WO2015115314A1

WO2015115314A1 - Gas barrier film

Info

Publication number: WO2015115314A1
Application number: PCT/JP2015/051772
Authority: WO
Inventors: 森健太郎
Original assignee: 東レ株式会社
Priority date: 2014-01-29
Filing date: 2015-01-23
Publication date: 2015-08-06
Also published as: JP6578943B2; TW201534481A; CN105829093A; CN105829093B; JPWO2015115314A1; KR102355268B1; KR20160114038A; TWI668120B

Abstract

The purpose of the present invention is to provide a gas barrier film which exhibits high gas barrier performance, while having excellent bending resistance. A gas barrier film according to the present invention sequentially comprises, on at least one surface of a polymer base, an inorganic layer (A) and a silicon compound layer (B) in this order from the polymer base side. The silicon compound layer (B) contains at least silicon compounds having structures represented by SiN_xH_y, SiO_pN_q and SiO_a(OH)_4-2a (wherein x + y = 4, p + q =4, a < 2 and x, y, p, q > 0); and the inorganic layer (A) and the silicon compound layer (B) are in contact with each other.

Description

Gas barrier film

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

A film of an inorganic substance (including inorganic oxides) such as aluminum oxide, silicon oxide, magnesium oxide, etc. on the surface of the polymer substrate is deposited by physical vapor deposition (PVD) such as vacuum deposition, sputtering, or ion plating. A gas barrier film formed using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, a photochemical vapor deposition method, or the like. This film is used as a packaging material for foods, pharmaceuticals, and the like that require blocking of various gases such as water vapor and oxygen, and as an electronic device member such as a flat-screen TV and a solar battery.

As a gas barrier property improving technique, for example, a gas containing an organic silicon compound vapor and oxygen is used to form a silicon oxide as a main component on a substrate by a plasma CVD method, and at least one kind of carbon, hydrogen, silicon and oxygen. A method for improving gas barrier properties while maintaining transparency by using a contained compound has been 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 using a smooth base material in which protrusions and unevenness causing generation of pinholes and cracks that reduce the gas barrier property are reduced or surface smoothing is used. Some have used a base material provided with an undercoat layer for the purpose of conversion (Patent Documents 2, 3 and 4). Also known is 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 5 and 6).

JP-A-8-142252 JP 2002-113826 A International Publication No. 2012/137762 International Publication No. 2013/061726 International Publication No. 2011/007543 International Publication No. 2011/004698

However, as in Patent Document 1, in the method of forming a gas barrier layer mainly composed of silicon oxide by the plasma CVD method, the film quality of the formed gas barrier layer differs depending on the type of substrate, and stable gas barrier properties are obtained. It was not obtained. In order to stabilize the gas barrier property, it is necessary to increase the film thickness, and as a result, there is a problem that the bending resistance is lowered and the manufacturing cost is increased. In addition, as in Patent Document 2, a method using a smooth substrate for forming a gas barrier layer or a method using a substrate provided with an undercoat layer for the purpose of smoothing the surface includes pinholes and cracks. Although the gas barrier property is improved by preventing the occurrence of the above, the performance improvement is insufficient. On the other hand, Patent Documents 3 and 4 have a problem that although the film quality of the formed gas barrier layer is improved, the performance is improved, but it is difficult to stably exhibit a high gas barrier property. In addition, in the method of forming a gas barrier layer with a polysilazane layer disclosed in Patent Documents 5 and 6, the gas barrier film is easily affected by conditions at the time of forming the layer, and a gas barrier film having sufficient gas barrier properties can be stably obtained. Needed to laminate a plurality of polysilazane layers. As a result, there has been a problem that the bending resistance is lowered and the manufacturing cost is increased.

The present invention has been made in view of the background of the prior art, and it is an object of the present invention to provide a gas barrier film having a high gas barrier property and excellent in bending resistance and adhesion without being thickened or multilayered. .

The present invention employs the following means in order to solve such problems. That is,
(1) A gas barrier film having an inorganic layer [A] and a silicon compound layer [B] in this order from the polymer substrate side on at least one side of the polymer substrate, wherein the silicon compound layer [B] , Silicon having a structure represented by at least SiN _x H _y , SiO _p N _q and SiO _a (OH) _4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) A gas barrier film containing a compound and in contact with an inorganic layer [A] and a silicon compound layer [B].

Further, as a preferred embodiment of the present invention, there are the following means.
(2) The gas barrier film according to (1), wherein the inorganic layer [A] contains a zinc compound and a silicon oxide.
(3) In the ²⁹ Si CP / MAS NMR spectrum of the silicon compound layer [B], when the total peak area of −30 to −120 ppm is defined as 100, the total peak area of −30 to −50 ppm is 10 or more, −50 The gas barrier film according to (1) or (2), wherein the total peak area at ˜−90 ppm is 10 or more and the total peak area at −90 to −120 ppm is 80 or less.
(4) The gas barrier film according to any one of (1) to (3), wherein the inorganic layer [A] is any one selected from the following inorganic layers [A1] to [A3].
Inorganic layer [A1]: Inorganic layer consisting of coexisting phases of (i) to (iii) (i) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide Inorganic layer [A2]: From the coexisting phase of zinc sulfide and silicon dioxide Inorganic layer [A3]: An inorganic layer mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0. (5) The inorganic layer [A] is the inorganic layer. Layer [A1], and the inorganic layer [A1] has a zinc atom concentration of 20 to 40 atom%, a silicon atom concentration of 5 to 20 atom%, and an aluminum atom concentration of 0.5 to 0.5 as measured by ICP emission spectroscopy. The gas barrier film according to (4), which is constituted by a composition having 5 atom% and an oxygen atom concentration of 35 to 70 atom%.
(6) The inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] has a molar fraction of zinc sulfide to the total of zinc sulfide and silicon dioxide of 0.7 to 0.9. The gas barrier film according to (4), which is constituted by a certain composition.
(7) Between the polymer substrate and the inorganic layer [A], there is an undercoat layer [C] including a structure obtained by crosslinking a polyurethane compound [C1] having an aromatic ring structure (1) ) To (6).
(8) The gas barrier film according to (7), wherein the undercoat layer [C] contains an organosilicon compound and / or an inorganic silicon compound.

The present invention also provides the following electronic device using a gas barrier film.
(9) An electronic device using the gas barrier film according to any one of (1) to (8).

According to the present invention, a gas barrier film having a high gas barrier property against water vapor and excellent in bending resistance and adhesion is provided.

It is sectional drawing which showed an example of the gas barrier film of this invention. It is the schematic which shows typically the winding-type sputtering apparatus for manufacturing the gas barrier film of this invention. It is the schematic which shows typically the winding type CVD apparatus for manufacturing the gas barrier film of this invention. 2 is a graph showing a ²⁹ Si CP / MAS NMR spectrum of the silicon compound layer [B] of the gas barrier film of the present invention obtained in Example 1. FIG. It is the schematic of a bending resistance test. It is sectional drawing which showed an example of the gas barrier film of this invention.

