KR20160146900A - Gas barrier film and electronic device using same - Google Patents

Abstract

The object of the present invention is to provide a gas barrier film excellent in storage stability, particularly in a storage condition under severe conditions (high temperature and high humidity conditions). The present invention relates to a gas barrier film having a gas barrier layer having at least Al atoms and Si atoms on a substrate, wherein the gas barrier layer has a structure in which the constituent elements of each constituent element based on the measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy In the Al distribution curve with respect to the distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and the total amount (100 at%) of all the elements in the gas barrier layer among the distribution curves, Is a gas barrier film having a region in which the composition continuously changes in the layer thickness direction and the amount of Al atoms on the side opposite to the substrate side of the gas barrier layer is larger than the amount of Al atoms on the substrate side.

Description

TECHNICAL FIELD [0001] The present invention relates to a gas barrier film and an electronic device using the gas barrier film.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film and an electronic device using the film. More particularly, the present invention relates to a gas barrier film for use in an electronic device such as an organic electroluminescence (EL) device, a solar cell device, And an electronic device using the same.

BACKGROUND ART Conventionally, a gas barrier film formed by laminating a plurality of layers including a thin film of a metal oxide such as aluminum oxide, magnesium oxide, silicon oxide, or the like on the surface of a plastic substrate or a film has been widely used as a barrier against various gases such as water vapor and oxygen For example, packaging for preventing deterioration of foods, industrial products, medicines, and the like.

In addition to packaging applications, development of flexible electronic devices such as flexible solar cell devices, organic electroluminescence (EL) devices, and liquid crystal display devices has been desired and many studies have been made. However, in these flexible electronic devices, a very high gas barrier property of the glass substrate level is required, so that a gas barrier film having sufficient performance in the present situation has not yet been obtained.

As a method of forming such a gas-barrier film, a chemical vapor deposition method (plasma CVD method) in which an organosilicon compound represented by tetraethoxysilane (TEOS) is used to grow on a substrate while oxygen plasma oxidation is performed under reduced pressure (Dry method) such as a physical deposition method (vacuum evaporation method or sputter method) in which metal Si is evaporated by using an atomic layer deposition (ALD) method or a semiconductor laser and deposited on a substrate in the presence of oxygen is known.

The inorganic film forming method by the vapor-phase method (dry method) is suitably applied to the formation of an inorganic film such as silicon oxide, silicon nitride, or silicon oxynitride. The composition range of the inorganic film for obtaining good gas barrier property is studied, The layer composition of the layer is reviewed.

In addition, as described above, it is very difficult to form a film having no defect in the gas-phase method (dry method). For example, it is necessary to make the film-forming rate extremely low to suppress the generation of defects. As a result, at an industrial level where productivity is required, the gas barrier property required for a flexible electronic device is not obtained. It has been studied that the film thickness of the inorganic film is simply increased by vapor phase method (dry method), or a plurality of inorganic films are laminated. For example, Patent Document 1 discloses a gas barrier film in which a plurality of inorganic films such as silicon oxide, silicon nitride, and silicon oxynitride are laminated in Example 3, and Al is formed on the substrate by atomic layer deposition (ALD) (Al, an inorganic film such as silicon oxide, silicon nitride, or silicon oxynitride) formed on the ALD layer by a plasma CVD method, and a second barrier layer An inorganic film such as silicon nitride, silicon nitride, or silicon oxynitride; and a CVD layer) are stacked. The barrier layer (ALD layer + CVD layer) laminated by the dry method of Patent Document 1 forms a uniform so-called " interface " without substantially crossing the intermediate regions of the upper and lower layers. Further, in Patent Document 1, it is a (technical) phenomenon to improve the barrier property and the heat resistance by improving the adhesion between the base material and the CVD layer due to curing of the ALD layer (lower layer). As for the composition modification of the interface between the upper and lower layers It is not mentioned. In the gas barrier film obtained by simply increasing the thickness of the inorganic film by such a vapor-phase method (dry method) or by laminating a plurality of inorganic films as in Patent Document 1, defects grow continuously or cracks increase, The improvement of the sex was not reached.

Such defects of the inorganic film cause defects in the organic EL device, for example, in the case where the non-light emitting black spot called a dark spot is caused to occur or the size of the dark spot grows under high temperature and high humidity, do.

On the other hand, in addition to the film formation by the vapor-phase method (dry method) so far, as one of the methods of forming the gas barrier layer, a solution of the inorganic precursor compound is applied on the inorganic film by the above-described vapor-phase method (dry method) Is modified by heat to effectively repair the defects of the inorganic film formed by the vapor phase method described above and further to improve the gas barrier property of the laminated film itself. In particular, by using polysilazane as the inorganic precursor compound Studies have been made to develop a high gas barrier property by restoration of the defects described above.

However, the formation of a dense silicon oxynitride film or a silicon oxide film by thermal modification or wet heat modification of polysilazane requires a high temperature of 450 DEG C or more, and it is impossible to apply it to a flexible substrate such as a plastic.

As a means for solving such a problem, there has been proposed a gas barrier film formed by forming a silicon oxynitride film or a silicon oxide film by irradiating a coating film formed by coating from a polysilazane solution with vacuum ultraviolet light.

(Hereinafter also referred to as "VUV", "VUV light") having a larger energy than the inter-atomic bonding force of the polysilazane, , A silicon oxynitride film or a silicon oxide film can be formed at a relatively low temperature by advancing the oxidation reaction by active oxygen or ozone while directly cutting the silicon oxide film.

Normally, when a polysilazane is applied on a resin film substrate and ultraviolet (VUV; for example, excimer) irradiation is performed, the vicinity of the surface of the irradiated surface is modified to form a barrier layer (nitrogen high concentration layer). At the same time, it is believed that oxidation behavior, which is presumed to be the transfer of moisture from the substrate side, occurs, and the inside of the barrier layer becomes an oxide film (silicon oxide layer).

In the gas barrier film comprising such a barrier layer, for example, Patent Document 2 discloses a method in which a polysilazane is applied on a resin film substrate to form a first polysilazane film and irradiate vacuum ultraviolet light, Discloses a gas barrier film formed by forming a second polysilazane film and irradiating vacuum ultraviolet light. That is, Patent Document 2 discloses a form of a gas-barrier film in which a process of irradiating a polysilazane film with vacuum ultraviolet light is repeated and a first and second gas barrier layers are laminated. In the gas barrier film described in Patent Document 2, by irradiating the first and second polysilazane films with vacuum ultraviolet light (excimer) respectively, the surfaces of the first and second polysilazane films are modified with glass, .

U.S. Patent Application Publication No. 2013/009264 Japanese Patent Application Laid-Open No. 2009-255040

However, the gas barrier film described in Patent Document 2 exhibits a behavior that rapidly deteriorates under high temperature and high humidity conditions. That is, in the gas barrier film obtained by repeating the process of irradiating the polysilazane film with vacuum ultraviolet light and laminating the gas barrier layers, a high gas barrier property can be obtained, while a structure in which the gas barrier layers are laminated In the structure having two or more layers, deterioration under high temperature and high humidity was remarkable.

SUMMARY OF THE INVENTION An object of the present invention is to provide a gas storage device which is excellent in storage stability without deterioration even under severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions) To provide a barrier film.

In order to achieve the above object, the present inventors have conducted intensive studies and found that a layer containing Al such as an aluminum compound in the upper layer is laminated on a layer containing Si (silica) such as polysilazane in the lower layer, It has been found that by irradiating vacuum ultraviolet light, the vacuum ultraviolet light can escape from the layer containing Al in the upper layer and reach the layer containing Si in the lower layer. As a result, the modification proceeds at the interface between the upper and lower layers, and a continuous Al atom gradation structure is formed in the film thickness direction, thereby forming a region (referred to as a modified region) excellent in both heat resistance and gas barrier properties. Due to the formation of such modified regions, the intermediate regions (near the interfaces) of the upper and lower layers surely cross each other, so that a single gas barrier layer having no distinction between the upper and lower layers is formed. It has been found that gas barrier films having such an integral gas barrier layer can achieve both high barrier properties and heat resistance.

That is, a feature of the present invention resides in a continuous Al atomic gradation structure (a) in an integral gas barrier layer which does not distinguish between upper and lower layers formed from a layer containing Al in the upper layer and a layer containing Si The structure in which the Al atoms are continuously changed (particularly, increased) in composition in the layer thickness direction; a modified region). Specifically, the above object of the present invention can be achieved by the following gas barrier films (1) to (7).

(1) A gas barrier film having a gas barrier layer having at least Al atoms and Si atoms on a substrate,

A distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and a distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, In the Al distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer,

The Al atoms of the gas barrier layer have regions in which the composition continuously changes in the layer thickness direction,

Wherein the amount of Al atoms on the side opposite to the substrate side of the gas barrier layer is larger than the amount of Al atoms on the substrate side.

(2) The gas barrier film as described in (1) above, wherein the gas barrier layer has a region in which the Al atoms continuously increase from the substrate side.

(3) In the Al distribution curve, the region continuously increasing from the substrate side has a slope of 0.5 at% / nm (in terms of SiO ₂ ) or more and _{2 at} % / nm (in terms of SiO ₂ ) (2). ≪ / RTI >

(4) The gas barrier according to any one of (1) to (3) above, wherein all of the elements in the gas barrier layer are composed of Al atoms, Si atoms, O atoms, N atoms and C atoms Sex Film.

(5) The gas barrier layer according to any one of the above (1) to (5), wherein, among the distribution curves of the respective constituent elements based on the measurement of the element distribution in the depth direction by X-ray photoelectron spectroscopy on the above- And a Si distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer, the region continuously decreasing from the substrate side has a slope of -2 at% / nm (in terms of SiO ₂ ) The gas barrier film according to any one of (1) to (4).

(6) The method as described in any one of (1) to (5) above, wherein an Al distribution curve and an Si distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer have regions in which Al atoms and Si atoms intersect. Wherein the gas barrier film is formed of a thermoplastic resin.

(7) An electronic device using the gas barrier film according to any one of (1) to (6).

According to the gas barrier film of the present invention, there is no deterioration even under harsh conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions), and storage stability is excellent, and high gas barrier properties can be maintained.

1 (A) shows a process for producing a gas barrier film of the present invention, in which a layer containing an aluminum compound as an upper layer is laminated on a layer composed of a polysilazane as a lower layer and irradiated with vacuum ultraviolet light FIG. 1B is a diagram schematically showing a modified region (continuous change region of Al atoms) formed by irradiation and modification of vacuum ultraviolet light in FIG. 1A, Of the gas barrier film of the present invention in which an integral gas barrier layer having no uniform (" interfacial ") structure is formed, and a change in the amount of aluminum atom in the depth direction of the gas barrier layer are schematically shown 1C is a diagram schematically showing a layer configuration of a conventional gas barrier film described in Patent Document 1 and a change in the atomic weight of Al in the depth direction of the gas barrier layer.
Fig. 2 is a graph showing the relationship between the gas barrier properties of all the gas barrier layers of the gas barrier film obtained in Example 1 having the layer structure in which the gas barrier layer and the modified gas barrier layer are laminated in this order, FIG. 3 is a view showing a distribution curve of each constituent element based on the measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy. The reformed gas barrier layer shown in Fig. 1 is obtained by forming a polysilazane layer irradiated with vacuum ultraviolet light (excimer) on the lower layer, applying only an aluminum compound (not containing polysilazane) to the upper layer, Is irradiated and reformed.
Fig. 3 is a graph showing the relationship between the gas barrier properties of all the gas barrier layers of the gas barrier film obtained in Example 2 having the layer structure in which the gas barrier layer and the modified gas barrier layer are laminated in this order on the substrate as one embodiment of the gas barrier film of the present invention FIG. 3 is a view showing a distribution curve of each constituent element based on the measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy. The reformed gas barrier layer shown in Fig. 2 is obtained by forming a polysilazane layer irradiated with vacuum ultraviolet light (excimer) on the lower layer, applying only an aluminum compound (not containing polysilazane) to the upper layer, Is irradiated and reformed.
Fig. 4 is a graph showing the relationship between the gas barrier properties of all the gas barrier layers of the gas barrier film obtained in Example 3 having the layer structure in which the gas barrier layers and the modified gas barrier layers are laminated in this order on the substrate as one embodiment of the gas barrier film of the present invention FIG. 3 is a view showing a distribution curve of each constituent element based on the measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy. The modified gas barrier layer shown in Fig. 3 is formed by applying polysilazane not irradiated with vacuum ultraviolet light to the lower layer, applying only aluminum compound (not containing polysilazane) to the upper layer, irradiating vacuum ultraviolet light (excimer) , And a layer obtained by modification.
Fig. 5 is a graph showing the relationship between the lower barrier layer (finally constituting a part of the reforming barrier layer of the gas-barrier film), which is formed during the manufacturing process, among the ordinary gas barrier layer or the reforming barrier layer of the gas- Fig. 2 is a schematic view showing one embodiment of a vacuum plasma CVD apparatus used for forming a dielectric layer.
Fig. 6 is a graph showing the relationship between the gas barrier properties of the gas barrier film of the present invention (Examples 1 to 3 and Comparative Examples 1 and 2) and the modified barrier layer of the gas barrier film of the present invention Is a schematic view showing another embodiment of a vacuum plasma CVD apparatus used for forming a gas barrier layer (a gas barrier layer other than a reforming barrier layer, which is formed between a substrate and a reforming barrier layer; Examples 1 to 3).
7 is a graph showing the relationship between the formation of the reforming barrier layer of the gas barrier film of the present invention (layer in which the lower barrier layer and the Al-containing barrier layer in the upper layer are modified so as to form an unified interface without any interface; Examples 1 to 3) Fig. 3 is a schematic view showing a form of a vacuum ultraviolet ray irradiation apparatus used for forming a barrier layer. Fig.
8 is a schematic diagram showing a form of an atomic layer deposition apparatus (ALD apparatus) used for forming the first barrier layer thin film (inorganic compound layer; ALD layer) of Comparative Example 1. Fig.
9 is a diagram schematically showing the layer structure of the gas barrier film of Comparative Example 2. Fig.
10 is a diagram showing distribution curves of respective constituent elements based on measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy for all gas barrier layers of the gas-barrier film obtained in Comparative Example 2. Fig.
11A is a diagram schematically showing the layer structure before the lower gas barrier layer and the upper gas barrier layer formed in the manufacturing process of the gas barrier film of Examples 1 and 2 are modified, (B) are diagrams schematically showing the layer constitution of the gas barrier film of Examples 1 and 2.
12A is a diagram schematically showing a layer structure before the lower gas barrier layer and the upper gas barrier layer are formed in the process of manufacturing the gas barrier film of Example 3. FIG. ) Is a diagram schematically showing the layer structure of the gas barrier film of Example 3. Fig.

The present invention provides a gas barrier film having a gas barrier layer having at least Al atoms and Si atoms on a substrate,

A distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and a distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, In the Al distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer,

The Al atoms of the gas barrier layer have regions in which the composition continuously changes in the layer thickness direction,

And the amount of Al atoms on the side opposite to the substrate side of the gas barrier layer is larger than the amount of Al atoms on the substrate side. By such a constitution, storage stability under long-term storage stability, particularly under severe conditions such as high temperature and high humidity, is excellent, and high gas barrier property can be maintained.

The mechanism of action of the gas barrier film of the present invention which is excellent in storage stability, in particular, storage stability under high temperature and high humidity, is considered as follows. However, even when the gas barrier film of the present invention exhibits the action and effect of the present invention by a mechanism other than the above-mentioned mechanism, the technical scope of the present invention is not limited at all.

Means for Solving the Problems In order to achieve the above object, the inventors of the present invention conducted intensive studies and found that the behavior of the gas barrier film of Patent Document 2 rapidly deteriorating when it is placed under a high temperature and high humidity is that the first gas barrier layer on the substrate is made of polysilazane (Reforming of the glassy material) does not progress to the inside when the second gas barrier layer is formed so that the gas barrier layer is exposed to high temperature and high humidity (for example, a dump heat (DH) (Mechanism) that it is corroded and rapidly deteriorated in the environment. As a result of further research based on this new finding, it has been found that a layer containing Al such as an aluminum compound (referred to as an Al-containing layer) is formed on a layer containing Si (silica) such as polysilazane Layered and modified with vacuum ultraviolet light such as excimer, vacuum ultraviolet light exits from the Al-containing layer and is irradiated to the Si-containing layer in the lower layer. At this time, the modification proceeds at the interface between the Si-containing layer in the lower layer and the Al-containing layer in the upper layer, and a region (modified region) having excellent both heat resistance and barrier properties is formed in the interface region. By forming the modified region in the interfacial region (including the interface region) between the Si-containing layer and the Al-containing layer, it is possible to repair defects of the Si-containing layer and to provide the resulting gas-barrier film with high gas barrier properties and heat resistance (Mechanism) that storage stability is not deteriorated even under severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions), and thus the present invention has been completed. In the gas barrier film of the present invention, unlike Patent Document 1, uniformly called " interface " as in Patent Document 1 does not exist by forming the modified region by surely crossing the middle region of the upper and lower layers, It is found that an integral gas barrier layer having no distinction between upper and lower layers is formed.

