JP2018140552A - 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 an inorganic layer [A] 2 containing Si, O and N on at least one side of a substrate 1, and in which the inorganic layer [A] satisfies the formula (1) at all measurement points in the depth direction and the inorganic layer [A] satisfies the formula (2). An inorganic layer [B] 3 may be provided between the substrate and the inorganic layer [A]. Formula (1): [SiOH/Si]>0.02; Formula (2): [SiOH/Si]>[SiOH/Si].SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate used for 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). In addition, as a gas barrier property improving technique other than a film forming method such as a plasma CVD method, a method of forming a silicon oxide film by a liquid phase deposition method (Patent Document 2), or a polysilazane film coated on a substrate is a silicon oxide film. And a method of converting into a silicon oxynitride film (Patent Documents 3 to 9).

Japanese Patent No. 3859518 JP 2002-072177 A Japanese Patent No. 5734675 Japanese Patent No. 5444722 Japanese Patent No. 5531892 International Publication No. 2011-074440 International Publication No. 2015/115314 International Publication No. 2016/052123 JP 2015-149404 A

  However, as in Patent Document 1, the method of forming an inorganic layer mainly composed of silicon oxide by plasma CVD does not provide stable and high gas barrier properties because it is difficult to suppress defects in the inorganic layer. It was. Further, Patent Document 2 discloses an effect of preventing gas permeation and improving adhesion by forming a layer mainly composed of silicon oxide containing a silanol group by a liquid phase deposition method. However, the gas barrier property was insufficient, the composition between the surface layer side and the inside of the layer was not changed, and the durability was insufficient. Further, Patent Document 3 (inhibiting the formation of silicon oxide and silanol structures and forming an inorganic layer having a high nitrogen concentration region) and Patent Document 4 (silanol by removing water) formed an inorganic layer with polysilazane on a substrate. In the case of forming a modified layer having a different nitrogen content on the surface by promoting the dehydration reaction of the structure, the presence of the Si—OH structure in the layer is insufficient, and the layer is further formed by gas permeation from the substrate side. However, the oxidation inside the polysilazane layer easily proceeds from the substrate side, and the film quality stability under high temperature and high humidity was insufficient. In addition, a polysilazane layer is formed on the gas barrier layer, and Patent Document 5 (a moisture trap layer that suppresses silanolation is formed inside the polysilazane layer by the first gas barrier layer) and Patent Document 6 (second In the case of forming a polysilazane layer on the gas barrier layer and forming a layer containing a silanol group on the substrate side of the polysilazane layer and a gas barrier layer not containing a silanol group on the surface side) As a result, the oxidized region on the surface layer side lacks the ability to protect the inside of the layer due to the lack of Si—OH structure, and the composition (structure) change between the surface layer side and the inside of the layer is also insufficient. The film quality stability of was insufficient. Furthermore, due to insufficient performance of the underlying gas barrier layer, the oxidation inside the polysilazane layer could not be suppressed from the substrate side, and as shown in the comparative examples described later, the bending resistance was insufficient. In Patent Documents 7 and 8, a polysilazane layer is formed on a gas barrier layer having high performance. However, conditions for forming the polysilazane layer (such as exposure of the coating liquid to the atmosphere during coating) and coating composition Depending on the conversion conditions, the suppression of oxidation inside the polysilazane layer was insufficient, the composition (structure) change between the surface layer side and the inside of the layer was insufficient, and the durability was lowered as shown in Comparative Examples described later. Further, although Patent Document 9 attempts to suppress oxidation of the silicon oxynitride film, the compatibility between the Si—O structure on the surface layer side and the Si—OH structure is insufficient, and the composition change between the surface layer side and the inside of the layer is insufficient. Further, the durability was lowered, and sufficient gas barrier properties were not obtained for electronic device applications.

  In view of the background of such prior art, the present invention provides a laminate having a high gas barrier property against water vapor and film quality stability under high temperature and high humidity without being thickened or multilayered, and at the same time having a bending resistance. Is to provide.

