for forming the [A] layer on the polymer substrate (or on the layer provided on the polymer substrate (for example, on an undercoat layer described later)) is not particularly limited, and zinc oxide and silicon dioxide It can be formed by vacuum deposition, sputtering, ion plating, etc. using a mixed sintered material of aluminum oxide, but the film hardness of the [A] layer is 0.5 GPa or more with good reproducibility and stability. In order to form in a range of 0.0 GPa or less, a method of forming the [A] layer in a state where the temperature of the surface on which the [A] layer is formed is controlled at 50 ° C. or higher and 150 ° C. or lower is preferable. In addition, when using a single material of zinc oxide, silicon dioxide, and aluminum oxide, zinc oxide, silicon dioxide, and aluminum oxide are simultaneously formed from different vapor deposition sources or sputter electrodes, and mixed to obtain the desired composition. Can be formed. Among these methods, the [A] layer forming method of the gas barrier layer of the gas barrier film of the present invention is more preferably a sputtering method using a mixed sintered material from the viewpoint of gas barrier properties and composition reproducibility of the formed layer. preferable.

[[B] layer: coexistence phase of zinc sulfide and silicon dioxide]
Next, the details of the [B] layer that is preferably used as the first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) in the present invention. explain. 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 . 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.

  In the gas barrier film of the present invention, the reason why the gas barrier property is improved by applying the [B] layer as the first layer is that the crystalline component contained in zinc sulfide and silicon dioxide in the zinc sulfide-silicon dioxide coexisting phase. It is assumed that the coexistence with the amorphous component of the present invention suppresses the crystal growth of zinc sulfide, which tends to form microcrystals, and the particle size is reduced, so that the layer is densified and the permeation of oxygen and water vapor is suppressed. ing. 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. Therefore, it is considered that the deterioration of the gas barrier property due to the generation of cracks could be suppressed by applying the layer composed of the zinc sulfide-silicon dioxide coexisting phase.

  The composition of the [B] 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 may be a shortage of oxide that suppresses the crystal growth of zinc sulfide. The gas barrier property may not be obtained. Also, when the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is less than 0.7, the amorphous component of silicon dioxide inside the layer may increase and the flexibility of the layer may decrease, The flexibility of the gas barrier film with respect to mechanical bending may be reduced. The mole fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is more preferably in the range of 0.75 to 0.85.

  The component contained in the [B] layer is 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 [B] layer, and preferably 80% by mass or more.

  [B] The composition of the layer is formed with the same composition as the mixed sintered material used when forming the layer. Therefore, the composition of the first layer is adjusted by using a mixed sintered material having a composition suitable for the purpose. Is possible.

  In the composition analysis of the layer [B], 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, 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. In addition, since the [B] layer is a composite layer of sulfide and oxide, analysis by Rutherford back scattering method capable of analyzing the composition ratio of sulfur and oxygen is performed. [B] When an inorganic layer or resin layer is laminated on the layer, the thickness of the inorganic layer or resin layer measured by cross-sectional observation with a transmission electron microscope is removed by ion etching or chemical treatment, and then the ICP It can be analyzed by emission spectroscopic analysis and Rutherford backscattering method.

  The method for forming the [B] layer on the polymer substrate (or on the layer provided on the polymer film substrate) is not particularly limited, and using a mixed sintered material of zinc sulfide and silicon dioxide, Although it can be formed by a vacuum evaporation method, a sputtering method, an ion plating method, etc., in order to form the film hardness of the [B] layer in a range of 0.5 GPa or more and 5.0 GPa or less with good reproducibility, [ The method of forming a [B] layer in the state which controlled the temperature of the surface which forms a B] layer at 50 to 150 degreeC is preferable. In addition, when using a single material of zinc sulfide and silicon dioxide, it is possible to form films by simultaneously forming zinc sulfide and silicon dioxide from different vapor deposition sources or sputter electrodes, and mixing them to have a desired composition. it can. Among these methods, the [B] 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.