In addition, although the production method is not particularly limited, since the interfacial regions are easily mixed by the film formation method by the application method, the gradation structure (modification) in which Al atoms (and Si atoms) continuously increase Area) that is easy to make. Further, by making the upper layer an Al-containing layer, vacuum ultraviolet light is irradiated to the lower Si-containing layer that has passed through this layer. At this time, the region near the interface is modified in the film thickness direction, and in the resulting gas-barrier film, the effect of greatly improving gas barrier property and heat resistance is exhibited. After forming the Si-containing layer subjected to the excimer treatment in the lower layer, only the compound containing Al such as an aluminum compound (not containing the Si-containing compound such as polysilazane) is applied to the upper layer and irradiated with vacuum ultraviolet light The gas barrier property is greatly improved in the entire gas barrier layer, and the gas barrier property and gas barrier property are both satisfied. Therefore, the storage stability is improved, especially under severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration (Mechanism) that there is no deterioration even under the conditions of high temperature, low temperature, and high temperature, so that storage stability is excellent, high gas barrier properties can be maintained, and defects such as dark spots can be reduced in an organic EL device or the like . In addition, only the compound containing Si such as polysilazane not subjected to vacuum ultraviolet light irradiation treatment in the lower layer and the compound containing Al such as an aluminum compound in the upper layer (not including the compound containing Si such as polysilazane) A new modified region formed of a compound containing Al, such as an aluminum compound in the interfacial region, and a Si-containing compound such as polysilazane, is applied to the gas- The gas barrier property is greatly improved in the entire gas barrier layer, and both the gas barrier property and the high heat resistance are both satisfied. Therefore, even under severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions) There is no deterioration, storage stability is excellent, high gas barrier property can be maintained, and further, in an organic EL device or the like Size may be achieved such widespread reduction in defects such as spots, where they will find out the action (mechanism). From these findings, we have come to know the gas barrier film of the present invention described in the above (1) to (6).

In addition, the above-mentioned mechanism (mechanism) is based on estimation, and the present invention is not limited to the above-mentioned mechanism (mechanism).

Hereinafter, preferred embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

In the present specification, " X to Y " representing the range means " X or more and Y or less ". Unless otherwise stated, the measurement of the operation and physical properties is carried out under the conditions of room temperature (20 to 25 ° C) / relative humidity of 40 to 50%.

<Gas Barrier Film>

The gas barrier film of the present invention has a substrate and a gas barrier layer (also referred to as a modified gas barrier layer) having the following characteristics. That is, the reformed gas barrier layer has at least Al atoms and Si atoms, and among the distribution curves of the respective constituent elements based on the measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy on the gas barrier layer, (100 at%) of all the elements in the gas barrier layer in the layer thickness direction of the gas barrier layer and the Al distribution curve of the gas barrier layer in the layer thickness direction And the Al atomic amount on the side opposite to the substrate side of the gas barrier layer is larger than the Al atomic amount on the substrate side.

The gas barrier film may further include another member. The gas-barrier film of the present invention may have other members, for example, between the substrate and the reformed gas barrier layer, on the reformed gas barrier layer, or on the other surface of the substrate on which the reformed gas barrier layer is not formed do. Here, the other member is not particularly limited, and a member used in a conventional gas barrier film can be similarly used or appropriately modified. Specifically, examples of the gas barrier layer, the protective layer, the smoothing layer, the anchor coat layer, the bleed-out preventing layer, and the functional layer of the decaying or antistatic layer having moisture adsorbability may be mentioned.

The gas barrier unit having the modified gas barrier layer may be formed on one surface of the substrate or may be formed on both surfaces of the substrate. The gas barrier layer unit may include a layer which does not necessarily have gas barrier properties, and may include a gas barrier layer other than the modified gas barrier layer as long as the effect of the present invention is not impaired .

(Basic layer composition of gas barrier film)

Hereinafter, the gas barrier film of the present invention will be described with reference to the drawings. Fig. 1 (A) shows a state in which a layer containing an aluminum compound as an upper layer is laminated on a layer made of a polysilazane as a lower layer in the process of producing the gas barrier film of the present invention, and a vacuum ultraviolet ray is irradiated Fig. FIG. 1B is a diagram showing a state in which a modified region (continuous change region of Al atoms) is formed by irradiation and modification of vacuum ultraviolet light in FIG. 1A, Is a schematic view showing a basic layer structure of the gas barrier film of the present invention in which an integral reforming gas barrier layer is formed and a change in the atomic weight of Al in the depth direction of the modified gas barrier layer. FIG. 1C is a diagram schematically showing the layer configuration of the conventional gas barrier film described in Patent Document 1 and the change in the atomic weight of Al in the depth direction of the gas barrier layer.

First, as shown in Fig. 1 (C), in the existing gas-impermeable film 11 ', a lower layer of an aluminum-containing layer (Al-containing silicon oxide (An inorganic film such as silicon oxide, silicon nitride, or silicon oxynitride) 19 formed on the upper layer by a dry method (plasma CVD method), for example, a silicon nitride film, an inorganic film such as silicon nitride, Layer structure. The aluminum-containing layer 18 as the lower layer and the gas barrier layer 19 containing Si as the upper layer laminated by the dry method as shown in Fig. 1C are formed so that the middle regions of the upper and lower layers 18 and 19 do not substantially cross Called &quot; interface &quot; 20 is uniformly formed, and the upper and lower layers are laminated on the boundary. That is, the Al atoms in the depth (film thickness) direction of the gas barrier layer (upper and lower layers 18 and 19) are present only in the lower layer 18 and the Al atomic amount in the lower layer 18 is constant with respect to the depth direction. Therefore, since the modified region (continuous change region of Al atoms) 16 as shown in Fig. 1B, which is the basic layer constitution of the gas barrier film of the present invention, is not formed, (Without a uniform interface) is not formed. As a result, the above-mentioned modification effect can not be obtained, and thus there has been a problem that the gas barrier film 11 'in which the inorganic films 18 and 19 are laminated is continuously grown in defects or cracks are increased .

1 (A), a layer (silica-containing layer) 13 composed of polysilazane as a lower layer and formed on the base material 12 in the process of producing a gas-barrier film, The layer 14 containing the aluminum compound as the upper layer is laminated on the layer 14 and the layer is modified by irradiating the ultraviolet ray 15 with the vacuum ultraviolet ray 15. The ultraviolet ray 15 passes through the layer 14 containing the aluminum compound, Of the polysilazane (13). At that time, the modification proceeds at the interface between the lower layer polysilazane layer 13 and the upper layer aluminum compound layer 14, and the interfacial region has a modified region Continuously changing regions of Al atoms) are widely formed. As a result, as shown in Fig. 1 (B), the modified region (continuous change region of Al atoms) 16 is formed in the gas barrier film 11 of the present invention, and the upper and lower layers 13, The reformed gas barrier layer 17 having no uniform interface (no uniform interface) is formed. With such a constitution, storage stability can be maintained, and high gas barrier properties can be maintained without deterioration even under storage conditions, especially in severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions). It is also possible to considerably reduce defects such as dark spots in the organic EL element and the like.

Hereinafter, each structural member (requirement) will be described.

〔materials〕

In the gas barrier film of the present invention, a plastic film or a plastic sheet is preferably used as the substrate, and a film or sheet made of a colorless transparent resin is more preferably used. The plastic film to be used is not particularly limited in terms of the material and thickness of the film so long as it can hold the modified gas barrier layer and the like, and can be appropriately selected in accordance with the intended use and the like. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, Polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, polyetherimide resin, cellulose acylate resin, polyurethane resin, A fluorene ring-modified polycarbonate resin, an alicyclic modified polycarbonate resin, a fluorene ring-modified polyester resin, and an acryloyl compound.

The thickness of the substrate used in the gas barrier film according to the present invention is not particularly limited as it is appropriately selected depending on the application, but is typically 1 to 800 占 퐉, preferably 10 to 200 占 퐉. These plastic films (substrates) may have functional layers such as a transparent conductive layer, a primer layer, and a clear hard coat layer. As for the functional layer, those described in paragraphs &quot; 0036 &quot; to &quot; 0038 &quot; in Japanese Patent Laid-Open Publication No. 2006-289627 can be preferably employed in addition to those described above.

The base material preferably has a high surface smoothness. As the surface smoothness, it is preferable that the average surface roughness (Ra) is 2 nm or less. Although there is no particular lower limit, it is practically 0.01 nm or more. If necessary, both sides of the substrate, at least the side forming the modified gas barrier layer, may be polished to improve the smoothness.

In addition, the examples described above may be an unstretched film or a stretched film.

The substrate used in the present invention can be produced by a conventionally known general method.

At least the side of the substrate on which the reformed gas barrier layer according to the present invention is formed may be subjected to various known processes for improving the adhesion, such as corona discharge treatment, flame treatment, oxidation treatment or plasma treatment, , And it is preferable to perform the above processes in combination as necessary.

[Modified gas barrier layer]

The reformed gas barrier layer of the present invention comprises (1) a gas barrier layer having at least Al atoms and Si atoms, (2) an element distribution in the depth (film thickness) direction by the X-ray photoelectron spectroscopy on the reformed gas barrier layer (100 at%) of all the elements in the gas barrier layer in the thickness direction of the gas barrier layer and the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, (3) the Al atomic amount on the side opposite to the substrate side of the modified gas barrier layer is smaller than the Al atomic amount on the substrate side It features many.

(Constituent elements of the reformed gas barrier layer; requirement (1) above)

The reformed gas barrier layer formed on the upper portion of the substrate (which may not be directly on the other layer but interposed therebetween) has at least Al atoms and Si atoms. This is because, in the present invention, as described above, a layer containing an upper Al (for example, a layer containing an aluminum compound) is formed on a layer containing a Si atom (for example, a polysilazane layer) Layer) are laminated and irradiated with vacuum ultraviolet light to be reformed, whereby an integral reformed gas barrier layer having no distinction between upper and lower layers (having no uniform interface) is formed. Therefore, as the layer containing Si atoms, for example, Si atoms, N atoms and C atoms are contained as the remaining elements in the reformed gas barrier layer after irradiation with vacuum ultraviolet light into the layer made of polysilazane. In addition, O atoms may be included (see Figs. 2 to 4). As the layer containing Al, an element remaining after irradiation with vacuum ultraviolet light into a layer containing an aluminum compound (for example, ALCH: aluminum ethyl acetoacetate diisopropylate used in Examples) O atoms and C atoms. Therefore, the reformed gas barrier layer has at least Al atoms and Si atoms. Preferably, all the elements in the reformed gas barrier layer are composed of Al atoms, Si atoms, O atoms, N atoms, and C atoms, thereby improving the function and characteristics of the reformed gas barrier layer . However, the modified gas barrier layer may contain other elements as long as the effect of the present invention is not impaired. (Identification) of the elements included in the modified gas barrier layer of the present invention can be performed by measuring the element distribution in the depth direction (layer thickness direction) by X-ray photoelectron spectroscopy on the gas barrier layer (Figs. 2 to 4 Reference). The following description will be made with reference to the drawings.

In this embodiment, as shown in Figs. 2 and 3, it is preferable that all the elements in the modified gas barrier layer are Al atoms, Si atoms, O atoms and N atoms. With such a constitution, as shown in Examples 1 and 2 of Tables 1 and 2, it is possible to achieve both high gas barrier property and heat and humidity resistance, and also to reduce defects such as dark spots (DS) in the organic EL element It is excellent in that it can be done. This is because the modified gas barrier layer shown in Figs. 2 and 3 is formed by forming a polysilazane layer by irradiating vacuum ultraviolet light (excimer) to the lower layer, applying only an aluminum compound (not containing polysilazane) to the upper layer, In the resulting gas-barrier film, by irradiating ultraviolet light (excimer) and modifying it, defective restoration of the lower layer is possible, and the modified region where the region near the interface is modified in the film thickness direction is excellent in barrier property, (The retention ratio in Table 1) is improved in the whole gas barrier layer, and both the high gas barrier property and the heat resistance are improved, and furthermore, the defects such as dark spots in the organic EL devices and the like are reduced Dark spot incidence rate). It is also preferable that all the elements in the reformed gas barrier layer have Al atoms, Si atoms, O atoms and C atoms (in which no N atoms are left in Fig. 4). In this case as well, the same effect as in Figs. 2 to 4 can be obtained.

In this embodiment, it is particularly preferable that all the elements in the reformed gas barrier layer are Al atoms, Si atoms, O atoms, N atoms and C atoms, as shown in Fig. With such a constitution, as shown in Example 3 of Tables 1 and 2, it is possible to achieve both a higher gas barrier property and a higher heat resistance, as well as to further reduce defects such as dark spots (DS) in the organic EL element It is excellent in that it can be done. This is because the modified gas barrier layer of FIG. 4 is formed by applying polysilazane not irradiating vacuum ultraviolet light to the lower layer, applying only aluminum compound (not including polysilazane) to the upper layer, collecting vacuum ultraviolet light In the resulting gas-barrier film, the region in the vicinity of the interface is widely modified by the film thickness direction, defect restoration of the lower layer is possible, and a new layer formed of the aluminum-polysilazane in the interface region is obtained. (Retention ratio in Table 1) is significantly improved over the entire gas barrier layer, and both the gas barrier property and the wet heat resistance are both satisfied, and furthermore, the organic EL Defects such as dark spots in devices and the like can be greatly reduced (see the dark spot occurrence rate in Table 2).

(Compositional change of the Al atoms in the layer thickness direction of the reformed gas barrier layer; requirement (2) and (3)

In the present invention, among the distribution curves of the respective constituent elements based on the measurement of the element distribution in the depth direction by the X-ray photoelectron spectroscopy on the modified gas barrier layer, the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer (100 at%) of the total elements in the gas barrier layer, the Al atom of the modified gas barrier layer and the region where the composition continuously changes in the layer thickness direction (B), and a continuous change region (16) of Al atoms) which is excellent in both heat resistance and barrier properties. Preferably, the modified gas barrier layer has a region (region A) in which Al atoms continuously increase from the substrate side. With such a constitution, storage stability can be maintained, and high gas barrier properties can be maintained without deterioration even under storage conditions, especially in severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions). It is also possible to considerably reduce defects such as dark spots in organic EL devices and the like (see Tables 1 and 2 in Examples 1 to 3). More preferably, in the Al distribution curve, the region A continuously growing from the substrate side has a slope of 0.5 at% / nm (in terms of SiO ₂ ) or more and 2.5 at% / nm (in terms of SiO ₂ ) , And it is particularly preferable to have a slope of not less than 0.5 at% / nm (in terms of SiO ₂ ) and not more than _{2 at} % / nm (in terms of SiO ₂ ). If the slope of the Al distribution curve in the region A is within the above range, the gas barrier properties accompanying the composition change hardly occur even after a long time under high temperature and high humidity (= high retention ratio as shown in Table 1) And is excellent in stability and storage stability under particularly harsh conditions (high temperature and high humidity conditions). In addition, as shown in Table 2, defects such as dark spots in organic EL devices and the like can be greatly reduced (see Tables 1 and 2 in Examples 1 to 3). Particularly, in the above Al distribution curve, the area A continuously increasing from the substrate side is preferably 1.0 at% / nm (in terms of SiO ₂ ) or more and 2.0 at% / nm (in terms of SiO ₂ ) in terms of SiO ₂₎ in a desirable, and (2) reducing defects such as dark spots having a gradient effect in the range below point of view .0.5at% / ㎚ (SiO ₂ basis) or more, 1.0at% / ㎚ (in terms of SiO ₂ ). &Lt; / RTI &gt;

2 to 4, in the Al distribution curve with respect to the distance from the surface of the modified gas barrier layer in the layer thickness direction of the modified gas barrier layer to the total amount (100 at%) of all the elements in the modified gas barrier layer, An area A (a region where the slope of the Al distribution curve is calculated) in which the composition continuously changes in the thickness direction of the Al atoms in the gas barrier layer, in particular, continuously increases from the substrate side is shown in the figure. As shown in Figs. 2 to 4, the Al atoms in the reformed gas barrier layer are continuously changed in the layer thickness direction, particularly in the region A (the region where the slope of the Al distribution curve is calculated: Region) is at least 10 nm thick, and the amount of change at a thickness of 5 nm is preferably 10 at% or less. This is because the modifying effect is high, and therefore, it is excellent in heat resistance and gas barrier properties.

In the present invention, among the distribution curves of the respective constituent elements based on the measurement of the element distribution in the depth direction by the X-ray photoelectron spectroscopy on the modified gas barrier layer, the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer And the region B continuously decreasing from the substrate side in the Si distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer is -2 at% / nm (in terms of SiO ₂ ) It is preferable to have a slope. More preferably, in the Si distribution curve, the region B continuously decreasing from the substrate side has a slope of -0.5 at% / nm (in terms of SiO ₂ ) or more and -2 at% / nm (in terms of SiO ₂ ) . If the slope of the Si distribution curve in the region B is within the above range, as shown in Table 2, as in the case of the effect of the gradation structure of the Al atoms, defects such as dark spots in the organic EL elements and the like are significantly reduced (Refer to the comparison between Example 3 (within the above range) and Examples 1 and 2 (outside the above range) in Table 2). In addition, even after exposure for a long period of time under high temperature and high humidity, there is almost no decrease in gas barrier property accompanying composition change (= high retention ratio as shown in Table 1) and storage stability, especially under severe conditions Stability is excellent.

In addition, up to about 100 nm (in terms of SiO ₂ ) of the abscissa (sputtering speed) of Figs. 2 and 3 is the modified gas barrier layer, and 100 nm or more corresponds to the first gas barrier layer. Up to approximately 80 nm (in terms of SiO ₂ ) of the horizontal axis (sputtering speed) in FIG. 4 is the modified gas barrier layer, and 80 nm or more corresponds to the first gas barrier layer.

