JP2018052040A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that has a high gas barrier property against water vapor and a high film quality stability.SOLUTION: Provided is a laminate having a layer [A]2 containing Si, O and N on at least one side of a substrate 1, and having 20 nm or more in the thickness direction of the layer [A]2 and having an inorganic layer [B]3 on the substrate side of the layer [A]2, thereby the Si-H bonds existing in the region where the element ratio O/Si of the layer [A]2 satisfies the range of 0<O/Si<0.150 can be protected from the side of the substrate 1, and the film quality stability of the layer [A]2 is improved.SELECTED DRAWING: Figure 1

Description

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

  Physical vapor deposition method (PVD method) such as vacuum deposition method, sputtering method, ion plating method using inorganic materials (including inorganic oxides) such as aluminum oxide, silicon oxide, magnesium oxide on the surface of the substrate Alternatively, an inorganic vapor deposition film is formed using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method. Laminates having gas barrier properties are used as packaging materials for foods and pharmaceuticals that require blocking of various gases such as water vapor and oxygen, and electronic device members such as flat-screen TVs and solar cells.

  As a gas barrier property improving technique, for example, by laminating an inorganic layer mainly composed of silicon oxide on a base material by a plasma CVD method using a gas containing an organic silicon compound vapor and oxygen, transparency can be achieved. A method for improving the gas barrier property while maintaining it is disclosed (Patent Document 1). Further, as a gas barrier property improving technique other than a film forming method such as a plasma CVD method, a method of converting a polysilazane film formed by a wet coating method into a silicon oxide film or a silicon oxynitride film (Patent Documents 2 to 9) is disclosed. ing.

Japanese Patent No. 3859518 Japanese Patent No. 5734675 Japanese Patent No. 5444722 Japanese Patent No. 5326052 Japanese Patent No. 5531892 Japanese Patent No. 5895684 International Publication No. 2016/052123 International Publication No. 2016/052123 JP 2015-149404 A

  However, as in Patent Document 1, in the method of forming an inorganic layer mainly composed of silicon oxide by plasma CVD, it is difficult to suppress defects in the inorganic layer, so that stable gas barrier properties cannot be obtained. In order to stabilize the gas barrier property or to obtain a high barrier property, it is necessary to increase the film thickness or laminate the layers, which causes problems such as a decrease in bending resistance and an increase in manufacturing cost. Moreover, in the method of forming an inorganic layer with the polysilazane of patent documents 2, 3, and 4, the layer is easily oxidized by gas permeation from the substrate side, and the stability of the layer under high temperature and high humidity is insufficient. Further, in Patent Documents 5, 6, 7, and 8, a polysilazane layer is formed on the first gas barrier layer, but the conditions for forming the layer (at the time of coating the coating solution exposed to the atmosphere or during the modification) Irradiation intensity) and the performance of the first gas barrier layer cause the oxidation in the polysilazane layer to progress, the film quality stability and durability are lowered, and sufficient gas barrier properties for electronic device applications are not obtained. Although Patent Document 9 attempts to suppress oxidation of the silicon oxynitride film, the composition has insufficient oxidation suppression, and sufficient gas barrier properties for electronic device applications are not obtained.

  In view of the background of such a conventional technique, the present invention is to provide a laminate having a high gas barrier property against water vapor and a high film quality stability without increasing the thickness or multilayer lamination.

In order to solve this problem, the present invention employs the following configuration.
[1]
A laminate having a layer [A] containing Si, O and N on at least one side of a substrate, wherein the element ratio O / Si of the layer [A] is 0 <O / Si <0.150 The laminated body which has the area | region which satisfy | fills the range of 20 nm or more in the thickness direction.
[2]
The laminate according to [1], wherein the layer [A] has a region in which the element ratio O / Si satisfies a range of 0 <O / Si <0.130 in the thickness direction of 20 nm or more.
[3]
The laminate according to [1] or [2], wherein the layer [A] has a region in which the element ratio O / Si satisfies a range of 0 <O / Si <0.100 in the thickness direction of 20 nm or more.
[4]
An inorganic layer [B] is provided between the substrate and the layer [A], and the inorganic layer [B] is zinc, silicon, tin, aluminum, indium, titanium, silver, zirconium, niobium, molybdenum. And a laminate according to any one of [1] to [3], which contains at least one element selected from the group consisting of palladium.
[5]
The laminate according to [4], wherein the inorganic layer [B] contains zinc and silicon.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has high gas barrier property with respect to water vapor | steam, and high film quality stability can be provided.

It is sectional drawing which showed an example of the laminated body of this invention. It is sectional drawing which showed an example of the laminated body of this invention.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

  The inventors of the present invention have made extensive studies for the purpose of obtaining a laminate having a high gas barrier property against water vapor and the like and a high film quality stability, and a layer containing Si, O, and N on at least one side of the substrate [ A], wherein the layer [A] has an area where the element ratio O / Si satisfies the range of 0 <O / Si <0.150 in the thickness direction by 20 nm or more. The present invention has been found to solve the above problems.

  Hereinafter, each component of the laminated body of this invention is demonstrated.

[Base material]
Examples of materials that can be used as the base material used in the present invention include metal substrates such as silicon, glass substrates, ceramic substrates, and resin films. It is preferable to have 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 base material used in the present invention is not particularly limited, but it is preferable that the main component is an organic polymer. Examples of organic polymers 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, polyimides, Examples include polycarbonate, polystyrene, polyvinyl alcohol, saponified ethylene vinyl acetate copolymer, various polymers such as polyacrylonitrile and polyacetal. Among these, a film made of polyethylene terephthalate, polyethylene naphthalate, or cycloolefin having excellent transparency, versatility, and mechanical properties is preferable. 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 substrate on the side where the layer [A] is formed is corona treated, plasma treated, ultraviolet treated, ion bombarded, solvent treated, organic or inorganic, or a mixture thereof. A pretreatment such as an undercoat layer forming treatment may be applied. Further, on the side opposite to the side on which the layer [A] is formed, a coating layer of an organic material, an inorganic material, or a mixture thereof may be laminated for the purpose of improving the slipping property at the time of winding the film.

  The thickness of the substrate used in the present invention can be appropriately selected depending on the use, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and preferably 5 μm or more from the viewpoint of securing strength against tension or impact. Furthermore, the thickness of the base material is more preferably 10 μm to 200 μm from the viewpoint of film processing and handling.

[Layer [A]]
In the present invention, the layer [A] preferably contains Si, O, and N, and has a region in which the element ratio O / Si satisfies the range of 0 <O / Si <0.150 in the thickness direction of 20 nm or more. .