[Second layer mainly composed of silicon compound]
Next, the details of the second layer containing a silicon compound as a main component will be described. The second layer in the present invention is a layer containing a silicon compound, and the silicon compound may contain silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, or a mixture thereof. In particular, the silicon compound preferably contains at least one selected from the group consisting of silicon dioxide, silicon carbide, silicon nitride, and silicon oxynitride.

The content of the silicon compound is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more. In addition, the silicon compound in the present invention is treated as a compound having a composition formula in which the composition ratio of each element whose component is specified by X-ray photoelectron spectroscopy, ICP emission spectroscopy, Rutherford backscattering method or the like is represented by an integer. 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 .
The gas barrier film of the present invention is mainly composed of a silicon compound in contact with a first layer composed mainly of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ). A gas barrier layer on which the second layer is disposed, and the first layer and the second layer have a high gas barrier by having a film hardness measured by a nanoindentation method of 0.5 GPa or more and 5.0 GPa or less. Since the gas barrier layer has flexibility as a whole, the gas barrier film is capable of maintaining high gas barrier properties because it is difficult to cause cracks and defects due to bending or external impact.

  The reason why the gas barrier property is improved by applying the second layer containing a silicon compound in the gas barrier film of the present invention is that the second layer contains silicon atoms having an atomic radius smaller than the zinc atoms of the first layer, It is considered that gas barrier properties are improved because silicon atoms can be efficiently filled into defect atom defects having a size of several nm or less existing on the surface of the first layer.

  In addition, the gas barrier film of the present invention preferably has a film hardness of 0.5 GPa or more and 5.0 GPa or less as measured by the second layer nanoindentation method containing a silicon compound as a main component. When the film hardness of the second layer is less than 0.5 GPa, the mechanical strength of the film is insufficient, so that the film is easily damaged by an impact received from the outside during film transportation or handling, and the gas barrier property may be lowered. . Further, when the film hardness of the first layer is higher than 5.0 GPa, the second layer cannot follow the bending and deformation, so that cracks may occur and the gas barrier property may be lowered. Therefore, it is preferable that the film hardness of the first layer, which is difficult to be damaged by an external impact, and to ensure bending resistance against bending or deformation, is in a range of 0.5 GPa or more and 5.0 GPa or less. Is more preferably 1.0 GPa or more and 3.0 GPa or less.

  The composition of the second layer containing a silicon compound as a main component can be measured by X-ray photoelectron spectroscopy. Here, the composition of the second layer in the present invention is the atomic concentration ratio of each element measured by the XPS method at the position where the thickness of the second layer becomes 1/2.

  When an inorganic layer or a resin layer is laminated on the second layer, after removing the thickness of the inorganic layer or the resin layer measured by cross-sectional observation with a transmission electron microscope by ion etching or chemical treatment, It can be removed by argon ion etching until the thickness of the second layer becomes 1/2 and analyzed by X-ray photoelectron spectroscopy.

  In the case where the second layer is a layer containing silicon oxide, the composition is such that the silicon (Si) atom concentration measured by X-ray photoelectron spectroscopy is 25 to 45 atom%, and the oxygen (O) atom concentration is 55 to 75 atom%. It is preferable that When the silicon (Si) atom concentration is lower than 25 atom% or the oxygen atom concentration is higher than 75 atom%, oxygen atoms bonded to silicon atoms are excessively increased, so that voids and defects increase in the layer, and the gas barrier property is lowered. There is a case. In addition, when the silicon (Si) atom concentration is higher than 45 atom% or the oxygen (O) atom concentration is lower than 55 atom%, the film becomes excessively dense, which may cause large curl or decrease in flexibility. As a result, cracks are likely to occur due to heat or external stress, and the gas barrier properties may be reduced. From this viewpoint, it is more preferable that the silicon (Si) atom concentration is 28 to 40 atom%, and the oxygen (O) atom concentration is 60 to 72 atom%, and further, the silicon (Si) atom concentration is 30 to 35 atom%, oxygen ( O) The atomic concentration is more preferably 65 to 70 atom%.

  The component contained in the second layer is not particularly limited as long as the silicon (Si) atom concentration and the oxygen (O) atom concentration are within the above-mentioned composition. For example, zinc (Zn), aluminum (Al), titanium (Ti) Further, a metal oxide formed from zirconium (Zr), tin (Sn), indium (In), niobium (Nb), molybdenum (Mo), tantalum (Ta), palladium (Pd), or the like may be included.