In the present invention, it is preferable that the Al distribution curve and the Si distribution curve with respect to the total amount (100 at%) of all the elements in the modified gas barrier layer have a region where Al atoms and Si atoms cross each other. With such a structure, the structure having a wide distribution of barrier properties is widely distributed. Therefore, there is no deterioration even under a severe storage condition (particularly, high temperature and high humidity conditions = high temperature and high humidity acceleration conditions) I can maintain sex. It is also possible to considerably reduce defects such as dark spots in organic EL devices and the like (see Figs. 2 to 4).

In the present invention, the content of Al atoms in the total amount (100 at%) of all the elements in the modified gas barrier layer is in the range of 5 to 50 at%, preferably 7 to 40 at%, more preferably 10 to 30 at%. When the content of Al atoms is 5 at% or more, it is excellent in that SiAlO regions having less dangling bonds can be formed. On the other hand, when the content of Al atoms is 50 at% or less, the stress caused by external stress such as thermal influence is excellently reduced. As a result, there is no deterioration even under the storage stability, particularly in severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions), and storage stability is excellent and high gas barrier properties can be maintained. It is also possible to considerably reduce defects such as dark spots in the organic EL element and the like.

In the present invention, the content of Si atoms relative to the total amount (100 at%) of all elements in the modified gas barrier layer is in the range of 5 to 50 at%, preferably 10 to 40 at%, more preferably 25 to 40 at%. When the content of Si atoms is 5 at% or more, the stress due to external stress such as thermal influence is excellently reduced. On the other hand, when the Si atom content is 50 at% or less, it is excellent in that SiAlO regions having less dangling bonds can be formed. As a result, there is no deterioration even under the storage stability, particularly in severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions), and storage stability is excellent and high gas barrier properties can be maintained. It is also possible to considerably reduce defects such as dark spots in the organic EL element and the like.

Hereinafter, a method of manufacturing the gas barrier layer (modified gas barrier layer and other gas barrier layers) will be described.

The gas barrier layer is produced by forming a gas barrier layer other than the modified gas barrier layer on the substrate, forming a lower inorganic compound layer (gas barrier layer or gas barrier precursor layer) on the substrate, (Gas barrier precursor layer) as an upper layer and irradiating vacuum ultraviolet rays to form a reformed gas barrier layer without distinction between upper and lower layers.

(Formation of a lower inorganic compound layer (gas barrier layer) or a precursor layer thereof)

The method of forming the inorganic compound layer (gas barrier layer) or the precursor layer in the lower layer is not particularly limited, and it is only necessary to form a layer containing Si as the inorganic compound layer (gas barrier layer) in the lower layer. Particularly, a coating film formed by applying a liquid containing an inorganic compound, preferably a liquid containing a silicon compound, to a vacuum film forming method (dry method) such as a physical vapor deposition method (PVD method) or a chemical vapor deposition method (CVD method) (Hereinafter, simply referred to as a coating method) is preferable. In the case of forming the lower inorganic compound layer (gas barrier layer) directly on the substrate without forming the gas barrier layer other than the modified gas barrier layer, the physical vapor deposition method or the chemical vapor deposition method is more preferable. When a gas barrier layer other than the modified gas barrier layer is provided on a substrate by a vacuum deposition method (dry method), a coating method (wet method) is more preferable as a method of forming the inorganic compound layer (gas barrier layer) (See Examples 1 to 3). The method of forming the lower precursor layer (gas barrier precursor layer) refers to a method of forming up to the coating film (precursor layer) before modification by a coating method (wet method). That is, in the formation step of the lower layer, a coating film (precursor layer) before reforming is formed, and then a coating film (precursor layer) of the upper layer is formed on the coating film (precursor layer) It is possible to use a method of integrally modifying upper and lower layers by modifying means (for example, vacuum ultraviolet ray irradiation treatment or the like) to form an integrated reformed gas barrier layer having no distinction between upper and lower layers (no interface) (Example 3, Figs. 12 (A) and 12 (B)).

Hereinafter, the vacuum film forming method (dry method) and the application method (wet method) will be described.

&Lt; Vacuum film forming method (dry method) >

The vacuum film forming method (dry method) is largely classified into physical vapor deposition (PVD) and chemical vapor deposition (CVD).

Among them, the physical vapor phase growth method (PVD method) is a method of depositing a target material, for example, a carbon film, on the surface of a material in a vapor phase by a physical method. For example, a sputtering method (DC sputtering , An RF sputtering method, an ion beam sputtering method, and a magnetron sputtering method), a vapor deposition method (such as a vacuum deposition method), and an ion plating method.

The sputtering method, which is a kind of the physical vapor deposition (PVD method), is a method in which a target is provided in a vacuum chamber, a rare gas element (usually argon) ionized by applying a high voltage is caused to collide with a target, To the substrate. At this time, a reactive sputtering method may be used, in which a nitrogen gas or an oxygen gas is flowed into the chamber to react the nitrogen and oxygen with an element bounced out from the target by argon gas to form an inorganic layer.

On the other hand, the chemical vapor deposition method (CVD method) is a method of depositing a film on a substrate by supplying a source gas containing a target thin film component and chemical reaction on the substrate surface or vapor phase. For the purpose of activating a chemical reaction, there is a method of generating a plasma or the like, and a thermal CVD method, a catalytic chemical vapor deposition method, a photo CVD method, a plasma CVD method (vacuum plasma CVD method, Plasma CVD method, etc.), and the like. Although not particularly limited, it is preferable to apply the plasma CVD method from the viewpoint of the film-forming speed and the processing area.

(Gas barrier layer) obtained by a plasma CVD method (for example, a vacuum plasma CVD method, a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure), which is a preferred form of the chemical vapor deposition method (CVD method) Is preferable because a desired compound can be produced by selecting conditions such as a metal compound as a raw material (also referred to as a raw material), a decomposition gas, a decomposition temperature, an input power and the like.

For example, when a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is produced. This is because the highly active charged particles and active radicals are present at a high density in the plasma space, so that the multistage chemical reaction is promoted at a very high rate in the plasma space, and the elements present in the plasma space are thermodynamically stable compounds in a very short time Because it is transformed.

As the raw material compound, it is preferable to use a silicon compound, a titanium compound, and an aluminum compound. These raw material compounds may be used alone or in combination of two or more. The reason for including the aluminum compound here is that Al may be contained in the range of the lower layer of the reformed gas barrier layer. That is, in the present invention, since the gradient of the Al atoms is required to be between the upper layer and the lower layer, a structure having a concentration gradient of Al atoms can be formed even if the lower layer contains a small amount of Al.

By appropriately selecting the source gas containing the raw material compound and the decomposition gas, a desired lower inorganic compound layer (gas barrier layer) can be obtained. The lower inorganic compound layer (gas barrier layer) formed by the CVD method is preferably a layer containing an oxide, a nitride, an oxynitride, or an oxynitride and not containing an Al component.

Hereinafter, the vacuum plasma CVD method, which is a preferred form of the CVD method, will be described in detail.

5 is a schematic view showing an example of a vacuum plasma CVD apparatus used for forming an inorganic compound layer (gas barrier layer) in the lower layer according to the present invention.

5, the vacuum plasma CVD apparatus 101 has a vacuum chamber 102, and a susceptor 105 is disposed on the bottom surface side of the inside of the vacuum chamber 102. A cathode electrode 103 is disposed on a ceiling side of the inside of the vacuum chamber 102 at a position facing the susceptor 105. A heating medium circulation system 106, a vacuum evacuation system 107, a gas introducing system 108 and a high frequency power source 109 are disposed outside the vacuum chamber 102. A heating medium is disposed in the heating medium circulation system 106. The heating medium circulation system 106 is provided with a pump for moving the heating medium, a heating device for heating the heating medium, a cooling device for cooling, a temperature sensor for measuring the temperature of the heating medium, A cooling device 160 is installed.

As a preferred embodiment of the lower inorganic compound layer (gas barrier layer) formed by the CVD method according to the present invention, the inorganic compound layer (gas barrier layer) in the lower layer contains carbon (C), silicon (Si) , And oxygen (O). A more preferable form is a layer which satisfies the following requirements (i) to (iii).

However, various requirements concerning the inorganic compound layer (gas barrier layer) in the lower layer shown below relate only to the lower inorganic compound layer (gas barrier layer) obtained in the manufacturing process. In the final reformed gas barrier layer, since the upper and lower layers can not be discriminated, a region corresponding to the inorganic compound layer (gas barrier layer) in the lower layer can not be specified. Therefore, various requirements and the like concerning the inorganic compound layer (gas barrier layer) in the lower layer shown below are those in which a desired lower inorganic compound layer (gas barrier layer) is formed in the manufacturing process, (To be measured by extracting a suitable number of samples) before reforming (= during manufacturing). On the other hand, for the gas barrier layer other than the reformed gas barrier layer (for example, a layer formed between the substrate and the reformed gas barrier layer or the like), the production method of the lower inorganic compound layer (gas barrier layer) The method (dry method) is preferably applied. With respect to the gas barrier layer other than such a reformed gas barrier layer, a layer which satisfies the following various requirements in the gas barrier film (after the production) is more preferable.

(I) the distance L from the surface of the inorganic compound layer (gas barrier layer) in the lower layer in the film thickness direction of the inorganic compound layer (gas barrier layer) in the lower layer and the total amount of silicon atoms, oxygen atoms and carbon atoms A silicon distribution curve showing the relationship of the ratio of silicon atomic ratio (atomic ratio of silicon), oxygen showing the relationship between the ratio of oxygen atomic ratio to the total amount of L, silicon atom, oxygen atom and carbon atom A distribution curve and a carbon distribution curve showing the relationship between the ratio of carbon atoms in L to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of carbon), the lower inorganic compound layer (gas barrier layer (Atomic ratio of oxygen), (atomic ratio of silicon) (atomic ratio: O> Si> C (atomic ratio)) in the region of 90% or more (upper limit: 100% );

(Ii) said carbon distribution curve has at least two extreme values;

(Iii) a subtraction value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter simply referred to as "C _max -C _min Quot; tea &quot;) is not less than 3 at%.

Hereinafter, the requirements of (i) to (iii) will be described.

The inorganic compound layer (gas barrier layer) of the lower layer is formed by (i) a distance L from the surface of the lower inorganic compound layer (gas barrier layer) in the film thickness direction of the lower inorganic compound layer (gas barrier layer) A silicon distribution curve showing the relationship between the ratio of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of silicon), the oxygen atomic ratio to the total amount of L, silicon atoms, oxygen atoms, (Atomic ratio of oxygen), and an oxygen distribution curve showing the relationship between the above-mentioned L and the ratio of the atomic ratio of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atomic ratio of carbon) (Upper limit: 100%) of the film thickness of the inorganic compound layer (gas barrier layer) in the lower layer, and is a region where the atomic ratio of oxygen, the atomic ratio of silicon, ) In the order of (Atomic ratio: O > Si > C). When the above condition (i) is satisfied, the gas barrier property and the bendability of the resulting gas barrier film can be improved. Here, in the above carbon distribution curve, the relationship between the atomic ratio of oxygen, the atomic ratio of silicon, and the atomic ratio of carbon is at least 90 (atomic ratio) of the film thickness of the inorganic compound layer (gas barrier layer) , More preferably at least 93% (upper limit: 100%), and more preferably at least 93% (upper limit: 100%). Here, at least 90% or more of the film thickness of the inorganic compound layer (gas barrier layer) in the lower layer does not need to be continuous in the inorganic compound layer (gas barrier layer) in the lower layer and merely satisfies the above-mentioned relationship in 90% .

Further, it is preferable that the inorganic compound layer (gas barrier layer) in the lower layer has (ii) the carbon distribution curve has at least two extreme values. The inorganic compound layer (gas barrier layer) in the lower layer preferably has at least three extreme values of the carbon distribution curve, more preferably at least four extreme values, but may have five or more. When the extreme value of the carbon distribution curve is two or more, the gas barrier property in the case of bending the obtained gas barrier film can be improved. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, and more preferably 25 or less. However, the number of extreme values is not limited to the film thickness of the inorganic compound layer (gas barrier layer) , It can not be uniformly defined.

Here, in the case of having at least three extreme values, it is preferable that one of the extreme values of the carbon distribution curve and the extreme value adjacent to the extreme value in the film thickness direction of the lower inorganic compound layer (gas barrier layer) (Hereinafter simply referred to as &quot; distance between extreme values &quot;) of the distance L from the surface of the compound layer (gas barrier layer) is preferably 200 nm or less, more preferably 100 nm or less, Or less. If the distance between the extreme values is such that the inorganic compound layer (gas barrier layer) in the lower layer exists in a region having a large carbon atom ratio (maximum value) at an appropriate cycle, appropriate bending property is given to the lower inorganic compound layer It is possible to more effectively suppress and prevent the occurrence of cracks during bending of the film. In the present specification, the term "extreme value" refers to the distance from the surface of the inorganic compound layer (gas barrier layer) in the lower layer in the film thickness direction of the lower inorganic compound layer (gas barrier layer) It means the maximum value or the minimum value of mercy. In the present specification, the term &quot; maximum value &quot; means that the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from increase to decrease when the distance from the surface of the inorganic compound layer (gas barrier layer) And the distance from the surface of the lower inorganic compound layer (gas barrier layer) in the film thickness direction of the lower inorganic compound layer (gas barrier layer) to the surface of the lower inorganic compound layer (gas barrier layer) Means that the value of the atomic ratio of the element at the further changed position in the range of 20 nm is reduced by 3 at% or more. That is, when the value is changed in the range of 4 to 20 nm, the value of the atomic ratio of the element in any one range may be reduced by 3 at% or more. Similarly, in the present specification, the "minimum value" means that the value of the atomic ratio of the element (oxygen, silicon or carbon) changes from decrease to increase when the distance from the surface of the inorganic compound layer (gas barrier layer) And the distance from the surface of the inorganic compound layer (gas barrier layer) in the lower layer in the thickness direction of the inorganic compound layer (gas barrier layer) as the lower layer to the surface of the inorganic compound layer Means that the value of the atomic ratio of the element at the further changed position in the range of 20 nm is increased by 3 at% or more. That is, when the value is changed in the range of 4 to 20 nm, the value of the atomic ratio of the element in any one range may be increased by 3 at% or more. Here, the lower limit of the distance between the extreme values in the case of having at least three extreme values is not particularly limited, as the distance between extreme values is smaller, and the effect of improving crack prevention / prevention at the time of bending of the gas- In consideration of the bending property of the inorganic compound layer (gas barrier layer), the effect of suppressing / preventing the cracks, the thermal expansion property, and the like, it is preferably 10 nm or more and more preferably 30 nm or more.

The inorganic compound layer (gas barrier layer) in the lower layer has a ratio of a maximum value and a minimum value of the atomic ratio of carbon in the carbon distribution curve (hereinafter, simply referred to as "C _max -C _{min difference} "), Is preferably 3 at% or more. When the cut-off value is 3 at% or more, gas barrier properties in the case of bending the obtained gas-barrier film can be improved. C _max -C _min More preferably at least 5 at%, even more preferably at least 7 at%, particularly preferably at least 10 at%. The C _max -C _min By making a difference, the gas barrier property can be further improved. In the present specification, the &quot; maximum value &quot; is the atomic ratio of each element that becomes the maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in the present specification, the "minimum value" is the atomic ratio of each element which is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Where C _max C _min The upper limit of the difference is not particularly limited, but is preferably 50 at% or less, more preferably 40 at% or less, in consideration of the effect of improving crack prevention / prevention at the time of bending of the gas barrier film.

In the present invention, the oxygen distribution curve of the lower inorganic compound layer (gas barrier layer) preferably has at least one extreme value, more preferably at least two extreme values, and more preferably at least three extreme values desirable. When the oxygen distribution curve has at least one extreme value, the gas barrier property of the obtained gas barrier film is improved compared with the gas barrier film having no extreme value. The upper limit of the extreme value of the oxygen distribution curve is not particularly limited, but is preferably 20 or less, more preferably 10 or less, for example. Even in the number of extreme values of the oxygen distribution curve, there is a part due to the film thickness of the inorganic compound layer (gas barrier layer) in the lower layer, and therefore it can not be uniformly defined. In addition, in the case of having at least three extreme values, it is preferable that one of the extreme values of the oxygen distribution curve and the extreme value adjacent to the extreme value, in the film thickness direction of the lower inorganic compound layer (gas barrier layer) (Gas barrier layer) is preferably 200 nm or less, and more preferably 100 nm or less. Such a distance between the extreme values can more effectively suppress and prevent the occurrence of cracks during bending of the gas-barrier film. Here, in the case of having at least three extreme values, the lower limit of the distance between the extreme values is not particularly limited. However, considering the effect of improving crack prevention / prevention at the time of bending of the gas barrier film, thermal expansion, More preferably 30 nm or more.