The inventors have made extensive studies for the purpose of obtaining a gas barrier film having a high gas barrier property against water vapor and the like, and having excellent bending resistance and adhesion, and at least one side of the polymer base material is inorganic. Layer [A] and represented by SiN _x H _y , SiO _p N _q and SiO _a (OH) _{4-2 a} (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) When the silicon compound layer [B] containing three silicon compounds having a structure is laminated so as to be in this order, it has been found that the above-mentioned problems are solved.
The meanings of the three structures are as follows.
SiN _x H _y : Nitrogen and hydrogen are bonded to a silicon atom present in the compound, and the number of bonds from silicon to each element is x and y.
SiO _p N _q : Oxygen and nitrogen are bonded to a silicon atom present in the compound, and the number of bonds from silicon to each element is p and q.
SiO _a (OH) _4-2a : The structure of the compound when the silicon atom is 1.

FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention. As shown in FIG. 1, the gas barrier film of the present invention has an inorganic layer [A] (reference numeral 2), SiN _x H _y , SiO on one side of the polymer base material (reference numeral 1) from the polymer base material side. A silicon compound layer [B] (reference numeral 3) containing three silicon compounds having a structure represented by _p N _q and SiO _a (OH) _4-2a (x + y = 4, a ≦ 2) is laminated in this order. It is what you are doing. In addition, the example of FIG. 1 shows the minimum structure of the gas barrier film of the present invention, and only the inorganic layer [A] and the silicon compound layer [B] are arranged on one side of the polymer substrate. However, another layer may be disposed between the polymer base material and the inorganic layer [A], and the other side of the polymer base material 1 opposite to the side on which the inorganic layer [A] is laminated. These layers may be arranged.

The reason why a remarkable effect is obtained in the present invention is estimated as follows. That is, by contacting the inorganic layer [A] and the silicon compound layer [B], defects such as pinholes and cracks existing near the surface of the inorganic layer [A] on the side on which the silicon compound layer [B] is formed are treated. The components constituting the silicon compound layer [B] are filled, and high barrier properties can be expressed. In addition, since the above three types of silicon compounds can easily form chemical bonds with the components constituting the inorganic layer [A], the adhesion between the inorganic layer [A] and the silicon compound layer [B] is improved. Needless to say, excellent adhesion can be obtained also when another layer is laminated on the silicon compound layer [B]. Furthermore, since the silicon compound layer [B] including the above structure is excellent in flexibility, excellent bending resistance can be obtained.

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

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

The surface of the polymer base on which the inorganic layer [A] is formed has a corona treatment, a plasma treatment, an ultraviolet treatment, an ion bombard treatment, a solvent treatment, an organic substance or an inorganic substance to improve adhesion and smoothness. A pretreatment such as an undercoat layer forming treatment composed of the above mixture 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 polymer substrate used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and preferably 5 μm or more from the viewpoint of securing strength against tension or impact. Furthermore, the thickness of the polymer substrate is more preferably 10 μm or more and 200 μm or less because of the ease of film processing and handling.

[Inorganic layer [A]]
The inorganic layer [A] in the present invention includes zinc (Zn), silicon (Si), aluminum (Al), titanium (Ti), zirconium (Zr), tin (Sn), indium (In), niobium (Nb), Examples include oxides, nitrides, sulfides, or mixtures of elements such as molybdenum (Mo) and tantalum (Ta). Although it will not specifically limit if such an inorganic substance is included, It is preferable that inorganic layer [A] contains a silicon oxide, and it is more preferable that a zinc compound and a silicon oxide are further included. In addition, as the inorganic layer [A] from which high gas barrier properties can be obtained, any one selected from the following inorganic layers [A1] to [A3] is preferably used.
Inorganic layer [A1]: Inorganic layer consisting of coexisting phases of (i) to (iii) (i) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide Inorganic layer [A2]: From the coexisting phase of zinc sulfide and silicon dioxide Each of the inorganic layers [A3]: [A3]: the inorganic layers [A1] to [A3] each of which is mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0 Details will be described later.

The thickness of the inorganic layer [A] 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. If the thickness of the layer is small, there may be places where sufficient gas barrier properties cannot be secured, and the gas barrier properties may vary within the polymer substrate surface. In addition, if the thickness of the layer is too large, the stress remaining in the layer becomes large, so that the inorganic layer [A] is liable to be cracked by bending or external impact, and the gas barrier properties are lowered with use. There is a case. Therefore, the thickness of the inorganic layer [A] is 10 nm or more, more preferably 100 nm or more, while 1,000 nm or less and 500 nm or less. The thickness of the inorganic layer [A] can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).

The center plane average roughness SRa of the inorganic layer [A] used 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 [A] becomes large, and a gap is formed between the sputtered particles to be laminated. The improvement effect may be difficult to obtain. Further, when SRa is larger than 10 nm, the film quality of the silicon compound layer [B] laminated on the inorganic layer [A] is not uniform, and the gas barrier property may be lowered. Therefore, SRa of the inorganic layer [A] is preferably 10 nm or less, and more preferably 7 nm or less.

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

[Inorganic layer [A1]]
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 [A1], 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. Note that silicon dioxide (SiO ₂ ) may be generated (SiO to SiO ₂ ) that slightly deviates from the composition ratio of silicon and oxygen in the composition formula on the left, depending on the conditions at the time of production. It shall be described as SiO ₂ . 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 [A1] in the gas barrier film of the present invention is that the crystalline component contained in zinc oxide and the amorphous component of silicon dioxide coexist. It is presumed that the crystal growth of zinc oxide, which tends to generate crystals, is suppressed and the particle diameter 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 [A1] can be measured by ICP emission spectroscopy as described later. The zinc atom concentration measured by ICP emission spectroscopy is 20 to 40 atom%, the silicon atom concentration is 5 to 20 atom%, the aluminum atom concentration is 0.5 to 5 atom%, and the O atom concentration is 35 to 70 atom%. preferable. When the zinc atom concentration is higher than 40 atom% or the silicon atom concentration is lower than 5 atom%, the silicon dioxide and / or aluminum oxide that suppresses the crystal growth of zinc oxide is insufficient, so that void portions and defect portions increase. High gas barrier properties may not be obtained. When the zinc atom concentration is lower than 20 atom% or the silicon atom concentration is higher than 20 atom%, the amorphous component of silicon dioxide inside the layer may increase and the flexibility of the layer may be lowered. On the other hand, when the aluminum atom concentration is higher than 5 atom%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that the film becomes hard, and cracks are likely to occur due to heat and external stress. When the aluminum atom concentration is smaller than 0.5 atom%, the affinity between zinc oxide and silicon dioxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved, so that the flexibility may be lowered. In addition, when the oxygen atom concentration is higher than 70 atom%, the amount of defects in the inorganic layer [A1] increases, so that a desired gas barrier property may not be obtained. When the oxygen atom concentration is lower than 35 atom%, the oxidation state of zinc, silicon, and aluminum becomes insufficient, the crystal growth cannot be suppressed, and the particle diameter increases, so that the gas barrier property may be lowered. From the tendency of the content of each atom shown above, the zinc atom concentration is 25 to 35 atom%, the silicon atom concentration is 10 to 15 atom%, the aluminum atom concentration is 1 to 3 atom%, and the oxygen atom concentration is 50 to 64 atom%. It is more preferable.