In order to solve this problem, the present invention employs the following configuration.
[1]
A laminate having an inorganic layer [A] containing Si, O, and N on at least one surface of a substrate, wherein the inorganic layer [A] satisfies the formula (1) at all measurement points in the depth direction. And the laminated body with which the said inorganic layer [A] satisfy | fills Formula (2).
Formula (1): [SiOH / Si]> 0.02
Formula (2) [SiOH / Si] _{A20 or less} > [SiOH / Si] _{A20 super}
[SiOH / Si]: Ratio of relative ionic strength SiOH ⁺ detected by Tof-SIMS analysis to relative ionic strength Si ⁺ [SiOH / Si] _{A20 or less} : depth from the surface side in the depth direction of the inorganic layer [A] [SiOH / Si] average value [SiOH / Si] in the region of 0 nm or more and 20 nm or less: more than _A20 : in the region where the depth from the surface side in the depth direction of the inorganic layer [A] is more than 20 nm Average value of [SiOH / Si] [2]
The laminate according to [1], wherein the [SiOH / Si] _{A20 or less} is 0.05 or more.
[3]
The laminate according to [1] or [2], wherein the [SiOH / Si] _{A20 or more} is less _than 0.1.
[4]
Between the base material and the inorganic layer [A], there is an inorganic layer [B], and the inorganic layer [B] is zinc, silicon, tin, aluminum, indium, titanium, silver, zirconium, niobium, The laminate according to any one of [1] to [3], containing at least one element selected from the group consisting of molybdenum and palladium.
[5]
The laminate according to [4], wherein the inorganic layer [B] contains at least silicon and zinc.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which has the high gas barrier property with respect to water vapor | steam, the film quality stability under high temperature and high humidity, and a bending resistance simultaneously 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. It is sectional drawing which showed an example of the bending resistance test 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 high gas barrier properties against water vapor and the like, film quality stability under high temperature and high humidity, and at the same time bending resistance, and at least one side of the substrate. And an inorganic layer [A] containing Si, O and N, wherein the inorganic layer [A] satisfies the formula (1) at all measurement points in the depth direction, and the inorganic layer [A] A] satisfies the formula (2). Thus, the inventors have found that the above-described problems can be solved.

  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 the adhesion and smoothness, the surface of the substrate on the side on which the inorganic layer [A] is formed has corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, organic matter or inorganic matter, 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 inorganic 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.

[Inorganic layer [A]]
In the present invention, the inorganic layer [A] contains Si, O, and N, satisfies the formula (1) at all measurement points in the depth direction, and the inorganic layer [A] satisfies the formula (2). Is preferred.
Formula (1): [SiOH / Si]> 0.02
Formula (2) [SiOH / Si] _{A20 or less} > [SiOH / Si] _{Over A20} .

Here, [SiOH / Si] in the formula (1) is a ratio of relative ionic strength SiOH ⁺ and relative ionic strength Si ⁺ detected by Tof-SIMS (Time-Of-Flight Secondary Ion Spectrometry) analysis. In addition, [SiOH / Si] _{A20 or less} and [SiOH / Si] _A20 above in the formula (2) are the surface in the depth direction of the inorganic layer [A] measured under the conditions described in the Examples section, respectively. Surface of the inorganic layer [A] in the depth direction measured with the average value of [SiOH / Si] at the measurement points in the region where the depth from the side is 0 nm or more and 20 nm or less, and the conditions described in the Examples section It is an average value of [SiOH / Si] at measurement points in a region where the depth from the side exceeds 20 nm.

  Here, all measurement points in the depth direction of the inorganic layer [A] are all the measurement points obtained in the depth direction of the inorganic layer [A] when measurement is performed under the conditions described in the section of the examples. Refers to the measurement point. Moreover, satisfy | filling Formula (1) with all the measurement points in the depth direction of inorganic layer [A] is obtained in the depth direction of inorganic layer [A] measured on the conditions described in the term of the Example. Satisfying the expression (1) for all the measurement points.

Also, that the inorganic layer [A] satisfies the formula (2) means that the depth from the surface side in the depth direction of the inorganic layer [A] is an average value in a region of 0 nm or more and 20 nm or less ([SiOH / Si] _{A20 below)} refers to a greater than the average value of the measurement point in the region depth is 20nm than from the surface side in the depth direction of the inorganic layer _{[a] ([SiOH / Si} ] A20 _greater).

  The fact that the inorganic layer [A] satisfies the formula (1) at all measurement points in the depth direction indicates that the inorganic layer [A] has an Si—OH structure and an Si—H structure in the entire layer. The fact that the inorganic layer [A] satisfies the formula (2) has a change in the structure in which the inorganic layer [A] is included in the surface side 20 nm region and the region other than the surface side 20 nm region (region inside the layer). In addition, the region on the surface side of 20 nm is a region where both the Si—OH structure and the Si—O structure are present, and the region inside the layer is a region where both the Si—OH structure and the Si—NH structure are present. Represent. Here, the region of 20 nm on the surface side is a region of 0 nm or more and 20 nm or less in the depth direction from the surface of the inorganic layer [A] opposite to the substrate.

  The reason why a laminated body having high gas barrier properties and stability of film quality under high temperature and high humidity and at the same time bending resistance can be obtained by applying the inorganic layer [A] of the present invention is estimated as follows. ing.