Further, a minus value (hereinafter simply referred to as "O _max -O _{min difference} ") of the difference between the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the lower inorganic compound layer (gas barrier layer) is 3 at% , More preferably at least 6 at%, and even more preferably at least 7 at%. When the cut-off value is 3 at% or more, the gas barrier property in the case of bending the obtained gas-barrier film is further improved. Here, O _max -O _min The upper limit of the difference is not particularly limited, but is preferably 50 at% or less, more preferably 40 at% or less, in consideration of the effect of improving crack prevention / prevention at the time of bending of the gas barrier film.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve can be measured by X-ray photoelectron spectroscopy (XPS) and a rare gas ion sputtering such as argon, So-called XPS depth profile measurement, in which sequential surface composition analysis is performed while exposure is performed. The distribution curve obtained by such XPS depth profile measurement can be prepared, for example, with the ordinate axis as the atomic ratio (unit: at%) of each element and the abscissa axis as the etching time (sputter time). In the distribution curve of the element having the abscissa as the etching time, the etching time is longer than the etching rate of the lower inorganic compound layer (gas barrier layer) in the film thickness direction of the lower inorganic compound layer (gas barrier layer) Quot; the distance from the surface of the lower inorganic compound layer (gas barrier layer) in the film thickness direction of the lower inorganic compound layer (gas barrier layer) &quot; to the distance L from the surface of the lower layer The distance from the surface of the lower inorganic compound layer (gas barrier layer) calculated from the relationship between the etching rate and the etching time employed in the measurement of the depth profile can be adopted. Further, the silicon distribution curve, the oxygen distribution curve, the carbon distribution curve and the oxygen carbon distribution curve can be prepared by the following measurement conditions.

(Measuring conditions)

Etching ion species: argon (Ar ⁺ )

The etching rate (SiO ₂ Thermal oxide conversion value): 0.05 nm / sec

Etching interval (SiO ₂ conversion value): 10 nm

X-ray photoelectron spectrometer: manufactured by Thermo Fisher Scientific, model name "VG Theta Probe"

Irradiation X-ray: Single crystal spectroscopy AlKα

X-ray spot and its size: 800 x 400 탆 oval

The film thickness (dry film thickness) of the lower inorganic compound layer (gas barrier layer) formed by the above plasma CVD method is not particularly limited. For example, the film thickness per one layer of the inorganic compound layer (gas barrier layer) in the lower layer is preferably 20 to 3000 nm, more preferably 50 to 2500 nm, and particularly preferably 100 to 1000 nm. With such a film thickness, the gas barrier film can exert excellent gas barrier property and crack prevention / prevention effect at the time of bending. In the case where the lower inorganic compound layer (gas barrier layer) formed by the above plasma CVD method is composed of two or more layers, the inorganic compound layer (gas barrier layer) in each lower layer has the above-described film thickness desirable.

In the present invention, from the viewpoint of forming a lower inorganic compound layer (gas barrier layer) having uniform gas barrier properties over the whole film surface, the lower inorganic compound layer (gas barrier layer) In a direction parallel to the surface of the compound layer (gas barrier layer)). Here, the fact that the inorganic compound layer (gas barrier layer) in the lower layer is substantially the same in the film surface direction means that the measurement of the XPS depth profile is carried out for any two measurement points on the film surface of the inorganic compound layer (gas barrier layer) Wherein when the oxygen distribution curve, the carbon distribution curve and the oxygen carbon distribution curve are created, the carbon distribution curve obtained at any two of the measurement points has the same extreme value, and the carbon in each carbon distribution curve Means that the absolute value of the difference between the maximum value and the minimum value of the atomic ratios of the atoms is equal to or less than 5 at%.

Further, in the present invention, it is preferable that the carbon distribution curve is substantially continuous. Here, the term "substantially continuous carbon distribution curve" means that the atomic ratio of carbon in the carbon distribution curve does not include discontinuously changing portions. Specifically, it means that the lower layer The distance (x, unit: nm) from the surface of the inorganic compound layer (gas barrier layer) in the lower layer in the film thickness direction of at least one of the inorganic compound layers (gas barrier layers) at%), it means that the condition expressed by the following formula (1) is satisfied.

[Equation 1]

In the gas barrier film according to the present invention, the lower inorganic compound layer (gas barrier layer) satisfying all of the conditions (i) to (iii) may have only one layer or two or more layers . When two or more lower inorganic compound layers (gas barrier layers) are provided, the material of the inorganic compound layers (gas barrier layers) in the lower layer may be the same or different.

The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve satisfy 90% of the film thickness of the inorganic compound layer (gas barrier layer) (I) in the above-mentioned region is satisfied, the atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the inorganic compound layer (gas barrier layer) Is preferably 20 to 50 at%, more preferably 25 to 40 at%. The atomic ratio of the content of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the lower inorganic compound layer (gas barrier layer) is preferably 45 to 75 at%, more preferably 50 to 70 at% Is more preferable. The atomic ratio of the content of carbon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the lower inorganic compound layer (gas barrier layer) is preferably 0.5 to 25 at%, more preferably 1 to 20 at% Is more preferable.

In the present invention, the method of forming the inorganic compound layer (gas barrier layer) in the lower layer is not particularly limited, and the conventional method can be applied similarly or by modifying it appropriately. The inorganic compound layer (gas barrier layer) in the lower layer is preferably formed by a chemical vapor deposition (CVD) method, particularly a plasma chemical vapor deposition method (plasma CVD, plasma enhanced chemical vapor deposition (PECVD) More preferably formed by a plasma CVD method in which a substrate is disposed on a pair of film-forming rollers and a plasma is generated by discharging between the pair of film-forming rollers.

Hereinafter, a method of forming a lower inorganic compound layer (gas barrier layer) on a substrate by a plasma CVD method in which a substrate is placed on a pair of film-forming rollers and a plasma is generated by discharging between the pair of film-forming rollers do.

&Lt; Method of forming inorganic compound layer (gas barrier layer) in the lower layer by plasma CVD &

As a method of forming the inorganic compound layer (gas barrier layer) in the lower layer according to the present invention on the surface of the substrate, plasma CVD is preferably employed from the viewpoint of gas barrier property. The plasma CVD method may be a plasma CVD method using a Penning discharge plasma method.

When plasma is generated in the plasma CVD method, it is preferable that a plasma discharge is generated in a space between a plurality of film-forming rollers. By using a pair of film-forming rollers, It is more preferable to discharge plasma between the pair of film forming rollers to generate plasma. In this manner, by using a pair of film-forming rollers, a substrate is disposed on the pair of film-forming rollers, and the discharge is caused to occur between the pair of film-forming rollers, whereby the surface portion of the substrate existing on one film- It is possible to simultaneously form the surface portion of the substrate existing on the other film-forming roller while forming the film, and not only the thin film can be efficiently produced, but the film-forming rate is doubled as compared with the plasma CVD method It is possible to at least double the extreme value in the carbon distribution curve and effectively form a layer satisfying all of the conditions (i) to (iii) Lt; / RTI &gt;

When discharging between the pair of film forming rollers in this manner, it is preferable to alternately reverse the polarities of the pair of film forming rollers. The film forming gas used in such a plasma CVD method preferably contains an organic silicon compound and oxygen, and the content of oxygen in the film forming gas is sufficient to completely oxidize the entire amount of the organic silicon compound in the film forming gas It is preferable that the oxygen concentration is less than the theoretical oxygen amount. In the gas barrier film of the present invention, it is preferable that the inorganic compound layer (gas barrier layer) in the lower layer is a layer formed by a continuous film forming process.

From the viewpoint of productivity, the gas barrier film of the present invention preferably forms the lower inorganic compound layer (gas barrier layer) on the surface of the substrate by a roll-to-roll method. An apparatus that can be used for producing the inorganic compound layer (gas barrier layer) as the lower layer by such a plasma CVD method is not particularly limited, but includes at least a pair of film-forming rollers and a plasma power source, It is preferable that the apparatus is configured so as to be capable of discharging between a pair of film forming rollers. For example, in the case of using the manufacturing apparatus shown in Fig. 6, the roll-to- .

Hereinafter, with reference to FIG. 6, a method of forming the lower inorganic compound layer (gas barrier layer) by a plasma CVD method in which a substrate is disposed on a pair of film-forming rollers and a plasma is generated by discharging between the pair of film- Will be described in more detail. 6 is a schematic diagram showing an example of a manufacturing apparatus which can be preferably used for producing an inorganic compound layer (gas barrier layer) as a lower layer from the present manufacturing method. In the following description and drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted.

The manufacturing apparatus 31 shown in Fig. 6 is provided with a delivery roller 32, delivery rollers 33, 34, 35 and 36, deposition rollers 39 and 40, a gas supply pipe 41, Magnetic field generators 43 and 44 provided inside the film-forming rollers 39 and 40, and a winding roller 45. The magnetic-field generating devices 43 and 44 are disposed in the vicinity of the winding rollers 39 and 40, respectively. In this manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating devices 43 and 44 are connected to a vacuum chamber Respectively. In this manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

The specific form (apparatus configuration, etc.) of such a manufacturing apparatus, the method of forming the deposition gas barrier layer by the plasma CVD method using such a manufacturing apparatus, the film forming gas, the film forming conditions, Quot; 0185 &quot; to &quot; 0208 &quot; and their corresponding drawings in Japanese Laid-Open Patent Publication No. 2014-218012, paragraphs &quot; 0091 &quot; to &quot; 0116 &quot; and corresponding drawings in Japanese Laid-Open Patent Publication No. 2014-141056, 0181 &quot; to &quot; 0201 &quot; of the Japanese Patent Application Laid-Open No. 47790 and its corresponding drawings, etc., and can be suitably referred to.

By appropriately adjusting, for example, the kind of the raw material gas, the electric power of the electrode drum of the plasma generating device, the pressure in the vacuum chamber, the diameter of the film forming roller, and the conveying speed of the film (substrate) An inorganic compound layer (gas barrier layer) as a lower layer which satisfies the above requirements (i) to (iii) can be efficiently formed on the surface of the substrate.

The raw material gas, the reaction gas, the carrier gas, and the discharge gas may be used alone or as a mixture of two or more species of the deposition gas (raw material gas) supplied to the opposite space from the gas supply pipe 41. The source gas in the deposition gas used for forming the inorganic compound layer (gas barrier layer) 3 in the lower layer can be appropriately selected depending on the material of the lower inorganic compound layer (gas barrier layer) 3 to be formed. As such a raw material gas, for example, an organic silicon compound containing silicon or an organic compound gas containing carbon may be used. Examples of such organic silicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane , Trimethylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) Of these organosilicon compounds, among the organosilicon compounds, the handling properties of the compounds and the gas barrier properties of the lower inorganic compound layer (gas barrier layer) in the lower layer obtained Hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable. These organosilicon compounds may be used singly or in combination of two or more. Further, the organosilicon compounds containing carbon Examples of the water gas include methane, ethane, ethylene, and acetylene. These organosilicon compound gases and organic compound gases are appropriately selected depending on the kind of the inorganic compound layer (gas barrier layer) 3 in the lower layer Is selected.

As the film forming gas, a reactive gas may be used in addition to the raw material gas. As such a reaction gas, a gas which reacts with the raw material gas and is made of an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As the reaction gas for forming the oxide, for example, oxygen and ozone can be used. As the reaction gas for forming the nitride, for example, nitrogen and ammonia can be used. These reaction gases may be used singly or in combination of two or more. For example, in the case of forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride may be used in combination .

As the film forming gas, a carrier gas may be used, if necessary, in order to supply the raw material gas into the vacuum chamber. As the film forming gas, a discharge gas may be used, if necessary, in order to generate a plasma discharge. As the carrier gas and the discharge gas, any well-known gas may be used. For example, a rare gas such as helium, argon, neon, or xenon; Hydrogen can be used.

In the case where such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is preferably set such that the ratio of the reactive gas is excessively higher than the ratio of the amount of the reactive gas, . (Gas barrier layer) 3 which is formed by lowering the proportion of the reaction gas excessively, whereby superior barrier property and bending resistance can be obtained. When the film forming gas contains the organic silicon compound and oxygen, it is preferable that the total amount of the organic silicon compound in the film forming gas is not more than the theoretical oxygen amount required for complete oxidation.

The pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted in accordance with the kind of the raw material gas or the like, but is preferably set in the range of 0.5 Pa to 50 Pa.

In order to discharge between the film forming roller 39 and the film forming roller 40 in the plasma CVD method as described above, the electrode drum (in this embodiment, the film forming roller 39 and 40) can be appropriately adjusted in accordance with the kind of the raw material gas, the pressure in the vacuum chamber, and the like, and it is preferable that the power is in the range of 0.1 to 10 kW . If the applied electric power is 100 W or more, generation of particles can be sufficiently suppressed. On the other hand, if the applied electric power is 10 kW or less, the amount of heat generated during film formation can be suppressed and the temperature of the surface of the substrate . Therefore, the base material is not thermally deformed, and wrinkles are prevented from occurring at the time of film formation.

The feed speed (line speed) of the base material 2 can be suitably adjusted in accordance with the type of the raw material gas or the pressure in the vacuum chamber, but is preferably in the range of 0.25 to 100 m / min and in the range of 0.5 to 20 m / min . When the line speed is 0.25 m / min or more, generation of wrinkles due to heat on the substrate can be effectively suppressed. On the other hand, when it is 100 m / min or less, it is excellent in that productivity can be maintained, and a sufficient film thickness can be ensured as the inorganic compound layer (gas barrier layer) in the lower layer.

As described above, as a more preferable mode of the present embodiment, a lower layer inorganic compound layer (gas barrier layer) according to the present invention is formed by using a plasma CVD apparatus (roll-to-roll system) having counter roll electrodes shown in Fig. 6 And the film is formed by the plasma CVD method. This is because, in the case of mass production using a plasma CVD apparatus (roll-to-roll system) having counter roll electrodes, it has excellent flexibility (bending property), and is excellent in mechanical strength, This is because the lower inorganic compound layer (gas barrier layer) can be produced efficiently. Such a manufacturing apparatus is excellent in that it is inexpensive and can mass-produce a gas-barrier film which is required to have durability against a temperature change used for a solar cell, an electronic part, and the like.

<Coating method>

The inorganic compound layer (gas barrier layer) in the lower layer according to the present invention can be formed by, for example, a method of forming a coating film formed by applying a liquid containing an inorganic compound, preferably a silicon compound, As shown in Fig. When the coating method is used to form the inorganic compound layer (gas barrier layer) as the lower layer constituting the reformed gas barrier layer, as in the layer constitution shown in Figs. 11 and 12 of Examples 1 to 3, It is preferable to form a gas barrier layer other than the reformed gas barrier layer. As a method of forming the gas barrier layer other than the reformed gas barrier layer, a vacuum film formation method (dry method) similar to the above-described method of forming the inorganic compound layer (gas barrier layer) in the lower layer is preferable, and physical vapor deposition or chemical vapor deposition Method is more preferable, and it is particularly preferable to form it by the plasma CVD method. Therefore, the method of forming the gas barrier layer other than the reformed gas barrier layer is the same as the method of forming the inorganic compound layer (gas barrier layer) in the lower layer by the above vacuum film formation method (dry method), and the description thereof is omitted . Hereinafter, as a method of forming the inorganic compound layer (gas barrier layer) in the lower layer by the coating method, the inorganic compound is not limited to the silicon compound, but the inorganic compound layer Barrier layer) can be formed.

(Silicon compound)

The silicon compound is not particularly limited as long as it is capable of preparing a coating liquid containing a silicon compound.

Specific examples thereof include perhydropolysilazane (PHPS), organopolysilazane, silsesquioxane, tetramethylsilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, trimethylethoxy Silane, dimethyldiethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetramethoxysilane, hexamethyldisiloxane, hexamethyldisilazane, 1,1-dimethyl-1-silacyclobutane, trimethylvinylsilane, But are not limited to, methoxydimethylvinylsilane, trimethoxyvinylsilane, ethyltrimethoxysilane, dimethyldivinylsilane, dimethylethoxyethylsilane, diacetoxydimethylsilane, dimethoxymethyl-3,3,3-trifluoropropylsilane , 3,3,3-trifluoropropyltrimethoxysilane, aryltrimethoxysilane, ethoxydimethylvinylsilane, arylaminotrimethoxysilane, N-methyl-N-trimethylsilylacetamide, 3-aminopropyl Trimethoxysilane, methyltrivinylsilane, di But are not limited to, acetoxymethylvinylsilane, methyltriacetoxysilane, aryloxydimethylvinylsilane, diethylvinylsilane, butyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, tetravinylsilane, triacetoxyvinylsilane, Trimethoxy silane, trimethoxy silane, trimethoxy silane, 3-trifluoroacetoxypropyl trimethoxy silane, diaryl dimethoxy silane, butyl dimethoxy vinyl silane, trimethyl-3-vinyl thiopropyl silane, phenyl trimethyl silane, Silane, 3-acryloxypropyldimethoxymethylsilane, 3-acryloxypropyltrimethoxysilane, dimethylisopentyloxyvinylsilane, 2-aryloxyethylthiomethoxytrimethylsilane, 3-glycidoxypropyltrimethoxysilane , 3-arylaminopropyltrimethoxysilane, hexyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, dimethylethoxyphenylsilane, benzoyloxytrimethylsilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, dimethylethoxy-3-glycidoxypropylsilane, dibutoxydimethylsilane, 3-butylaminopropyltrimethylsilane , Dimethylaminopropyltriethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, diacetoxymethylphenylsilane, dimethyl-p-tolyl Vinyl silane, p-styryltrimethoxysilane, diethylmethylphenylsilane, benzyldimethylethoxysilane, diethoxymethylphenylsilane, decylmethyldimethoxysilane, diethoxy-3-glycidoxypropylmethylsilane, octyloxytrimethylsilane , Phenyltrivinylsilane, tetraaryloxysilane, dodecyltrimethylsilane, diarylmethylphenylsilane, diphenylmethylvinylsilane, diphenylethoxymethylsilane, diacetoxydiphenylsilane, dibenzyldimethylsilane, dia Lauryl phenyl silane, octadecyl trimethyl silane, methyl octadecyl dimethyl silane, docosyl methyl dimethyl silane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3- Tetramethyldisilazane, 1,3-bis (dimethylvinylsilyl) benzene, 1,3-bis (3-acetoxypropyl) , 3,5-trivinylcyclotrisiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. These silicon compounds may be used singly or in combination of two or more.