  The reason why a laminate having high gas barrier properties and high film quality stability can be obtained by applying the layer [A] of the present invention is estimated as follows. That is, in the layer [A] containing Si, O, and N, the region where the element ratio O / Si satisfies the range of 0 <O / Si <0.150 is a region where oxidation is suppressed. Since oxygen atoms interact strongly with water molecules and easily form hydrogen bonds, a region where many oxygen atoms are present is a region where water molecules are likely to exist stably. On the contrary, in the region where oxidation is suppressed, water molecules are less likely to exist stably, and thus the region has high gas barrier properties.

  Furthermore, in the region where oxidation is suppressed, the number of Si—O bonds is limited, and the four bonds of silicon atoms are bonded to atoms other than oxygen atoms. The atom other than the oxygen atom is not particularly limited, and examples thereof include a nitrogen atom, a silicon atom, and a hydrogen atom. Among these, since the nitrogen atom has three bonds, the Si—N bond contributes to densification of the layer and imparts high gas barrier properties to the layer. In addition to the property of repelling water (hydrophobicity), the Si—H bond bonded to a hydrogen atom can also be given flexibility by terminating the bond with a hydrogen atom, and bends the laminate of the present invention. This is an area with excellent bending resistance that can relieve the stress generated at the time and suppress a decrease in gas barrier properties due to crack generation. The layer [A] has a region in which the element ratio O / Si satisfies the range of 0 <O / Si <0.150 in the thickness direction by 20 nm or more, so that the entire laminate has high gas barrier properties and high film quality stability. It becomes the laminated body which has.

  Here, regarding the region where the element ratio O / Si satisfies the range of 0 <O / Si <0.150, it is sufficient that at least one place in the thickness direction is 20 nm or more in the thickness direction of the layer [A]. There may be two or more locations.

  Further, the layer [A] has a region in which the element ratio O / Si satisfies the range of 0 <O / Si <0.130 in the thickness direction of 20 nm or more from the viewpoint of obtaining higher gas barrier properties and higher film quality stability. More preferably, the region satisfying the range of 0 <O / Si <0.100 is more preferably 20 nm or more in the thickness direction.

  Here, the composition distribution in the thickness direction of the layer [A] can be obtained by a conventionally known composition analysis method, for example, a method using XPS analysis (X-ray photoelectron spectroscopy) and etching in combination.

  Hereinafter, a method using XPS analysis and etching in the present invention will be described.

The etching rate of the laminate of the present invention is different for each layer. Therefore, once obtained based on the etching rate in terms of SiO ₂ , the thickness of each layer is determined by specifying the interface of each layer based on the cross-sectional observation image by TEM (transmission electron microscope) of the same sample as the XPS analysis. Ask for. Each layer in the composition distribution in the thickness direction is specified while comparing the thickness per each layer obtained based on the cross-sectional observation image with the composition distribution in the thickness direction obtained from the XPS analysis. The thickness direction is corrected by applying a coefficient to the thickness of each layer obtained from the XPS analysis so that the thickness of each layer obtained from the XPS analysis matches the thickness of each layer obtained from the cross-sectional observation image.

  In the composition analysis in line with the gist of the present invention, the resolution in the thickness direction is important, and the etching depth per measurement point is 2 nm. Having a region satisfying the range of 0 <O / Si <0.150 in the thickness direction of 20 nm or more means connecting continuous measurement points satisfying the range of 0 <O / Si <0.150 obtained from XPS analysis. The length of the line segment obtained by means that it is 20 nm or more in the thickness direction. More specifically, since the etching depth per measurement point is 2 nm, there are 11 or more measurement points continuously satisfying the range of 0 <O / Si <0.150. In this case, the length of the line segment obtained by connecting the measurement points satisfying the range of 0 <O / Si <0.150 is 20 nm or more.

  For example, 1 to 4 measurement points continuous from the surface layer side to the base material side of the layer [A] are measurement points satisfying a range of 0 <O / Si <0.150, and the surface layer of the layer [A] The fifth measurement point from the side toward the substrate side is a measurement point that does not satisfy the range of 0 <O / Si <0.150, and is continuous from the surface layer side of the layer [A] toward the substrate side. When 6 to 13 measurement points are measurement points satisfying the range of 0 <O / Si <0.150, a line segment (6 nm) obtained from 1 to 4 measurement points and 6 to 13 measurement points are obtained. The total of the line segments (14 nm) obtained at the points is 20 nm. In such a case, it does not correspond to having a region satisfying the range of 0 <O / Si <0.150 in the thickness direction of 20 nm or more. .

Furthermore, from the viewpoint of obtaining a high gas barrier property, the layer [A] preferably contains a component having a bond represented by Si—H (hereinafter also referred to as Si—H bond). In addition to the water-repellent property (hydrophobicity), the Si—H bond can also impart flexibility by terminating the bond with a hydrogen atom, and relaxes the stress generated when the laminate of the present invention is bent. Therefore, it is possible to suppress a decrease in gas barrier properties due to crack generation and to obtain high bending resistance. Here, whether or not the layer [A] contains a component having a bond represented by Si—H is determined by analysis by Fourier transform infrared spectroscopy, and Si is 2140-2260 cm ⁻¹ . If it has a peak showing -H stretching vibration, it is judged to contain a component having a bond represented by Si-H.

  In addition, from the viewpoint of obtaining high gas barrier properties and high film quality stability, the layer [A] is a region where the outermost surface side 20 nm satisfies the element ratio O / Si range of 0.150 ≦ O / Si. Preferably there is. Here, the region on the outermost surface side of 20 nm is a region of 0 nm to 20 nm in the thickness direction from the surface of the layer [A] on the side opposite to the substrate. A region in which the element ratio O / Si satisfies the range of 0.150 ≦ O / Si is a region having a high film density because the region has few Si—H bonds. By making the outermost surface side a region having a high film density, it is possible to protect Si—H bonds existing in a region where the element ratio O / Si satisfies the range of 0 <O / Si <0.150 from the outermost surface side. And the film quality stability of the layer [A] is improved. A layer having a high gas barrier property and high film quality stability as a whole of the laminate because the outermost surface side 20 nm of the layer [A] is a region where the element ratio O / Si satisfies the range of 0.150 ≦ O / Si. Become a body.

(Thickness of layer [A])
In the present invention, the thickness of the layer [A] is preferably 50 to 500 nm, more preferably 90 to 500 nm. If the thickness of the layer [A] is less than 50 nm, stable gas barrier properties may not be obtained. When the thickness of the layer [A] is greater than 500 nm, the stress remaining in the layer [A] increases, and cracks may occur in the layer [A], which may reduce the gas barrier properties. The thickness of the layer [A] can be measured from a cross-sectional observation image by TEM.