  The thickness of the second layer is preferably 10 nm or more, and more preferably 50 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 the gas barrier property varies. The thickness of the second layer is preferably 500 nm or less, and more preferably 200 nm or less. When the thickness of the layer is greater than 500 nm, the stress remaining in the layer increases, so that the second layer is liable to be cracked by bending or external impact, and the gas barrier property may be lowered with use.

  The method for forming the second layer is not particularly limited. For example, the second layer can be formed by a film forming method such as a vacuum evaporation method, a sputtering method, or a chemical vapor deposition method (abbreviated as a CVD method). In order to efficiently fill the atoms contained in the second layer with cracks, pinholes, atomic defects, etc. existing on the surface, the surface of the first layer is controlled at 50 ° C. or higher and 150 ° C. or lower. A method of forming the second layer while treating the surface of the first layer with high energy so that the atoms constituting the second layer are activated is preferable. When the temperature of the surface of the first layer forming the second layer is higher than 150 ° C., the formation particles of the second layer are activated and the bond between silicon and oxygen is strengthened. In some cases, the film hardness of the second layer is greater than 5.0 GPa, and cracks may occur due to bending during handling and the gas barrier properties may decrease.

  As a method for forming the second layer, for example, in the case of a vacuum deposition method, oxygen gas, carbon dioxide gas or the like is used during film formation with a deposition source in a state where the surface of the first layer is controlled at 50 ° C. or more and 150 ° C. An ion beam assisted deposition method is preferred, in which a reactive gas plasma is generated, the plasma is further accelerated to form a beam, and the second layer is formed while treating the surface of the first layer.

  In the case of sputtering, in the state where the surface of the first layer is controlled at 50 ° C. or higher and 150 ° C. or lower, plasma of reactive gas such as oxygen gas or carbon dioxide gas is generated and accelerated separately from the plasma for sputtering the target material. An ion beam assisted sputtering method is preferably used in which the second layer is formed while the first layer surface is processed while being converted into a beam.

  In the case of the CVD method, in a state where the surface of the first layer is controlled at 50 ° C. or more and 150 ° C. or less, a high-density plasma of a reactive gas such as oxygen gas or carbon dioxide gas is generated by an induction coil, and the first plasma is generated. A plasma CVD method using an inductively coupled CVD electrode that simultaneously performs the surface treatment of the layer and the formation of the second layer by the polymerization reaction of the monomer gas of the silicon-based organic compound is preferable.

  Among these methods, the method applied to the formation of the second layer used in the present invention efficiently fills the defects in the surface of the first layer with atoms contained in the second layer, and further covers the surface of the first layer with a large area. A plasma CVD method using an inductively coupled CVD electrode that can be uniformly processed is more preferable.

  The silicon-based organic compound used in the CVD method is a compound containing silicon inside the molecule. For example, silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethyl Silane, propoxysilane, dipropoxysilane, tripropoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetramethyldisiloxane, hexamethyldisiloxane, tetramethoxysilane, tetraethoxysilane Tetrapropoxysilane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, undecamethylcyclohexasiloxane Hexane, dimethyl disilazane, trimethyl disilazane, tetramethyl disilazane, hexamethyl disilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, decamethylcyclopentasiloxane silazane, such undecapeptide methyl cyclohexasilane La disilazane and the like. Among these, hexamethyldisiloxane, tetraethoxysilane, and hexamethyldisilazane are preferable from the viewpoint of handling.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The center surface average roughness SRa of the undercoat layer is preferably 10 nm or less. When SRa is 10 nm or less, it is easy to form a homogeneous first layer on the undercoat layer, and it is preferable because repeated reproducibility of gas barrier properties is improved. When the SRa on the surface of the undercoat layer is greater than 10 nm, the uneven shape on the surface of the first layer on the undercoat layer also increases, and gaps are formed between the stacked sputtered particles. In some cases, it is difficult to obtain an improvement effect, and cracks due to stress concentration are likely to occur in portions where there are many irregularities, which may reduce the reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the undercoat layer is preferably 10 nm or less, more preferably 7 nm or less.

