TW201534481A - Gas barrier film - Google Patents

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 SiNxHy, SiOpNq and SiOa(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 gas barrier film of the present invention is used for food applications requiring high gas barrier properties, packaging applications for pharmaceuticals, or electronic devices such as solar cells, electronic paper, and organic electroluminescence (EL) displays.

On the surface of the polymer substrate, physical vapor deposition (PVD), plasma chemical vapor deposition, thermal chemical vapor deposition, vacuum vapor deposition, sputtering, ion plating, etc. a gas barrier film formed by forming a film of an inorganic material (including an inorganic oxide) such as alumina, cerium oxide or magnesium oxide by a chemical vapor deposition method (CVD method) such as a photochemical vapor deposition method, or the like. A packaging material such as a food or a pharmaceutical product that requires a barrier of various gases such as water vapor or oxygen, and an electronic device member such as a thin television or a solar battery are used.

As a gas barrier improving technique, for example, a gas using a vapor containing an organic cerium compound and oxygen is used, and a plasma CVD method is used to form a cerium oxide as a main component and at least one type of carbon and hydrogen. A method of improving gas barrier properties while maintaining transparency and a compound of oxygen and oxygen (Patent Document 1). In addition, as a gas barrier property improvement technique other than the film formation method using a plasma CVD method or the like, there is a smooth substrate using a pinhole having a reduced gas barrier property or a protrusion or unevenness which is a cause of cracking, or Use a primer layer for surface smoothing The substrate (patent documents 2, 3 and 4). Further, a method of converting a polyazirazolium film formed by a wet coating method into a ruthenium oxide film or a ruthenium oxynitride film is known (Patent Documents 5 and 6).

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-142252

Patent Document 2: Japanese Laid-Open Patent Publication No. 2002-113826

Patent Document 3: International Publication No. 2012/137662

Patent Document 4: International Publication No. 2013/061726

Patent Document 5: International Publication No. 2011/007543

Patent Document 6: International Publication No. 2011/004698

However, as in Patent Document 1, in the method of forming a gas barrier layer containing cerium oxide as a main component by a plasma CVD method, the film quality of the gas barrier layer formed is different depending on the type of the substrate. Stable gas barrier. In order to stabilize the gas barrier properties, it is necessary to thicken the film, and as a result, there is a problem that the bending resistance is lowered or the manufacturing cost is increased. Further, as disclosed in Patent Document 2, a method of using a smoother for a substrate on which a gas barrier layer is formed and a method of providing a substrate having an undercoat layer for smoothing of a surface are used, although the occurrence of pinholes or cracks is prevented. The gas barrier property is increased, but the improvement in performance is not sufficient. On the other hand, in Patent Documents 3 and 4, since the film quality of the gas barrier layer formed is improved, although the performance is improved, there is a problem that it is difficult to stably exhibit high gas barrier properties. In addition, it is disclosed in Patent Documents 5 and 6. In the method of forming a gas barrier layer by using a polyazide layer, it is susceptible to the conditions at the time of forming a layer, and in order to stably obtain a gas barrier film having sufficient gas barrier properties, it is necessary to laminate a plurality of layers of polycondensation. Azane layer. As a result, there is a problem that the bending resistance is lowered or the manufacturing cost is increased.

The present invention has been made in view of the above-described technical background, and it is an object of the invention to provide a gas barrier film which has high gas barrier properties and is excellent in bending resistance and adhesion even without thick film formation or multilayer lamination.

In order to solve such a problem, the present invention employs the following means. which is,

(1) A gas barrier film which is provided on at least one side of a polymer substrate, and has a gas barrier film of an inorganic layer [A] and a ruthenium compound layer [B] in this order from the polymer substrate side. The bismuth compound layer [B] contains 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) The structure of the ruthenium compound, and the inorganic layer [A] is adjacent to the ruthenium compound layer [B].

Further, as a preferred aspect 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 cerium oxide.

(3) The gas barrier film according to (1) or (2), wherein, in the ²⁹ Si CP/MAS NMR spectrum of the ruthenium compound layer [B], when the sum of the peak areas of -30 to -120 ppm is 100 The sum of the peak areas of -30~-50ppm is more than 10, the sum of the peak areas of -50~-90ppm is more than 10, and the sum of the peak areas of -90~-120ppm is 80 or less.

(4) The gas barrier film according to any one of (1) to (3), wherein the inorganic layer [A] is selected from the following inorganic layers [A1] to [A3];

Inorganic layer [A1]: an inorganic layer formed by the coexistence phase of (i) to (iii)

(i) zinc oxide

(ii) cerium oxide

(iii) Alumina

Inorganic layer [A2]: an inorganic layer formed by the coexistence of zinc sulfide and ceria

Inorganic layer [A3]: an inorganic layer containing a ruthenium oxide having an atomic ratio of an oxygen atom to a ruthenium atom of 1.5 to 2.0 as a main component.

(5) The gas barrier film according to (4), wherein the inorganic layer [A] is the inorganic layer [A1], and the inorganic layer [A1] has a zinc atom concentration of 20 as determined by ICP emission spectrometry. It is composed of a composition of ~40 atom%, a germanium atom concentration of 5 to 20 atom%, an aluminum atom concentration of 0.5 to 5 atom%, and an oxygen atom concentration of 35 to 70 atom%.

(6) The gas barrier film according to (4), wherein the inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] is vulcanized in combination with zinc sulfide and cerium oxide. The molar fraction of zinc is composed of a composition of 0.7 to 0.9.

(7) The gas barrier film according to any one of (1) to (6), wherein the undercoat layer [C] is provided between the polymer substrate and the inorganic layer [A], the undercoat layer [C] A structure obtained by crosslinking a polyurethane compound [C1] having an aromatic ring structure.

(8) The gas barrier film according to (7), wherein the aforementioned undercoat layer [C] pack Contains a cockroach compound and/or an inorganic hydrazine compound.

Further, in the present invention, the following electronic device using a gas barrier film is also provided.

(9) An electronic device using the gas barrier film according to any one of (1) to (8).

According to the present invention, there is provided a gas barrier film which has high gas barrier properties against water vapor and is excellent in bending resistance and adhesion.

1‧‧‧ polymer substrate

2‧‧‧Inorganic layer [A]

3‧‧‧矽 compound layer [B]

4‧‧‧Undercoat [C]

5‧‧‧ polymer substrate

6a‧‧‧Wind-type sputtering device

6b‧‧‧Wind-through CVD apparatus

7‧‧‧The take-up room

8‧‧‧Rolling roll

9, 10, 11‧‧‧ rolled out side guide rolls

12‧‧‧Clean roller

13‧‧‧Splated electrode

14‧‧‧ CVD electrode

15,16,17‧‧‧Winding side guide rolls

18‧‧‧Winding roller

19‧‧‧ gas barrier film

20‧‧‧Metal cylinder

21‧‧‧The opposite side of the surface formed with the inorganic layer [A] and the bismuth compound layer [B]

Fig. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention.

Fig. 2 is a schematic view showing a wound-type sputtering apparatus for producing a gas barrier film of the present invention.

Fig. 3 is a schematic view showing a winding-type CVD apparatus for producing a gas barrier film of the present invention.

Fig. 4 is a graph showing the ²⁹ Si CP/MAS NMR spectrum of the ruthenium compound layer [B] of the gas barrier film of the present invention obtained in Example 1.

Figure 5 is a schematic view of the bending resistance test.

Fig. 6 is a cross-sectional view showing an example of the gas barrier film of the present invention.

[Formation of the Invention]

In order to obtain a gas barrier film having high gas barrier properties such as water vapor and excellent in bending resistance and adhesion, the inventors have repeatedly studied intensively and found that inorganic substances are formed on at least one side of the polymer substrate. Layer [A] and contains 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 When the ruthenium compound layer [B] of the three ruthenium compounds of the structure shown is laminated in such a manner as to be adjacent to each other, the above problem can be solved.

Furthermore, the meanings of the above three structures are as follows.