Of these, polysilazanes such as perhydro polysilazane, organopolysilazane and the like in that they have few defects such as film formability and cracks, and that they have few residual organic substances; Polysiloxane such as silsesquioxane and the like are preferred, polysilazane is more preferable, and perhydro polysilazane is particularly preferable in view of high gas barrier performance, bending property and high barrier property even when high temperature and high humidity conditions are maintained Do.

The polysilazane is a silicon-and polymers having nitrogen bond, Si-N, Si-H, SiO _2, Si ₃ N _4, and on both sides of the intermediate solid solution ceramic precursor weapons, such as SiO _x N _y has a bond, such as NH Lt; / RTI &gt;

Specifically, the polysilazane preferably has a structure represented by the following general formula (1).

[Formula 1]

In the general formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. Here, R ₁ , R ₂ and R ₃ may be the same or different from each other. Here, examples of the alkyl group include a straight chain, branched chain or cyclic alkyl group having 1 to 8 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include an aryl group having 6 to 30 carbon atoms. More specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group and terphenyl group; A phenanthrenyl group, a phenanthrenyl group, an acenaphthylenyl group, a playadenyl group, an acenaphthenyl group, a phenalenyl group, a phenanthryl group, a phenanthryl group, an acenaphthyl group, A condensed polycyclic hydrocarbon group such as a thienyl group, a thienyl group, a thienyl group, a thienyl group, a trityl group, a fluoranthenyl group, an acenetanthrylenyl group, an aceantrylenyl group, a triphenylrenyl group, a pyrenyl group, a chrysenyl group and a naphthacenyl group. (Trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms and having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. More specifically, examples include a 3- (triethoxysilyl) propyl group and a 3- (trimethoxysilyl) propyl group. Examples of the substituent present in the case of R ₁ to R ₃ include, but not limited to, an alkyl group, a halogen atom, a hydroxyl group (-OH), a mercapto group (-SH), a cyano group (-CN) Sulfo group (-SO ₃ H), carboxyl group (-COOH), nitro group (-NO ₂ ) and the like. In addition, the substituents present in some cases are not the same as the substituents R ₁ to R ₃ . For example, when R ₁ to R ₃ are alkyl groups, they are not substituted with an alkyl group. Of these groups, R ₁ , R ₂ and R _{3 preferably} represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

In the general formula (1), n is an integer, and the polysilazane having the structure represented by the general formula (1) is preferably determined to have a number average molecular weight of 150 to 150,000 g / mol.

In the compound having the structure represented by the general formula (1), one preferred form is a perhydro polysilazane (PHPS) in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

The specific compound of the polysilazane which can be used in the present invention, the content of the polysilazane in the coating film layer before the modification treatment, and the inorganic precursor compound other than the polysilazane contained in the coating liquid containing the polysilazane, For example, International Publication Numbers; (Paragraphs [0038] to [0052]) to [0172] of Japanese Patent Laid-Open Publication No. 2013-226758 described in WO 2015/053405 A1 (in Japanese Patent Laid-Open Publication No. 2015-033764) 0105 "to" 0117 "of Japanese Patent Laid-Open Publication No. 2014-218012 can be suitably employed.

In the case of using polysilazane, the content of polysilazane in the inorganic compound layer (gas barrier precursor layer) in the lower layer before the modification treatment (for example, plasma treatment or ultraviolet ray irradiation treatment) 100% by mass when the total mass of the light-emitting layer (light-emitting layer, electron-transporting layer, electron-transporting layer, and precursor layer) is 100% by mass. When the inorganic compound layer (gas barrier precursor layer) in the lower layer before the vacuum ultraviolet ray irradiation treatment (modification treatment) contains a substance other than polysilazane, the content of the polysilazane in the precursor layer is preferably not less than 10% by mass 99 mass% or less, more preferably 40 mass% or more and 95 mass% or less, and particularly preferably 70 mass% or more and 95 mass% or less.

The method of forming the inorganic compound layer (gas barrier layer) in the lower layer by the coating method is not particularly limited and a known method can be applied. However, in the organic solvent, a silicon compound and, if necessary, It is preferable to apply a coating liquid for forming an inorganic compound layer (gas barrier layer) by a known wet coating method, evaporate and remove the solvent, and then carry out the modification treatment.

(Coating liquid for forming an inorganic compound layer (gas barrier layer) in the lower layer)

The solvent for preparing the coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer is not particularly limited as long as it can dissolve the silicon compound. (Solvent) described in paragraphs &quot; 0109 &quot;, &quot; 0185 &quot;, and paragraphs &quot; 0118 &quot; to &quot; 0119 &quot; in WO 2015/053405 A1 can be suitably employed.

The concentration of the silicon compound in the coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer is not particularly limited and varies depending on the film thickness of the layer and the time for which the coating liquid is used, but is preferably from 1 to 80% , More preferably 5 to 50 mass%, and particularly preferably 10 to 40 mass%.

The coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer preferably contains a catalyst in order to promote the modification. As the catalyst applicable to the present invention, a basic catalyst is preferred, and in particular, those disclosed in International Publication Nos. Quot; 0111 &quot; of WO2015 / 053405 A1, a form (catalyst) described in paragraph &quot; 0121 &quot; of Japanese Patent Laid-Open Publication No. 2014-218012, and the like. The concentration of the catalyst to be added at this time is preferably in the range of 0.1 to 10 mass%, more preferably 0.5 to 7 mass%, based on the silicon compound. By setting the added amount of the catalyst within this range, it is possible to avoid formation of excess silanol, decrease in film density, increase in film defect, and the like due to the rapid progress of the reaction.

The coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer may contain, if necessary, 0112 "of WO 2015/053405 A1, and the additive exemplified in paragraph" 0124 "of Japanese Patent Laid-Open Publication No. 2014-218012 can be used.

Further, as described in Japanese Patent Application Laid-Open No. 2005-231039, a sol-gel method can be used for forming the inorganic compound layer (gas barrier layer) in the lower layer. The coating liquid used when forming the lower inorganic compound layer (gas barrier layer) which is a modified layer by the sol-gel method includes at least one of a silicon compound, a polyvinyl alcohol-based resin and an ethylene / vinyl alcohol copolymer desirable. Further, it is preferable that the coating liquid contains a sol-gel process catalyst, an acid, water, and an organic solvent. In the sol-gel method, an inorganic compound layer (gas barrier layer) as a lower layer which is a modified layer is obtained by polycondensation using such a coating liquid. As the silicon compound, it is preferable to use an alkoxide represented by the general formula R ^A _O Si (OR ^B ) _p . Here, R ^A and R ^B each independently represent an alkyl group having 1 to 20 carbon atoms, O represents an integer of 0 or more, and p represents an integer of 1 or more. Specific examples of the above alkoxysilane include tetramethoxysilane (Si (OCH ₃ ) ₄ ), tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), tetrapropoxysilane (Si (OC ₃ H ₇ ) ₄ ), tetrabutoxysilane (Si (OC ₄ H ₉ ) ₄ ), and the like. When the polyvinyl alcohol resin and the ethylene / vinyl alcohol copolymer are used in combination in the coating liquid, the blending ratio of the polyvinyl alcohol resin: ethylene / vinyl alcohol copolymer = 10: 0.05 to 1: 10: 6. The content of the polyvinyl alcohol resin and / or the ethylene / vinyl alcohol copolymer in the coating liquid is in the range of 5 to 500 parts by mass, preferably about 20 to 200 parts by mass based on 100 parts by mass of the total amount of the silicon compound It is preferable to prepare the mixture at the blending ratio of the parts. As the polyvinyl alcohol-based resin, those generally obtained by saponifying polyvinyl acetate can be used. Examples of the polyvinyl alcohol-based resin include a partially saponified polyvinyl alcohol-based resin in which a few hundreds of percent of the acetic acid groups remain, a fully saponified polyvinyl alcohol in which no acetic acid group remains, or a modified polyvinyl alcohol- . As specific examples of the polyvinyl alcohol-based resin, Kurarupo (registered trademark) manufactured by Kuraray Co., Ltd., Koserol (registered trademark) manufactured by Nippon Gohsei Kaikako Co., Ltd. and the like can be used. In the present invention, as the ethylene / vinyl alcohol copolymer, a saponification product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer can be used. Specifically, it is a partial saponification product in which the acetic acid group is present in an amount of several tens% by mole, and includes completely saponified products in which only a few mol% of the acetic acid groups remain or acetic acid groups do not remain. The degree of saponification is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. The content of the ethylene-derived repeating unit (hereinafter also referred to as &quot; ethylene content &quot;) in the ethylene / vinyl alcohol copolymer is usually 0 to 50 mol%, preferably 20 to 45 mol% . Specific examples of the ethylene / vinyl alcohol copolymer include Ebal (registered trademark) EP-F101 (ethylene content: 32 mol%) manufactured by Kuraray Co., Ltd., Soanol (registered trademark) D2908 manufactured by Nippon Gohsei Kaikaku Co., Content: 29 mol%) and the like can be used. As the sol-gel catalyst, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and others can be used. The acid is used as a catalyst for the hydrolysis of the above-mentioned sol-gel catalyst, mainly alkoxide or silane coupling agent. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid. The coating liquid preferably contains water at a ratio of 0.1 to 100 moles, preferably 0.8 to 2 moles, per 1 mole of the total molar amount of the alkoxide.

As the organic solvent used for the coating liquid by the sol-gel method, for example, (Solvent) described in paragraph &quot; 0114 &quot; of WO 2015/053405 A1 can be suitably employed. Further, for example, a silane coupling agent and the like may be added to the coating liquid by the sol-gel method.

(A method of applying a coating liquid for forming an inorganic compound layer (gas barrier layer) in the lower layer)

As a method of applying the coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer, a conventionally well-known wet coating method may be employed. Specific examples include International Publication Number; Quot; 0201 &quot; in WO 2015/053405 A1, the form (coating method) described in paragraph &quot; 0125 &quot; in Japanese Patent Laid-Open Publication No. 2014-218012, and the like.

The coating thickness can be appropriately set in accordance with the purpose. For example, the coating thickness per one layer of the inorganic compound layer (gas barrier layer) in the lower layer is preferably about 10 nm to 10 탆, more preferably 15 nm to 1 탆, and more preferably 20 to 500 nm Is more preferable. When the film thickness is 10 nm or more, sufficient barrier property can be obtained. When the film thickness is 10 m or less, stable coating property can be obtained at the time of layer formation, and high light ray transmittance can be realized.

It is preferable to dry the coating film after applying the coating solution. By drying the coating film, a solvent such as an organic solvent contained in the coating film can be removed. At this time, the solvent contained in the coating film may be entirely dried, but a part of the solvent may be left. Even when a part of the solvent remains, a preferable lower inorganic compound layer (gas barrier layer) can be obtained. Further, the remaining solvent can be removed later.

The drying temperature of the coating film varies depending on the substrate to which it is applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 DEG C is used as a substrate, the drying temperature may be selected from the group consisting of: 0117 "of WO2015 / 053405 A1, the form (temperature) described in paragraph" 0129 "of Japanese Patent Laid-Open Publication No. 2014-218012, and the like. It is preferable to set the drying time in a short time, for example, when the drying temperature is 150 ° C, it is preferable to set it within 30 minutes. Also, the drying atmosphere may be selected from the group consisting of: International Publication Number; 0117 "in WO 2015/053405 A1, the form (atmosphere) described in paragraph" 0129 "in Japanese Patent Laid-Open Publication No. 2014-218012, and the like can be appropriately employed.

The coating film obtained by applying the coating liquid for forming the inorganic compound layer (gas barrier layer) in the lower layer may include a step of removing water before the reforming treatment or during the reforming treatment. Methods for removing moisture include, for example, those disclosed in International Publication Number; Quot; 0118 &quot; of WO 2015/053405 A1 can be suitably employed.

&Lt; Modification Treatment of Lower Layer of Inorganic Compound Layer (Gas Barrier Layer)

The modifying treatment of the lower inorganic compound layer (gas barrier layer) formed by the coating method in the present invention refers to a reaction of the silicon compound with silicon oxide or silicon oxynitride, and specifically, a gas barrier film Means a treatment for forming an inorganic thin film having a level capable of contributing to the gas barrier property (the water vapor permeability is 1 x 10 &lt; ^-3 &gt; g / m2 day or less) as a whole. Such a modifying treatment may be applied to the inorganic compound layer (gas barrier precursor layer) in the lower layer (see Examples 1 and 2), but may be applied collectively to the upper and lower inorganic compound layers (gas barrier precursor layer) . In this case, after the inorganic compound layer (gas barrier precursor layer) as the lower layer is formed, the inorganic compound layer (gas barrier precursor layer) of the upper layer is formed by the coating method without the modification treatment, The reformed gas barrier layer having no distinction between the upper and lower layers may be formed (see Example 3).

The reaction of the silicon compound with silicon oxide or silicon oxynitride can be suitably selected by a known method. Specific examples of the reforming treatment include a plasma treatment, an ultraviolet ray irradiation treatment, and a heat treatment. However, in the case of the modification by the heat treatment, since the silicon oxide film or the silicon oxynitride layer is formed at a high temperature of 450 DEG C or more by the substitution reaction of the silicon compound, adaptation to a flexible substrate such as a plastic is difficult. Therefore, it is preferable that the heat treatment is performed in combination with other reforming treatment.

Therefore, from the viewpoint of adaptation to a plastic substrate, a telephone reaction by a plasma treatment or an ultraviolet ray irradiation treatment capable of a telephone reaction at a lower temperature is preferable as the reforming treatment.

(Plasma treatment)

In the present invention, the plasma treatment which can be used as the reforming treatment means a treatment of irradiating the coating film with a plasma to modify (a telephone reaction), and a known method can be used. Preferably, have. The atmospheric pressure plasma CVD method for performing the plasma CVD process in the vicinity of the atmospheric pressure is not required to be reduced in pressure as compared with the plasma CVD process under vacuum and has high productivity because the plasma density is high and the deposition rate is fast, Compared to the process conditions, under a high pressure condition to be atmospheric pressure, the average free process of the gas is very short, and a very homogeneous film is obtained.

In the case of the atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing a Group 18 atom of the long-form periodic table, more specifically, Quot; 0123 &quot; of WO 2015/053405 A1 can be suitably employed.

(Heat treatment)

The coating film containing the silicon compound is combined with another modifying treatment, preferably an excimer irradiation treatment to be described later, and subjected to heat treatment, whereby the modifying treatment can be performed efficiently.

In the case of forming a layer by the sol-gel method, it is preferable to use a heat treatment. As the heating conditions, the condensation is carried out by heating and drying at a temperature of preferably 50 to 300 ° C, more preferably 70 to 200 ° C, preferably 0.005 to 60 minutes, more preferably 0.01 to 10 minutes, An inorganic compound layer (gas barrier layer) as a lower layer can be formed.

As the heat treatment, for example, an International Publication Number; Quot; 0116 &quot; of WO 2015/053405 A1 can be suitably employed.

The temperature of the coating film at the time of the heat treatment is preferably adjusted suitably in the range of 50 to 250 캜, and more preferably in the range of 50 to 120 캜.

The heating time is preferably in the range of 1 second to 10 hours, more preferably in the range of 10 seconds to 1 hour.

(Ultraviolet ray irradiation treatment)

As a method of the reforming treatment, treatment by ultraviolet irradiation is preferred. It is possible to form a silicon oxide film or a silicon oxynitride film having high denseness and insulation at a low temperature, ozone or active oxygen atoms generated by ultraviolet rays (which cooperate with ultraviolet light) and have high oxidation ability.

This ultraviolet ray irradiation causes the substrate to be heated and the O ₂ and H ₂ O contributing to the ceramics (silica telephone), the ultraviolet absorber and the polysilazane are excited and excited themselves, so that the polysilazane is excited, The ceramics of the silazane is promoted, and the obtained inorganic compound layer (gas barrier layer) in the lower layer is further densified.

The ultraviolet ray irradiation may be carried out at any time point after the coating film is formed.

In the ultraviolet ray irradiation treatment, any one of commercially available ultraviolet ray generating devices can be used.

In the present invention, the term "ultraviolet ray" generally means an electromagnetic wave having a wavelength of 10 to 400 nm, but in the case of ultraviolet irradiation processing other than the vacuum ultraviolet ray (10 to 200 nm) Ultraviolet rays of 375 nm are used.

It is preferable to set the irradiation intensity and the irradiation time within the range in which the base material carrying the inorganic compound layer (gas barrier layer) as the lower layer to be irradiated is not damaged by ultraviolet irradiation.

For example, a 2 kW (80 W / cm x 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm 2, preferably 50 to 200 mW / Cm &lt; 2 &gt; so that irradiation can be performed for 0.1 second to 10 minutes.