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

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

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

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

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

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

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

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

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

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

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples. In the following description, Example 1 is replaced with Reference Example 1.

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

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

(2) Center plane average roughness SRa
Using a three-dimensional surface roughness measuring machine (manufactured by Kosaka Laboratory), the surface of each layer was measured under the following conditions.
System: Three-dimensional surface roughness analysis system “i-Face model TDA31”
X-axis measurement length / pitch: 500 μm / 1.0 μm
Y-axis measurement length / pitch: 400 μm / 5.0 μm
Measurement speed: 0.1 mm / s
Measurement environment: temperature 23 ° C., relative humidity 65%, in air.

(3) Water vapor permeability (g / (m ² · 24 hr · atm))
By the calcium corrosion method described in Japanese Patent No. 4407466, the water vapor permeability was measured in an atmosphere at a temperature of 40 ° C. and a humidity of 90% RH. The number of samples for measuring the water vapor transmission rate is 2 samples per level, the number of measurement is 5 times for each sample, and the average value of the obtained 10 points is the water vapor transmission rate (g / (m ² · 24 hr · atm) ).

(4) Temperature measurement of the surface forming the first layer and the second layer The thermocouple was attached to the surface forming the first layer and the second layer with a heat-resistant tape so that the metal part was not exposed, and the temperature was measured. The highest temperature measured when the first layer and the second layer were formed in each example and comparative example was defined as the respective surface temperature.
・ Device (data logger): DQ1860 (manufactured by DATAPAQ)
・ Sampling period: 0.1 second ・ Thermocouple: K type.

(5) Composition of the first layer ([A] layer, Al ₂ O ₃ layer, ZnO layer) and second layer (SiO ₂ layer) The composition analysis of the [A] layer and the second layer is performed by X-ray photoelectron spectroscopy. (XPS method).
The layer was removed from the surface layer by argon ion etching until the thickness of the layer became 1/2, and the content ratio of each element was measured under the following conditions.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
Excitation X-ray: monochromic AlKα
・ X-ray output: 300W
-X-ray diameter: 800 μm
-Photoelectron escape angle: 45 °
Ar ion etching: 2.0 kV, 10 mPa.

(6) Composition of the [B] layer The composition analysis of the [B] layer was performed by ICP emission spectroscopic analysis (manufactured by Seiko Denshi Kogyo Co., Ltd., SPS4000). Each element was quantitatively analyzed by using AN-2500 (Voltage Co., Ltd.) to determine the composition ratio of zinc sulfide and silicon dioxide.

(7) Hardness of the first layer and the second layer The hardness of the first layer and the second layer was measured by a nanoindentation method (continuous stiffness measurement method). The nano-indentation method is a method in which the indenter is microvibrated during the indentation test, and the response amplitude and phase difference with respect to the vibration are obtained as a function of time. This is a method of continuously calculating the gradient. It calculated by averaging the data of the area | region of the indentation depth = about 7 nm-about 15 nm in the hardness-indentation depth diagram obtained by the following measuring apparatus and measurement conditions.

・ Measuring device: Nano Harder Nano Indenter manufactured by MTS Systems
DCM
・ Measurement method: Nanoindentation method (continuous stiffness measurement method)
・ Indenter used: Triangular pyramid indenter made of diamond ・ Measurement atmosphere: Room temperature and in air.

(8) Bending resistance As shown in FIG. 4, the gas barrier film 4 was sampled at 100 mm × 140 mm per two specimens per level, and in this sample, the surface on the opposite surface 6 side to the surface on which the first layer and the second layer were formed. A metal cylinder 5 having a diameter of 5 mm is fixed at the center, and the holding angle of the cylinder is 0 ° (the sample is in a flat state) along the cylinder, and the holding angle to the cylinder is 180 ° (the folded state by the cylinder). After performing 100 bending operations within the range, the water vapor permeability was evaluated by the method shown in (3). The number of measurements was 5 for each specimen, and the average value of the 10 points obtained was the water vapor permeability after the flex resistance test.