SiN _x H _y : nitrogen and hydrogen are bonded to a ruthenium atom present in the compound, and the number of bonds to each element is x and y.

SiO _p N _q : nitrogen and hydrogen are bonded to a ruthenium atom present in the compound, and the number of bonds to each element is p and q.

SiO _a (OH) _4-2a : a structure of a compound in which the _ruthenium atom is 1.

Fig. 1 is a cross-sectional view showing an example of a gas barrier film of the present invention. In the gas barrier film of the present invention, as shown in Fig. 1, an inorganic layer [A] (symbol 2) and a layer are sequentially laminated on the polymer substrate (symbol 1) from the polymer substrate side. A ruthenium compound layer [B] (symbol 3) of three ruthenium compounds having a structure represented by SiN _x H _y , SiO _p N _q and SiO _a (OH) _4-2a (x+y=4, a≦2) . In addition, the example of Fig. 1 shows the minimum configuration of the gas barrier film of the present invention, and only the inorganic layer [A] and the ruthenium compound layer [B] are disposed on one side of the polymer substrate, but in the polymer. Other layers may be disposed between the substrate and the inorganic layer [A], and other layers may be disposed on the side of the polymer substrate 1 opposite to the side of the laminated inorganic layer [A].

The reason why the remarkable effect is obtained in the present invention is presumed as follows. In other words, the inorganic layer [A] and the ruthenium compound layer [B] are bonded to each other in the form of pinholes or cracks existing in the vicinity of the surface of the inorganic layer [A] on the side where the ruthenium compound layer [B] is formed. The composition of the ruthenium compound layer [B] exhibits high barrier properties. Further, since the above three kinds of ruthenium compounds easily form a chemical bond with the components constituting the inorganic layer [A], the inorganic layer is of course [A]. The adhesion to the ruthenium compound layer [B] is increased, and excellent adhesion can be obtained even when another layer is laminated on the ruthenium compound layer [B]. Further, since the ruthenium compound layer [B] having the above-described structure is excellent in flexibility, excellent bending resistance can be obtained.

[polymer substrate]

The polymer base material used in the present invention preferably has a film form from the viewpoint of ensuring flexibility. The composition of the film may be a single layer film or a film of two or more layers formed, for example, by a co-extrusion method. The type of the film can be a film obtained by extending in the uniaxial direction or the biaxial direction.

The material of the polymer base material used in the present invention is not particularly limited, but an organic polymer is preferred as a main constituent component. Examples of the organic polymer which can be suitably used in the present invention include crystalline polyolefins such as polyethylene and polypropylene, amorphous cyclic polyolefins having a cyclic structure, polyethylene terephthalate or poly Polyesters such as ethylene naphthalate, polyamines, polycarbonates, polystyrenes, polyvinyl alcohols, saponified products of ethylene vinyl acetate copolymers, various polymers such as polyacrylonitrile, polyacetal, etc. . Among these, an amorphous cyclic polyolefin or polyethylene terephthalate which is excellent in transparency, versatility, and mechanical properties is preferable. In addition, the organic polymer may be either a homopolymer or a copolymer, and the organic polymer may be used alone or in combination of plural kinds.

The surface of the polymer substrate on the side where the inorganic layer [A] is formed may be subjected to corona treatment, plasma treatment, ultraviolet treatment, ion bombardment treatment, solvent treatment, or organic matter in order to improve adhesion or smoothness. Formation of an undercoat layer composed of an inorganic substance or a mixture thereof Processing before processing. Further, for the purpose of improving the slipperiness at the time of winding up the film on the side opposite to the side on which the inorganic layer [A] is formed, a coating of an organic substance or an inorganic substance or a mixture of these may be laminated.

The thickness of the polymer substrate to be used in the present invention is not particularly limited, but is preferably 500 μm or less from the viewpoint of ensuring flexibility, and is preferably from the viewpoint of ensuring strength against stretching or punching. 5 μm or more. Further, the thickness of the polymer substrate is preferably from 10 μm to 200 μm from the viewpoint of easiness of processing or handling of the film.

[Inorganic layer [A]]

The inorganic layer [A] in the present invention may be exemplified by zinc (Zn), bismuth (Si), aluminum (Al), titanium (Ti), zirconium (Zr), tin (Sn), indium (In), and antimony (Nb). An oxide, a nitride, a sulfide, or a mixture of the elements of molybdenum (Mo), tantalum (Ta), or the like. The inorganic layer is not particularly limited as long as it contains such an inorganic material, but the inorganic layer [A] preferably contains a cerium oxide, and more preferably further contains a zinc compound and a cerium oxide. Further, as the inorganic layer [A] having high gas barrier properties, any one selected from the following inorganic layers [A1] to [A3] can be used.

Inorganic layer [A1]: an inorganic layer formed by the coexistence phase of (i) to (iii)

(i) zinc oxide

(ii) cerium oxide

(iii) Alumina

Inorganic layer [A2]: an inorganic layer formed by the coexistence of zinc sulfide and ceria

Inorganic layer [A3]: an inorganic layer containing a cerium oxide having an atomic ratio of an oxygen atom to a cerium atom of 1.5 to 2.0 as a main component

The respective details of the inorganic layers [A1] to [A3] are as follows.

The thickness of the inorganic layer [A] in the present invention is preferably 10 nm or more and 1,000 nm or less in terms of the thickness of the layer exhibiting gas barrier properties. If the thickness of the layer is small, a gas barrier property cannot be sufficiently ensured, and gas barrier properties may be uneven in the surface of the polymer substrate. In addition, when the thickness of the layer is too large, the stress remaining in the layer becomes large, and cracking is likely to occur in the inorganic layer [A] due to bending or punching from the outside, and the gas barrier property may be lowered depending on the use. Therefore, the thickness of the inorganic layer [A] is 10 nm or more, more preferably 100 nm or more, and on the other hand, it is 1,000 nm or less and 500 nm or less. The thickness of the inorganic layer [A] is usually determined by cross-sectional observation by 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 more than 10 nm, the uneven shape on the surface of the inorganic layer [A] becomes large, and a gap is formed between the deposited particles of the deposited layer, so that the film quality is hard to be dense, and it is difficult to obtain a gas barrier property even if a thick film thickness is formed. The situation of the effect. In addition, when the SRa is greater than 10 nm, the film quality of the ruthenium compound layer [B] laminated on the inorganic layer [A] is not uniform, and the gas barrier properties may be lowered. Therefore, the SRa of the inorganic layer [A] is preferably 10 nm or less, more preferably 7 nm or less.

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

The method of forming the inorganic layer [A] in the present invention is not particularly limited, and can be formed, for example, by a vacuum deposition method, a sputtering method, an ion plating method, a CVD method, or the like. Among these methods, from the viewpoint of easily and densely forming the inorganic layer [A], a sputtering method or a CVD method is preferred.

[Inorganic layer [A1]]

For the inorganic layer [A], a coexisting phase of (i) zinc oxide, (ii) cerium oxide, and (iii) aluminum oxide (hereinafter also referred to as (i) zinc oxide, (ii) cerium oxide. And (iii) the inorganic layer [A1] of the layer formed by the "co-existing phase of alumina" as "Zinc oxide-ceria-alumina coexisting phase", and it demonstrates in detail. Further, cerium oxide (SiO ₂ ) depends on the conditions at the time of formation, and forms a certain deviation (SiO~SiO ₂ ) from the composition ratio of cerium to oxygen in the composition formula of the left, but is described herein as oxidizing.矽 or SiO ₂ . Regarding the deviation of the composition ratio from the chemical formula, zinc oxide and aluminum oxide are treated in the same manner, and there is no deviation from the composition ratio depending on the conditions at the time of formation, and each is described as zinc oxide or ZnO, alumina or Al ₂ O. ₃ .

In the gas barrier film of the present invention, the gas barrier property is improved by using the inorganic layer [A1], and it is presumed that the crystalline component contained in the zinc oxide is amorphous with cerium oxide. When the components coexist, the crystal growth of zinc oxide which is likely to generate microcrystals is suppressed, and the particle size is reduced, the layer is densified, and the penetration of water vapor is suppressed.