(Step of providing layer [A])
In the present invention, a silicon compound having a polysilazane skeleton is preferably used as a raw material for the layer [A]. As the silicon compound having a polysilazane skeleton, for example, a compound having a partial structure represented by the following chemical formula (1) can be preferably used. Specifically, at least one selected from the group consisting of perhydropolysilazane, organopolysilazane, and derivatives thereof can be used. In the present invention, it is preferable to use perhydropolysilazane in which all of R ₁ , R ₂ , and R _{3 represented} by the following chemical formula (1) are hydrogen from the viewpoint of improving gas barrier properties, but part or all of hydrogen is used. May be an organopolysilazane substituted with an organic group such as an alkyl group. Moreover, you may use by a single composition and may mix and use two or more components. Note that n represents an integer of 1 or more.

  The step of providing the layer [A] in the present invention includes the step [a] of applying a coating liquid containing a silicon compound having a polysilazane skeleton to provide a coating film, the step of drying the coating film [b], and the coating film. It is preferable to have the process [c] which performs a light irradiation process and carries out composition conversion of the said coating film in this order. Other steps may be included as long as the steps [a], [b], and [c] are included. Details of each step will be described below.

[Step [a]]
The step [a] is preferably a step of applying a coating liquid containing a silicon compound having a polysilazane skeleton to provide a coating film.

  Here, as a process of providing a coating film by applying the coating liquid in the step [a], a known method can be used, and a roll coating method, a gravure coating method, a knife coating method, a dip coating method, a spray coating method. It is preferable to apply on the substrate by a method such as slit die coating. In the present invention, from the viewpoint of suppressing the oxidation of the layer [A], it is more preferable to select a method in which the coating liquid can be applied without being exposed to oxygen or water vapor until immediately before coating, and the supply of the coating liquid is dry nitrogen. It is preferable to use a liquid-feeding solution or a sealed syringe pump, and it is particularly preferable to apply the solution onto the substrate by a slit die coating method.

  Moreover, in this invention, it is preferable to dilute the coating material containing the compound represented by the said Chemical formula (1) using an organic solvent from a viewpoint of coating suitability. Specifically, using a hydrocarbon solvent such as xylene, toluene, terpene, or solvesso, or an ether solvent such as diethyl ether, dibutyl ether, diisopropyl ether, butyl ethyl ether, or tetrahydrofuran, the solid content concentration is 15% by mass. It is preferable to use after diluting. These solvents may be used alone or in combination of two or more.

  Various additives can be blended in the coating material containing the silicon compound forming the layer [A], if necessary, as long as the effect of the layer [A] is not impaired. 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.

[Step [b]]
The step [b] is preferably a step [b] for drying the coating film. Specifically, in the step [b], it is preferable to remove the diluted solvent by heating and drying the coated film. 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., and more preferably 50 to 120 ° C. from the viewpoint of suppressing oxidation of the layer [A]. The heat treatment time is preferably 10 seconds to 30 minutes, more preferably 10 seconds to 10 minutes. When the heat treatment time exceeds 30 minutes or the heating temperature exceeds 150 ° C., oxidation of the coating film proceeds and high gas barrier properties may be deteriorated. Therefore, it is preferably within 30 minutes. Further, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Furthermore, the humidification treatment may be performed in the atmosphere or in a state enclosed in an inert gas.

[Step [c]]
Step [c] is preferably a step of subjecting the coating film to an active energy ray irradiation treatment. Specifically, in the step [c], the coating film after humidification is subjected to light irradiation treatment such as plasma treatment, ultraviolet ray irradiation treatment, flash pulse treatment, etc., so that the composition of the coating film is changed, and the layer [A of the present invention [A] ] Can be obtained.

  As the active energy ray irradiation treatment, ultraviolet treatment is preferably used because it is simple and excellent in productivity, and it is easy to obtain a uniform layer [A] composition. 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% by volume or less, and more preferably 0.5% by volume or less. For reducing the oxygen concentration, dry nitrogen is preferably used. The relative humidity may be arbitrary.

  As an ultraviolet ray generation source, a known source such as a high pressure mercury lamp, a metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp, or an excimer lamp using argon, krypton, xenon, or the like can be used. In view of production efficiency and easy formation of the laminate of the present invention, it is preferable to use a xenon excimer lamp. Although the wavelength of the ultraviolet rays to be irradiated is not particularly limited, it is preferably 10 to 200 nm, more preferably 100 to 200 nm, and further preferably 150 to 180 nm from the viewpoint of production efficiency.

  Moreover, you may irradiate the ultraviolet-ray with the same or different wavelength in multiple times from a viewpoint of production efficiency. For example, when irradiating ultraviolet rays having different wavelengths twice, it is preferable to use any one of a high pressure mercury lamp, a metal halide lamp, and a microwave type electrodeless lamp as an ultraviolet ray generation source in the first irradiation. 200 to 380 nm is preferable, 280 to 380 nm is more preferable, and 315 to 380 nm is more preferable. Subsequently, in the second irradiation, it is preferable to use a xenon excimer lamp as an ultraviolet ray generation source, and the wavelength of the ultraviolet ray is preferably 10 to 200 nm, more preferably 100 to 200 nm, and further preferably 150 to 180 nm.

Integrated light quantity of ultraviolet irradiation is preferably from ^{1.5~10J / cm 2, 2.5~7J / cm} 2 is more preferable. When the integrated light amount is 1.5 J / cm ² or more, a desired layer [A] composition that suppresses oxidation can be obtained, and when the integrated light amount is 10 J / cm ² or less, damage to the substrate is achieved. Can be reduced, which is preferable.

  Moreover, in this invention, in order to improve production efficiency in the case of ultraviolet treatment, it is more preferable to perform ultraviolet treatment, heating the coating film after humidification. As heating temperature, 40-100 degreeC is preferable and 50-80 degreeC is more preferable. A heating temperature of 40 ° C. or higher is preferable because high production efficiency can be obtained, and a heating temperature of 100 ° C. or lower is less likely to cause deformation or alteration of other materials such as a base material, and the layer [A] is oxidized. Since it can suppress, it is preferable.

[Inorganic layer [B]]
In the laminated body of this invention, it is preferable to have an inorganic layer [B] between a base material and layer [A] from a viewpoint from which a high gas barrier property and high film quality stability are acquired. By including the inorganic layer [B] on the base material side of the layer [A], the element ratio O / Si of the layer [A] is present in a region satisfying the range of 0 <O / Si <0.150. The bond can be protected from the substrate side, and the film quality stability of the layer [A] is improved. Therefore, by having the inorganic layer [B] between the base material and the layer [A], it is possible to realize high gas barrier properties and high film quality stability as the whole laminate.