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

A sputtering target, which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide, is sputtered using a winding-type sputtering / chemical vapor deposition apparatus (hereinafter abbreviated as sputtering / CVD apparatus) shown in FIG. The electrode 14 is installed, sputtering with argon gas and oxygen gas is performed, and an [A] layer (ZnO—SiO ₂ —Al ₂ O ₃ layer) is formed on the surface of the polymer substrate 1 as a first layer. Aimed at 150 nm.

The specific operation is as follows. First, unwinding is performed in a winding chamber 8 of a sputtering / CVD apparatus 7 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 14. The roll 9 is set so that the surface on which the first layer of the polymer substrate 1 is provided faces the sputter electrode 14, unwinds, and is heated to a temperature of 100 ° C. via the guide rolls 10, 11, 12. Passed through the main drum 13. Argon / oxygen gas plasma is generated by introducing argon gas and oxygen gas with a partial pressure of oxygen gas of 10% so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and applying 3,000 W of input power from a DC pulse power supply. Then, an [A] layer was formed on the surface of the polymer substrate 1 by sputtering. The thickness of the 1st layer was adjusted with the film conveyance speed. The surface of the polymer substrate 1 received the heating temperature of the main drum 13 and the plasma heat, and the temperature was 111 ° C. Then, it wound up on the winding roll 18 via the guide rolls 15, 16, and 17.

  The composition of the first layer was such that the Zn atom concentration was 29.4 atom%, the Si atom concentration was 12.3 atom%, the Al atom concentration was 1.7 atom%, and the O atom concentration was 56.6 atom%. A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the first layer was formed, and the film thickness was evaluated by the center plane average roughness SRa of the surface of the first layer and the nanoindentation method. The results are shown in Table 1.

(Formation of the second layer)
Using the sputtering / CVD apparatus having the structure shown in FIG. 5, chemical vapor deposition (hereinafter abbreviated as CVD) using hexamethyldisilazane as a raw material was performed on the first layer of the polymer substrate 1. As two layers, SiO ₂ layers were provided aiming at a thickness of 100 nm.

The specific operation is as follows. In the winding chamber 8 of the sputtering / CVD apparatus 7, the polymer base material 1 was set on the unwinding roll 9, unwound, and heated to a temperature of 100 ° C. via the guide rolls 10, 11, 12. Passed through the main drum 13. Oxygen gas 45 sccm and hexamethyldisilazane 5 sccm are introduced so that the degree of vacuum is 2 × 10 ⁻¹ Pa, and plasma is generated by applying an input power of 2,000 W to the induction coil 20 of the CVD electrode 19 from a high frequency power source. Then, a second layer was formed on the first layer of the polymer substrate 1 by CVD. Then, it wound up on the winding roll 18 via the guide rolls 15, 16, and 17, and obtained the gas-barrier film.

  The composition of the second layer was such that the Si atom concentration was 33.0 atom% and the O atom concentration was 67.0 atom%. A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the second layer was formed, and the film thickness was evaluated by the center surface average roughness SRa of the surface of the second layer and the nanoindentation method. The results are shown in Table 1.

  In addition, 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 the water vapor permeability before and after the bending resistance test was evaluated. The results are shown in Table 1.

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

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

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

  Next, a 150 nm-thick [A] layer was provided as a first layer on the undercoat layer in the same manner as in Example 1. A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the first layer was formed, and the film thickness was evaluated by the center plane average roughness SRa of the surface of the first layer and the nanoindentation method. The results are shown in Table 1.

Next, a SiO ₂ layer having a thickness of 100 nm was provided as a second layer on the first layer in the same manner as in Example 1. A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the second layer was formed, and the film thickness was evaluated by the center surface average roughness SRa of the surface of the second layer and the nanoindentation method. The results are shown in Table 1.

  In addition, 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 the water vapor permeability before and after the bending resistance test was evaluated. The results are shown in Table 1.