The composition of the inorganic layer [A1] 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 [A1] It is possible to adjust the composition of the layer [A1].

The composition of the inorganic layer [A1] is calculated as a composition ratio of zinc oxide, silicon dioxide, aluminum oxide, and the inorganic oxide contained by quantifying each element of zinc, silicon, and aluminum by ICP emission spectroscopy. The oxygen atoms are calculated on the assumption that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively. The ICP emission spectroscopic analysis is an analysis method capable of simultaneously measuring multiple elements from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and can be applied to composition analysis. When an inorganic layer or a resin layer is further laminated on the inorganic layer [A1], ICP emission spectroscopic analysis can be performed after removing the layer by ion etching or chemical treatment as necessary.

[Inorganic layer [A2]]
Next, a coexisting phase of zinc sulfide and silicon dioxide (hereinafter referred to as a coexisting phase of zinc sulfide and silicon dioxide) is preferably used as the inorganic layer [A] in the present invention. The details of the inorganic layer [A2], which is a layer formed from the above, will be described. In this case as well, silicon dioxide (SiO ₂ ) may be generated (SiO to SiO ₂ ) slightly deviating from the composition ratio of silicon and oxygen in the composition formula on the left depending on the conditions at the time of production. Alternatively, it will be expressed as SiO 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 [A2] in the gas barrier film of the present invention is that the crystalline component contained in zinc sulfide and the amorphous component of silicon dioxide coexist. It is presumed that the crystal growth of zinc sulfide, which tends to generate crystals, is suppressed 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 by applying this inorganic layer [A2] that the gas barrier property fall resulting from the production | generation of the crack at the time of use was also suppressed.

The composition of the inorganic layer [A2] is preferably such that the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. If the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is greater than 0.9, there will be insufficient 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. Also, if the molar fraction of zinc sulfide relative to the total of zinc sulfide and silicon dioxide is less than 0.7, the amorphous component of silicon dioxide inside the inorganic layer [A2] increases and the flexibility of the layer decreases. The flexibility of the gas barrier film against mechanical bending may be reduced. A more preferable range of the molar fraction of zinc sulfide with respect to the total of zinc sulfide and silicon dioxide is 0.75 to 0.85 from the tendency due to the content of each compound shown above.

Since the composition of the inorganic layer [A2] 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 [A2] It is possible to adjust the composition.

In the composition analysis of the inorganic layer [A2], the composition ratio of zinc and silicon is first 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 [A2] 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 [A2], 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.

[Inorganic layer [A3]]
Next, the inorganic layer [A3] mainly composed of a silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0, which is preferably used as the inorganic layer [A] in the present invention. Details will be described. Here, the main component means 60% by mass or more of the entire inorganic layer [A3], and preferably 80% by mass or more. The main component silicon dioxide (SiO ₂ ) may be slightly shifted from the composition ratio of silicon and oxygen in the composition formula (SiO to SiO ₂ ) depending on the conditions at the time of generation. It will be expressed as silicon dioxide or SiO ₂ .

The formation method of the inorganic layer [A3] is preferably a CVD method capable of forming a dense film. In the CVD method, a gas of silane or an organosilicon compound, which will be described later, is used as a monomer, activated by high-intensity plasma, and a dense film can be formed by a polymerization reaction. Examples of the organic silicon compound include methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, ethylsilane, diethylsilane, triethylsilane, tetraethylsilane, propoxysilane, dipropoxysilane, tripropoxysilane, tetrapropoxysilane, tetra Methoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethyldisiloxane, tetramethyldisiloxane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, undecamethylcyclohexasiloxane, Dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, hexamethyldisilazane, hexamethylcyclotrisilazane Octamethylcyclotetrasilazane, decamethylcyclopentasiloxane silazane, such undecapeptide methyl cyclohexasilane La disilazane and the like. Of these, hexamethyldisiloxane and tetraethoxysilane are preferred from the viewpoint of handling.

The composition of the inorganic layer [A3] can be measured by X-ray photoelectron spectroscopy (XPS method) as described later. The number ratio of oxygen atoms to silicon atoms measured by XPS method is preferably in the range of 1.5 to 2.0, more preferably in the range of 1.4 to 1.8. 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.

[Silicon compound layer [B]]
Next, the silicon compound layer [B] will be described in detail. In the present invention, the silicon compound layer [B] includes SiN _x H _y , SiO _p N _q and SiO _a (OH) _4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0 ) Is a layer containing a silicon compound having a structure represented by: For the purpose of controlling the refractive index, hardness, adhesion, etc., other silicon compounds such as alkoxysilane and organopolysiloxane may be included. The composition of each compound in the silicon compound layer [B] can be measured by ²⁹ Si CP / MAS NMR method.

The reason why the gas barrier property is improved by applying the silicon compound layer [B] in the gas barrier film of the present invention is estimated as follows (i) and (ii).

(I) First, as a contribution to the layer, the layer contains silicon oxynitride represented by SiO _p N _q , so that the layer becomes denser than the layer formed only of SiO ₂ , and oxygen and water vapor are transmitted. Since it is suppressed, it becomes a layer with a high gas barrier property, and in addition, since it is more flexible than a layer formed only of Si ₃ N ₄ , cracks are hardly generated against heat and external stress during use. It is presumed that the layer can suppress a decrease in gas barrier properties due to crack generation.

(Ii) Next, the following are estimated as contributions by laminating the inorganic layer [A] and the silicon compound layer [B] in contact with each other.
The defect that the inorganic layer [A] has, such as pinholes and cracks, is filled with the components constituting the silicon compound layer [B], and high barrier properties can be expressed.
When the silicon compound layer [B] is in contact with the inorganic layer [A], components such as zinc contained in the inorganic layer [A] act as a catalyst to easily improve the film quality of the silicon compound layer [B]. Further, the gas barrier property is further improved.

By including three types of silicon compounds, it is easier to form a chemical bond with the component constituting the inorganic layer [A] than the layer formed using only SiO _p N _q as the main component. Adhesion in the interface region between A] and the silicon compound layer [B] is improved, and excellent bending resistance during use can be obtained.