  First, in the inorganic layer [A] containing Si, O, and N, by satisfying the formula (1) at all measurement points in the depth direction, the inorganic layer [A] has an Si—OH structure and Si in the entire layer. It has a -H structure and the layer exhibits flexibility. The existence of a measurement point that does not satisfy the formula (1) means that there is a region that does not satisfy the formula (1). In this case, the film is excessively dense with few Si—OH and Si—H structures. Thus, flexibility is insufficient, cracks are likely to occur due to heat and external stress, and gas barrier properties may be reduced. Next, in addition to flexibility, the Si—H structure can also impart water repellent properties (hydrophobicity), making it difficult for water molecules to be stably present and exhibiting high gas barrier properties. Furthermore, since the inorganic layer [A] has a sufficient Si—OH structure and Si—H structure, adhesion in the interface region on the substrate side of the inorganic layer [A] is improved, and gas barrier properties due to layer peeling are improved. Prevent decline. In particular, when laminating the inorganic layer [B] and the inorganic layer [A], which will be described later, in the vicinity of the surface of the inorganic layer [B] on the side on which the inorganic layer [A] is to be formed, These defects are filled with a component constituting the inorganic layer [A], and it is possible to develop a high barrier property, and the adhesion in the interface region between the inorganic layer [A] and the inorganic layer [B] is also improved.

  Subsequently, when the inorganic layer [A] satisfies the formula (2), the inorganic layer [A] has a change in the structure including the surface side 20 nm region and the region inside the layer, and the surface side region 20 nm. Is a region where both the Si—OH structure and the Si—O—Si structure are present, and the region inside the layer is a region where both the Si—OH structure and the Si—NH structure are present.

  The region inside the layer is a region where oxidation is suppressed, in which there are many Si—NH structures as well as the aforementioned Si—OH structure and Si—H structure. Since oxygen atoms interact strongly with water molecules and easily form hydrogen bonds, a region where an excessive amount of Si—O structure exists 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. In addition, when a large amount of Si-NH structure is present, flexibility can be imparted, stress generated when the laminate of the present invention is bent can be relaxed, and deterioration in gas barrier properties due to crack generation can be suppressed, and bending resistance can be prevented. This is an excellent area.

  On the other hand, the region on the surface side of 20 nm is a region in which more Si—O—Si structures are formed in addition to the Si—OH structure described above. The Si—NH structure that causes low density does not remain only on the surface side, and the surface side is made a region having a higher film density than the inside of the layer, so that a highly reactive Si—NH structure existing inside the layer Can be protected from the surface side, and the film quality stability of the inorganic layer [A] is improved. When the surface side 20 nm region contains a lot of Si—NH structure and the inorganic layer [A] does not satisfy the formula (2), the film quality stability of the inorganic layer [A] is lowered, and the surface side Si— The NH structure reduces the film density on the surface side, and the Si-NH structure on the surface side reacts with oxygen in the air to promote the oxidation of the layer and the oxidation proceeds to the inside of the layer, so that the entire layer is flexible. Become scarce.

Furthermore, from the viewpoint of obtaining high gas barrier properties, film quality stability under high temperature and high humidity, and bending resistance, [SiOH / Si] _{A20 or less} is preferably 0.05 or more, and 0.1 or more. It is more preferable. [SiOH / Si] When _{A20 or less} is 0.05 or more, the region of 20 nm on the surface side of the inorganic layer [A] becomes a region where oxidation has progressed to protect the Si—NH structure in the region inside the layer. The film quality stability of the layer [A] is improved.

Further, from the viewpoint of obtaining high gas barrier properties, film quality stability under high temperature and high humidity, and flex resistance, it is preferable that [SiOH / Si] _A20 exceeds 0.1. [SiOH / Si] When _A20 is less than 0.1, the region inside the inorganic layer [A] has a Si—NH structure and a Si—NH structure, and has a gas barrier property and flexibility. Is a compatible area.

  In addition, from the viewpoint of obtaining a laminate having high bending resistance, the inorganic layer [A] is preferably a layer present in the outermost layer of the laminate. When a layer having a highly reactive Si—NH structure is further present on the 20 nm region on the outermost surface side of the inorganic layer [A], the Si—NH structure reacts with oxygen in the air to oxidize. However, under high temperature and high humidity, the oxidation reaction becomes a driving force, and the oxidation of the inside of the inorganic layer [A] proceeds and the film quality stability may be lowered. Therefore, the 20 nm region on the outermost surface side of the inorganic layer [A] is preferably a region existing in the outermost layer of the laminate.

  Here, [SiOH / Si] in the depth direction of the inorganic layer [A] can be calculated by repeating the surface etching and the Tof-SIMS analysis.

The etching rate of the laminate of the present invention differs for each sample and each layer. Therefore, the thickness of the inorganic layer [A] up to the boundary on the substrate side is once determined based on the etching rate in terms of SiO ₂ , and a cross-sectional observation by the TEM (transmission electron microscope) of the same sample as the Tof-SIMS analysis. Based on the image, the interface of each layer is specified to determine the thickness of the inorganic layer [A]. And the thickness of the inorganic layer [A] calculated | required from Tof-SIMS analysis so that the thickness of the inorganic layer [A] calculated | required from Tof-SIMS analysis and the thickness of the inorganic layer [A] calculated | required from the cross-sectional observation image may correspond. By correcting the thickness by a coefficient, the accurate depth of the measurement value can be calculated.