  The inorganic layer [B] of the present invention is at least one element selected from the group consisting of zinc, silicon, tin, aluminum, indium, titanium, silver, zirconium, niobium, molybdenum and palladium from the viewpoint of obtaining high gas barrier properties. It is preferable to contain. As long as the above is satisfied, other elements, oxides, nitrides, sulfides, or a mixture thereof may be contained. Moreover, it is more preferable that the inorganic layer [B] contains zinc and silicon from the viewpoint of obtaining high gas barrier properties.

  The thickness of the inorganic layer [B] in the present invention is preferably 10 nm or more and 1,000 nm or less as the thickness of the layer exhibiting gas barrier properties. 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 plane. In addition, when the thickness of the layer is greater than 1,000 nm, the stress remaining in the layer increases, so that the inorganic layer [B] is liable to crack due to bending or external impact, and the gas barrier properties are increased with use. May decrease. Therefore, the thickness of the inorganic layer [B] is preferably 10 nm or more and 1,000 nm or less, and more preferably 50 nm or more and 500 nm or less from the viewpoint of ensuring flexibility. The thickness of the inorganic layer [B] can be measured from a cross-sectional observation image by TEM.

  The center plane average roughness SRa of the inorganic layer [B] in the present invention is preferably 10 nm or less. When SRa is larger than 10 nm, the irregular shape on the surface of the inorganic layer [B] becomes large, and gaps are formed between the stacked particles, so that the film quality is difficult to be dense and the gas barrier property is improved even if the film thickness is increased. The effect may be difficult to obtain. Further, when SRa is larger than 10 nm, the film quality of the layer [A] laminated on the inorganic layer [B] is not uniform, and the gas barrier property may be lowered. Therefore, SRa of the inorganic layer [B] is preferably 10 nm or less, and more preferably 7 nm or less. SRa of the inorganic layer [B] in the present invention can be measured using a three-dimensional surface roughness measuring machine.

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

Furthermore, from the viewpoint of obtaining high gas barrier properties and high film quality stability, the inorganic layer [B] preferably satisfies the following [B1] and / or [B2].
Inorganic layer [B1]: Inorganic layer consisting of coexisting phases of (i) to (iii) (i) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide inorganic layer [B2]: From the coexisting phase of zinc sulfide and silicon dioxide Hereinafter, details of each of the inorganic layers [B1] and [B2] will be described.

[Inorganic layer [B1]]
In the present invention, (i) zinc oxide, (ii) silicon dioxide, and (iii) a coexisting phase of aluminum oxide (hereinafter referred to as (i) zinc oxide, (ii) silicon dioxide, And (iii) the inorganic layer [B1], which is a layer composed of the coexisting phase of aluminum oxide (sometimes referred to as “zinc oxide-silicon dioxide-aluminum oxide coexisting phase”) will be described in detail. In addition, the “zinc oxide-silicon dioxide-aluminum oxide coexisting phase” 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 inorganic layer [B1] in the laminate 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 the non-silicon dioxide It is presumed that the coexistence of the crystalline component suppresses crystal growth of zinc oxide, which tends to generate microcrystals, and the particle size is reduced, so that the layer is densified and the permeation of water vapor is suppressed.

  In addition, the coexistence of aluminum oxide can suppress the crystal growth more than the case of coexistence of zinc oxide and silicon dioxide, so that the layer can be further densified, and accordingly, cracks during use can be reduced. It is considered that the gas barrier property deterioration due to the generation could be suppressed.

  The composition of the inorganic layer [B1] is such that the zinc atom concentration is 1 to 35 atm%, the silicon atom concentration is 5 to 25 atm%, the aluminum atom concentration is 1 to 7 atm%, and the oxygen atom concentration is 50 to 70 atm%. preferable. When the zinc atom concentration is less than 1 atm% or the silicon atom concentration is more than 25 atm%, the ratio of zinc atoms that make the gas barrier layer a highly flexible property decreases, so the flexibility of the laminate decreases. There is. From this viewpoint, the zinc atom concentration is more preferably 3 atm% or more. If the zinc atom concentration is higher than 35 atm% or the silicon atom concentration is lower than 5 atm%, the ratio of silicon atoms decreases, so that the gas barrier layer tends to become a crystal layer and cracks are likely to occur. From this viewpoint, the silicon atom concentration is more preferably 7 atm% or more. When the aluminum atom concentration is less than 1 atm%, the affinity between zinc oxide and silicon dioxide is impaired, and therefore there are cases where voids and defects are likely to occur in the gas barrier layer. On the other hand, if the aluminum atom concentration is higher than 7 atm%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that cracks are likely to occur against heat and external stress. When the oxygen atom concentration is less than 50 atm%, zinc, silicon, and aluminum are insufficiently oxidized, and the light transmittance may decrease. On the other hand, when the oxygen atom concentration is higher than 70 atm%, oxygen is taken in excessively, so that voids and defects increase, and the gas barrier property may deteriorate.

  The composition of the inorganic layer [B1] 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, the inorganic layer [B1] It is possible to adjust the composition of the layer [B1].

  The composition of the inorganic layer [B1] can be determined by a conventionally known composition analysis method, and can be measured, for example, by XPS analysis. Here, since the outermost surface of the inorganic layer [B1] is generally over-oxidized and differs from the internal composition ratio, the outermost layer is etched by about 5 nm by sputter etching using argon ions as a pretreatment for analysis by XPS analysis. Then, the atomic concentration obtained by performing composition analysis is defined as the atomic concentration in the present invention. In addition, when the layer is further laminated | stacked on inorganic layer [B1], it can measure by XPS analysis, after removing a layer by ion etching or a chemical | medical solution process as needed.

[Inorganic layer [B2]]
Next, the coexisting phase of zinc sulfide and silicon dioxide (hereinafter referred to as the coexisting phase of zinc sulfide and silicon dioxide is referred to as “zinc sulfide-silicon dioxide coexisting phase”) that is preferably used as the inorganic layer [B] in the present invention. The details of the inorganic layer [B2], which is a layer formed from the above, 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 silicon dioxide or SiO It shall be written as ₂ . Regarding the deviation of the composition ratio from the chemical formula, the same applies to zinc sulfide, and it is expressed as zinc sulfide or ZnS regardless of the deviation of the composition ratio depending on the conditions at the time of production.

  The reason why the gas barrier property is improved by applying the inorganic layer [B2] in the laminate of the present invention is that the crystalline component contained in the zinc sulfide and the amorphous component of silicon dioxide in the zinc sulfide-silicon dioxide coexisting phase It is presumed that the coexistence with the above suppresses the crystal growth of zinc sulfide, which is likely to produce microcrystals, and the particle diameter is reduced, so that the layer is densified and the permeation of 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. On the other hand, since it becomes a layer which is hard to generate | occur | produce a crack, it is thought that the gas barrier property fall resulting from the production | generation of the crack at the time of use was also suppressed by applying this inorganic layer [B2].