The thickness of the silicon compound layer [B] used in the present invention is preferably from 50 nm to 2,000 nm, more preferably from 50 nm to 1,000 nm. If the thickness of the silicon compound layer [B] is small, stable water vapor barrier performance may not be obtained. When the thickness of the silicon compound layer [B] becomes too large, the residual stress in the silicon compound layer [B] increases, causing the polymer substrate to warp, and the silicon compound layer [B] and / or the inorganic layer [A] ] May be cracked to lower the gas barrier properties.

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

The center surface average roughness SRa of the silicon compound layer [B] used in the present invention is preferably 10 nm or less. It is preferable to set SRa to 10 nm or less because the repeatability of gas barrier properties is improved. When the SRa on the surface of the silicon compound layer [B] is larger than 10 nm, cracks due to stress concentration are likely to occur in a portion with many irregularities, which may cause a decrease in reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the silicon compound layer [B] is preferably 10 nm or less, more preferably 7 nm or less.

SRa of the silicon compound layer [B] in the present invention can be measured using a three-dimensional surface roughness measuring machine.

FIG. 4 shows the ²⁹ Si CP / MAS NMR spectrum of the silicon compound layer [B] of the present invention. The absorption of silicon is observed in the chemical shift region of −30 to −50 ppm, −50 to −90 ppm region, and −90 to −120 ppm. From the left of the figure, SiN _x H _y , SiO _p N _q and SiO _a (OH) _4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) is present (reference: P. Diehl, E. Fluck) , R. Kosfeld et al. “NMR Basic Principles and Progress” published by Springer-Verlag Berlin Heidelberg, 1981, pages 152-163). When the sum of peak areas from -30 to -120 ppm is taken as 100, the sum of peak areas from -30 to -50 ppm is 10 or more, the sum of peak areas from -50 to -90 ppm is 10 or more, and the peak is from -90 to -120 ppm. A total area of 80 or less is preferable because it is a layer having high gas barrier properties and excellent bending resistance and adhesion. Further, assuming that the total peak area of −30 to −120 ppm is 100, the total peak area of −30 to −50 ppm is 10 to 40, the total peak area of −50 to −90 ppm is 10 to 40, and −90 to − More preferably, the total peak area at 120 ppm is 30-80. When the above range is not satisfied, the silicon compound layer [B] becomes an excessively dense film and lacks flexibility, and cracks are likely to occur due to heat or external stress, and gas barrier properties may be lowered. In contrast, the silicon compound layer [B] may not be dense enough to provide sufficient gas barrier properties. From this point of view, the total peak area of −30 to −50 ppm is 13 to 30, the total peak area of −50 to −90 ppm is 13 to 35, and the total peak area of −90 to −120 ppm is 40 to 75. It is more preferable. From the viewpoint of water vapor permeability, the silicon compound layer [B] preferably contains 0.1 to 100% by mass of the total of the three silicon compounds of the present invention.

As a raw material of the silicon compound layer [B] used in the present invention, a silicon compound having a polysilazane skeleton is preferably used. 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. Alternatively, an organopolysilazane substituted with an organic group such as an alkyl group may be used. 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.

Next, a method for forming the silicon compound layer [B] of the present invention will be described. First, the solid content concentration of the paint containing the compound (1) on the inorganic layer [A] is adjusted so that the thickness after drying becomes a desired thickness, and reverse coating, gravure coating, rod coating, bar coating It is preferably applied by a method, a die coating method, a spray coating method, a spin coating method or the like. Moreover, in this invention, it is also preferable to dilute the coating material containing the said Chemical formula (1) using an organic solvent from a viewpoint of coating suitability. Specifically, hydrocarbon solvents such as xylene, toluene, terpene, and solvesso, ether solvents such as dibutyl ether, ethyl butyl ether, and tetrahydrofuran can be used. And it is preferable to use it, diluting solid content concentration to 10 mass% or less. These solvents may be used alone or in combination of two or more.

Various additives can be blended in the coating material containing the raw material of the silicon compound layer [B] as necessary within a range that does not impair the effect of the silicon compound layer [B]. 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.

Next, it is preferable to dry the coated film after application to remove the diluted solvent. Here, there is no restriction | limiting in particular as a heat source used for drying, Arbitrary heat sources, such as a steam heater, an electric heater, and an infrared heater, can be used. In order to improve gas barrier properties, the heating temperature is preferably 50 to 150 ° C. The heat treatment time is preferably several seconds to 1 hour. Furthermore, the temperature may be constant during the heat treatment, or the temperature may be gradually changed. Further, during the drying treatment, the heat treatment may be performed while adjusting the humidity within the range of 20 to 90% RH in terms of relative humidity. You may perform the said heat processing in the state enclosed with air | atmosphere or inert gas.

Next, the composition of the coating film is modified by subjecting the dried coating film to active energy ray irradiation treatment such as plasma treatment, ultraviolet irradiation treatment, and flash pulse treatment, and contains the three types of silicon compounds of the present invention. A silicon compound layer [B] can be obtained. As the active energy ray 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 silicon compound layer [B]. The ultraviolet treatment may be performed under atmospheric pressure or reduced pressure, but it is preferable to perform ultraviolet treatment under atmospheric pressure from the viewpoint of versatility and production efficiency. From the viewpoint of composition control of the silicon compound layer [B], the oxygen gas partial pressure is preferably 1.0% or less, and more preferably 0.5% or less. The relative humidity can be set to a desired composition ratio. In the ultraviolet treatment, it is more preferable to reduce the oxygen concentration using nitrogen gas.

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 the like can be used, but a xenon lamp is used in the present invention from the viewpoint of production efficiency. It is preferable.

The accumulated amount of ultraviolet irradiation is preferably 0.5 to 10 J / cm ² , more preferably 0.8 to 7 J / cm ² . If the integrated light quantity is 0.5 J / cm ² or more, a desired silicon compound layer [B] composition can be obtained, which is preferable. Moreover, it is preferable if the integrated light quantity is 10 J / cm ² or less because damage to the polymer substrate and the inorganic layer [B] can be reduced.

In the present invention, it is more preferable to perform the ultraviolet treatment while heating the coating film after drying in order to improve the production efficiency during the ultraviolet treatment. The heating temperature is preferably 50 to 150 ° C, more preferably 80 to 130 ° C. A heating temperature of 50 ° C. or higher is preferable because high production efficiency can be obtained, and a heating temperature of 150 ° C. or lower is preferable because deformation and alteration of other materials such as a polymer base material hardly occur.