Further, it is considered that by coexisting alumina, it is possible to further suppress the crystal growth since the zinc oxide and the ceria are coexisted, and the layer can be further densified, and the crack is caused by the use. The gas barrier properties caused by the formation are reduced and can be suppressed.

The composition of the inorganic layer [A1] can be measured by ICP emission spectrometry as described later. The concentration of zinc atoms determined by ICP emission spectrometry is preferably 20 to 40 atom%, the concentration of germanium atoms is preferably 5 to 20 atom%, the concentration of aluminum atoms is preferably 0.5 to 5 atom%, and the concentration of O atoms is preferably 35. ~70atom%. If the zinc atom concentration is greater than 40 atom% or the germanium atom concentration is less than 5 atom%, the crystal growth of zinc oxide can be suppressed. The cerium oxide and/or the aluminum oxide system are insufficient, and the void portion or the defective portion is increased, and high gas barrier properties are not obtained. When the zinc atom concentration is less than 20 atom% or the germanium atom concentration is more than 20 atom%, the amorphous component of the ceria having a layer may increase and the flexibility of the layer may be lowered. In addition, when the aluminum atom concentration is more than 5 atom%, the affinity between zinc oxide and cerium oxide becomes excessively high, and the film becomes hard, and cracks are likely to occur in heat or external stress. When the aluminum atom concentration is less than 0.5 atom%, the affinity between zinc oxide and cerium oxide becomes insufficient, and the bonding force between the particles forming the layer cannot be improved, and the flexibility may be lowered. Further, when the oxygen atom concentration is more than 70 atom%, the amount of defects in the inorganic layer [A1] increases, and the desired gas barrier properties may not be obtained. When the oxygen atom concentration is less than 35 atom%, the oxidation state of zinc, bismuth, and aluminum becomes insufficient, and crystal growth cannot be suppressed, and the particle diameter becomes large, so that the gas barrier property may be lowered. According to the tendency of the content of each atom shown above, the zinc atom concentration is preferably 25 to 35 atom%, the germanium 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%. .

Since the composition of the inorganic layer [A1] is formed by the same composition as the mixed sintered material used in the formation of the layer, the inorganic layer can be adjusted by using a mixed sintered material having a composition conforming to the composition of the target layer. The composition of [A1].

The composition of the inorganic layer [A1] was determined by ICP emission spectrometry to quantify each element of zinc, bismuth, and aluminum, and was calculated as a composition ratio of zinc oxide to cerium oxide, aluminum oxide, and inorganic oxide contained therein. Further, the oxygen atom system is calculated by presupposing that each of a zinc atom, a germanium atom, and an aluminum atom exists as zinc oxide (ZnO), germanium dioxide (SiO ₂ ), or aluminum oxide (Al ₂ O ₃ ). The ICP emission spectroscopic analysis is an analytical method capable of performing multi-element simultaneous measurement from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and is applicable to composition analysis. When the inorganic layer or the resin layer is further laminated on the inorganic layer [A1], the layer may be removed by ion etching or chemical treatment as necessary, and then ICP emission spectroscopic analysis is performed.

[Inorganic layer [A2]]

Next, in the present invention, a coexistence phase of zinc sulfide and ceria which is used as the inorganic layer [A] is used (hereinafter, the coexistence phase of zinc sulfide and ceria is also referred to as "zinc sulfide-ceria coexisting phase"). The inorganic layer [A2] of the layer formed will be described in detail. Further, here, cerium oxide (SiO ₂ ) also depends on the conditions at the time of its formation, and generates a certain deviation (SiO~SiO ₂ ) from the composition ratio of cerium to oxygen in the composition formula of the left, but is described as two. Cerium oxide or SiO ₂ . Regarding the deviation of the composition ratio from the chemical formula, the zinc sulfide is treated in the same manner, and the deviation of the composition ratio depending on the conditions at the time of formation is described as zinc sulfide or ZnS.

In the gas barrier film of the present invention, the gas barrier property is improved by using the inorganic layer [A2], and it is presumed that the crystalline component contained in the zinc sulfide is amorphous with cerium oxide. The components coexist, and the crystal growth of zinc sulfide which is likely to generate microcrystals is suppressed, and the particle size is reduced, the layer is densified, and the penetration of water vapor is suppressed.

Further, it is considered that the zinc sulfide-ceria coexisting phase containing zinc sulfide which is inhibited by crystal growth is higher in flexibility than the layer formed only of inorganic oxide or metal oxide, and is derived from heat or from The external stress is less likely to cause a crack layer. Therefore, by using the inorganic layer [A2], the gas barrier property due to the generation of cracks during use is lowered. Low, can also be suppressed.

The composition of the inorganic layer [A2] is preferably from 0.7 to 0.9 in terms of the total amount of zinc sulfide relative to the total of zinc sulfide and cerium oxide. When the molar fraction of zinc sulfide is more than 0.9 with respect to the total of zinc sulfide and cerium oxide, the cerium oxide system which can suppress the growth of the crystal of zinc sulfide is insufficient, and the void portion or the defective portion is increased, and it is impossible to obtain The specified gas barrier condition. In addition, when the molar fraction of zinc sulfide is less than 0.7 in total of zinc sulfide and cerium oxide, the amorphous component of cerium oxide in the inorganic layer [A2] increases, and the flexibility of the layer is lowered. Therefore, for mechanical bending, the flexibility of the gas barrier film is lowered. According to the tendency of the content of each compound shown above, the molar fraction of zinc sulfide is more preferably in the range of 0.75 to 0.85 with respect to the total of zinc sulfide and cerium oxide.

Since the composition of the inorganic layer [A2] is formed by the same composition as the mixed sintered material used in the formation of the layer, the inorganic layer [A2] can be adjusted by using a mixed sintered material having a composition in accordance with the purpose. composition.

The composition analysis of the inorganic layer [A2] was first determined by ICP emission spectrometry to determine the composition ratio of zinc and bismuth. Based on this value, the Rutherford backscattering method was used to quantitatively analyze each element. The composition ratio of zinc sulfide to cerium oxide and other inorganic oxides contained therein. The ICP emission spectroscopic analysis is an analytical method capable of performing multi-element simultaneous measurement from an emission spectrum generated when a sample is introduced into a plasma light source unit together with argon gas, and is applicable to composition analysis. In addition, the Rutherford backscattering method irradiates charged particles accelerated by high voltage to the sample, which can be bounced back from it. The number and energy of the charged particles are used to identify and quantify the elements, and the composition ratio of each element is known. Further, since the inorganic layer [A2] is a composite layer of a sulfide and an oxide, analysis using a Rutherford backscattering method capable of analyzing the composition ratio of sulfur to oxygen was carried out. When the inorganic layer or the resin layer is further laminated on the inorganic layer [A2], the layer may be removed by ion etching or chemical treatment as needed, and then analyzed by ICP emission spectrometry and Rutherford backscattering.

[Inorganic layer [A3]]

Next, the inorganic layer [A3] which is used as the main component of the inorganic layer [A] having an atomic ratio of an oxygen atom to a ruthenium atom of 1.5 to 2.0 as the main component of the inorganic layer [A] will be described in detail. The term "main component" as used herein means 60% by mass or more, preferably 80% by mass or more of the entire inorganic layer [A3]. Further, the main component of cerium oxide (SiO ₂ ) depends on the conditions at the time of formation, and generates a certain deviation (SiO~SiO ₂ ) from the composition ratio of cerium to oxygen of the above composition formula, but it is described as Ceria or SiO ₂ .