(Example 3)
The heating temperature of the main drum 13 when forming the first layer is 130 ° C., the [A] layer is provided to have a thickness of 150 nm, the heating temperature of the main drum 13 when forming the second layer is 130 ° C., A gas barrier film was obtained in the same manner as in Example 2 except that the [B] layer was provided to have a thickness of 100 nm.

Example 4
The heating temperature of the main drum 13 when forming the first layer is 60 ° C., the [A] layer is provided to have a thickness of 150 nm, the heating temperature of the main drum 13 when forming the second layer is 70 ° C., A gas barrier film was obtained in the same manner as in Example 2 except that the [B] layer was provided to have a thickness of 100 nm.

(Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the [A] layer having a thickness of 450 nm was provided as the first layer.

(Example 6)
A gas barrier film was obtained in the same manner as in Example 2 except that a SiO ₂ layer having a thickness of 400 nm was provided as the second layer.

(Example 7)
A sputter target sintered at a composition mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 87/10/3 is used for the sputter electrode 14 when forming the first layer, and the [A] layer has a thickness of 150 nm. A gas barrier film was obtained in the same manner as in Example 2 except that it was provided.

  The composition of the first layer was such that the Zn atom concentration was 36.9 atom%, the Si atom concentration was 7.1 atom%, the Al atom concentration was 1.8 atom%, and the O atom concentration was 54.2 atom%.

(Example 8)
A sputter target sintered at a composition mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 67/30/3 is used as the sputter electrode 14 when forming the first layer, and the [A] layer has a thickness of 150 nm. A gas barrier film was obtained in the same manner as in Example 2 except that it was provided.

  The composition of the first layer was such that the Zn atom concentration was 23.7 atom%, the Si atom concentration was 16.1 atom%, the Al atom concentration was 1.8 atom%, and the O atom concentration was 58.4 atom%.

Example 9
A gas barrier film was obtained in the same manner as in Example 2 except that the heating temperature of the main drum 13 when forming the second layer was 130 ° C., and the SiO ₂ layer was provided so as to have a thickness of 100 nm.

(Example 10)
A [B] layer having a thickness of 150 nm is formed on the undercoat layer using a sputter target which is a mixed sintered material formed of zinc sulfide and silicon dioxide on the undercoat layer, using the winding type sputtering apparatus 7 having the structure shown in FIG. A gas barrier film was obtained in the same manner as in Example 2 except that the film was provided.

The specific operation for forming the [B] layer is as follows. First, in the winding roll 8 of the sputtering / CVD apparatus 7 in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar composition ratio of 80/20 is installed on the sputtering electrode 14, the embodiment is applied to the winding roll 9. The polymer substrate 1 provided with 2 undercoat layers was set, unwound, and passed through the main drum 13 heated to a temperature of 100 ° C. via the guide rolls 10, 11, and 12. Argon gas was introduced so that the degree of vacuum was 2 × 10 ⁻¹ Pa, and an applied power of 1,000 W was applied by a high-frequency power source to generate argon gas plasma. By sputtering, [B] on the undercoat layer A layer was formed. The thickness was adjusted by the film transport speed. The surface of the undercoat layer received the heating temperature of the main drum 13 and the plasma heat, and the temperature was 113 ° C. Then, it wound up on the winding roll 18 via the guide rolls 15, 16, and 17.

  The composition of the first layer had a zinc sulfide molar fraction of 0.80.

(Comparative Example 1)
A gas barrier film was obtained in the same manner as in Example 1 except that the SiO ₂ layer was not formed as the second layer.

(Comparative Example 2)
A gas barrier film was obtained in the same manner as in Example 2 except that the [A] layer having a thickness of 1,050 nm was provided as the first layer, and the SiO ₂ layer was not formed as the second layer.

(Comparative Example 3)
The heating temperature of the main drum 13 when forming the first layer is 160 ° C., the [A] layer is provided to have a thickness of 150 nm, the heating temperature of the main drum 13 when forming the second layer is 160 ° C., A gas barrier film was obtained in the same manner as in Example 2 except that the [B] layer was provided to have a thickness of 100 nm.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Example 2, except that the heating temperature of the main drum 13 when forming the first layer was 160 ° C., and the [A] layer was provided to have a thickness of 150 nm.