[Undercoat layer [C]]
The gas barrier film of the present invention is preferably provided with an undercoat layer [C] between the polymer substrate and the inorganic layer [A] in order to improve gas barrier properties and flex resistance. When defects such as protrusions and small scratches are present on the polymer substrate, pinholes and cracks also occur in the inorganic layer [A] laminated on the polymer substrate starting from the defects, resulting in gas barrier properties and resistance. Since the flexibility may be impaired, it is preferable to provide the undercoat layer [C] of the present invention. In addition, even when the difference in thermal dimensional stability between the polymer substrate and the inorganic layer [A] is large, it is preferable to provide the undercoat layer [C] because the gas barrier property and the bending resistance may be lowered. . The undercoat layer [C] used in the present invention preferably includes a structure obtained by crosslinking the polyurethane compound [C1] having an aromatic ring structure from the viewpoint of thermal dimensional stability and flex resistance. Furthermore, it is more preferable to contain one or more silicon compounds selected from ethylenically unsaturated compounds [C2], photopolymerization initiators [C3], organic silicon compounds [C4] and inorganic silicon compounds [C5].

[Polyurethane compound having an aromatic ring structure [C1]]
The polyurethane compound [C1] having an aromatic ring structure that can be used in the present invention has an aromatic ring and a urethane bond in the main chain or side chain. For example, a hydroxyl group and an aromatic ring are present in the molecule. It can be obtained by polymerizing the epoxy (meth) acrylate (c1), the diol compound (c2), and the diisocyanate compound (c3).

Examples of the epoxy (meth) acrylate (c1) having a hydroxyl group and an aromatic ring in the molecule include aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, and hydroquinone. This can be obtained by reacting the diepoxy compound with a (meth) acrylic acid derivative.

Examples of the diol compound (c2) include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol Neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2 , 4,4-Tetramethyl-1,3-cyclobutanediol, 4,4 ' Thiodiphenol, bisphenol A, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4 4,4′-isopropylidenephenol, 4,4′-isopropylidenebindiol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, etc. it can. These can be used alone or in combination of two or more.

Examples of the diisocyanate compound (c3) include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4. -Aromatic diisocyanates such as diphenylmethane diisocyanate, aliphatic diisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate Diisocyanate compounds, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexylene diisocyanate Alicyclic isocyanate compounds such as xylylene diisocyanate, aromatic aliphatic isocyanate compounds such as tetramethyl xylylene diisocyanate. These can be used alone or in combination of two or more.

The component ratios of (c1), (c2), and (c3) are not particularly limited as long as they are within a desired weight average molecular weight. The polyurethane compound [C1] having an aromatic ring structure of the present invention preferably has a weight average molecular weight (Mw) of 5,000 to 100,000. A weight average molecular weight (Mw) of 5,000 to 100,000 is preferable because the resulting cured film has excellent thermal dimensional stability and flex resistance. In addition, the weight average molecular weight (Mw) in this invention is the value measured using the gel permeation chromatography method and converted with standard polystyrene.

[Ethylenically unsaturated compound [C2]]
Examples of the ethylenically unsaturated compound [C2] that can be used as a raw material for the undercoat layer [C] include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like. Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Epoxy acrylates such as polyfunctional (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol S type epoxy di (meth) acrylate, etc. It is. Among these, polyfunctional (meth) acrylates excellent in thermal dimensional stability and surface protection performance are preferable. Moreover, these may be used by a single composition, and may mix and use two or more components.

The content of the ethylenically unsaturated compound [C2] is not particularly limited, but from the viewpoint of thermal dimensional stability and surface protection performance, the total amount with the polyurethane compound [C1] having an aromatic ring structure is 100% by mass. It is preferably in the range of -90% by mass, more preferably in the range of 10-80% by mass.

[Photoinitiator [C3]]
The photopolymerization initiator [C3] that can be used as a raw material for the undercoat layer [C] is particularly limited as long as the gas barrier property and the bending resistance of the gas barrier film of the present invention can be maintained and the photopolymerization can be started. Not. The following are illustrated as a photoinitiator which can be used suitably for this invention.
2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexylphenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] Phenyl} -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] 1- [4- (4-morpholinyl) phenyl] -1-alkyl phenone photopolymerization initiator such as butanone.
Acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
A titanocene photopolymerization initiator such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Photopolymerization initiators having an oxime ester structure such as 1,2-octanedione, 1- [4- (phenylthio)-, 2- (0-benzoyloxime)].

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

The content of the photopolymerization initiator [C3] is not particularly limited, but is in the range of 0.01 to 10% by mass with respect to 100% by mass of the total amount of polymerizable components from the viewpoint of curability and surface protection performance. The range is preferably 0.1 to 5% by mass.

[Organic silicon compound [C4]]
Examples of the organosilicon compound [C4] that can be used as the raw material for the undercoat layer [C] include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropi Methyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanate propyl triethoxysilane, and the like.

Among these, from the viewpoint of curability and polymerization activity by active energy ray irradiation, selected from the group consisting of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Organosilicon compounds containing at least one of these are preferred. Moreover, these may be used by a single composition, and may mix and use two or more components.

The content of the organosilicon compound [C4] is not particularly limited, but is preferably in the range of 0.01 to 10% by mass in 100% by mass of the total amount of polymerizable components from the viewpoint of curability and surface protection performance. The range of 0.1 to 5% by mass is more preferable.

[Inorganic silicon compound [C5]]
The inorganic silicon compound [C5] that can be used as the raw material for the undercoat layer [C] is preferably silica particles from the viewpoint of surface protection performance and transparency, and the primary particle diameter of the silica particles is in the range of 1 to 300 nm. Preferably, it is in the range of 5 to 80 nm. In addition, the primary particle diameter here refers to the particle diameter d calculated | required by applying the specific surface area s calculated | required by the gas adsorption method to following formula (2).
d = 6 / ρs (2) where ρ is the density of the particles.

[Thickness of undercoat layer [C]]
The thickness of the undercoat layer [C] is preferably from 200 nm to 4,000 nm, more preferably from 300 nm to 3,000 nm, and further preferably from 500 nm to 2,000 nm. If the thickness of the undercoat layer [C] is too small, the adverse effects of defects due to protrusions or small scratches present on the polymer substrate may not be suppressed. If the thickness of the undercoat layer [C] is too large, the smoothness of the undercoat layer [C] is reduced, and the uneven shape on the surface of the inorganic layer [A] laminated on the undercoat layer [C] is also increased. Since gaps are formed between the sputtered particles to be stacked, the film quality is difficult to be dense, and the effect of improving the gas barrier property may be difficult to obtain.

The center surface average roughness SRa of the undercoat layer [C] is preferably 10 nm or less. SRa of 10 nm or less is preferable because a homogeneous inorganic layer [A] can be easily obtained on the undercoat layer [C], and the reproducibility of gas barrier properties is improved. If the SRa on the surface of the undercoat layer [C] is too large, the uneven shape on the surface of the inorganic layer [A] on the undercoat layer [C] also increases and gaps are formed between the laminated sputtered particles, so that the film quality is improved. In some cases, the gas barrier property is hardly obtained and the effect of improving the gas barrier property is hardly obtained. In addition, since cracks due to stress concentration are likely to occur in portions where there are many irregularities, it may cause a reduction in the reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the undercoat layer [C] is preferably 10 nm or less, more preferably 7 nm or less.