The method for forming the inorganic layer [A3] is preferably a CVD method capable of forming a dense film. In the CVD method, a gas of a decane or an organic ruthenium compound described later can be used as a monomer, activated by a high-strength plasma, and a dense film can be formed by a polymerization reaction. The organoindole compound referred to herein may, for example, be methyl decane, dimethyl decane, trimethyl decane, tetramethyl decane, ethyl decane, diethyl decane, triethyl decane or tetraethyl decane. Propoxy decane, dipropoxy decane, tripropoxy decane, tetrapropoxy decane, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, dimethyl dioxane, four Methyldioxane, hexamethyldioxane, hexamethylcyclotrioxane, octamethylcyclotetraoxane, decamethyl Cyclopentane oxirane, undecylcyclohexaoxane, dimethyldioxane, trimethyldioxane, tetramethyldiazepine, hexamethyldioxane, six Methylcyclotriazane, octamethylcyclotetraazane, decamethylcyclopentaazane, undecylcyclohexaazaxane, and the like. Among them, hexamethyldioxane and tetraethoxydecane are preferred in terms of handling.

The composition of the inorganic layer [A3] can be measured by X-ray photoelectron spectroscopy (XPS method) as will be described later. The atomic ratio of the oxygen atom to the ruthenium atom measured by the 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 atomic ratio of the ruthenium atom to the oxygen atom is more than 2.0, the amount of oxygen atoms contained therein increases, and the void portion or the defective portion increases, and the specified gas barrier property may not be obtained. Further, when the atomic ratio of the ruthenium atom to the oxygen atom is less than 1.5, the oxygen atom is reduced, and although it is a dense film, the flexibility may be lowered.

[矽 compound layer [B]]

Next, the ruthenium compound layer [B] will be described in detail. The ruthenium compound layer [B] in the present invention contains SiN _x H _y , SiO _p N _q and SiO _a (OH) _4-2a (x+y=4, p+q=4, a≦2, x, A layer of a ruthenium compound of the structure shown by y, p, q > 0). Other ruthenium compounds such as alkoxy decane or organopolysiloxane may be contained for the purpose of controlling the refractive index, hardness, adhesion, and the like. Further, the composition of each compound of the ruthenium compound layer [B] can be determined by a ²⁹ Si CP/MAS NMR method.

In the gas barrier film of the present invention, the gas barrier properties are good by using the ruthenium compound layer [B], and it is presumed to be as follows (i) and (ii).

(i) First, as a contribution of the layer, it is estimated that the layer contains a layer of germanium oxynitride represented by SiO _p N _q and is denser than a layer formed only of SiO ₂ , since oxygen and water vapor are suppressed. It penetrates to form a layer with high gas barrier properties, and since the softness is higher than that of a layer formed only of Si ₃ N ₄ , cracks are less likely to occur for heat or external stress during use, and cracks can be suppressed. A layer that is formed and has a reduced gas barrier property.

(ii) Next, as a contribution of laminating the inorganic layer [A] and the yttrium compound layer [B], the following is presumed.

Among the defects such as pinholes or cracks which the inorganic layer [A] has, the components constituting the ruthenium compound layer [B] are filled, and high barrier properties can be exhibited.

When the ruthenium compound layer [B] is adjacent to the inorganic layer [A], the component such as zinc contained in the inorganic layer [A] acts as a catalyst, and the film quality of the ruthenium compound layer [B] is easily modified. Further improve the gas barrier properties.

Since the ruthenium compound contains three kinds of ruthenium compounds, the inorganic layer [A] and the ruthenium compound are more likely to form a chemical bond with the component constituting the inorganic layer [A] than the layer formed only of SiO _p N _q as a main component. The adhesion of the interface region of the layer [B] is increased, and excellent bending resistance at the time of use can be obtained.

The thickness of the ruthenium compound layer [B] used in the present invention is preferably 50 nm or more and 2,000 nm or less, more preferably 50 nm or more and 1,000 nm. When the thickness of the ruthenium compound layer [B] is small, there is a case where stable water vapor barrier properties cannot be obtained. When the thickness of the ruthenium compound layer [B] is too large, the stress remaining in the ruthenium compound layer [B] becomes large, and the polymer substrate warps, in the ruthenium compound layer [B] and/or the inorganic layer [A]. Cracks occur and there is a case where the gas barrier property is lowered.

The thickness of the bismuth compound layer [B] is self-transmissive electronic display The cross-sectional observation image of the micromirror (TEM) was measured.

The center plane average roughness SRa of the ruthenium compound layer [B] used in the present invention is preferably 10 nm or less. When the SRa is 10 nm or less, it is preferable because the repeatability of gas barrier properties is increased. When the SRa of the surface of the ruthenium compound layer [B] is more than 10 nm, cracks due to stress concentration tend to occur in a portion having a large number of irregularities, which may cause a decrease in reproducibility of gas barrier properties. Therefore, in the present invention, the SRa of the ruthenium compound layer [B] is preferably 10 nm or less, more preferably 7 nm or less.

The SRa system of the ruthenium 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 ruthenium compound layer [B] of the present invention. In the range of chemical shift of -30~-50ppm, range of -50~-90ppm and absorption of -90~-120ppm, it means that SiN _x H _y and SiO _p are from the left of the figure. N _q and SiO _a (OH) _4-2a (x+y=4, p+q=4, a≦2, x, y, p, q>0) exist (Reference: P. Diehel, E. Fluck, R. Kosfeld, et al., "NMR Basic Principles and Progress" Springer-Verlag Berlin Heid elberg, 1981, pp. 152-163). Moreover, when the sum of the peak areas of -30 to -120 ppm is 100, if the sum of the peak areas of -30 to -50 ppm is 10 or more, the sum of the peak areas of -50 to -90 ppm is 10 or more, and -90 to -120 ppm. When the sum of the peak areas is 80 or less, it is preferable because it has a high gas barrier property and is excellent in bending resistance and adhesion. Furthermore, when the sum of the peak areas of -30~-120ppm is 100, the sum of the peak areas of the better -30~-50ppm is 10~40, and the sum of the peak areas of -50~-90ppm is 10~40, and - The sum of the peak areas of 90~-120ppm is 30~80. When the above range is not satisfied, the ruthenium compound layer [B] is excessively a dense film, and the flexibility is insufficient, and cracks are likely to occur due to heat or stress from the outside, and the gas barrier properties may be lowered. Further, conversely, the compactness of the ruthenium compound layer [B] is insufficient, and sufficient gas barrier properties cannot be obtained. Based on this point of view, it is better that the sum of the peak areas of the above -30~-50ppm is 13~30, and the sum of the peak areas of -50~-90ppm is 13~35, and the sum of the peak areas of -90~-120ppm is 40. ~75. From the viewpoint of water vapor permeability, the ruthenium compound layer [B] is preferably contained in an amount of from 0.1 to 100% by mass based on the total of the three kinds of ruthenium compounds of the present invention.

As the raw material of the ruthenium compound layer [B] used in the present invention, an ruthenium compound having a polyazaxane skeleton is preferably used. As the anthracene compound having a polyazane 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 perhydropolyazane, organopolyazane, and derivatives thereof can be used. In the present invention, from the viewpoint of improving gas barrier properties, it is preferred to use a hydrogen peroxane which is represented by the following chemical formula (1), wherein R ₁ , R ₂ and R ₃ are all hydrogen, but An organopolyazane in which a part or the whole of hydrogen is substituted with an organic group such as an alkyl group can be used. Further, it may be used in a single composition or in combination of two or more components. Furthermore, n represents an integer of 1 or more.

Next, a method of forming the ruthenium compound layer [B] of the present invention will be described. First, it is more preferable to adjust the solid content concentration of the coating material containing the compound (1) so that the thickness after drying becomes a desired thickness on the inorganic layer [A], by reverse coating method, gravure roll Coating by a coating method, a bar coating method, a bar coating method, a die coating method, a spray coating method, a spin coating method, or the like. Further, in the present invention, from the viewpoint of coating suitability, it is preferred to dilute the coating material containing the above chemical formula (1) using an organic solvent. Specifically, a hydrocarbon solvent such as xylene, toluene, turpentine or Solvesso, an ether solvent such as dibutyl ether, ethyl butyl ether or tetrahydrofuran, or the like can be used. Further, it is preferred to use a solid component concentration diluted to 10% by mass or less. These solvents may be used alone or in combination of two or more.