Examples of such means for generating ultraviolet rays include a metal halide lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp (having a single wavelength of 172 nm, 222 nm, Manufactured by DENKISA CORPORATION, manufactured by MDCOM, etc.), UV light laser, and the like, but there is no particular limitation. When the generated ultraviolet rays are irradiated to the inorganic compound layer (gas barrier layer) in the lower layer, ultraviolet rays from the source are reflected by the reflection plate and then the inorganic compound layer (gas barrier layer ). The time required for ultraviolet irradiation is generally from 0.1 second to 10 minutes, preferably from 0.5 second to 3 minutes, although it depends on the composition and concentration of the substrate used and the inorganic compound layer (gas barrier layer) as the lower layer.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)

In the present invention, the most preferable modification treatment method is a treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet ray irradiation uses light energy of 100 to 200 nm, which is larger than the interatomic bonding force in the polysilazane compound, preferably light energy of 100 to 180 nm, (About 200 占 폚 or less) by advancing the oxidation reaction by active oxygen or ozone while directly cutting the silicon oxide film by the action of only the photon which is called a photocatalyst. When the excimer irradiation process is performed, it is preferable to use heat treatment in combination as described above, and the details of the heat treatment conditions at that time are as described above.

The radiation source in the present invention may be one which generates light having a wavelength of 100 to 230 nm, preferably 100 to 180 nm, but preferably an excimer radiator having a maximum emission at about 172 nm (for example, Xe excimer Lamp), a low pressure mercury vapor lamp having a bright line at about 185 nm, an intermediate pressure and high pressure mercury vapor lamp having a wavelength component of 230 nm or less, and an excimer lamp having a maximum emission at about 222 nm.

Oxygen is required for the reaction at the time of ultraviolet irradiation, but since the vacuum ultraviolet ray absorbs by oxygen, the efficiency in the ultraviolet ray irradiation step tends to be lowered. It is preferable to perform it in a low state. That is, the oxygen concentration at the time of irradiation with the vacuum ultraviolet ray is preferably 10 to 20,000 volume ppm, and more preferably 50 to 10,000 volume ppm. In addition, the water vapor concentration between the telephone processes is preferably in the range of 1000 to 4000 ppm by volume.

In the vacuum ultraviolet irradiation step, the roughness of the vacuum ultraviolet rays on the coating film surface received by the polysilazane coating film (lower layer gas barrier precursor layer) is preferably 1 mW / cm 2 to 10 W / cm 2, more preferably 30 mW / Cm 2, more preferably from 50 mW / cm 2 to 160 mW / cm 2. If it is 1 mW / cm &lt; 2 &gt; or more, a sufficient modifying efficiency is obtained, and if it is 10 W / cm &lt; 2 &gt; or less, abrasion is hardly caused in the coating film,

The irradiation energy amount (accumulated light amount) of the vacuum ultraviolet ray on the coating film surface is preferably 10 to 10000 mJ / cm 2, more preferably 100 to 8000 mJ / cm 2, and still more preferably 200 to 6000 mJ / cm 2. If it is 10 mJ / cm 2 or more, the modification can sufficiently proceed. If it is 10000 mJ / cm 2 or less, cracks due to over-reforming and thermal deformation of the substrate are hard to occur.

The vacuum ultraviolet light used for the modification may be generated by a plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . The gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as a carbon-containing gas) may be used alone or in combination with a rare gas or H ₂ as the main gas, Is preferably added in a small amount. Plasma generation methods include capacitively coupled plasma and the like.

As a reaction mechanism in which silicon nitride and further silicon oxide are presumed to be generated from perhydro polysilazane in the vacuum ultraviolet ray irradiation process when the silicon compound as the preferred form is perhydro polysilazane (PHPS), for example, number; Quot; 0220 &quot; to &quot; 0228 &quot; in WO 2015/053405 A1, and paragraphs 0125 to 0133 in Japanese Patent Laid-Open Publication No. 2015-033764.

The method of measuring the silica conversion rate ( _x in SiO _x ) can be measured by, for example, the XPS method.

The film composition of the inorganic compound layer (gas barrier layer) in the lower layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. Further, the inorganic compound layer (gas barrier layer) in the lower layer can be cut and the cut surface can be measured by measuring the atomic composition ratio by an XPS surface analyzer. In this case, it is preferable to form a lower inorganic compound layer (gas barrier layer) on the substrate and to measure the film composition (atomic composition ratio) of the lower inorganic compound layer (gas barrier layer) as the sample for analysis.

The film density of the inorganic compound layer (gas barrier layer) in the lower layer can be appropriately set in accordance with the purpose. For example, the film density of the inorganic compound layer (gas barrier layer) in the lower layer is preferably in the range of 1.5 to 2.6 g / cm 3. In this range, the denseness of the film becomes higher, and deterioration of the barrier property and deterioration of the oxidation of the film due to humidity are difficult to occur.

The inorganic compound layer (gas barrier layer) in the lower layer may be a single layer or a laminated structure of two or more layers.

When the inorganic compound layer (gas barrier layer) in the lower layer is a laminated structure of two or more layers, the inorganic compound layer (gas barrier layer) in each lower layer may have the same composition or different compositions. When the inorganic compound layer (gas barrier layer) in the lower layer has a laminated structure of two or more layers, the inorganic compound layer (gas barrier layer) in the lower layer may be composed of only the layer formed by the vacuum film forming method, Or may be a combination of a layer formed by a vacuum deposition method and a layer formed by a coating method.

The inorganic compound layer (gas barrier layer) in the lower layer is preferably a layer containing a nitrogen element or a carbon element in view of stress relaxation property and absorption of ultraviolet rays used in formation of an inorganic compound layer (gas barrier layer) . By including these elements, it is possible to obtain a gas barrier layer that has properties such as stress relaxation and ultraviolet ray absorption, and is excellent in the storage stability of the modified region of the reformed gas barrier layer without distinction between the upper and lower layers, particularly under severe conditions (high temperature and high humidity conditions = Is not deteriorated and storage stability is excellent, and high gas barrier property can be maintained.

The chemical composition in the inorganic compound layer (gas barrier layer) in the lower layer is determined depending on the kind and amount of the silicon compound and the like when forming the inorganic compound layer (gas barrier layer) in the lower layer and the conditions for modifying the layer containing the silicon compound And the like.

(Inorganic compound layer (gas barrier layer) in the lower layer or its precursor layer)

The lower inorganic compound layer (gas barrier layer) or its precursor layer obtained by the above-mentioned forming method preferably contains an inorganic compound containing no Si atom and not containing Al atoms, and contains 20 to 50 at% of Si atoms . The inorganic compound contained in the lower inorganic compound layer (gas barrier layer) or the precursor layer is not particularly limited, and examples thereof include metal oxides, metal nitrides, metal carbides, metal oxynitrides and metal oxycarbonates. Among them, oxides, nitrides, carbides, oxynitrides or oxycarbides containing at least one metal selected from Si, Al, In, Sn, Zn, Ti, Cu, And is preferably an oxide, a nitride or an oxynitride of a metal selected from Si, Al, In, Sn, Zn and Ti, more preferably an oxide, a nitride or an oxynitride of at least one of Si and Al Do. The reason for this is that Al may be contained in the range of the lower layer of the reformed gas barrier layer. That is, in the present invention, since the gradient of the Al atoms is required to be between the upper layer and the lower layer, a structure having a concentration gradient of Al atoms can be formed even if the lower layer contains a small amount of Al. Specific examples of the preferable inorganic compound include complexes such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, titanium oxide or aluminum silicate. Other elements may be contained as a secondary component. Here, the precursor layer (gas barrier precursor layer) of the inorganic compound layer (gas barrier layer) in the lower layer refers to a state before modification by a coating method. That is, in the step of forming the inorganic compound layer (gas barrier layer) in the lower layer, the inorganic compound layer (gas barrier layer) is stopped in the state of the precursor layer and then the precursor layer of the inorganic compound layer It is possible to form the reformed gas barrier layer having no distinction between the upper and lower layers by collectively modifying the upper and lower layers by a means (for example, a vacuum ultraviolet ray irradiation treatment or the like) (Example 3, B).

The content of the inorganic compound contained in the inorganic compound layer (gas barrier layer) in the lower layer or the precursor layer thereof is not particularly limited, but is preferably 50 mass% or more in the inorganic compound layer (gas barrier layer) More preferably 95% by mass or more, particularly preferably 98% by mass or more, and particularly preferably 100% by mass or more (that is, the inorganic compound layer (gas barrier layer) ) Is most preferable.

The inorganic compound layer (gas barrier layer) in the lower layer contains an inorganic compound to have gas barrier properties. The gas barrier property of the inorganic compound layer (gas barrier layer) in the lower layer is such that the vapor permeability (WVTR) of the lower inorganic compound layer (gas barrier layer) is 0.1 g / ( M 2 · day), and more preferably 0.01 g / (m 2 · day) or less.

(Gas barrier layer other than the modified gas barrier layer and method of forming the same)

In the present invention, as shown in Figs. 11 (B) and 12 (B) of Examples 1 to 3, a gas barrier layer other than the reformed gas barrier layer may be included. The gas barrier layer other than the reformed gas barrier layer is preferably formed between the substrate and the reformed gas barrier layer, from the viewpoint of enhancing the adhesion between the substrate and the reformed gas barrier layer, gas barrier property, . This gas barrier layer preferably contains the same inorganic compound as the inorganic compound layer (gas barrier layer) in the lower layer. The gas barrier layer is preferably formed by the vacuum film forming method (dry method), particularly the plasma CVD method, among the above-mentioned method of forming the inorganic compound layer (gas barrier layer) in the lower layer. The lower inorganic compound layer (gas barrier layer) formed on the gas barrier layer formed by the vacuum film formation method (dry method) is preferably formed by a coating method (wet method) (see Examples 1 to 3). That is, the structure, characteristics, and detailed formation method of the gas barrier layer other than the reformed gas barrier layer are the same as those described in the above-described lower inorganic compound layer (gas barrier layer) and formation method thereof, .

(A method of forming the upper inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer)

According to the method of the present invention, the step of forming the inorganic compound layer (gas barrier precursor layer) in the upper layer and the step of forming the modified gas barrier layer are the steps of preparing a coating liquid containing Al by a coating method, (A gas barrier precursor layer as an upper layer) by applying the coating liquid onto a barrier layer or a precursor layer thereof; and irradiating the coating film with vacuum ultraviolet rays to form a gas barrier precursor layer as an upper layer (in the case of a precursor layer, (Including a reforming gas barrier layer forming step). Hereinafter, such a method of forming the inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer in the upper layer will be described.

&Lt; Preparation of Coating Solution >

To the coating liquid, a solution containing an inorganic compound, preferably a silicon compound, used in the coating method of the inorganic compound layer (gas barrier layer) of the lower layer or the precursor layer of the above- May be used as the coating liquid A. Or (ii) a coating liquid B using a metal compound containing Al, without using a liquid containing an inorganic compound (see Examples 1 to 3).

(I) Method of preparing coating liquid A

The coating liquid A is prepared by first reacting a liquid containing an inorganic compound, preferably a silicon compound, a metal compound containing Al, and a catalyst, if necessary, in a solvent, and applying the coating liquid A To prepare a coating liquid A for forming a compound layer (gas barrier precursor layer). The inorganic compound is not limited to a silicon compound but may be any inorganic compound layer (gas barrier precursor layer) as an upper layer.

Specific examples of the silicon compound are the same as those described in the section "formation of the inorganic compound layer (gas barrier layer) of the lower layer or the precursor layer thereof", and a description thereof will be omitted here. Of these, polysilazanes such as perhydro polysilazane, organopolysilazane and the like in view of few defects such as film formability and cracks and few residual organic substances; Polysiloxane such as silsesquioxane and the like are preferable, polysilazane is more preferable, perhydropolysilazane is particularly preferable because barrier properties are maintained even at bending and at high temperature and high humidity, Do.

Examples of the metal compound containing Al include aluminum (Al), and if necessary, beryllium (Be), boron (B), magnesium (Mg), silicon (Si), calcium (Ca) (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Pd) (Ga), Ge, Ge, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, (Pd), Ag, Cd, In, Sn, Ba, La, Ce, Pr, Ne, (Pd), Sm, Eu, Gd, Terbium, Dy, Ho, Er, Thium, Yb, Lutetium (Hg), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum The second to the fourteenth group of the long period type periodic table such as lead (Tl), lead (Pb), and radium (Ra) There may be mentioned a compound comprising a.

Among them, a compound containing titanium (Ti), iron (Fe), or copper (Cu) together with an aluminum (Al) compound or Al can be preferably used. These metals are preferably elements that are likely to form a coordination bond with the nitrogen atom in the polysilazane, and it is more preferable to use Al with a high Lewis acidity, or Ti, Fe or Cu together with Al.

Examples of the metal compound (aluminum compound) containing Al include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum s-butoxide, aluminum t- Aluminum acetyl acetonate, and triethyl di aluminum tri-s-butoxide. However, from the viewpoint of more efficiently forming a high-performance upper-layer gas barrier precursor layer and furthermore a reformed gas barrier layer, it is preferable to use a metal alkoxide compound containing at least an Al element or a metal alkoxide compound containing at least Al And a chelate compound having a? -Diketone as a ligand can be preferably used.

Examples of? -diketones include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4- Dimethyl-2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3- 1,3-cyclohexanedione, 1-cyclohexyl-1,3-butanedione, and the like.

More specific examples of the metal alkoxide compound containing an Al element include, for example, aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri n- Aluminum tri-tert-butoxide, acetalkoxy aluminum diisopropylate, aluminum diisopropylate mono sec-butylate, aluminum oxide isopropoxide trimer, aluminum oxide octylate trimer, .

More specific examples of other metal alkoxide compounds that can be used in combination with the metal alkoxide compound containing Al element include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, , Tri-tert-butyl borate, magnesium ethoxide, magnesium ethoxyethoxide, magnesium methoxyethoxide, calcium methoxide, calcium ethoxide, calcium isopropoxide, titanium tetramethoxide, titanium tetraethoxide, Titanium tetraisopropoxide, titanium tetraisopropoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium diisopropoxide isobutoxide, titanium di- tertiarybutoxy diisopropoxide, Butoxide, titanium tetraisooctyloxide, titanium tetrastearyl alkoxide, vanadium triisobutoxide oxide, Such as iron n-propoxide, chromium isopropoxide, manganese methoxide, iron methoxide, iron ethoxide, iron n-propoxide, iron isopropoxide, cobalt isopropoxide, A metal alkoxide, a metal alkoxide, a metal alkoxide, a metal alkoxide, a metal alkoxide, a titanium alkoxide, a titanium alkoxide, a titanium alkoxide, a titanium alkoxide, Propoxide, yttrium isopropoxide, zirconium ethoxide, zirconium n-propoxide, zirconium n-propoxide, germanium n-butoxide, germanium tert-butoxide, ethyltriethoxy germanium, strontium isopropoxide, Zirconium butoxide, niobium n-butoxide, niobium tert-butoxide, molybdenum ethoxide, indium isopropoxide, indium Tin butoxide, barium diisopropoxide, barium tert-butoxide, lanthanum isopropoxide, lanthanum isopropoxide, lanthanum isopropoxide, lanthanum isopropoxide, But are not limited to, methoxyethoxide, cerium n-butoxide, cerium tert-butoxide, praseodymium methoxyethoxide, neodymium methoxyethoxide, samarium isopropoxide, hafnium ethoxide, hafnium n-butoxide, hafnium tert -Butoxide, tantalum methoxide, tantalum ethoxide, tantalum n-butoxide, tantalum butoxide, tungsten ethoxide, thallium ethoxide, and compounds having the following structures.

[Formula 2]

As the metal alkoxide compound, silsesquioxane may also be used.

Silsesquioxane is a siloxane-based compound having a main chain skeleton composed of Si-O bonds and is also referred to as T resin. Compared to a general silica represented by the general formula [SiO ₂ ], silsesquioxane (Also referred to as polysilsesquioxane) is represented by the general formula [RSiO _{1 . 5} ]. A polysiloxane synthesized by hydrolysis-polycondensation of one alkoxy group of a tetraalkoxysilane (Si (OR ') ₄ ) represented by tetraethoxysilane with an alkyl group or an aryl group as a substituent (RSi (OR') ₃ ) , And the shape of the molecular arrangement is typically amorphous, ladder-like, or basket-shaped (complete condensation cage shape).

Silsesquioxane may be synthesized or commercially available. Specific examples of the latter are X-40-2308, X-40-9238, X-40-9225, X-40-9227, x-40-9246, KR-500 and KR-510 (all manufactured by Shin- ), SR2400, SR2402, SR2405, FOX14 (perhydrosilsesquioxane) (all manufactured by Dow Corning Toray Co., Ltd.) and SST-H8H01 (perhydrosilsesquioxane) (manufactured by Gelest).

Among these metal alkoxide compounds, a compound having a branched alkoxy group is preferable from the viewpoints of reactivity and solubility, and a compound having a 2-propoxy group or a sec-butoxy group is more preferable.

Among the chelate compounds having? -diketone as a ligand, more specific examples of the chelate compound containing an Al element include aluminum acetylacetonate, aluminum ethyl acetoacetate diisopropylate (ALCH), aluminum ethylacetoacetate di (ethyl acetoacetate) (2,4-pentanedionato) aluminum, aluminum alkyl acetoacetate di (meth) acrylate di (meth) acrylate monohydrate, Isopropylate and the like.