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

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

[Electronic device]
Since the gas barrier film of the present invention has a high gas barrier property, it can be used in various electronic devices. For example, it can be suitably used for an electronic device such as a back sheet of a solar cell or a flexible circuit board. Since the electronic device using the gas barrier film of the present invention has an excellent gas barrier property, it is possible to suppress degradation of the device performance due to water vapor or the like.

[Other uses]
Since the gas barrier film of the present invention has a high gas barrier property, 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 methods]
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 A sample for cross-sectional observation was prepared by a focused ion beam (FIB) method using a micro sampling system (FB-2000A manufactured by Hitachi, Ltd.). 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 inorganic layer [A], silicon compound layer [B], and undercoat layer [C] The thickness of was measured.

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

(3) Water vapor permeability (g / (m ² · d))
A calcium layer having a thickness of 100 nm is formed on the silicon compound layer [B] side of the gas barrier film by vacuum deposition, and then aluminum having a thickness of 3000 nm so as to cover the entire calcium layer on the calcium layer by vacuum deposition. A layer was formed. Furthermore, after the aluminum layer was formed, glass having 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, and after the treatment, the amount of calcium corroded by water vapor was calculated to measure the amount of water vapor permeated. The number of samples of water vapor permeability was 2 samples per level, the number of measurements was 5 times for each sample, and the average value of 10 points obtained was the water vapor permeability (g / (m ² · d)).

(4) Composition of inorganic layer [A1] The composition analysis of [A1] was performed by ICP emission spectroscopic analysis (manufactured by SII Nanotechnology, SPS4000). Samples sampled at the stage of forming the inorganic layer [A1] on the polymer substrate or undercoat layer (before the silicon compound layer [B] is laminated) are thermally decomposed with nitric acid and sulfuric acid, and heated and dissolved with dilute nitric acid And then filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom, a silicon atom, and an aluminum atom was measured, and it converted into atomic ratio. The oxygen atoms were calculated values assuming that zinc atoms, silicon atoms, and aluminum atoms exist as zinc oxide (ZnO), silicon dioxide (SiO ₂ ), and aluminum oxide (Al ₂ O ₃ ), respectively.

(5) Composition of inorganic layer [A2] The composition analysis of the inorganic layer [A2] was performed by ICP emission spectroscopic analysis (SPS4000, manufactured by SII Nanotechnology). Samples sampled at the stage of forming the inorganic layer [A2] on the polymer substrate or undercoat layer (before the silicon compound layer [B] is laminated) are thermally decomposed with nitric acid and sulfuric acid and heated with dilute nitric acid Dissolved and filtered. The insoluble matter was ashed by heating, melted with sodium carbonate, dissolved with dilute nitric acid, and made up to a constant volume with the previous filtrate. About this solution, content of a zinc atom and a silicon atom was measured. Next, based on this value, the Rutherford backscattering method (AN-2500 manufactured by Nissin High Voltage Co., Ltd.) was used to quantitatively analyze zinc atoms, silicon atoms, sulfur atoms, and oxygen atoms. And the composition ratio of silicon dioxide.

(6) Composition of inorganic layer [A3] The composition analysis of inorganic layer [A3] was performed by calculating the atomic ratio of oxygen atoms to silicon atoms by using X-ray photoelectron spectroscopy (XPS method). The measurement conditions were as follows.
Apparatus: Quantera SXM (manufactured by PHI)
Excitation X-ray: monochromatic AlKα1,2
X-ray diameter: 100 μm
Photoelectron escape angle: 10 °.

(7) Composition of silicon compound layer [B],
A powder sample obtained by scraping the silicon compound layer [B] with a single blade is filled in a 7.5 mmφ sample tube, and a composition analysis is performed using ²⁹ Si CP / MAS NMR, and a spectrum as shown in FIG. 4 is obtained. Asked. The sum of peak areas of −30 to −50 ppm, the sum of peak areas of −50 to −90 ppm, and the sum of peak areas of −90 to −120 ppm when the sum of peak areas of −30 to −120 ppm in the spectrum is defined as 100 was calculated. . The measurement conditions were as follows.
Equipment: CMX-300 manufactured by Chemanetics
Measurement nuclear frequency: 59.636511 MHz ( ²⁹ Si nucleus)
Spectrum width: 30.03 kHz
Pulse width: 4.5 sec (90 ° pulse), 2.2 sec (45 ° pulse)
Pulse repetition time: ACQTM; 0.0682 sec, PD; 5.0 sec
Contact time: 2.0 sec
Observation point: 2048 data points; 8192
Reference material: Hexamethylcyclotrisiloxane (external standard; -9.66 ppm)
Temperature: Room temperature (about 22 ° C)
Sample rotation speed: 5.0 kHz
Peak area calculation: integration method.

(8) Flexibility Two samples of gas barrier film were sampled per 100 mm × 140 mm per level. As shown in FIG. 5, the gas barrier film is formed of a metal cylinder having a diameter of 5 mm at the center on the side opposite to the surface (reference numeral 21) on which the inorganic layer [A] and silicon compound layer [B] of (reference numeral 19) are formed. In the range where the holding angle of the cylinder is 0 ° (the sample is in a flat state) and the holding angle to the cylinder is 180 ° (a state where the sample is folded back) along the cylinder. After performing the folding operation, the water vapor permeability was evaluated by the method shown in (3). The number of measurements was 5 for each specimen, and the average value of the 10 points obtained was the water vapor permeability after the flex resistance test.

(9) Adhesiveness In accordance with JIS K5600-5-6: 1999, the silicon compound layer [B] was cut into a 1 × 1 mm square lattice pattern of 25 squares to evaluate the adhesiveness. The evaluation results were classified into 6 levels from classification 0 to classification 5 in order from the one with good adhesion.

[Method for Forming Inorganic Layer [A] in Examples 1 to 11]
(Formation of inorganic layer [A1])
Sputtering, which is a mixed sintered material formed of zinc oxide, silicon dioxide and aluminum oxide on one side of a polymer substrate (reference numeral 5) using a winding type sputtering apparatus (reference numeral 6a) having the structure shown in FIG. Sputtering was performed using a target to provide an inorganic layer [A1].