In the coating material containing the raw material of the ruthenium compound layer [B], various additives may be blended as needed within the range which does not impair the effect of the ruthenium compound layer [B]. For example, a stabilizer such as a catalyst, an antioxidant, a photostabilizer or a UV absorber, a surfactant, a leveling agent, an antistatic agent or the like can be used.

Next, it is preferred to dry the coating film after coating to remove the dilution solvent. Here, the heat source for drying is not particularly limited, and any heat source such as a steam heater, an electric heater, or an infrared heater can be used. Further, in order to improve gas barrier properties, the heating temperature is preferably carried out at 50 to 150 °C. Further, the heat treatment time is preferably from several seconds to one hour. Further, the temperature during the heat treatment may be fixed, or the temperature may be gradually changed. Further, in the drying treatment, the humidity may be adjusted while the relative humidity is adjusted in the range of 20 to 90% RH. The heat treatment described above can be carried out in the air or in a state in which an inert gas is enclosed.

Then, the dried coating film is subjected to active energy ray irradiation treatment such as plasma treatment, ultraviolet irradiation treatment, or flash pulse treatment, and the composition of the coating film is denatured to obtain three kinds of cerium compounds of the present invention.矽 compound layer [B]. As the active energy ray irradiation treatment, it is preferable to use ultraviolet ray treatment from the viewpoint of simplicity, productivity, and uniform composition of the ruthenium compound layer [B]. The ultraviolet treatment may be either atmospheric pressure or reduced pressure, but from the viewpoint of versatility and production efficiency, it is preferred to carry out ultraviolet treatment under atmospheric pressure. The oxygen concentration at the time of the ultraviolet treatment is preferably 1.0% or less, and more preferably 0.5% or less from the viewpoint of composition control of the ruthenium compound layer [B]. The relative humidity can be set to a desired composition ratio. Further, in the above ultraviolet treatment, it is more preferable to use nitrogen gas to lower the oxygen concentration.

As the ultraviolet light generating source, a high pressure mercury lamp metal halide lamp, a microwave type electrodeless lamp, a low pressure mercury lamp, a xenon lamp, or the like can be used. However, from the viewpoint of production efficiency, it is preferable to use a xenon lamp in the present invention.

The cumulative amount of light by ultraviolet irradiation is preferably from 0.5 to 10 J/cm ² , more preferably from 0.8 to 7 J/cm ² . When the cumulative amount of light is 0.5 J/cm ² or more, the desired composition of the ruthenium compound layer [B] can be obtained, which is preferable. In addition, when the cumulative amount of light is 10 J/cm ² or less, damage to the polymer base material or the inorganic layer [B] can be reduced, which is preferable.

Further, in the present invention, in order to improve the production efficiency in the ultraviolet treatment, it is more preferable to perform ultraviolet treatment while heating and drying the coating film. The heating temperature is preferably from 50 to 150 ° C, more preferably from 80 to 130 ° C. If the heating temperature is 50 ° C or more, since high production efficiency is obtained, Preferably, when the heating temperature is 150 ° C or lower, deformation or deterioration of other materials such as a polymer substrate is less likely to occur, which is preferable.

[Undercoat [C]]

In the gas barrier film of the present invention, in order to improve gas barrier properties and improve bending resistance, it is preferred to provide an undercoat layer [C] between the polymer substrate and the inorganic layer [A]. When there are disadvantages such as protrusions or small scratches on the polymer substrate, pinholes or cracks may be generated in the inorganic layer [A] laminated on the polymer substrate due to the aforementioned disadvantages, and the gas barrier is impaired. It is preferable to provide the undercoat layer [C] of the present invention in the case of the property or the resistance to bending. In addition, when the difference in thermal dimensional stability between the polymer substrate and the inorganic layer [A] is large, gas barrier properties or bending resistance are also lowered. Therefore, it is preferred to provide the undercoat layer [C]. Further, the undercoat layer [C] used in the present invention preferably contains a polyurethane compound [C1] having an aromatic ring structure from the viewpoint of thermal dimensional stability and bending resistance. The structure obtained by cross-linking is more preferably one or more selected from the group consisting of an ethylenically unsaturated compound [C2], a photopolymerization initiator [C3], and an organic onium compound [C4] and an inorganic onium compound [C5].矽 compound.

[Polyurethane compound having an aromatic ring structure [C1]]

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

As an epoxy having a hydroxyl group and an aromatic ring in the molecule ( Methyl) acrylate (c1), a epoxide of an aromatic diol such as a bisphenol A type, a hydrogenated bisphenol A type, a bisphenol F type, a hydrogenated bisphenol F type, a resorcinol or a hydroquinone The compound is obtained by reacting with a (meth)acrylic acid derivative.

As the diol compound (c2), for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1 can be used. , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4 - dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentyl Glycol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-sulfur Phenol, bisphenol A, 4,4'-methylene diphenol, 4,4'-(2-sub-lower Diphenol, 4,4'-dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene phenol, 4,4'-isopropylidene glycol, Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, bisphenol A, and the like. These may be used alone or in combination of two or more.

Examples of the diisocyanate compound (c3) include 1,3-diisocyanate benzene, 1,4-diisocyanate benzene, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 2, Aromatic diisocyanate such as 4-diphenylmethane diisocyanate or 4,4-diphenylmethane diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene Aliphatic diisocyanate compound, isophorone diisocyanate, dicyclohexylmethane, such as diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isocyanuric acid diisocyanate, isocyanuric acid triisocyanate, etc. An alicyclic isocyanate compound such as 4,4-diisocyanate or methylcyclohexylene diisocyanate, xylene diisocyanate, tetramethylphthalic acid diisocyanate, or the like An aromatic aliphatic isocyanate compound or the like. These may be used alone or in combination of two or more.

The component ratios of the above (c1), (c2), and (c3) are not particularly limited as long as they are in the range of the desired weight average molecular weight. The weight average molecular weight (Mw) of the aromatic cyclic compound-containing polyurethane compound [C1] of the present invention is preferably 5,000 to 100,000. When the weight average molecular weight (Mw) is 5,000 to 100,000, the obtained hardened film is excellent in thermal dimensional stability and bending resistance. Further, the weight average molecular weight (Mw) in the present invention is a value measured by gel permeation chromatography in terms of standard polystyrene.

[Ethylenically unsaturated compound [C2]]

The ethylenically unsaturated compound [C2] which can be used as a raw material of the undercoat layer [C] includes, for example, 1,4-butanediol di(meth)acrylate and 1,6-hexanediol II ( Di(meth)acrylate such as methyl)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl) Polyfunctional (meth) acrylate such as acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A epoxy di(meth) acrylate, bisphenol F epoxy bis(meth) acrylate An epoxy acrylate such as bisphenol S-type epoxy di(meth)acrylate. Among these, a polyfunctional (meth)acrylate excellent in thermal dimensional stability and surface protection performance is preferred. Further, these may be used in a single composition or in combination of two or more components.

The content of the ethylenically unsaturated compound [C2] is not particularly limited, but is from the viewpoint of thermal dimensional stability and surface protective properties, and a polyurethane compound [C1] having an aromatic ring structure. The total amount of 100% by mass is preferably in the range of 5 to 90% by mass, more preferably in the range of 10 to 80% by mass.

[Photopolymerization initiator [C3]]

As the photopolymerization initiator [C3] which can be used as a raw material of the undercoat layer [C], as long as the gas barrier properties and the bending resistance of the gas barrier film of the present invention can be maintained, photopolymerization can be started, and there is no particular Limited. As the photopolymerization initiator which can be suitably used in the present invention, the following can be exemplified.

2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexylphenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1 -ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4- (2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one, methyl phenylglyoxylate, 2-methyl-1-(4) -methylthiophenyl)-2-N- Orolinyl propan-1-one, 2-benzyl-2-dimethylamino-1-(4-N- Phenylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- An alkylphenone-based photopolymerization initiator such as phenyl)phenyl]-1-butanone.

Oxidation of fluorenylphosphine with 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide The system is a photopolymerization initiator.

Titanocene-based light of bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium Polymerization initiator.