More specific examples of the chelate compound having β-diketone as a ligand, which can be used in combination with the chelate compound containing the Al element, include beryllium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate , Tris (2,4-pentanedionato) chromium, tris (2,4-pentanedionato) manganese, tris (2,4-pentanedionato) Tris (2,4-pentanedionato) cobalt, nickel acetylacetonate, bis (2,4-pentanedionato) copper, gallium acetylacetonate, yttrium acetylacetonate, tetra (2,4-pentanedionato) zirconium, molybdenum acetylacetonate, palladium acetylacetonate, silver acetylacetonate, cadmium acetylacetonate (2,4-pentanedionato) indium, tin acetylacetonate, barium acetylacetonate, lanthanacetylacetonate, cerium acetylacetonate, praseodymium acetylacetonate, neodymium acetylacetonate, samarium acetylacetonate, Europium acetylacetonate, gadolinium acetylacetonate, gadolinium acetylacetonate, terbium acetylacetonate, holmium acetylacetonate, ytterbium acetylacetonate, lutetium acetylacetonate, hafnium acetylacetonate, tantalum tetramethoxide acetylacetonate, iridium acetylacetonate, Lebanyl acetylacetonate, thallium acetylacetonate, lead acetylacetonate, and the like.

Among the chelate compounds having a? -diketone as a ligand, a metal compound having an acetylacetonate group is preferable. Since the acetylacetonate group has an interaction with the central element of the alkoxide compound by the carbonyl structure, the acetyl acetonate group is preferable because handling becomes easy. More preferably, the alkoxide group or the compound having a plurality of acetylacetonate groups is more preferable in view of reactivity and film composition.

In particular, when the metal compound containing Al is an alkoxide compound of aluminum or a chelate compound having a? -Diketone as a ligand, or an alkoxide compound in which titanium, iron or copper is used in combination with aluminum or? As a ligand. As a central element of these metal alkoxide compounds or chelate compounds having a? -Diketone as a ligand, an element which is likely to form a coordination bond with a nitrogen atom in the polysilazane is preferable, and Al having high Lewis acidity alone or Al It is more preferable to use Ti, Fe, or Cu in combination.

More preferably, the alkoxide compound of aluminum is aluminum tri-sec-butoxide or aluminum diisopropylate mono sec-butylate. As the other alkoxide compound, titanium tetraisopropoxide may be used in combination with the aluminum alkoxide compound.

The chelate compound containing an Al element having a more preferable? -Diketone as a ligand is specifically exemplified by aluminum ethyl acetoacetate diisopropylate (ALCH), aluminum ethyl acetoacetate di-n-butylate, or aluminum diethyl Acetacetate mono-n-butylate. As other chelating compounds, titanium diisopropoxy bis (acetylacetonate), bis (2,4-pentanedionato) copper (II) (copper acetylacetonate), tris (2,4-pentanedionato) iron (III) (iron acetylacetonate) may be used in combination.

As the chelate compound having the above-described metal alkoxide compound or? -Diketone as a ligand, a commercially available product or a synthetic product may be used. Specific examples of commercially available products include, for example, metal alkoxide compounds such as AMD (aluminum diisopropylate mono sec-butylate), ASBD (aluminum secondary butylate), Flanact (registered trademark) AL-M (acetal- Isopropylate, manufactured by Ajinomoto Fine Chemical Co., Ltd.), and Orgatics series (manufactured by Matsumoto Fine Chemicals Co., Ltd.). Examples of chelate compounds having a commercially available? -Diketone as a ligand include ALCH (aluminum ethyl acetoacetate diisopropylate), ALCH-TR (aluminum tris ethyl acetoacetate), aluminum chelate M (aluminum alkyl acetoacetate diisopropyl Aluminum chelate D (aluminum bisethylacetoacetate monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) (manufactured by Kawaken Fine Chemicals Co., Ltd.), orgatix series (manufactured by Matsumoto Fine Chemical Co., Ltd.) and the like.

The solvent for preparing the coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer is not particularly limited as long as it can dissolve the silicon compound (polysilazane) and the metal compound containing Al, (In particular polysilazane), which does not contain water and a reactive group (for example, a hydroxyl group or an amine group) that easily reacts with a silicon compound (particularly polysilazane) A solvent is preferable, and an aprotic organic solvent is more preferable. Specifically, examples of the solvent include aprotic solvents; Examples of the solvent include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, such as pentane, 2,2,4-trimethylpentane, hexane, cyclohexane, toluene, xylene, salvesso and terpene; Halogenated hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ether such as dibutyl ether, dioxane, tetrahydrofuran, mono- and polyalkylene glycol dialkyl ether (diglyme), and ether such as alicyclic ether. The solvent may be used alone or in the form of a mixture of two or more. In addition, it is preferable to reduce the oxygen concentration and the water content in advance before using the above-mentioned solvent. Means for reducing the oxygen concentration and moisture content in the solvent are not particularly limited, and conventionally known methods can be applied.

The concentration of the silicon compound (particularly, polysilazane) in the coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer is not particularly limited and may vary depending on the film thickness of the layer or the time for which the coating liquid is used However, it is preferably 1 to 80 mass%, more preferably 5 to 50 mass%, and particularly preferably 10 to 40 mass%.

The addition amount of the Al-containing metal compound is preferably 5 to 20 mol% of the Al element based on the silicon (Si) element in the silicon compound (particularly polysilazane). The amount of the Al-containing metal compound added is more preferably 5 to 15 mol%, and more preferably 7 to 15 mol%, based on the silicon atom (Si) in the silicon compound (particularly polysilazane). If it is 5 mol% or more, a gas barrier film having better storage stability under high temperature and high humidity can be obtained. If it is 20 mol% or less, the gas barrier properties of the upper inorganic compound layer (gas barrier precursor layer) and further the reformed gas barrier layer can be improved. When two or more kinds of aluminum metal compounds are used, it is preferable that the total amount of the Al elements contained in these is in the above range.

The addition amount of the Al-containing metal compound is preferably 10 mol% or less in the amount of the metal other than Al relative to the silicon (Si) element in the silicon compound (particularly polysilazane). The addition amount of the Al-containing metal compound is more preferably 5 mol% or less, and more preferably 1 mol% or less, with respect to the silicon atom (Si) in the silicon compound (particularly polysilazane). That is, the lower limit is 0 mol% (a form containing no metal other than Al). If it is 10 mol% or less, the gas barrier properties of the upper inorganic compound layer (gas barrier precursor layer) and further the modified gas barrier layer are improved, and a gas barrier film having better storage stability under high temperature and high humidity can be obtained. When a metal compound containing two or more kinds of Al is used, it is preferable that the total amount of the metal elements other than Al contained in the metal compound is in the above range.

The coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer preferably contains a catalyst in order to promote the modification. As the catalyst applicable to the coating liquid A, a basic catalyst is preferred and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, Amine catalysts such as N, N ', N'-tetramethyl-1,3-diaminopropane and N, N, N', N'- Metal compounds such as Pt compounds such as Natta, Pd compounds such as propionic acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst to be added at this time is preferably in the range of 0.1 to 10 mass%, more preferably 0.5 to 7 mass%, based on the silicon compound (particularly polysilazane). By setting the added amount of the catalyst within this range, it is possible to avoid formation of excess silanol, a decrease in film density, and an increase in film defect due to the rapid progress of the reaction. Among these catalysts, the amine catalyst may also serve as the above-described additive compound.

To the coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, additives such as the following can be used if necessary. For example, cellulose ethers, cellulose esters; Natural resins such as ethyl cellulose, nitrocellulose, cellulose acetate, and cellulose acetobutyrate; For example, synthetic resin such as rubber, rosin resin and the like; For example, a condensation resin such as a polymerization resin; For example, aminoplasts, in particular urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates, polysiloxanes and the like.

In the method of forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, a silicon compound (particularly polysilazane) is added under an environment of a water concentration (water vapor concentration) of not more than 100 ppm by volume, preferably an oxygen concentration of not more than 200 vol ppm, And a metal compound containing Al are reacted to prepare a coating liquid A for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer. However, even if the moisture concentration (water vapor concentration) or the oxygen concentration is out of the above range, it is sufficient to be used as the coating liquid A for forming the desired inorganic compound layer (gas barrier precursor layer) It is possible.

The reaction of the silicon compound (particularly polysilazane) proceeds by the absorption of vacuum ultraviolet light (~180 nm), and a dense gas barrier layer is formed. However, in the step of preparing the coating liquid A, when the silicon compound (particularly polysilazane) reacts with water or oxygen in the environment, since the oxidation reaction has already proceeded in the step of irradiating the vacuum ultraviolet light, Ultraviolet light is not sufficiently absorbed. This is because the Si-N of the silicon compound (especially polysilazane) absorbs the ultraviolet ray of the vacuum, but when the Si-N of the silicon compound (particularly polysilazane) reacts to become Si-O, And it is considered that vacuum ultraviolet light is not absorbed.

In the method described in the above-mentioned Patent Document 2, in the step of preparing the coating liquid, the oxidation reaction of the polysilazane can proceed by the action of water in the alcohol or the atmosphere. In this case, before the vacuum ultraviolet light is irradiated, since the oxidation reaction is already proceeding, the vacuum ultraviolet light can not be sufficiently absorbed, and Si-N remains in the reformed gas barrier layer. If Si-N remains in the reformed gas barrier layer, it reacts under high temperature and high humidity, and gas barrier property may be lowered.

According to the method of forming the inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer in the upper layer of the present invention, it is possible to form the reformed gas barrier layer in an environment where the water concentration (water vapor concentration) is 100 ppm by volume or less, preferably 200 ppm by volume or less By preparing a coating liquid A for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer by reacting a silicon compound (particularly polysilazane) with a metal compound containing Al, a silicon compound (particularly polysilazane ) And moisture or oxygen can be suppressed. As a result, since the vacuum ultraviolet light can be effectively absorbed, Si-N remaining in the reformed gas barrier layer formed after the irradiation with the ultraviolet ultraviolet light can be reduced. Therefore, it is excellent in that a gas barrier film excellent in storage stability under high temperature and high humidity can be obtained.

According to the method of forming the inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer in the upper layer, the silicon compound (silicon compound) can be formed under an environment where the water concentration (water vapor concentration) is 100 ppm by volume or less, and preferably the oxygen concentration is 200 ppm by volume or less Particularly a polysilazane) and a metal compound containing Al are preferably reacted to prepare a coating liquid A for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer. If the water concentration (water vapor concentration) exceeds 100 vol ppm, the oxidation reaction of the silicon compound (particularly polysilazane) in the coating liquid A may be accelerated by the action of water. If the oxygen concentration exceeds 200 vol. Ppm, the oxidation reaction of the silicon compound (particularly polysilazane) in the coating liquid A may proceed due to oxygen in the environment during the liquid bath. However, even if the moisture concentration (water vapor concentration) or the oxygen concentration is out of the above range, as long as the effect of the present invention is not impaired, the coating liquid A (gas barrier precursor layer) for forming the inorganic compound layer .

The reaction of a silicon compound (particularly polysilazane) with a metal compound containing Al is carried out under an environment of a moisture concentration (water vapor concentration) of preferably 0 to 50 volume ppm, more preferably 0 to 30 volume ppm It is good. The reaction of the silicon compound (particularly polysilazane) with the metal compound containing Al is preferably carried out in an environment of an oxygen concentration of preferably 0 to 100 ppm by volume, more preferably 0 to 30 ppm by volume .

Such an environment can be realized by preparing a liquid tank facility such as a glove box in which water concentration (water vapor concentration) and oxygen concentration are controlled. As the gas that satisfies the atmosphere, which is used at the time of preparing the coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, it is preferable to use dry inert gas. As the inert gas, nitrogen, argon, helium and the like are exemplified. However, from the viewpoint of cost, it is preferable to use dry nitrogen gas. The adjustment of the oxygen concentration can be adjusted by measuring the flow rate of the oxygen gas and the inert gas introduced into the liquid tank facility such as a glove box and changing the flow rate ratio. The water concentration (water vapor concentration) in the atmosphere can be lowered by drying using a drying agent such as molecular sieves. Further, the oxygen concentration in the atmosphere can be lowered by, for example, a method of reacting with a catalyst such as a metal copper or the like and adsorbing it on an oxygen scavenger.

In preparing the coating liquid A for forming the upper inorganic compound layer (gas barrier precursor layer), a silicon compound (particularly polysilazane), a metal compound containing Al and, if necessary, a catalyst are mixed in an organic solvent , And the mixture is heated and stirred to react.

The liquid bath temperature depends on the solvent to be used, but is preferably 30 to 100 ° C, more preferably 40 to 90 ° C, and even more preferably 50 to 80 ° C. When the liquid bath temperature is 30 占 폚 or higher, the reaction between the silicon compound (particularly polysilazane) and the metal compound containing Al proceeds efficiently, so that a gas barrier film excellent in storage stability under high temperature and high humidity can be obtained. On the other hand, if the liquid bath temperature is 100 DEG C or lower, the crosslinking reaction of the silicon compound (particularly polysilazane) is suppressed, which is preferable.

The reaction time is not particularly limited, but is preferably 10 minutes to 10 hours, more preferably 30 minutes to 4 hours, and further preferably 1 to 2 hours. When the reaction time is 10 minutes or more, the reaction between the silicon compound (particularly polysilazane) and the metal compound containing Al proceeds sufficiently, so that a gas barrier film excellent in storage stability can be obtained. On the other hand, if the reaction time is 10 hours or less, the crosslinking reaction of the polysilazanes is suppressed, which is preferable.

(Ii) Method of preparing coating liquid B

The coating liquid B is prepared by mixing a metal compound containing Al and a catalyst as necessary in a solvent without using a liquid containing an inorganic compound to form a coating liquid B (forming an inorganic compound layer (gas barrier precursor layer) (See Examples 1 to 3).

The coating liquid B is prepared in the same manner as the coating liquid A except that the liquid containing the inorganic compound (preferably silicon compound) is not used in the coating liquid A, The description will be omitted or simplified here.

First, also in the coating liquid B, the metal compound containing Al is the same as that described in the &quot; Preparation method of coating liquid A &quot;, and thus a detailed description thereof will be omitted here. That is, also in the coating liquid B, from the viewpoint of forming a high-performance upper-layer gas barrier precursor layer and furthermore a reformed gas barrier layer, the metal compound containing Al is preferably a metal alkoxide compound containing at least an Al element Alternatively, a chelate compound containing at least an element of Al and having? -Diketone as a ligand can be preferably used.

The solvent used in the coating liquid B is not particularly limited as long as it can dissolve a metal compound containing Al because the silicon compound (polysilazane) is not used, and the method of preparing the coating liquid A The same solvent as that used for the coating liquid A described in the section &quot; A detailed description of these solvents will be omitted.

The solvent used in the coating liquid B does not contain an inorganic compound (particularly, a silicon compound) in addition to the solvent that can be used for the coating liquid A, and therefore, for example, an alcohol solvent, a ketone solvent, , Ester solvents, aprotic solvents, and the like.

Examples of the alcohol solvent include alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert- sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, Glycol monopropyl ether, propylene glycol monobutyl ether and the like are preferable.

Examples of the ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso butyl ketone, methyl n-pentyl ketone, Methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, acetophenone, Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, Dione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4 And? -Diketones such as heptanedione. These ketone-based solvents may be used singly or in combination of two or more kinds.

Examples of the amide-based solvent include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N-dimethylformamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpiperidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine and the like. These amide solvents may be used alone or in combination of two or more.

Examples of the ester solvent include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, iso- sec-butyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, Acetic acid ethyl ester, acetic acid ethylene glycol monomethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl acetate, acetic acid ethyleneglycol monomethyl ether, Ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene acetic acid Recurring monoethyl ether, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, propionic acid n Butyl, propyl isoamyl, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate and diethyl phthalate . These ester solvents may be used singly or in combination of two or more.

Examples of the aprotic solvent include acetonitrile, dimethylsulfoxide, N, N, N ', N'-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N- Piperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl- 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidone, and the like. These aprotic solvents may be used alone or in combination of two or more.

As the organic solvent used in the coating liquid B, an alcohol solvent is preferable in the organic solvent. In addition, it is preferable to reduce the oxygen concentration and the water content in advance before using the above-mentioned solvent. The means for reducing the oxygen concentration and the water content in the solvent is not particularly limited and conventionally known methods can be applied.

The concentration of the Al-containing metal compound in the coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer is not particularly limited as long as it can effectively exhibit the action and effect of the present invention, It is possible to improve the defect repair effect of the lower layer and the storage stability due to the effect of improving the gas barrier property accompanied with the formation of the concentration gradient of Al atoms in the film thickness direction due to the modification of the intermediate region (interface region), especially the harsh conditions (high temperature and high humidity conditions = It is possible to provide a gas barrier film which is excellent in storage stability and can maintain a high barrier property. From this point of view, the concentration of the Al-containing metal compound in the coating liquid B varies depending on the layer thickness and the coating time of the coating liquid B, but is preferably 0.5 to 20% by mass, 0.7 to 10% by mass, particularly preferably 1 to 8% by mass. When the amount of the metal compound containing Al is 0.5% by mass or more, a gas barrier film having better storage stability under high temperature and high humidity can be obtained. When the amount of the metal compound containing Al is 20 mass% or less, the gas barrier property of the upper inorganic compound layer (gas barrier precursor layer) and further the modified gas barrier layer can be improved. When two or more kinds of aluminum metal compounds are used, it is preferable that the total amount of the Al elements contained in these is in the above range.

The coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer preferably contains a catalyst in order to promote the modification. As the catalyst applicable to the coating liquid B, the same catalyst as that applicable to the coating liquid A described in the &quot; Preparation method of coating liquid A &quot; Detailed description of these catalysts is omitted. The concentration of the catalyst to be added at this time is preferably from 0.1 to 10 mass%, more preferably from 0.5 to 7 mass%, based on the Al-containing metal compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excess silanol formation due to the rapid progress of the reaction in the interface region of the upper and lower layers, decrease in film density, increase in film defect, and the like. Among these catalysts, the amine catalyst may also serve as the above-described additive compound.