In addition, regarding the boundary of the inorganic layer [A] on the substrate side, the component of the substrate or the layer adjacent on the substrate side (for example, C ⁺ ions in the case of a plastic substrate) is detected abruptly (by an order of magnitude). The measurement point that has been started is determined as a measurement point that exceeds the boundary on the base material side, and the measurement point immediately before the measurement point that has been rapidly detected is taken as the measurement point in the region of the inorganic layer [A]. . Further, since the outermost surface 1 nm of the inorganic layer [A] is generally contaminated with dirt and foreign matter, etching using an Ar gas cluster ion beam (Ar-GCIB) is performed as a pretreatment for Tof-SIMS analysis. The measurement point after removing the 1 nm region is regarded as the measurement value of the first surface.

  In the Tof-SIMS analysis in accordance with the gist of the present invention, the resolution in the depth direction is important, and the etching depth per measurement point is preferably 0.1 to 2 nm. Etching can be performed by a conventionally known method, but from the viewpoint of resolution in the depth direction, it is preferable to use Ar-GCIB to set the etching depth per measurement point to 1 nm.

(Thickness of inorganic layer [A])
In the present invention, the thickness of the inorganic layer [A] is preferably 50 to 500 nm, and more preferably 90 to 400 nm. If the thickness of the inorganic layer [A] is less than 50 nm, stable gas barrier properties may not be obtained. When the thickness of the inorganic layer [A] is greater than 500 nm, the stress remaining in the inorganic layer [A] increases, and cracks may occur in the inorganic layer [A], which may lower the gas barrier properties. The thickness of the inorganic layer [A] can be measured from a cross-sectional observation image by TEM.

(Step of providing inorganic layer [A])
In the present invention, a silicon compound having a polysilazane skeleton is preferably used as a raw material for the inorganic 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.

  The step of providing the inorganic layer [A] in the present invention includes the step [a] of applying a coating solution containing a silicon compound having a polysilazane skeleton to provide a coating film, the step of drying the coating film [b], and applying light to the coating film. It is preferable to have the process [c] which performs an irradiation process in this order. Further, the step [c] is a step [c-1] for curing the surface of the coating film by applying a light irradiation treatment to the coating film, a step [c-2] for cooling the coating film, and a light irradiation treatment for the coating film. It is more preferable to have the step [c-3] for converting the composition of the coating film in this order. Other steps may be included as long as the steps [a] to [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 inorganic layer [A], it is more preferable to select a method in which the coating solution can be applied without being exposed to oxygen or water vapor until just before coating. It is preferable to use a liquid delivery pump or a sealed syringe pump, and it is particularly preferable to apply the liquid 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 inorganic layer [A], if necessary, as long as the effect of the inorganic 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 achieve both gas barrier properties and flex resistance, the heating temperature is preferably 50 to 150 ° C., and more preferably 60 to 120 ° C. from the viewpoint of suppressing oxidation of the inorganic 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 gas barrier properties and bending resistance may be deteriorated. Further, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Furthermore, the heat 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 applying a light irradiation treatment to the coating film. Specifically, in the step [c], the coating film can be converted by subjecting the humidified coating film to light irradiation treatment such as plasma treatment, ultraviolet ray irradiation treatment, and flash pulse treatment. The light irradiation treatment may be single irradiation or multiple times of irradiation. Furthermore, from the viewpoint of production efficiency, the step [c] more preferably includes the steps [c-1] to [c-3] described below in this order.

[Step [c-1]]
Step [c-1] is preferably a step of curing the surface of the coating film by subjecting the coating film to light irradiation treatment. Specifically, in step [c-1], the surface of the coating film can be cured by subjecting the dried coating film to light irradiation treatment such as plasma treatment, ultraviolet ray irradiation treatment, flash pulse treatment and the like. As the light irradiation treatment, it is preferable to use an ultraviolet treatment since it is simple and excellent in productivity, and it is easy to uniformly cure the surface of the coating film. 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 2.0% by volume or less, and more preferably 1.0% by volume or less. In the ultraviolet treatment, it is more preferable to reduce the oxygen concentration using nitrogen gas. The relative humidity may be arbitrary.