  The inorganic layer [B2] is preferably composed of a composition in which the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. 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 silicon dioxide to suppress zinc sulfide crystal growth, resulting in an increase in voids and defects, resulting in the prescribed gas barrier properties. May not be obtained. In addition, if the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is smaller than 0.7, the amorphous component of silicon dioxide inside the inorganic layer [B2] increases and the flexibility of the layer decreases. The flexibility to mechanical bending may be reduced. A more preferable range of the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.75 to 0.85.

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

  In the composition analysis of the inorganic layer [B2], 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 are analyzed. And the composition ratio of other inorganic oxides contained. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis. In Rutherford backscattering method, a charged particle accelerated by a high voltage is irradiated on a sample, and the number of charged particles bounced from the sample and the element are identified and quantified from the energy, and the composition ratio of each element can be known. Note that since the inorganic layer [B2] 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 an inorganic layer or a resin layer is further laminated on the inorganic layer [B2], the layer is removed by ion etching or chemical treatment as necessary, and then analyzed by ICP emission spectroscopic analysis and Rutherford backscattering method. be able to.

As described above, by satisfying [B1] and / or [B2] as the inorganic layer [B], higher gas barrier properties and high film quality stability can be obtained, but the inorganic layer [B] is limited to the above. It is also preferable that the inorganic layer [B] satisfy the following [B3] instead of the above. Moreover, you may apply the inorganic layer [B4] which consists of aluminas as another inorganic layer [B].
Inorganic layer [B3]: Inorganic layer mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0 Hereinafter, details of inorganic layers [B3] and [B4] will be described. To do.

[Inorganic layer [B3]]
The inorganic layer [B3], which is preferably used as the inorganic layer [B] in the present invention and has a silicon oxide as a main component and having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0, will be described in detail. To do. Here, the main component means that the silicon oxide is 60% by mass or more of the entire inorganic layer [B3], and preferably 80% by mass or more. Incidentally, silicon dioxide (SiO _2), depending on the conditions at the time of generation, those slightly deviated from the composition ratio of silicon and oxygen of the composition formula (SiO~SiO ₂₎ although it is possible to produce silicon dioxide or SiO It shall be written as ₂ . Therefore, the atomic ratio of oxygen atoms to silicon atoms is determined by XPS analysis, and all silicon oxides in the inorganic layer [B] are changed to SiO _x (x is the atomic ratio of oxygen atoms to silicon atoms determined by XPS analysis). Assuming that it is, the silicon oxide content in the inorganic layer [B] is determined.

  The formation method of the inorganic layer [B3] is preferably a CVD method capable of forming a dense film. In the CVD method, a monomer gas of an organosilicon compound described later can be activated by high-intensity plasma, and a dense film can be formed by a polymerization reaction. Examples of the organosilicon compound here include silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, propoxysilane, dipropoxysilane, tripropoxysilane, and tetrapropoxysilane. , Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethyldisiloxane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, undecamethylcyclohexa Siloxane, dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, hexamethyldisilazane, hexamethylcyclotri Razan, octamethylcyclotetrasilazane, decamethylcyclopentasiloxane silazane, such undecapeptide methyl cyclohexasilane La disilazane and the like. Of these, hexamethyldisiloxane and tetraethoxysilane are preferable in terms of safety in handling.

  The composition of the inorganic layer [B3] is such that the atomic ratio of oxygen atoms to silicon atoms is preferably in the range of 1.5 to 2.0, and more preferably in the range of 1.6 to 1.8. preferable. 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 form a dense film, but flexibility may be lowered. The composition of the inorganic layer [B3] can be determined by a conventionally known composition analysis method, and can be measured, for example, by XPS analysis.

[Inorganic layer [B4]]
Next, details of the inorganic layer [B4], which is preferably used as the inorganic layer [B] in the present invention, will be described. The inorganic layer [B4] is a layer made of alumina. The layer made of alumina is preferable from the viewpoints of cost, production equipment, coloring, food hygiene, and the like. As a method of forming the inorganic layer [B4], for example, a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of the physical vapor deposition method on the laminate include a vacuum vapor deposition method and a sputtering method. Particularly, the vacuum vapor deposition method is preferable because it is easy to control the degree of oxidation, and an electron beam vapor deposition method capable of increasing the energy of metal vapor is also available. preferable. The composition of the inorganic layer [B4] can be determined by a conventionally known composition analysis method, and can be measured, for example, by XPS analysis.

[Anchor coat layer [C]]
An anchor coat layer is preferably formed on the surface of the substrate applied to the present invention for the purpose of improving gas barrier properties, bending resistance, and adhesion. By having an anchor coat layer on the surface of the base material of the obtained laminate, the inorganic layer [B] or / and the layer [ The flatness of A] is improved, and the gas barrier properties, flex resistance and adhesion are improved.

  In order to ensure the surface diffusibility of the sputtered particles flying on the anchor coat layer during the sputtering of the inorganic layer [B], the pencil hardness of the anchor coat layer is preferably H or more and 3H or less (the pencil hardness is (Soft) 10B-B, HB, F, H-9H (hard). If it is softer than H, mixing is likely to occur when sputtered particles come in, and sufficient surface diffusivity cannot be obtained, so it may be difficult to make the inorganic layer [B] dense. On the other hand, if it is harder than 3H, the flexibility of the laminate may be impaired, and cracking may easily occur in the inorganic layer [B] and / or the layer [A].

  Examples of the material used for the anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. These may be used alone or in combination of two or more. As a material for the anchor coat layer used in the present invention, a two-part curable resin comprising a main agent and a curing agent is preferable from the viewpoint of solvent resistance, and a polyester resin, a urethane resin, and an acrylic resin are mainly used from the viewpoint of gas barrier properties and water resistance. It is more preferable to use as. The curing agent is not particularly limited as long as it does not impair the properties such as gas barrier properties and transparency, and general curing agents such as isocyanate and epoxy can be used. These anchor coat layers may contain known additives.

  The thickness of the anchor coat layer used in the present invention is preferably 0.3 to 10 μm. When the thickness of the layer is less than 0.3 μm, the surface roughness of the inorganic layer [B] and / or the layer [A] may be increased due to the influence of the unevenness of the base material, and the gas barrier property is lowered. There is a case. When the thickness of the layer exceeds 10 μm, the stress remaining in the layer of the anchor coat layer increases and the base material warps and cracks occur in the inorganic layer [B] and / or the layer [A]. May decrease. Therefore, the thickness of the anchor coat layer is preferably 0.3 to 10 μm. Furthermore, 1 to 3 μm is more preferable from the viewpoint of ensuring flexibility.