The specific operation is as follows. First, a winding chamber (symbol 7) of a winding-type sputtering apparatus in which a sputtering target sintered with a zinc oxide / silicon dioxide / aluminum oxide composition mass ratio of 77/20/3 is installed on the sputtering electrode (symbol 13). Among them, the polymer substrate is set on the unwinding roll (symbol 8) so that the surface on which the inorganic layer [A1] is provided faces the sputter electrode, unwinding, unwinding side guide roll (symbol 9, 10 and 11) and passed through a cooling drum (reference numeral 12). Argon gas and oxygen gas were introduced at an oxygen gas partial pressure of 10% so that the degree of decompression was 2 × 10 ⁻¹ Pa, and an argon / oxygen gas plasma was generated by applying an input power of 4,000 W from a DC power source. The inorganic layer [A1] was formed on the surface of the polymer substrate by sputtering. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll (code | symbol 18) via the winding side guide roll (code |

symbol

15,16,17).

(Formation of inorganic layer [A2])
A sputter target, which is a mixed sintered material formed of zinc sulfide and silicon dioxide, is formed on one surface of a polymer substrate (reference numeral 5) using a winding type sputtering apparatus (reference numeral 6a) having the structure shown in FIG. Sputtering was used to provide an inorganic layer [A2].

The specific operation is as follows. First, unwinding in a winding chamber (symbol 7) of a winding type sputtering apparatus in which a sputtering target sintered with a zinc sulfide / silicon dioxide molar ratio of 80/20 is installed on the sputtering electrode (symbol 13). The polymer base material was set on the roll (symbol 8), unwound, and passed through the cooling drum (symbol 12) through the unwinding side guide rolls (symbol 9, 10, 11). Argon gas was introduced so that the degree of decompression was 2 × 10 ⁻¹ Pa, and an applied power of 500 W was applied from a high-frequency power source to generate argon gas plasma, and an inorganic layer [on the surface of the polymer substrate by sputtering [ A2] was formed. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll (code | symbol 18) via the winding side guide roll (code |

symbol

15,16,17).

(Formation of inorganic layer [A3])
Using a roll-up type CVD apparatus (symbol 6b) having the structure shown in FIG. 3, chemical vapor deposition using hexamethyldisiloxane as a raw material was performed on one side of the polymer substrate (5) to form an inorganic layer [A3 ] Was provided.

The specific operation is as follows. First, in the winding chamber (symbol 7) of the winding type CVD apparatus, the polymer base material is set on the unwinding roll (symbol 8), unwinding, and unwinding side guide rolls (symbols 9, 10, 11). ) Was passed through a cooling drum (reference numeral 12). Oxygen gas 0.5 L / min and hexamethyldisiloxane 70 cc / min are introduced so that the degree of decompression is 2 × 10 ⁻¹ Pa, and plasma is generated by applying an input power of 3,000 W from a high-frequency power source to the CVD electrode. Then, an inorganic layer [A3] was formed on the surface of the polymer substrate by CVD. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll via the winding side guide roll (code |

symbol

15,16,17).

[Synthesis example of polyurethane compound [C1] having an aromatic ring structure]
In a 5 liter four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (trade name: Epoxy ester 3000A, manufactured by Kyoeisha Chemical Co., Ltd.) and 710 parts by mass of ethyl acetate were placed, and the internal temperature was 60 ° C It was heated so that it might become. As a synthesis catalyst, 0.2 part by mass of di-n-butyltin dilaurate was added, and 200 parts by mass of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. Reaction was continued for 2 hours after completion | finish of dripping, and 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries Ltd.) was dripped over 1 hour continuously. The reaction was continued for 5 hours after the dropwise addition to obtain a polyurethane compound having an aromatic ring structure with a weight average molecular weight of 20,000.

Example 1
A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the polymer substrate, and the inorganic layer [A1] was provided on one side of the polymer substrate so as to have a thickness of 180 nm. . As for the composition of the inorganic layer [A1], the Zn atom concentration was 27.5 atom%, the Si atom concentration was 13.1 atom%, the Al atom concentration was 2.3 atom%, and the O atom concentration was 57.1 atom%. A test piece having a length of 100 mm and a width of 100 mm was cut out from the film on which the inorganic layer [A1] was formed, and the center plane average roughness SRa of the inorganic layer [A1] was evaluated. The results are shown in Table 1.

Next, as a coating liquid for forming the silicon compound layer [B], 100 parts by mass of a coating agent mainly composed of perhydropolysilazane (“NN120-20” manufactured by AZ Electronic Materials, solid content concentration: 20% by mass) A coating liquid 1 diluted with 300 parts by mass of butyl ether was prepared. The coating liquid 1 is applied onto the inorganic layer [A1] with a micro gravure coater (gravure wire number 200UR, gravure rotation ratio 100%), dried at 120 ° C. for 1 minute, dried, and then subjected to UV treatment under the following conditions. A silicon compound layer [B] having a thickness of 120 nm was provided to obtain a gas barrier film.
Ultraviolet treatment device: MEIRH-M-1-152-H (manufactured by M. D. Excimer)
Introduced gas: N ₂
Oxygen concentration: 300-800ppm
Integrated light quantity: 3,000 mJ / cm ²
Sample temperature control: 100 ° C.

The obtained gas barrier film was subjected to composition analysis using ²⁹ Si CP / MAS NMR method, and the total peak area of −30 to −50 ppm when the total peak area of −30 to −120 ppm in the obtained spectrum was taken as 100. The sum of peak areas from -50 to -90 ppm and the sum of peak areas from -90 to -120 ppm were calculated. The results are shown in Table 1.

Further, a test piece having a length of 100 mm and a width of 140 mm was cut out from the obtained gas barrier film, and the water vapor permeability was evaluated. The results are shown in Table 1.

(Example 2)
A polyethylene terephthalate film (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) having a thickness of 50 μm was used as the polymer substrate.
As a coating liquid for forming the undercoat layer [C], 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), and 1-hydroxy- 5 parts by mass of cyclohexyl phenyl-ketone (trade name: “IRGACURE” (registered trademark) 184) manufactured by BASF Japan Ltd.) and 3-methacryloxypropylmethyldiethoxysilane (trade name: KBM-503) manufactured by Shin-Etsu Silicone Co., Ltd. 3 A coating liquid 2 was prepared by blending part by mass, 170 parts by mass of ethyl acetate, 350 parts by mass of toluene, and 170 parts by mass of cyclohexanone. Next, the coating liquid 2 is applied onto the polymer substrate with a micro gravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to UV treatment under the following conditions. An undercoat layer [C] having a thickness of 1,000 nm was provided.

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

Next, an inorganic layer [A1] and a silicon compound layer [B] were provided on the undercoat layer [C] in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

Example 3
A gas barrier film was prepared in the same manner as in Example 1 except that an amorphous cyclic polyolefin film having a thickness of 100 μm (“ZEONOR FILM” ZF14 manufactured by ZEON Corporation) (“ZEONOR” is a registered trademark) was used as the polymer substrate. Obtained.