As the ultraviolet ray generation source, known ones such as a high pressure mercury lamp, a metal halide lamp, a microwave method electrodeless lamp, a low pressure mercury lamp, a xenon lamp, etc. can be used. It is preferable to use either a metal halide lamp or a microwave type electrodeless lamp. Although the wavelength of the ultraviolet rays to be irradiated is not particularly limited, it is preferably 200 to 380 nm, more preferably 280 to 380 nm, and further preferably 315 to 380 nm from the viewpoint of production efficiency.
Integrated light quantity of ultraviolet irradiation is preferably from 0.2~2.0J / cm ^2, more preferably 0.3~1.0J / cm ^2, more preferably 0.4~0.8J / cm ² . When the integrated light quantity is 0.2 J / cm ² or more, the surface of the coating can be cured, and when the integrated light quantity is 2.0 J / cm ² or less, the polymer substrate and the inorganic layer [A] are damaged. This is preferable because it can be reduced.

[Step [c-2]]
It is preferable that process [c-2] is process [c-2] which cools a coating film. Specifically, after light irradiation in the step [c-1], the coating film is cooled to suppress oxidation of the coating film, and the composition conversion to the coating film of the present invention in the step [c-3] is achieved. It becomes possible efficiently. -10-25 degreeC is preferable and, as for the cooling temperature of a coating film, 0-15 degreeC is more preferable. The relative humidity may be arbitrary.

  The cooling time is preferably 10 seconds to 3 hours, more preferably 1 minute to 1 hour. The atmosphere during cooling may be in the air, under reduced pressure, or in a state enclosed in an inert gas, but from the viewpoint of production efficiency, the state in the air or in an inert gas is preferable.

[Step [c-3]]
Step [c-3] is preferably a step of subjecting the coating film to light irradiation treatment to convert the coating composition. Specifically, in step [c-3], the coating film can be subjected to composition conversion by subjecting the coating film after drying to light irradiation treatment such as plasma treatment, ultraviolet ray irradiation treatment, and flash pulse treatment. As the light irradiation treatment, it is preferable to use an ultraviolet treatment since it is simple and excellent in productivity and it is easy to obtain a uniform composition of the inorganic layer [A]. 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.

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 quantity is 1.5 J / cm ² or more, a composition of a desired inorganic layer [A] that suppresses oxidation can be obtained, and when the integrated light quantity is 10 J / cm ² or less, damage to the substrate is caused. 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 cooling. As heating temperature, 40-100 degreeC is preferable and 50-80 degreeC is more preferable. When the heating temperature is 40 ° C. or higher, high production efficiency is obtained, and when the heating temperature is 100 ° C. or lower, deformation or alteration of other materials such as a substrate hardly occurs, and the layer of the inorganic layer [A] It is preferable because internal oxidation can be suppressed.

[Inorganic layer [B]]
In the laminate of the present invention, the inorganic layer [B] is provided between the substrate and the inorganic layer [A] from the viewpoint of obtaining high gas barrier properties, film quality stability under high temperature and high humidity, and bending resistance. It is preferable to have. By having the inorganic layer [B] on the substrate side of the inorganic layer [A], the Si—NH structure existing inside the layer of the inorganic layer [A] can be protected from the substrate side. The film quality stability of A] is improved. Therefore, by having the inorganic layer [B] between the base material and the inorganic 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 silicon and zinc 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 inorganic 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, it is preferable that the inorganic layer [B] satisfies the following [B1] and / or [B2] from the viewpoint of obtaining high gas barrier properties, film quality stability under high temperature and high humidity, and bending resistance.
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, so that voids and defects may easily 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 2 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] and / or the inorganic layer is more effective than the case where the inorganic layer [B] or the inorganic layer [A] is directly formed on the base material. The flatness of the layer [A] is improved, and 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 inorganic 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 inorganic layer [A] may increase 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 is greater than 10 μm, the stress remaining in the anchor coat layer increases and the base material warps and cracks are generated in the inorganic layer [B] and / or the inorganic 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 inorganic layer [A] after inorganic 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.), observe the cross section of the observation sample at an acceleration voltage of 300 kV, and measure the thickness of the inorganic layer [A], inorganic layer [B], and anchor coat layer did. 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 60 ° 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 in an atmosphere of a temperature of 60 ° 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 inorganic 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 60 ° 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 2 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 where the inorganic layer [B2] is formed on the substrate or undercoat layer (before the inorganic layer [A] is laminated) is thermally decomposed with nitric acid and sulfuric acid, and heated and dissolved with dilute nitric acid. Separated. 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. In addition, when the sample to analyze is what laminated | stacked inorganic layer [A] etc. on inorganic layer [B2], after removing layer [B] etc. by ion sputtering, composition analysis of inorganic layer [B2] I do.