  As a method of forming an anchor coat layer on the surface of the substrate, a solvent, a diluent, etc. are added to the material of the above-mentioned anchor coat layer to form a coating, followed by a roll coating method, a gravure coating method, a knife coating method, a dip coating. An anchor coat layer can be formed by applying a coating film on a substrate by a method such as a spray coating method or the like, forming a coating film, and drying and removing a solvent, a diluent or the like. As a method for drying the coating film, a hot roll contact method, a heating medium (air, oil, etc.) contact method, an infrared heating method, a microwave heating method, or the like can be used. Among these, a gravure coating method is preferable as a method suitable for coating a layer having a thickness of 0.3 to 10 μm, which is a preferable thickness of the anchor coat layer of the present invention.

[Other layers]
On the outermost surface of the laminate of the present invention, a hard coat layer may be formed for the purpose of improving the scratch resistance within a range where the gas barrier property is not lowered, or a film made of an organic polymer compound is laminated. It is good also as a laminated structure. In addition, the outermost surface of a laminated body means the surface on the opposite side to the base material side of layer [A] after layer [A] was laminated | stacked on the base material here.

[Usage]
The laminate of the present invention can be suitably used as a gas barrier film taking advantage of high gas barrier properties against water vapor and high film quality stability.

[Electronic device]
Since the laminate of the present invention has high gas barrier properties and high film quality stability, 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. Since the electronic device using the laminate of the present invention has excellent gas barrier properties, it is possible to suppress degradation of the device performance due to water vapor or the like.

[Other uses]
Since the laminate of the present invention has high gas barrier properties and high film quality stability, it can be suitably used as a packaging film for foods and electronic parts, in addition to electronic devices.

  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. Unless otherwise stated, the number of evaluation n was 5 samples per level, and the average value of the measured values of the 5 samples obtained was used as the measurement result.

(1) Layer thickness The thickness of each layer was measured by cross-sectional observation with TEM. That is, a sample for cross-sectional observation is obtained by the FIB method using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.) (specifically, “Polymer Surface Processing” (by Atsushi Iwamori) p. 118-119). (Based on the method described in 1). 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 layer [A], the inorganic layer [B], and the anchor coat layer were measured. . The observation magnification was adjusted so that the proportion of the layer thickness in the observation image was 30 to 70%.

(2) Water vapor permeability (g / (m ² · day))-1 (differential pressure method)
The measurement was performed using a water vapor transmission rate measuring device (model name: DELTAPERRM (registered trademark)) manufactured by Technolox, England, under conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 50 cm ² . The number of samples was 2 samples per level, and the number of measurements was 5 times for the same sample. Data obtained by measuring five times for one sample were averaged, and the second decimal place was rounded off to obtain an average value for the sample. Similarly, after obtaining the average value of another sample, the average value of the two samples was further averaged, and the second decimal place was rounded off to obtain the water vapor permeability (g / (m ² · day)). . However, a measurement sample of 2.0 × 10 ⁻⁴ g / (m ² · day) or less by DELTAPERRM was measured by the calcium corrosion method (3) described later.

(3) Water vapor permeability (g / (m ² · day))-2 (calcium corrosion method)
The water vapor transmission rate under an atmosphere of a temperature of 40 ° C. and a relative humidity of 90% RH was measured by the calcium corrosion method described in Japanese Patent No. 4407466. Specifically, a calcium layer having a thickness of 100 nm was formed on the surface opposite to the substrate side of the layer [A] of the laminate by vacuum deposition. Next, an aluminum layer having a thickness of 3,000 nm was formed on the calcium layer by vacuum deposition so as to cover the entire calcium layer. Further, a glass with a thickness of 1 mm was bonded to the surface of the aluminum layer via a thermosetting epoxy resin and treated at 100 ° C. for 1 hour to obtain an evaluation sample. The obtained sample was treated at a temperature of 40 ° C. and a relative humidity of 90% RH for 800 hours. After the treatment, the amount of water vapor permeated by calculating the amount of calcium corroded by water vapor was calculated as the water vapor permeability (g / (m ² · day)).

(4) Composition of inorganic layer [B1], inorganic layer [B3], and inorganic layer [B4] Composition analysis of inorganic layer [B1], inorganic layer [B3], or inorganic layer [B4] was performed by XPS analysis. That is, after removing the outermost layer by etching about 5 nm by sputter etching using argon ions, the content ratio of each element was measured. It was assumed that there was no composition gradient in the layer, and the composition ratio at this measurement point was taken as the composition ratio of the layer. When the sample to be analyzed is further laminated on the inorganic layer [B1], inorganic layer [B3] or inorganic layer [B4], the layer was removed by ion etching or chemical treatment as necessary. Later, it can be measured by XPS analysis. The measurement conditions for XPS analysis were as follows.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
Excitation X-ray: monochromic AlKα
・ X-ray output: 300W
・ X-ray diameter: 800μm
-Photoelectron escape angle: 45 °
Ar ion etching: 2.0 kV, 10 mPa.

(5) Composition of inorganic layer [B2] The composition analysis of the inorganic layer [B2] was performed by ICP emission spectroscopic analysis (SPS4000, manufactured by SII Nanotechnology). The sample sampled at the stage of forming the inorganic layer [B2] on the base material or undercoat layer (before the layer [A] is laminated) is thermally decomposed with nitric acid and sulfuric acid, heated and dissolved with dilute nitric acid, and filtered. did. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom and a silicon atom was measured. Next, based on this value, the Rutherford backscattering method (AN-2500 manufactured by Nissin High Voltage Co., Ltd.) was used to quantitatively analyze zinc atoms, silicon atoms, sulfur atoms, oxygen atoms, and zinc sulfide. And the composition ratio of silicon dioxide. When the sample to be analyzed is a layer in which the layer [A] is laminated on the inorganic layer [B2], the composition analysis of the inorganic layer [B2] is performed after removing the layer [B] by ion sputtering. Do.