(Comparative Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the heating temperature of the main drum 13 when forming the second layer was 160 ° C., and the [B] layer was provided to a thickness of 100 nm.

(Comparative Example 6)
A gas barrier film was obtained in the same manner as in Example 2 except that an Al ₂ O ₃ layer having a thickness of 150 nm was provided instead of the first layer [A]. The Al ₂ O ₃ layer is a sputter target made of aluminum having a purity of 99.99% by mass, which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide when forming the [A] layer. Instead of being formed on the sputter electrode 14, it was formed in the same manner as the first layer of Example 2. The composition of the second layer was an Al atom concentration of 37.5 atom% and an O atom concentration of 62.5 atom%.

(Comparative Example 7)
A gas barrier film was obtained in the same manner as in Example 2 except that a ZnO layer having a thickness of 150 nm was provided instead of the first [A] layer. In addition, the ZnO layer replaces the sputter target which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide at the time of forming the [A] layer with a sputter target made of zinc having a purity of 99.99 mass%. It was formed in the same manner as the first layer of Example 2 except that it was installed on the sputter electrode 14. The composition of the second layer was an Al atom concentration of 50.2 atom% and an O atom concentration of 49.8 atom%.

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

DESCRIPTION OF SYMBOLS 1 Polymer substrate 2 Gas barrier layer 2a 1st layer 2b containing zinc oxide and silicon dioxide 2b 2nd layer containing silicon compound 3 Undercoat layer 4 Gas barrier film 5 Metal cylinder 6 The 1st layer and the 2nd layer are formed 7 Winding type sputtering / chemical vapor deposition apparatus 8 Winding chamber 9 Winding rolls 10, 11, 12 Winding side guide roll 13 Main drum 14 Sputtering electrodes 15, 16, 17 Winding side guide roll 18 Winding roll 19 CVD electrode 20 Induction coil

Claims (7)

A first layer mainly composed of a compound containing zinc oxide (ZnO) and / or zinc sulfide (ZnS) and silicon dioxide (SiO ₂ ) is formed on at least one surface of the polymer substrate, and a first layer mainly composed of a silicon compound. A gas barrier layer disposed in contact with the two layers in this order from the polymer base material, and the first layer and the second layer have a film hardness of 0.5 GPa or more measured by a nanoindentation method; 0GPa Ri der hereinafter gas barrier film having an undercoat layer between the polymeric substrate and the first layer, the undercoat layer is characterized in that it comprises a polyurethane compound having an aromatic ring structure. The first layer includes at least one selected from the group consisting of aluminum (Al), silicon (Si), gallium (Ga), tin (Sn), and indium (In). The gas barrier film according to 1. The first layer includes at least one selected from the group consisting of aluminum oxide (Al ₂ O ₃ ), gallium oxide (Ga ₂ O ₃ ), tin oxide (SnO ₂ ), and indium oxide (In ₂ O ₃ ). The gas barrier film according to claim 1, comprising: a gas barrier film. The gas barrier according to any one of claims 1 to 3, wherein the second layer contains a compound containing at least one selected from the group consisting of silicon carbide, silicon nitride, and silicon oxynitride as a main component. Sex film. The gas barrier film according to any one of claims 1 to 4 , wherein the first layer is any one of the following [A] layer and [B] layer.
[A] layer: layer consisting of a coexisting phase of zinc oxide-silicon dioxide-aluminum oxide [B] layer: layer consisting of a coexisting phase of zinc sulfide-silicon dioxide The first layer has a zinc (Zn) atom concentration of 10 to 40 atom%, a silicon (Si) atom concentration of 5 to 20 atom%, and an aluminum (Al) atom concentration of 0.5 to 0.5 as measured by X-ray photoelectron spectroscopy. The gas barrier film according to any one of claims 1 to 5 , which has 4 atom% and an oxygen (O) atom concentration of 50 to 70 atom%. The second layer of silicon (Si) atom concentration 25～45Atom% as measured by X-ray photoelectron spectroscopy, oxygen (O) atom concentration according to any one of claims 1 to 6 which is a 55～75Atom% Gas barrier film.

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