(6) [SiOH / Si] in the depth direction of the inorganic layer [A]
[SiOH / Si] in the depth direction of the inorganic layer [A] was measured by a method using both Tof-SIMS analysis and etching.
The measurement conditions were as follows.
Apparatus: TOF. SIMS 5 (made by ION-TOF)
Mass range (m / z): 0 to 3,000
・ Raster size: 150μm
・ Measurement vacuum (before sample introduction): 4 × 10 ⁻⁷ Pa or less ・ Neutralization of charge: Available ・ Acceleration at the latter stage: 10 kV
Primary ion species: Bi ₃ ⁺⁺
・ Primary ion acceleration voltage: 25 kV
・ Primary ion pulse width: 11.7 ns (bunching: available)
・ Secondary ion polarity: Positive ・ Etching ion: Ar-GCIB
・ Etching ion acceleration voltage: 10 kV
Ar cluster size (median): about 1,100
Etching time per measurement point: 2.2 seconds.

  The surface after removing the outermost layer 1 nm of the inorganic layer [A] by etching using an Ar gas cluster ion beam (Ar-GCIB) is regarded as the outermost layer of the inorganic layer [A], and the measurement point on the outermost surface is inorganic. The measurement point on the outermost surface of the layer [A] (measurement point 0 nm from the outermost layer of the inorganic layer [A]) was used.

Subsequently, measurement is performed while etching in the direction of the base material under the above conditions, and the measurement point where the base material component (C ⁺ ions, etc.) starts to be detected suddenly (by an order of magnitude) crosses the base side boundary. The measurement point in the region of the inorganic layer [A] was determined up to the measurement point immediately before the measurement point that was rapidly detected.

  The depth from the outermost surface of the inorganic layer [A] was determined as follows.

  The etching depth per etching is calculated by dividing the thickness of the inorganic layer [A] obtained from the cross-sectional observation image by TEM (transmission electron microscope) by the number of measurement points obtained by Tof-SIMS analysis. The

  The depth from the outermost surface of the inorganic layer [A] at each measurement point is calculated using the etching depth per one etching.

The measurement point existing in the region where the depth from the outermost surface side of the inorganic layer [A] is 0 nm or more and 20 nm or less is the maximum etching point from the first measurement point on the outermost surface side by the calculated etching depth. Up to the measurement point that is present on the surface side and closest to the depth of 20 nm from the outermost surface side. The measurement points obtained in this way are the measurement points existing in the region where the depth from the outermost surface side of the inorganic layer [A] is 0 nm or more and 20 nm or less, and by averaging these [SiOH / Si], [SiOH / Si] _{A20 or less} was calculated. Of all the measurement points obtained, the measurement points other than the measurement points existing in the region where the depth from the outermost surface side of the inorganic layer [A] is 0 nm or more and 20 nm or less are the outermost surfaces of the inorganic layer [A]. [SiOH / Si] _A20 by averaging the [SiOH / Si] of the measurement points existing in the region exceeding 20 nm from the side and the measurement points existing in the region exceeding 20 nm from the outermost surface side of the inorganic layer [A]. _Super calculated.

(7) Presence / absence of component having Si—H bond in inorganic layer [A] The presence / absence of the component having Si—H bond in inorganic layer [A] was confirmed by Fourier transform infrared spectroscopy. That is, the laminate was sampled to 10 mm × 10 mm, the surface of the inorganic layer [A] was pressure-bonded to the ATR crystal, measured under the following measurement conditions, and derived from Si—H at 2,140-2,260 cm ⁻¹ . The presence or absence of a peak 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 inorganic layer [A] The film quality stability of inorganic layer [A] was judged by the amount of change of the component having an Si—H bond of inorganic layer [A] before and after wet heat treatment. First, two samples of a laminate sampled to 10 mm × 10 mm were prepared, and for one sample, the presence or absence of a component having an Si—H bond in the inorganic layer [A] by the method of (7) described above without wet heat treatment It was confirmed. Thereafter, for the remaining one specimen, the component having the Si—H bond of the inorganic layer [A] by the method of (7) described above after the wet heat treatment for 72 hours under the conditions of a temperature of 85 ° C. and a relative humidity of 85% RH. The presence or absence was confirmed. The film quality stability was judged from the amount of change before and after the wet heat treatment as follows.
○: A component having a Si—H bond is included before and after the wet heat treatment, and the peak intensity does not change by 10% or more.
(Triangle | delta): Although the component which has Si-H bond was included before and behind wet heat processing, peak intensity decreased 10% or more.
X: A component having a Si—H bond is included before wet heat treatment, but a component having a Si—H bond is not included after wet heat treatment −: a component having a Si—H bond is not included before and after the wet heat treatment.