A photopolymerization initiator having an oxime ester structure, such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-benzylidenefluorene), or the like.

Among these, from the viewpoint of hardenability and surface protection properties, it is preferably 1-hydroxy-cyclohexylphenyl-ketone, 2-methyl-1-(4-methylthiophenyl)- 2-N- Polinyl propan-1-one, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine The photopolymerization initiator selected for the oxide. Further, these may be used in a single composition or in combination of two or more components.

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

[Organic hydrazine compound [C4]]

As the organic ruthenium compound [C4] which can be used as a raw material of the undercoat layer [C], for example, vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4-epoxy ring) Hexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Diethoxy decane, 3-glycidoxypropyltriethoxy decane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxy Decane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3 - aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-isocyanatepropyltriethoxydecane, and the like.

Among these, from the viewpoint of curability and polymerization activity due to irradiation with active energy rays, it is preferred to contain a substance selected from the group consisting of 3-methylpropenyloxypropyltrimethoxydecane, 3-methyl Acryloxy An organic ruthenium compound of at least one of the group consisting of propyl triethoxy decane, vinyl trimethoxy decane, and vinyl triethoxy decane. Further, these may be used in a single composition or in combination of two or more components.

The content of the organic ruthenium compound [C4] is not particularly limited, but is preferably in the range of 0.01 to 10% by mass based on 100% by mass of the total amount of the polymerizable component, from the viewpoint of the curability and the surface protective performance. More preferably, it is in the range of 0.1 to 5% by mass.

[Inorganic bismuth compound [C5]]

The inorganic cerium compound [C5] which can be used as a raw material of the undercoat layer [C] is preferably vermiculite particles from the viewpoint of surface protection properties and transparency, and the primary particle diameter of the vermiculite particles is preferably The range of 1 to 300 nm, more preferably 5 to 80 nm. In addition, the primary particle diameter as used herein refers to the particle diameter d obtained by applying the specific surface area s obtained by the gas adsorption method to the following formula (2).

d=6/ρs (2)

Here, the density of the ρ-based particles.

[Thickness of Undercoat [C]]

The thickness of the undercoat layer [C] is preferably 200 nm or more and 4,000 nm or less, more preferably 300 nm or more and 3,000 nm or less, and particularly preferably 500 nm or more and 2,000 nm or less. If the thickness of the undercoat layer [C] is too small, there is a case where the adverse effects of defects such as protrusions or small scratches existing on the polymer substrate cannot be suppressed. If the thickness of the undercoat layer [C] is too large, the smoothness of the undercoat layer [C] is lowered, and the uneven shape of the surface of the inorganic layer [A] laminated on the undercoat layer [C] is also increased. A gap is formed between the deposited sputtered particles, so that the film quality is difficult to be densified, and it is difficult to obtain an effect of improving gas barrier properties. condition.

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

The center plane average roughness SRa of the undercoat layer [C] is preferably 10 nm or less. When the SRa is 10 nm or less, the homogeneous inorganic layer [A] is easily obtained on the undercoat layer [C], and the repeatability of gas barrier properties is improved, which is preferable. If the SRa of the surface of the undercoat layer [C] is too large, the uneven shape of the surface of the inorganic layer [A] on the undercoat layer [C] also becomes large, and it is difficult to form a gap between the deposited particles of the deposited layer. It becomes dense and has a situation in which it is difficult to obtain an effect of improving gas barrier properties. In addition, since cracks due to stress concentration are likely to occur in a portion having a large number of irregularities, there is a case where the repeatability of gas barrier properties is lowered. Therefore, in the present invention, the SRa of the undercoat layer [C] is preferably 10 nm or less, more preferably 7 nm or less.

The 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 for the purpose of improving the scratch resistance can be formed in a range in which the gas barrier properties are not lowered, and a layered organic polymer compound can also be formed. The laminate of the film is composed. In addition, the outermost surface as used herein means that the inorganic layer [A] and the ruthenium compound layer [B] are adjacent to each other on the polymer substrate, and are not adjacent to the inorganic layer [A]. The surface of the ruthenium compound layer [B] on the side.

[electronic device]

The gas barrier film of the present invention can be used for each of them because of its high gas barrier property. A wide range of electronic devices. For example, it can be applied to an electronic device such as a back sheet of a solar cell or a flexible circuit substrate. The electronic device using the gas barrier film of the present invention can suppress the deterioration of performance of the device due to water vapor or the like because of excellent gas barrier properties.

[Other uses]

The gas barrier film of the present invention can be applied as a film for packaging of foods or electronic parts, in addition to an electronic device, because of its high gas barrier property.

[Examples]

Hereinafter, the present invention will be specifically described based on the examples. However, the invention is not limited by the following examples.

[Evaluation method]

First, the evaluation methods in the respective examples and comparative examples will be described. Unless otherwise specified, the number of n numbers is evaluated in five samples per level, and the average of the measured values of the obtained five samples is taken as the measurement result.

(1) Thickness of the layer

A sample for cross-section observation was produced by a focused ion beam (Focused Ion Beam: FIB) method using a microsampling system (FB-2000A manufactured by Hitachi, Ltd.). The cross section of the observation sample was observed by a transmission electron microscope (H-9000UHRII manufactured by Hitachi, Ltd.) at an acceleration voltage of 300 kV, and the inorganic layer [A], the ruthenium compound layer [B], and the primer were measured. The thickness of layer [C].

(2) Center surface average roughness SRa

The surface of each layer was measured under the following conditions using a three-dimensional surface roughness measuring machine (manufactured by Otaru Laboratory Co., Ltd.).

System: Three-dimensional surface roughness analysis system "i-Face model TDA31"

X-axis measurement length / spacing: 500μm / 1.0μm

Y-axis measurement length / spacing: 400μm / 5.0μm

Measuring speed: 0.1mm/s

Measurement environment: temperature 23 ° C, relative humidity 65% RH, in the atmosphere.

(3) Water vapor permeability (g/(m ² .d))

A calcium layer having a thickness of 100 nm is formed on the surface of the ruthenium compound layer [B] of the gas barrier film by vacuum evaporation, and secondly, by the same vacuum evaporation, the calcium layer is covered on the calcium layer to cover the entire calcium layer. An aluminum layer having a thickness of 3000 nm was formed. Further, after the aluminum layer was formed, a glass having a thickness of 1 mm was bonded to the aluminum layer via a thermosetting epoxy resin, and treated at 100 ° C for 1 hour to obtain an evaluation sample. The obtained sample was treated at a temperature of 40 ° C and a relative humidity of 90% RH for 800 hours. After the above treatment, the amount of calcium vaporized by the water vapor was calculated to determine the amount of penetration of water vapor. The number of water vapor permeability samples is 2 samples per level, the number of measurements is 5 times for each sample, and the average value of 10 points is taken as the water vapor permeability (g / (m ² .d) )).

(4) Composition of inorganic layer [A1]

The composition analysis of [A1] was carried out by ICP emission spectrometry (SPS4000, manufactured by SII NanoTechnology Co., Ltd.). The sample sampled at the stage of forming the inorganic layer [A1] on the polymer substrate or the undercoat layer (before the layer of the ruthenium compound layer [B]) is heated and decomposed in nitric acid and sulfuric acid, and dissolved in dilute nitric acid. Filter separation. The insoluble matter is melted by heating, ashed in sodium carbonate, dissolved in dilute nitric acid, and combined with the previous filtrate to make a constant volume. The content of the zinc atom, the ruthenium atom, and the aluminum atom was measured for this solution, and converted into an atomic ratio. Further, the oxygen atom is a calculated value obtained by presuming that zinc atoms, germanium atoms, and aluminum atoms are present as zinc oxide (ZnO), cerium oxide (SiO ₂ ), or aluminum oxide (Al ₂ O ₃ ).