(6) Composition distribution in the thickness direction of the layer [A] The composition distribution in the thickness direction of the layer [A] was measured using a method in which XPS analysis and ion etching were used in combination. Since the etching rate of the laminate of the present invention varies from layer to layer, the thickness per layer obtained by cross-sectional observation using the above-mentioned TEM was obtained from XPS analysis once obtained based on the etching rate in terms of SiO ₂ . While comparing with the composition distribution in the thickness direction, each layer in the composition distribution in the thickness direction was specified. The thickness direction was corrected by applying a coefficient to the thickness of each layer obtained from XPS analysis so that the thickness of each layer obtained from XPS analysis and the thickness of each layer obtained from cross-sectional observation coincided.
The measurement conditions were as follows.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
Excitation X-ray: monochromic AlKα
・ X-ray output: 300W
・ X-ray diameter: 800μm
-Photoelectron escape angle: 45 °
Ar ion etching: 2.0 kV, 10 mPa
・ Etching depth per measurement point: 2 nm
Here, since the etching depth per measurement point is 2 nm, having a region satisfying the O / Si range of the layer [A] in the thickness direction of 20 nm or more satisfies the O / Si range. The length of the line segment obtained by connecting the continuous measurement points satisfying a certain range of O / Si in the layer [A] is 20 nm or more in the thickness direction. There will be.

(7) Presence / absence of component having Si—H bond in layer [A] The presence / absence of a component having Si—H bond in layer [A] was confirmed by Fourier transform infrared spectroscopy. That is, the laminate was sampled to 10 mm × 10 mm, the surface of the layer [A] was pressure-bonded to an ATR crystal, measured under the following measurement conditions, and a peak derived from Si—H at 2,140-2,260 cm ⁻¹ . The presence or absence of was confirmed. When there was a peak, it was judged that the component which has Si-H bond was included, and when there was no peak, it was judged that the component which has Si-H bond was not included.
The measurement conditions were as follows.
・ Apparatus: FT / IR-6100
・ Light source: Standard light source ・ Detector: GTS
・ Resolution: 4cm ^-1
Number of integration: 256 times Measurement method: attenuated total reflection (ATR) method Measurement wave number range: 4,000 to 600 cm ^-1
ATR crystal: Ge prism, incident angle: 45 °.

(8) Film quality stability of layer [A] The film quality stability of layer [A] was judged by the change before and after the wet heat treatment in the presence or absence of a component having a Si—H bond in layer [A]. First, two samples of a laminate sampled at 10 mm × 10 mm were prepared, and for one sample, the presence or absence of a component having a Si—H bond in the layer [A] was performed by the method (7) described above without performing wet heat treatment. confirmed. Thereafter, the remaining one specimen was subjected to a wet heat treatment for 72 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 90% RH, and after the wet heat treatment, the component having the Si—H bond of the layer [A] by the method (7) described above. The presence or absence was confirmed. From the changes before and after the wet heat treatment, the film quality stability was judged as follows.
○: Contains a component having a Si—H bond before and after the wet heat treatment ×: Contains a component having a Si—H bond before the wet heat treatment, but does not contain a component having a Si—H bond after the wet heat treatment— It does not contain a component having Si-H bonds in the front and rear.

[Formation of Anchor Coat Layer [C] in Examples and Comparative Examples]
On the base material, as a coating liquid for forming an anchor coat layer, a coating liquid A was prepared by diluting 100 parts by mass of urethane acrylate (Forseed 420C manufactured by China Paint Co., Ltd.) with 70 parts by mass of toluene. Next, coating liquid A was applied to one side of the polymer film 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 (peak wavelength 365 nm). Irradiated with 0.0 J / cm ² and cured, an anchor coat layer having a thickness of 1 μm was provided.

[Method for Forming Inorganic Layer [B1] in Examples and Comparative Examples]
Using a winding-type sputtering apparatus, a sputter target (zinc oxide / silicon dioxide / aluminum oxide composition mass ratio of 77), which is a mixed sintered material formed of zinc oxide, silicon dioxide, and aluminum oxide on one side of the substrate. / 20/3), sputtering was performed under the following conditions to provide an inorganic layer [B1]. As for the composition of the inorganic layer [B1], the Zn atom concentration was 27.6 atm%, the Si atom concentration was 13.1 atm%, the Al atom concentration was 2.3 atm%, and the O atom concentration was 57.0 atm%.
・ Decompression degree: 2 × 10 ⁻¹ Pa
Introducing gas: Argon gas amount 45 ccm, oxygen gas amount 5 ccm
-Electric power: Applied power of 4,000 W is applied from a DC power source.

[Method for Forming Inorganic Layer [B2] in Examples and Comparative Examples]
Using a winding type sputtering apparatus, a sputter target (zinc sulfide / silicon dioxide molar composition ratio is 80/20), which is a mixed sintered material formed of zinc sulfide and silicon dioxide, on one side of the substrate Sputtering was performed under the following conditions to provide the inorganic layer [B2]. As for the composition of the inorganic layer [B2], the molar fraction of zinc sulfide was 0.80.
・ Decompression degree: 2 × 10 ⁻¹ Pa
・ Introducing gas: Argon gas ・ Power: 500 W of applied power is applied from a high frequency power source.

[Method for Forming Inorganic Layer [B3] in Examples and Comparative Examples]
Using a roll-up type CVD apparatus, chemical vapor deposition was performed on one side of the substrate using hexamethyldisiloxane as a raw material under the following conditions to provide an inorganic layer [B3]. In the composition of the inorganic layer [B3], the atomic ratio of oxygen atoms to silicon atoms was 1.95.
・ Decompression degree: 2 × 10 ⁻¹ Pa
Introducing gas: Oxygen gas 0.5 L / min, hexamethyldisiloxane 70 cc / min. Electric power: An applied power of 3,000 W is applied to the CVD electrode from a high frequency power source.

[Method for Forming Inorganic Layer [B4] in Examples and Comparative Examples]
Using a wind-up type vacuum deposition apparatus, aluminum of purity 99.99 mass% is heated and evaporated with an electron beam (output 5.1 kW) on one side of the substrate, and oxygen gas (2.0 L / min) is converted into metal vapor. An inorganic layer [B4] composed of a vapor-deposited thin film layer of alumina was provided in the same direction.

(Example 1: Sample 1)
A 100 μm thick polyethylene terephthalate (PET) film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) is used as a base material, and an anchor coat layer [C] is provided on one side of the base material. An inorganic layer [B1] was provided as a layer [B] to a thickness of 150 nm.

Subsequently, 100 parts by mass of a perhydropolysilazane solution (“NN120-20” manufactured by Merck Performance Materials LLC) in dibutyl ether as a coating liquid for forming layer [A], 100 parts by mass of dibutyl ether and 200 parts by mass of diisopropyl ether The coating liquid I is prepared by diluting the coating liquid I under a nitrogen stream, and the coating liquid 1 is applied onto the inorganic layer [B1] with a slit die coater (coating liquid supply means: syringe pump) in order to suppress oxidation of the layer [A]. It was applied and dried at 100 ° C. for 1 minute. Next, ultraviolet treatment was performed under the following treatment conditions to obtain a laminate provided with a layer [A] having a thickness of 150 nm.
・ Lamp model: MEBF-440HQ (MDI Excimer)
UV source: 172 nm xenon excimer lamp Irradiation intensity: 250 mW / cm ²
・ Introduced gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 5.0 J / cm ²
-Sample temperature control: 70 ° C.