(9) Flexural resistance test The laminate was sampled to 100 mm × 100 mm, and in this sample, the surface side where the inorganic layer [A] of the laminate was not laminated as shown in FIG. The formed surface was fixed to the apparatus as the inside, and a bending resistance test was performed under the following bending conditions. In this test, the smaller the bending radius described below, the more severe the test.
・ Equipment: Small desktop durability tester (manufactured by Yuasa System Equipment Co., Ltd., DLDM111LH (linear reciprocating specification), planar body no load U-shaped expansion test)
-Bending radius: 2 mm or 3 mm (Note that samples to be tested at 2 mm or 3 mm were prepared separately)
-Bending speed: 1 time / second-Bending frequency: 10,000 times Next, the bending resistance evaluations A and B described below were performed to evaluate the bending resistance.
-Flexibility evaluation A
After the bending resistance test, the inorganic layer [A] side of the bent portion was observed with a digital microscope (manufactured by Keyence Corporation, VHX1000) at a magnification of 100 to 500. The case where cracking / cracking of the inorganic layer [A] did not occur was determined as a determination A (good), and the case where it occurred was determined as a determination B (defective).
・ Bend resistance evaluation B
After the bending resistance test, the water vapor permeability was measured by the method of (2) or (3) with the inorganic layer [A] side of the bent portion as the measurement surface, and the water vapor permeability W ₀ before the bending resistance test was By dividing the water vapor permeability value W after the bending resistance test, the W / W ₀ value was obtained as a change ratio of the water vapor permeability before and after the bending resistance test. The case where the W / W ₀ value was less than 10 was judged as A (best), 10 to less than 100 was judged as B (good), and 100 or more was judged as C (bad).

[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)
Using a polyethylene terephthalate (PET) film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 23 μm as a base material, an anchor coat layer [C] is provided on one side of the base material, and an inorganic coating is further provided thereon. As the layer [B], an inorganic layer [B1] was provided to a thickness of 90 nm.

Next, as a coating liquid for forming the inorganic layer [A], 100 parts by mass of a perhydropolysilazane solution (“NN120-20” manufactured by Merck Performance Materials LLC) in dibutyl ether, 100 parts by mass of dibutyl ether and 200 of diisopropyl ether It diluted with the mass part and the coating liquid I was prepared under nitrogen stream. In order to suppress the oxidation of the coating liquid I, it apply | coated with the slit die coater (coating liquid supply means: syringe pump) on inorganic layer [B1], and it dried at 100 degreeC for 1 minute. Next, a laminate in which an inorganic layer [A] having a thickness of 130 nm is provided by performing an ultraviolet irradiation step [c-1], a cooling step [c-2], and an ultraviolet irradiation step [c-3] in this order under the following conditions. Got the body.
Ultraviolet irradiation process [c-1] Conditions / lamp type: LH-10-10 (manufactured by Heraeus Co., Ltd.)
・ Peak wavelength: 365nm
・ Valve: H valve ・ Introducing gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 0.7 J / cm ²
-Sample temperature control: 20 ° C
Cooling step [c-2] Conditions / Cooling temperature: 5 ° C.
・ Cooling time: 10 minutes ・ Cooling atmosphere: UV irradiation under N ₂ atmosphere [c-3] conditions ・ Lamp type: MEBF-440HQ (manufactured by 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: 4.0 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 conditions of the cooling step [c-2] were changed to the following conditions.
Cooling step [c-2] Conditions / Cooling temperature: 5 ° C.
Cooling time: 10 minutes Cooling atmosphere: air atmosphere (Example 3: Sample 3)
A laminate was obtained in the same manner as Sample 1 except that the conditions of the cooling step [c-2] were changed to the following conditions.
Cooling step [c-2] Conditions / Cooling temperature: 10 ° C.
-Cooling time: 1 hour-Cooling atmosphere: under air atmosphere (Example 4: Sample 4)
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 23 μm (“ZEONOR FILM” (registered trademark) ZF-14, manufactured by ZEON CORPORATION).

(Example 5: Sample 5)
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 90 nm.

(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 [B3] having a thickness of 300 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 [B4] having a thickness of 20 nm.

(Comparative Example 1: Sample 8)
A laminate was obtained in the same manner as Sample 1, except that the inorganic layer [B] was not provided and the inorganic layer [A] was directly laminated on the anchor coat layer [C].

(Comparative Example 2: Sample 9)
Using a polyethylene terephthalate (PET) film having a thickness of 23 μm as a base material (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.), the other methods were the same as in Example 2 of International Publication No. 2014/109231. A laminate was obtained.

(Comparative Example 3: Sample 10)
A polyethylene terephthalate (PET) film having a thickness of 23 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) is used as the substrate, and the others are the same as in Example 10 of International Publication No. 2014/109231. A laminate was obtained.

(Comparative Example 4: Sample 11)
A polyethylene terephthalate (PET) film having a thickness of 23 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) was used as the base material, and the others were the same as in Example 11 of International Publication No. 2015/115314, A laminate was obtained.

(Comparative Example 5: Sample 12)
After performing the ultraviolet irradiation step [c-1], a laminate was obtained in the same manner as the sample 1 except that the cooling step [c-2] and the ultraviolet irradiation step [c-3] were not performed.