(5) Composition of inorganic layer [A2]

The composition analysis of the inorganic layer [A2] was carried out by ICP emission spectrometry (SPS4000, manufactured by SII Nano-Technologies Co., Ltd.). The sample sampled at the stage of forming the inorganic layer [A2] on the polymer substrate or the undercoat layer (before the layer of the ruthenium compound layer [B]) is heated and decomposed in nitric acid and sulfuric acid, and dissolved in dilute nitric acid. Filter separation. The insoluble matter is melted by heating, ashed in sodium carbonate, dissolved in dilute nitric acid, and combined with the previous filtrate to make a constant volume. For this solution, the contents of zinc atoms and germanium atoms were determined. Secondly, based on this value, using the Rutherford backscattering method (Nissin-High Voltage (AN-2500)), quantitative analysis of zinc atoms, germanium atoms, sulfur atoms, oxygen atoms, and obtain zinc sulfide and two The composition ratio of cerium oxide.

(6) Composition of inorganic layer [A3]

The composition analysis of the inorganic layer [A3] was carried out by X-ray photoelectron spectroscopy (XPS method) to calculate the atomic ratio of oxygen atoms to ruthenium atoms. The measurement conditions are as follows.

Device: Quantera SXM (manufactured by PHI Corporation)

Excitation X-ray: monochromatic AlKα1, 2

X-ray diameter: 100μm

Photoelectron extraction angle: 10 °.

(7) the composition of the bismuth compound layer [B],

A powder sample obtained by subjecting the ruthenium compound layer [B] to a single-sided blade was filled in a sample tube of 7.5 mm Φ, and composition analysis was performed using a ²⁹ Si CP/MAS NMR method to obtain an example as shown in FIG. Spectrum. Calculate the sum of the peak areas of -30~-50ppm in the range of -30~-120ppm in the above spectrum, the sum of the peak areas of -50~-90ppm, and the sum of the peak areas of -90~-120ppm. The measurement conditions are as follows.

Device: CMX-300 manufactured by Chemagnetics

Determination of nuclear wave number: 59.636511MHz ( ²⁹ Si core)

Spectral 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: 2.0sec

Observation point: 2048 data points; 8192

Reference material: hexamethylcyclotrioxane (external reference; -9.66 ppm)

Temperature: room temperature (about 22 ° C)

Sample rotation number: 5.0kHz

Calculation of peak area: integral method.

(8) Bending resistance

The gas barrier film was sampled at 2 standards per level at 100 mm x 140 mm. As shown in Fig. 5, the central portion of the gas barrier film (symbol 19) on the side opposite to the surface (symbol 21) on which the inorganic layer [A] and the bismuth compound layer [B] are formed is fixed to a diameter of 5 mm. Metal cylinder (symbol 20), along this cylinder, from the angle of the cylinder around 0 ° (the state of the sample is flat) to the angle of the cylinder to 180 ° (folded on the cylinder) In the range, after 100 bending operations, the water vapor permeability was evaluated by the method shown in (3). The number of measurements was performed 5 times for each sample, and the resulting 10 points were obtained. The average value was taken as the water vapor permeability after the bending resistance test.

(9) Adhesion

According to JIS K5600-5-6:1999, a notch of 25 squares of a rectangular pattern of 1 × 1 mm was introduced into the ruthenium compound layer [B], and the adhesion was evaluated. The evaluation results are classified into six levels of category 0 to category 5 in order from the one with good adhesion.

[Formation Method of Inorganic Layer [A] in Examples 1 to 11]

(Inorganic layer [A1] formation)

Using a coiling type sputtering apparatus (symbol 6a) having the structure shown in Fig. 2, a mixed sintered material formed of zinc oxide and ceria and alumina is used on one side of the polymer substrate (symbol 5). The sputtering target is used to perform sputtering, and the inorganic layer [A1] is provided.

The specific operation is as follows. First, a coiling chamber of a coiling type sputtering apparatus in which a sputtering target having a zinc oxide/ceria/alumina composition ratio of 77/20/3 is provided is provided on a sputtering electrode (symbol 13). In (Sign 7), a polymer base material is attached to the take-up roll (symbol 8), and the surface on the side where the inorganic layer [A1] is provided is opposed to the sputtering electrode, and is wound up, and is passed through the take-up side guide roller ( Symbols 9, 10, 11) lead to the cleaning roller (symbol 12). Argon gas and oxygen gas having a partial pressure of oxygen of 10% were introduced in a manner of a degree of decompression of 2 × 10 ^-1 Pa, and 4,000 W of input power was applied by a DC power source to cause argon. Oxygen plasma is generated by sputtering on the surface of the polymer substrate to form an inorganic layer [A1]. The thickness is adjusted by the film transport speed. Then, the take-up side guide rolls (symbols 15, 16, 17) are taken up on a take-up roll (symbol 18).

(Formation of inorganic layer [A2])

Using a coil-type sputtering apparatus (symbol 6a) having the structure shown in Fig. 2, sputtering is performed on a surface of a polymer substrate (symbol 5) using a mixed sintered material formed of zinc sulfide and cerium oxide. The target is subjected to sputtering, and an inorganic layer [A2] is provided.

The specific operation is as follows. First, in the coiling electrode (symbol 13), a coiling chamber (symbol 7) of a coiling sputtering apparatus in which a sputtering target having a molar ratio of zinc sulfide/ceria having a molar ratio of 80/20 is provided is provided. The polymer substrate is mounted on the take-up roll (symbol 8), rolled up, and passed through the take-up side guide rolls (symbols 9, 10, 11) to the cleaning roll (symbol 12). Argon gas was introduced at a reduced pressure of 2 × 10 ^-1 Pa, and 500 W of input power was applied by a high-frequency power source to generate argon plasma, which was formed by sputtering on the surface of the polymer substrate. Inorganic layer [A2]. The thickness is adjusted by the film transport speed. Then, the take-up side guide rolls (symbols 15, 16, 17) are taken up on a take-up roll (symbol 18).

(Formation of inorganic layer [A3])

Using a take-up CVD apparatus (symbol 6b) having the structure shown in Fig. 3, chemical vapor deposition using hexamethyldioxane as a raw material is carried out on one surface of the polymer substrate (5). Set the inorganic layer [A3].

The specific operation is as follows. First, in the take-up chamber (symbol 7) of the take-up type CVD apparatus, a polymer base material is attached to the take-up roll (symbol 8), and is unwound, and the roll-out side guide rolls are passed (symbols 9, 10, 11) ), leading to the cleaning roller (symbol 12). Oxygen gas 0.5 L/min and hexamethyldioxane 70 cc/min were introduced so as to have a degree of pressure reduction of 2 × 10 ^-1 Pa, and 3,000 W of input power was applied to the CVD electrode from the high-frequency power source. The plasma is generated by forming an inorganic layer [A3] on the surface of the polymer substrate by CVD. The thickness is adjusted by the film transport speed. Then, the take-up side guide rolls (symbols 15, 16, 17) are taken up on the take-up roll.

[Synthesis Example of Polyurethane Compound [C1] Having an Aromatic Ring Structure]

To a 5-liter four-necked flask, 300 parts by mass of a bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Epoxyester 3000A) and 710 parts by mass of ethyl acetate were added. The temperature was raised in such a manner that the internal temperature became 60 °C. 0.2 parts by mass of di-n-butyltin dilaurate as a synthetic catalyst was added, and 200 parts by mass of dicyclohexylmethane-4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise for 1 hour while stirring. After the completion of the dropwise addition, the reaction was continued for 2 hours, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise for 1 hour. After the dropwise addition, the reaction was continued for 5 hours to obtain a polyurethane compound having an aromatic ring structure having 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 a polymer substrate, and an inorganic layer having a thickness of 180 nm was provided on one surface of the polymer substrate. [A1]. The inorganic layer [A1] has a Zn atom concentration of 27.5 atom%, a Si atom concentration of 13.1 atom%, an Al atom concentration of 2.3 atom%, and an O atom concentration of 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-surface 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 bismuth compound layer [B], 100 parts by mass of a coating agent containing a perhydropolyazane as a main component ("NN120-20" manufactured by AZ Electronic Materials Co., Ltd., solid content concentration: 20% by mass) was diluted with 300 parts by mass of dibutyl ether. 1. The coating liquid 1 was applied onto the inorganic layer [A1] by a micro-groove roll coater (groove roll No. 200UR, groove roll rotation ratio of 100%), dried at 120 ° C for 1 minute, and dried, as described below. Under the conditions of ultraviolet treatment, a ruthenium 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 (M.D. Excimer)

Introduced gas: N ₂

Oxygen concentration: 300~800ppm

Cumulative light amount: 3,000 mJ/cm ²

Sample temperature adjustment: 100 ° C.