Example 4
A gas barrier film was obtained in the same manner as in Example 2 except that an amorphous cyclic polyolefin film having a thickness of 100 μm (“ZEONOR FILM” ZF14 manufactured by Nippon Zeon Co., Ltd.) was used as the polymer substrate.

(Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A1] was provided to have a thickness of 950 nm.

(Example 6)
A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A2] was provided to a thickness of 150 nm in place of the inorganic layer [A1].

(Example 7)
A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A3] was provided to a thickness of 150 nm in place of the inorganic layer [A1].

(Example 8)
A gas barrier film was obtained in the same manner as in Example 2 except that the silicon compound layer [B] was provided to have a thickness of 50 nm.

Example 9
A gas barrier film was obtained in the same manner as in Example 2 except that the silicon compound layer [B] was provided to have a thickness of 1,000 nm.

(Example 10)
A gas barrier film was obtained in the same manner as in Example 2 except that when the silicon compound layer [B] was formed, the amount of UV irradiation integrated light was changed to 1,500 mJ / cm ² .

(Example 11)
A gas barrier film was obtained in the same manner as in Example 2 except that when the silicon compound layer [B] was formed, the UV irradiation integrated light amount was changed to 1,000 mJ / cm ² .

(Comparative Example 1)
Except that the inorganic layer [A] was not formed on the polymer substrate, and the silicon compound layer [B] was provided directly on the surface of the polymer substrate so as to have a thickness of 120 nm, the same as in Example 1. A gas barrier film was obtained.

(Comparative Example 2)
A gas barrier film was obtained in the same manner as in Example 1 except that the silicon compound layer [B] was not provided on the inorganic layer [A].

(Comparative Example 3)
In Example 1, the order of forming the inorganic layer [A] and the silicon compound layer [B] was changed to obtain a gas barrier film having a layer configuration different from that of Example 1.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Example 7 except that the silicon compound layer [B] was not provided on the inorganic layer [A].

(Comparative Example 5)
A gas barrier film was obtained in the same manner as in Example 2 except that the inorganic layer [A3] was provided on the inorganic layer [A] by the CVD method.

(Comparative Example 6)
Example 2 is the same as Example 2 except that instead of the silicon compound layer [B], _a layer made of only SiO _p N _q without SiN _x H _{y and} SiO _a (OH) _4-2a is formed. Thus, a gas barrier film was obtained.
In addition, the method of forming the layer consisting only of SiO _p N _q uses a winding type sputtering apparatus having the structure shown in FIG. 2, on one side of the polymer substrate, using a sputtering target formed of silicon nitride Sputtering was performed to provide a layer made of only SiO _p N _q . Specifically, first, in the winding chamber of a winding-type sputtering apparatus in which a sputtering target formed of silicon nitride is installed on the sputtering electrode, a polymer substrate is placed on the winding roll with a SiO _p N _q layer. The surface to be provided was set so as to face the sputter electrode, and the polymer substrate was unwound and passed through a cooling drum through a guide roll. Argon gas and oxygen gas were introduced into the sputtering chamber at an oxygen gas partial pressure of 10% so that the degree of vacuum was 2 × 10 ⁻¹ Pa. Further, by applying an input power of 1,000 W from a high frequency power source, argon / oxygen gas plasma was generated, and a SiO _p N _q layer was formed on the surface of the polymer substrate by sputtering. The thickness was adjusted by the film transport speed. Then, it wound up on the winding roll via the guide roll.

Since the gas barrier film of the present invention is excellent in gas barrier properties against oxygen gas, water vapor, etc., it can be usefully used, for example, as a packaging material for foods, pharmaceuticals, etc., and as a member for electronic devices such as thin televisions and solar cells. .

1 Polymer substrate 2 Inorganic layer [A]
3 Silicon compound layer [B]
4 Undercoat layer [C]
5 Polymer substrate 6a Winding type sputtering device 6b Winding type CVD device 7 Winding chamber 8 Unwinding rolls 9, 10, 11 Unwinding side guide roll 12 Cooling drum 13 Sputtering electrode 14

CVD electrodes

15, 16, 17 Winding Take-up side guide roll 18 Take-up roll 19 Gas barrier film 20 Metal cylinder 21 Surface opposite to the surface on which inorganic layer [A] and silicon compound layer [B] are formed

Claims

A gas barrier film having an inorganic layer [A] and a silicon compound layer [B] in this order from the polymer substrate side on at least one side of the polymer substrate, in which the silicon compound layer [B] is at least SiN a silicon compound having a structure represented by x H y , SiO p N q and SiO a (OH) 4-2a (x + y = 4, p + q = 4, a ≦ 2 x, y, p, q> 0) And a gas barrier film in which the inorganic layer [A] and the silicon compound layer [B] are in contact.
The gas barrier film according to claim 1, wherein the inorganic layer [A] contains a zinc compound and a silicon oxide.
In the 29 Si CP / MAS NMR spectrum of the silicon compound layer [B], when the total peak area of −30 to −120 ppm is defined as 100, the total peak area of −30 to −50 ppm is 10 or more, −50 to −90 ppm The gas barrier film according to claim 1 or 2, wherein the total peak area is 10 or more and the total peak area of -90 to -120 ppm is 80 or less.
The gas barrier film according to any one of claims 1 to 3, wherein the inorganic layer [A] is any one selected from the following inorganic layers [A1] to [A3].
Inorganic layer [A1]: Inorganic layer consisting of coexisting phases of (i) to (iii) (i) Zinc oxide (ii) Silicon dioxide (iii) Aluminum oxide Inorganic layer [A2]: From the coexisting phase of zinc sulfide and silicon dioxide Inorganic layer [A3]: inorganic layer mainly composed of silicon oxide having an atomic ratio of oxygen atoms to silicon atoms of 1.5 to 2.0
The inorganic layer [A] is the inorganic layer [A1], and the inorganic layer [A1] has a zinc atom concentration of 20 to 40 atom% and a silicon atom concentration of 5 to 20 atom% as measured by ICP emission spectroscopy. The gas barrier film according to claim 4, wherein the gas barrier film is composed of a composition having an aluminum atom concentration of 0.5 to 5 atom% and an oxygen atom concentration of 35 to 70 atom%.
The inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] has a composition in which the molar fraction of zinc sulfide to the total of zinc sulfide and silicon dioxide is 0.7 to 0.9. The gas barrier film according to claim 4, which is constituted.
An undercoat layer [C] including a structure obtained by crosslinking a polyurethane compound [C1] having an aromatic ring structure is provided between the polymer substrate and the inorganic layer [A]. The gas barrier film according to any one of the above.
The gas barrier film according to claim 7, wherein the undercoat layer [C] contains an organosilicon compound and / or an inorganic silicon compound.
An electronic device using the gas barrier film according to any one of claims 1 to 8.