(Comparative Example 6: Sample 13)
A laminate was obtained in the same manner as Sample 10 except that the conditions of the ultraviolet irradiation step [c-1] were changed to the following conditions. On the surface of the obtained laminate on the inorganic layer [A] side, generation of film wrinkles was visually confirmed, but the evaluation was continued as it was.
Ultraviolet irradiation process [c-1]
Lamp type: LH-10-10 (manufactured by Heraeus Co., Ltd.)
・ Peak wavelength: 365nm
・ Valve: H valve ・ Introducing gas: N ₂
・ Oxygen concentration: 500ppm
-Integrated light quantity: 3.0 J / cm ²
-Sample temperature control: 20 ° C.

(Comparative Example 7: Sample 14)
A laminated body was obtained in the same manner as in Example 1 except that the wet heat treatment step under the following conditions was performed instead of the steps [c-1] to [c-3] after drying when forming the inorganic layer [A]. .
Processing temperature: 85 ° C
Processing humidity: 85% RH
Processing time: 96 hours.

(Comparative Example 8: Sample 15)
A polyethylene terephthalate (PET) film having a thickness of 23 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) is used as the base material, and the others are the same as those of the gas barrier film 5 of the example of International Publication No. 2011/074440. By the method, a laminate was obtained.

(Comparative Example 9: Sample 16)
A polyethylene terephthalate (PET) film having a thickness of 23 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) is used as a base material, and the others are the same as those of the gas barrier film 9 of the example of International Publication No. 2011/074440. By the method, a laminate was obtained.

(Comparative Example 10: Sample 17)
A polyethylene terephthalate (PET) film having a thickness of 23 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) is used as the base material, and the others are the same as those of the gas barrier film 12 of the example of International Publication No. 2011/074440. By the method, a laminate was obtained.

(Comparative Example 11: Sample 18)
A laminate was obtained in the same manner as Sample 1 except that the inorganic layer [A] was not provided. Since the sample 18 is not provided with the inorganic layer [A], the bending resistance test is not performed.

(Comparative Example 12: Sample 19)
A laminate was obtained in the same manner as Sample 18, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B2] having a thickness of 90 nm. Since the sample 19 is not provided with the inorganic layer [A], the bending resistance test is not performed.

(Comparative Example 13: Sample 20)
A laminate was obtained in the same manner as Sample 18, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B3] having a thickness of 300 nm. Since the sample 20 is not provided with the inorganic layer [A], the bending resistance test is not performed.

(Comparative Example 14: Sample 21)
A laminate was obtained in the same manner as Sample 18, except that the inorganic layer [B] was changed from the inorganic layer [B1] to the inorganic layer [B4] having a thickness of 20 nm. Since the sample 21 is not provided with the inorganic layer [A], the bending resistance test is not performed.

  The evaluation results of the obtained laminate are shown in Tables 1 and 2.

  As is clear from Tables 1 and 2, the laminated bodies (samples 1 to 7) of the examples of the present invention have higher gas barrier properties than the corresponding laminated bodies (samples 18 to 21). I found it. In addition, the laminates of the examples of the present invention, compared with the laminates of the comparative examples that do not satisfy the present invention (samples 8 to 17), have high gas barrier properties, film quality stability and resistance to high temperatures and high humidity. It was found to have flexibility.

  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 Substrate 2 Inorganic layer [A]
3 Inorganic layer [B]
4 Anchor coat layer [C]
5 Laminate 6 Surface side where the inorganic layer [A] of the laminate is laminated 7 Surface side where the inorganic layer [A] of the laminate is not laminated 8 Movable plate 9 of the bending resistance test apparatus 9 Fixing of the bending resistance test apparatus Plate 10 Reciprocating direction of movable plate of bending resistance test equipment 11 Bending radius

Claims (5)

A laminate having an inorganic layer [A] containing Si, O, and N on at least one surface of the substrate, wherein the inorganic layer [A] is expressed by the formula (1) at all measurement points in the depth direction. A laminated body satisfying and the inorganic layer [A] satisfies the formula (2).
Formula (1): [SiOH / Si]> 0.02
Formula (2) [SiOH / Si] _{A20 or less} > [SiOH / Si] _{A20 super}
[SiOH / Si]: Ratio of relative ionic strength SiOH ⁺ detected by Tof-SIMS analysis to relative ionic strength Si ⁺ [SiOH / Si] _{A20 or less} : depth from the surface side in the depth direction of the inorganic layer [A] Average value [SiOH / Si] of measurement points in the region of 0 nm or more and 20 nm or less [SiOH / Si] _{more than A20} : in the region where the depth from the surface side in the depth direction of the inorganic layer [A] is more than 20 nm [SiOH / Si] average value of measurement points The laminate according to claim 1, wherein the [SiOH / Si] _{A20 or less} is 0.05 or more. The laminate according to claim 1 or 2, wherein the [SiOH / Si] _A20 exceeds 0.1.   There is an inorganic layer [B] between the base material and the inorganic 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 silicon and zinc.