For the obtained gas barrier film, the composition analysis was carried out by using a ²⁹ Si CP/MAS NMR method, and the sum of the peak areas of -30 to -50 ppm when the sum of the peak areas of -30 to -120 ppm in the obtained spectrum was 100 was calculated. The sum of the peak areas of -50~-90ppm and the sum of the peak areas of -90~-120ppm. 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 evaluation of the water vapor permeability was carried out. 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 a polymer substrate.

As a coating liquid for forming the undercoat layer [C], 150 parts by mass of the aforementioned polyurethane compound and 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate) were blended. DPE-6A), 5 parts by mass of 1-hydroxy-cyclohexylphenyl-ketone (manufactured by BASF Japan, trade name: "IRGACURE" (registered trademark) 184), and 3 parts by mass of 3-methylpropenyloxy group Propylmethyldiethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-503), 170 parts by mass of ethyl acetate, 350 parts by mass of toluene and 170 parts by mass of cyclohexanone, and prepared by coating Liquid 2. Next, using a micro-groove roll coater (groove roll No. 150UR, groove roll rotation ratio of 100%), the coating liquid 2 is coated on a polymer substrate, dried at 100 ° C for 1 minute, dried, and then dried. The ultraviolet treatment was applied under the conditions described, and an undercoat layer [C] having a thickness of 1,000 nm was provided.

UV treatment unit: LH10-10Q-G (Fusion UV system. Made by Japan)

Introduced gas: N ₂ (nitrogen inert BOX)

UV source: microwave mode electrodeless lamp

Cumulative light amount: 400mJ/cm ²

Sample temperature adjustment: room temperature.

Then, in the same manner as in Example 1, the inorganic layer [A1] and the ruthenium compound layer [B] were provided on the undercoat layer [C], and the same evaluation as in Example 1 was carried out. The results are shown in Table 1.

(Example 3)

Gas barrier properties were obtained in the same manner as in Example 1 except that an amorphous cyclic polyolefin film (Zeonor film ZF14, manufactured by Zeon Corporation, Japan) ("Zeonor" is a registered trademark) was used as the polymer substrate. film.

(Example 4)

A gas barrier film was obtained in the same manner as in Example 2 except that an amorphous cyclic polyolefin film (Zeonor film ZF14 manufactured by Zeon Corporation, Japan) having a thickness of 100 μm 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] having a thickness of 950 nm was provided.

(Example 6)

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

(Example 8)

A gas barrier film was obtained in the same manner as in Example 2 except that the ruthenium compound layer [B] having a thickness of 50 nm was provided.

(Example 9)

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

(Embodiment 10)

A gas barrier film was obtained in the same manner as in Example 2 except that the amount of accumulated ultraviolet light was changed to 1,500 mJ/cm ^{2 when the} ruthenium compound layer [B] was formed.

(Example 11)

A gas barrier film was obtained in the same manner as in Example 2 except that the amount of accumulated ultraviolet light was changed to 1,000 mJ/cm ² when the ruthenium compound layer [B] was formed.

(Comparative Example 1)

A gas barrier film was obtained in the same manner as in Example 1 except that the inorganic layer [A] was not formed on the polymer substrate, and the ruthenium compound layer [B] having a thickness of 120 nm was directly provided on the surface of the polymer substrate.

(Comparative Example 2)

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

(Comparative Example 3)

In the first embodiment, the order of formation of the inorganic layer [A] and the ruthenium compound layer [B] was exchanged to obtain a gas barrier film having a layer constitution different from that of the first embodiment.

(Comparative Example 4)

A gas barrier film was obtained in the same manner as in Example 7 except that the ruthenium 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)

The same procedure as in Example 2 was carried out except that in Example 2, a layer formed of SiO _p N _q was used instead of SiN _x H _y and SiO _a (OH) _4-2a instead of the ruthenium compound layer [B]. Gas barrier film.

Further, a method of forming a layer formed only of SiO _p N _q is formed by using a wound-type sputtering apparatus having the structure shown in Fig. 2 on the surface of a polymer substrate by using tantalum nitride. The sputtering target is used to perform sputtering, and a layer formed only of SiO _p N _q is provided. The specific operation is firstly in a coiling chamber in which a sputtering device of a sputtering target formed of tantalum nitride is provided on a sputtering electrode, and a polymer substrate is mounted on the winding roller to set SiO. The side of the side of the _p N _q layer faces the sputtering electrode, and the polymer substrate is taken up and passed through a guide roller to the cleaning roller. Argon gas and oxygen gas having a partial pressure of oxygen of 10% were introduced into the sputtering chamber so as to have a degree of pressure reduction of 2 × 10 ^-1 Pa. Furthermore, by applying a power of 1,000 W to the high frequency power source, argon is applied. Oxygen plasma is generated, and a SiO _p N _q layer is formed on the surface of the polymer substrate by sputtering. The thickness is adjusted by the film transport speed. Then, it is taken up on a take-up roll through a guide roll.

[Industrial availability]

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

1‧‧‧ polymer substrate

2‧‧‧Inorganic layer [A]

3‧‧‧矽 compound layer [B]

Claims (9)

A gas barrier film which is provided on at least one side of a polymer substrate, and has a gas barrier film of an inorganic layer [A] and a ruthenium compound layer [B] in this order from the polymer substrate side, and a ruthenium compound layer [B] contains 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 The ruthenium compound of the structure shown, and the inorganic layer [A] is adjacent to the ruthenium compound layer [B]. The gas barrier film of claim 1, wherein the inorganic layer [A] comprises a zinc compound and a cerium oxide. The gas barrier film of claim 1 or 2, wherein in the ²⁹ Si CP/MAS NMR spectrum of the ruthenium compound layer [B], when the total peak area of -30 to -120 ppm is 100, -30 to -50 ppm The sum of the peak areas is 10 or more, the sum of the peak areas of -50 to -90 ppm is 10 or more, and the sum of the peak areas 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 selected from any of the following inorganic layers [A1] to [A3]; the inorganic layer [A1]: Inorganic layer formed by the coexistence phase of (i) to (iii) (i) zinc oxide (ii) ceria (iii) alumina inorganic layer [A2]: formed by the coexistence of zinc sulfide and ceria Inorganic layer inorganic layer [A3]: an inorganic layer containing a ruthenium oxide having an atomic ratio of an oxygen atom to a ruthenium atom of 1.5 to 2.0 as a main component. The gas barrier film of claim 4, wherein the inorganic layer [A] is the inorganic In the layer [A1], the inorganic layer [A1] has a zinc atom concentration of 20 to 40 atom%, a germanium atom concentration of 5 to 20 atom%, an aluminum atom concentration of 0.5 to 5 atom%, and an oxygen atom as measured by ICP emission spectrometry. The composition is composed of a concentration of 35 to 70 atom%. The gas barrier film of claim 4, wherein the inorganic layer [A] is the inorganic layer [A2], and the inorganic layer [A2] is a molar of zinc sulfide relative to the total of zinc sulfide and cerium oxide. The composition is composed of a composition of 0.7 to 0.9. The gas barrier film according to any one of claims 1 to 6, wherein an undercoat layer [C] is provided between the polymer substrate and the inorganic layer [A], the undercoat layer [C] comprising The structure in which the aromatic cyclic structure of the polyurethane compound [C1] is crosslinked. The gas barrier film of claim 7, wherein the undercoat layer [C] comprises an organic cerium compound and/or an inorganic cerium compound. An electronic device using the gas barrier film of any one of claims 1 to 8.