(Example 2: Sample 2)
A laminate was obtained in the same manner as Sample 1, except that the discharge amount during the formation of the layer [A] was adjusted to change the thickness of the layer [A] to 400 nm.

(Example 3: Sample 3)
A laminate was obtained in the same manner as Sample 1, except that the discharge amount during the formation of the layer [A] was adjusted to change the thickness of the layer [A] to 550 nm. On the surface on the layer [A] side of the obtained laminate, the occurrence of cracks at locations unnecessary for measurement was visually confirmed, but the evaluation was continued using the other locations.

(Example 4: Sample 4)
A laminate was obtained in the same manner as Sample 1, except that the discharge amount during the formation of the layer [A] was adjusted to change the thickness of the layer [A] to 70 nm.

(Example 5: Sample 5)
A laminate was obtained in the same manner as Sample 1, except that the base material was changed to a cycloolefin polymer (COP) film having a thickness of 50 μm (“ZEONOR FILM” (registered trademark) ZF-14, manufactured by ZEON CORPORATION).

(Example 6: Sample 6)
A laminate was obtained in the same manner as Sample 1, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B2] having a thickness of 150 nm.

(Example 7: Sample 7)
A laminate was obtained in the same manner as Sample 1, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B3] having a thickness of 300 nm.

(Example 8: Sample 8)
A laminate was obtained in the same manner as Sample 1, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B4] having a thickness of 20 nm.

(Comparative Example 1: Sample 9)
A laminated body was obtained in the same manner as Sample 1, except that the inorganic layer [B] was not provided and the layer [A] was directly laminated on the anchor coat layer [C].

(Comparative Example 2: Sample 10)
A laminate was obtained in the same manner as in Example 1 except that the discharge amount during the formation of the layer [A] was adjusted to change the thickness of the layer [A] to 40 nm and the ultraviolet treatment was changed to the following treatment conditions. .
・ Lamp model: MEBF-440HQ (MDI Excimer)
UV source: 172 nm xenon excimer lamp Irradiation intensity: 250 mW / cm ²
・ Introduced gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 1.5 J / cm ²
-Sample temperature control: 70 ° C.

(Comparative Example 3: Sample 11)
A laminate was obtained in the same manner as in Example 1 except that the ultraviolet treatment during the formation of the layer [A] was changed to the following treatment conditions. On the surface on the layer [A] side of the obtained laminate, the generation of film wrinkles was visually confirmed, but the evaluation was continued as it was.
UV treatment device: CV-110QC-G (manufactured by Heraeus Co., Ltd.)
-Lamp model: LH-10-10
・ Peak wavelength: 365nm
・ Valve: H valve ・ Introducing gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 3.0 J / cm ²
-Sample temperature control: 22 ° C.

(Comparative Example 4: Sample 12)
A laminate was obtained in the same manner as in Example 1 except that the ultraviolet treatment during the formation of the layer [A] was changed to the following treatment conditions.
UV treatment device: CV-110QC-G (manufactured by Heraeus Co., Ltd.)
-Lamp model: LH-10-10
・ Peak wavelength: 365nm
・ Valve: H valve ・ Introducing gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 1.5 J / cm ²
-Sample temperature control: 22 ° C.

(Comparative Example 5: Sample 13)
A laminate was obtained in the same manner as in Example 1 except that the ultraviolet treatment after drying at the time of forming the layer [A] was changed to wet heat treatment under the following conditions.
Processing temperature: 85 ° C
Processing humidity: 85% RH
Processing time: 96 hours.

(Comparative Example 6: Sample 14)
Except for changing the inorganic layer [B] from the inorganic layer [B1] to the inorganic layer [B4] having a thickness of 20 nm and changing the coating liquid for forming the layer [A] from the coating liquid I to the following coating liquid II. In the same manner as in Example 1, a laminate was obtained.

  Perhydropolysilazane solution in dibutyl ether (“NAX120-20” manufactured by Merck Performance Materials LLC), perhydropolysilazane solution in dibutyl ether containing amine catalyst (“NAX120 manufactured by Merck Performance Materials LLC”) −20 ”) 20 parts by mass was diluted with 150 parts by mass of dibutyl ether and 150 parts by mass of diisopropyl ether to prepare a coating solution II.

(Comparative Example 7: Sample 15)
A laminate was obtained in the same manner as Sample 1 except that the layer [A] was not provided.

(Comparative Example 8: Sample 16)
A laminate was obtained in the same manner as Sample 1 except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B2] having a thickness of 150 nm and the layer [A] was not provided.

(Comparative Example 9: Sample 17)
A laminate was obtained in the same manner as Sample 1 except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B3] having a thickness of 300 nm and the layer [A] was not provided.

(Comparative Example 10: Sample 18)
A laminated body was obtained in the same manner as Sample 1 except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B4] having a thickness of 20 nm and the layer [A] was not provided.

  The evaluation results of the obtained laminate are shown in Table 1.

  As is clear from Table 1, the laminates of Examples 1 to 8 (Samples 1 to 8) of the present invention have higher gas barriers than the corresponding laminates of Comparative Examples 1 to 10 (Samples 9 to 18). And high film quality stability.

  Since the laminate 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 a member for electronic devices such as thin televisions and solar cells. The application is not limited to these.

1 base material 2 layer [A]
3 Inorganic layer [B]
4 Anchor coat layer [C]

Claims (5)

  A laminate having a layer [A] containing Si, O and N on at least one side of a substrate, wherein the element ratio O / Si of the layer [A] is 0 <O / Si <0.150 The laminated body which has the area | region which satisfy | fills the range of 20 nm or more in the thickness direction.   The laminate according to claim 1, wherein the layer [A] has a region in which the element ratio O / Si satisfies a range of 0 <O / Si <0.130 in the thickness direction of 20 nm or more.   The laminate according to claim 1 or 2, wherein the layer [A] has a region in which the element ratio O / Si satisfies a range of 0 <O / Si <0.100 in a thickness direction of 20 nm or more.   An inorganic layer [B] is provided between the substrate and the layer [A], and the inorganic layer [B] is zinc, silicon, tin, aluminum, indium, titanium, silver, zirconium, niobium, molybdenum. The laminate according to any one of claims 1 to 3, comprising at least one element selected from the group consisting of palladium and palladium.   The laminate according to claim 4, wherein the inorganic layer [B] contains zinc and silicon.

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