To the coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, additives such as the following can be used if necessary. As the additive which can be optionally used in the coating liquid B, the same additives as can be used in the coating liquid A described in the &quot; Preparation method of the coating liquid A &quot; can be used. A detailed description of these additives will be omitted.

In the method of forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, in an environment where the water concentration (water vapor concentration) is not more than 100 ppm by volume, preferably the oxygen concentration is not more than 200 ppm by volume, , And the mixture is stirred and mixed to prepare a coating liquid B for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer. However, even if the moisture concentration (water vapor concentration) and further the oxygen concentration are out of the above range, the coating liquid B for forming the desired inorganic compound layer (gas barrier precursor layer) Available.

According to the method of forming the inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer in the upper layer of the present invention, it is possible to form the reformed gas barrier layer in an environment where the water concentration (water vapor concentration) is 100 ppm by volume or less, preferably 200 ppm by volume or less , And a coating liquid B for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer is prepared by adding a metal compound containing Al to the solvent and mixing and stirring to remove water and oxygen during mixing, The reaction with oxygen can be suppressed. As a result, since the vacuum ultraviolet light can be effectively absorbed, Si-N remaining in the reformed gas barrier layer (particularly, the intermediate region) formed after the irradiation with the ultraviolet ultraviolet light can be reduced. Therefore, it is excellent in that a gas barrier film excellent in storage stability under high temperature and high humidity can be obtained.

According to the method of forming the upper inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer of the present invention, under an environment where the water concentration (water vapor concentration) is 100 vol ppm or less, and preferably the oxygen concentration is 200 vol ppm or less, It is preferable to add a metal compound containing Al to the solvent and mix and stir to prepare a coating liquid B for forming an inorganic compound layer (gas barrier precursor layer) in the upper layer. If the water concentration (water vapor concentration) exceeds 100 vol. Ppm, the oxidation reaction of the components in the coating liquid B may be promoted by the action of water. If the oxygen concentration exceeds 200 vol ppm, oxygen may be mixed into the coating liquid B due to the oxygen in the environment during the tank liquid. However, even if the moisture concentration (water vapor concentration) or the oxygen concentration is out of the above-mentioned range, as long as the effect of the present invention is not impaired, the coating for forming the inorganic compound layer (gas barrier precursor layer) It is sufficiently usable as the liquid B.

In the production of the coating liquid B, it is preferred that the water concentration (water vapor concentration) is set in an environment of preferably 0 to 50 vol. Ppm, more preferably 0 to 30 vol. Ppm. More preferably, the oxygen concentration is preferably 0 to 100 vol. Ppm, more preferably 0 to 30 vol. Ppm, in the production of the coating liquid B.

Such an environment can be realized by preparing a liquid tank facility such as a glove box in which water concentration (water vapor concentration) and oxygen concentration are controlled. It is preferable to use a dry inert gas as the gas that is used in the production of the coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer and satisfies the atmosphere. As the inert gas, nitrogen, argon, helium and the like are exemplified. However, from the viewpoint of cost, it is preferable to use dry nitrogen gas. The adjustment of the oxygen concentration can be adjusted by measuring the flow rate of the oxygen gas and the inert gas introduced into the liquid tank facility such as a glove box and changing the flow rate ratio. The water concentration (water vapor concentration) in the atmosphere can be lowered by drying using a drying agent such as molecular sieves. Further, the oxygen concentration in the atmosphere can be lowered by, for example, a method of reacting with a catalyst such as a metal copper or the like and adsorbing it on an oxygen scavenger.

When preparing the coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, a silicon compound (polysilazane in particular) is not used in the organic solvent. Therefore, the metal compound containing Al and the catalyst may be mixed and stirred if necessary. Particularly, since it is not necessary to carry out the reaction by heating, it is preferable because it can be prepared easily and at low cost.

The liquid bath temperature depends on the solvent to be used but is preferably 10 to 50 ° C, more preferably 15 to 30 ° C, and more preferably 18 to 25 ° C More preferable. When the liquid bath temperature is 10 占 폚 or higher, components such as a metal compound containing Al are efficiently dissolved and dispersed in a solvent, so that a gas barrier film excellent in storage stability under high temperature and high humidity can be obtained. On the other hand, if the liquid bath temperature is 50 캜 or lower, it is preferable that components such as Al-containing metal compounds and the like are suppressed from reacting with moisture and the like, in addition to the fact that the solvent is extremely evaporated in the bath liquid to cause fluctuation of concentration.

The liquid bath time is not particularly limited, but is preferably 10 minutes to 12 hours, more preferably 20 minutes to 2 hours, and more preferably 30 minutes To 2 hours. When the liquid bath time is 10 minutes or more, components such as a metal compound containing Al are efficiently dissolved and dispersed in a solvent, so that a gas barrier film excellent in storage stability can be obtained. On the other hand, if the liquid bath time is 12 hours or less, the components such as Al-containing metal compounds and the like are preferably prevented from reacting with water.

(A step of forming a coating film by applying the coating liquid A or B onto the inorganic compound layer (gas barrier layer) of the lower layer or the precursor layer thereof)

Subsequently, in the case of the coating liquid A obtained above, the coating liquid A (coating liquid A for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer) was applied on the lower inorganic compound layer (gas barrier layer) (An inorganic compound layer (gas barrier precursor layer) in the upper layer) is formed. Further, in the case of the coating liquid B obtained above, the coating liquid B (coating liquid B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer) was applied on the lower inorganic compound layer (gas barrier layer) or the precursor layer thereof , A coating film (an inorganic compound layer (gas barrier precursor layer) in the upper layer) is formed (see Examples 1 to 3).

As a method of applying the coating liquids A and B for forming the inorganic compound layer (gas barrier precursor layer) in the upper layer, a conventionally known appropriate wet coating method may be employed. Specific examples thereof include spin coating, roll coating, flow coating, inkjet, spray coating, printing, dip coating, flexible coating, bar coating and gravure printing.

The coating thicknesses of the coating liquids A and B can be appropriately set in accordance with the purpose. For example, the coating thickness per one layer of the inorganic compound layer (gas barrier precursor layer) in the upper layer is preferably 10 nm to 10 탆, more preferably 15 nm to 1 탆, and more preferably 20 to 500 nm Is more preferable. When the film thickness is 10 nm or more, sufficient barrier property can be obtained. When the film thickness is 10 m or less, stable coating property can be obtained at the time of layer formation, and high light ray transmittance can be realized.

The atmosphere for applying the application liquids A and B may be any one of an atmosphere under an atmosphere of atmospheric air (atmospheric environment) under a nitrogen atmosphere, under a vacuum atmosphere under an argon atmosphere, under a reduced-pressure atmosphere with an oxygen concentration controlled, Preferably in the same manner as in the step of preparing the coating liquids A and B, under an inert gas atmosphere in which the oxygen concentration is controlled to 200 ppm by volume or less and the water vapor concentration is controlled to be 100 ppm by volume or less.

After applying the coating liquids A to B, it is preferable to leave the coating liquid for a predetermined time (specifically, 30 minutes or less), and then dry the coated film. By drying the coating film, a solvent such as an organic solvent contained in the coating film can be removed. At this time, the solvent contained in the coating film may be all dried, but a part of the solvent may be left. Even when a part of the solvent remains, a preferable upper inorganic compound layer (gas barrier precursor layer) can be obtained. Further, the remaining solvent can be removed later.

The drying temperature of this coating film (gas barrier precursor layer in the upper layer) varies depending on the substrate to which it is applied, but is preferably 50 to 200 ° C. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 DEG C is used as a substrate, the drying temperature is preferably set to 150 DEG C or less in consideration of deformation of the substrate due to heat and the like. The temperature can be set by using a hot plate, an oven, a furnace, or the like. It is preferable to set the drying time in a short time, for example, when the drying temperature is 150 ° C, it is preferable to set it within 30 minutes. The drying atmosphere may be any one of conditions under an atmosphere of nitrogen, under an argon atmosphere, under a vacuum atmosphere, under a reduced-pressure atmosphere in which the oxygen concentration is controlled, but preferably, the coating liquid A or the coating liquid B It is preferable to carry out the treatment under an atmosphere of an inert gas whose vapor concentration (water concentration) is controlled to be not more than 100 ppm by volume, more preferably, the oxygen concentration is controlled not more than 200 ppm by volume.

Although the modifying treatment is carried out by irradiating vacuum ultraviolet rays to the coating film (gas barrier precursor layer in the upper layer) obtained as described later, the transmittance of light at 172 nm in the coating film (gas barrier precursor layer in the upper layer) immediately before irradiation with vacuum ultraviolet rays, Since either of the coating liquids A and B contains Al atoms, the coating film (upper gas barrier precursor layer) containing Al such as an aluminum compound which is a coating film (upper gas barrier precursor layer) (The gas barrier precursor layer in the upper layer) of the upper layer and reaches (irradiated) the gas barrier layer (or the precursor layer) containing Si in the lower layer, And a continuous Al atom gradation structure is formed in the film thickness direction, whereby a region (referred to as a modified region) having excellent both heat resistance and gas barrier properties is formed. From this point of view, the transmittance of 172 nm of the coating film (upper gas barrier precursor layer) immediately before irradiation with the vacuum ultraviolet ray is preferably 50% or less, more preferably 30% or less, and further preferably 10% or less . Since the transmittance of light of 172 nm in the coating film (upper gas barrier precursor layer) immediately before irradiation of the vacuum ultraviolet ray is 50% or less, it is advantageous in that the effect of the present invention described above can be effectively manifested. On the other hand, the lower limit value of the transmittance of 172 nm of the coating film (upper gas barrier precursor layer) immediately before the irradiation of the vacuum ultraviolet ray is not particularly limited, but if it is 10% or more, the modification is progressed sufficiently by the vacuum ultraviolet ray great. The transmittance of 172 nm of the coating film (upper gas barrier precursor layer) immediately before the irradiation of the vacuum ultraviolet ray is to be a value measured by the following method.

&Lt; Measurement of vacuum ultraviolet transmittance of the inorganic compound layer (gas barrier layer) of the upper layer and its precursor layer >

Using the coating solutions A to B, the following samples were prepared separately and the vacuum ultraviolet absorption spectrum was measured. More specifically, the coating liquids A to B were coated on a synthetic quartz substrate having a thickness of 0.7 mm so as to have a thickness of 120 nm using a spin coater under the same coating environment to form an inorganic compound layer (a gas barrier precursor layer ), The sample before and after irradiation of the vacuum ultraviolet ray is measured. In addition, the fabricated sample was transferred to a nitrogen-filled glove box (preferably a water vapor concentration (water vapor concentration) of 100 vol ppm or less, more preferably an oxygen concentration of 10 vol ppm or less) The transmittance (%) at 172 nm can be measured using a mercury lamp and a multi-detector (Maya 2000 pro) manufactured by Ocean Photonics.

(Step of modifying the intermediate region (near the interface) of the upper and lower layers by irradiating vacuum ultraviolet rays to the coating film (upper gas barrier precursor layer) to form a reformed gas barrier layer)

Subsequently, the obtained coating film (upper gas barrier precursor layer) is irradiated with vacuum ultraviolet rays to modify the intermediate region (near the interface) of the upper and lower layers to form a reformed gas barrier layer.

In the vacuum ultraviolet ray irradiation treatment, any one of commercially available vacuum ultraviolet ray generating devices can be used. For example, the method described in the above-mentioned "inorganic compound layer (gas barrier layer)" (ultraviolet ray irradiation treatment) can be applied.

The radiation source of the present invention can be applied to the type (radiation source) described in the section "inorganic compound layer (gas barrier layer) in the lower layer" (ultraviolet irradiation treatment).

Modification of the coating film can be realized in a short time by the energy of light of 100 to 180 nm (for example, 172 nm) having a short wavelength by the radiation source. More specifically, it is possible to modify the entire gas barrier precursor layer of the upper layer which is a coating film and modify the intermediate region (interface region) of the upper and lower layers (Examples 1 and 2). Further, in addition to the modification of the entire gas barrier precursor layer as the upper layer of the laminated coating film and the modification of the intermediate region (interface region) of the upper and lower layers, the modification of the entire gas barrier precursor layer as the lower layer under the laminated coating film can be realized See Example 3).

The vacuum ultraviolet ray irradiation is not particularly limited, but it is preferable that oxygen is supplied under the presence of oxygen rather than a complete inert gas atmosphere because the supply of oxygen from the surface of the coating film is important. Concretely, it is preferable that the vacuum ultraviolet irradiation is performed in an atmosphere having an oxygen concentration of 200 to 10,000 vol. Ppm. More preferably, the oxygen concentration at the time of vacuum ultraviolet irradiation is 500 to 5,000 volume ppm, more preferably 700 to 2,000 volume ppm. When the oxygen concentration is 200 vol ppm or more, oxygen is supplied during the irradiation of the vacuum ultraviolet ray. For example, in the coating film (upper gas barrier precursor layer) using the coating liquid A, a metal compound containing Al and a silicon compound ) Is sufficiently promoted and released out of the system as carbon dioxide derived from a metal compound containing Al, nitrogen oxide derived from a silicon compound (particularly polysilazane), and ammonia. Although the coating liquids A and B all contain a metal compound containing Al, if the ratio of the carbon atoms derived from the Al-containing metal compound in the reformed gas barrier layer is large, the gas barrier property may be deteriorated , It is considered that the gas barrier properties of the reformed gas barrier layer obtained by reacting with oxygen and being released as carbon dioxide out of the system can be improved. On the other hand, since the vacuum ultraviolet ray has absorption by oxygen, the reduction in efficiency in the vacuum ultraviolet ray irradiation step can be suppressed by performing the treatment in an atmosphere having an oxygen concentration of 10,000 ppm or less.

In addition, it is preferable that irradiation with vacuum ultraviolet rays is performed in a state where moisture concentration (water vapor concentration) is as low as possible. The water concentration (water vapor concentration) upon irradiation with vacuum ultraviolet rays is preferably 1000 volume ppm or less, and more preferably 200 volume ppm or less.

Vacuum ultraviolet irradiation is not particularly limited, but it is preferable that the temperature of the coating film (gas barrier precursor layer in the upper layer) is controlled at 50 to 120 캜. The temperature of the coating film (gas barrier precursor layer in the upper layer) upon vacuum ultraviolet irradiation is more preferably 60 to 100 占 폚, and more preferably 70 to 90 占 폚. By setting the temperature of the coating film (gas barrier precursor layer in the upper layer) at the time of vacuum ultraviolet irradiation to 50 캜 or higher, for example, the metal compound containing Al in the coating film (gas barrier precursor layer in the upper layer) Is excellent in that it is possible to shorten the irradiation time in obtaining a gas barrier film having a sufficiently promoted reaction of a silicon compound (particularly polysilazane), excellent gas barrier property and excellent storage stability under high temperature and high humidity . On the other hand, when the temperature of the coating film (gas barrier precursor layer in the upper layer) at the time of irradiation with vacuum ultraviolet rays is 120 ° C or lower, deformation due to heat of the plastic film base can be minimized. The specific means for controlling the temperature of the coating film is not particularly limited, and conventionally known methods can be appropriately used. Further, it is more preferable to control the temperature of the atmosphere at the time of vacuum ultraviolet irradiation to the above-mentioned range. Means for controlling the temperature of the atmosphere is not particularly limited, and conventionally known methods can be appropriately used. However, the coating film may be subjected to temperature control (such as heating) at room temperature. This is because a gas barrier film excellent in gas barrier property and excellent in storage stability under high temperature and high humidity can be obtained even if the coating film is subjected to temperature control (heating or the like) without any problem even if it is carried out at normal temperature.

In addition, in the vacuum ultraviolet irradiation step, the illuminance of the vacuum ultraviolet ray on the surface of the coating film (gas barrier precursor layer as the upper layer) formed from the coating liquids A to B for forming the inorganic compound layer (gas barrier precursor layer) The shape (roughness) described in the section "inorganic compound layer (gas barrier layer) in the lower layer" (ultraviolet ray irradiation treatment) can be applied. If it is 1 mW / cm 2 or more, sufficient reforming efficiency can be obtained, especially excellent modifying effect in the intermediate region (near the interface) of the upper and lower layers, and abrasion is less likely to occur in the gas barrier precursor layer , And it is excellent in that it is difficult to damage the substrate.

The irradiation energy amount (accumulated light amount) of the vacuum ultraviolet ray on the surface of the coating film (gas barrier precursor layer on the upper layer) formed from the coating liquids A to B for forming the upper inorganic compound layer (gas barrier precursor layer) (Irradiation energy amount (accumulated light amount)) described in the section "Inorganic compound layer (gas barrier layer) in the lower layer" (ultraviolet irradiation treatment) can be applied. When the amount of irradiation energy of the vacuum ultraviolet ray (accumulated light amount) is 10 mJ / cm 2 or more, the coating film is sufficiently reformed, and in particular, the vacuum ultraviolet light exits from the upper layer containing Al and is excellent in the middle region (Modified region) can be formed which is excellent in both heat resistance and gas barrier properties. As a result, it is possible to provide a gas barrier film which is excellent in storage stability without deterioration even under severe conditions (high temperature and high humidity conditions = high temperature and high humidity acceleration conditions) and can maintain high barrier properties. On the other hand, when the amount of irradiation energy of the vacuum ultraviolet rays (accumulated light amount) is 10,000 mJ / cm 2 or less, cracks due to over-reforming and thermal deformation of the substrate are hard to occur.

In addition, the vacuum ultraviolet light used for the modification may be generated by a plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as a carbon-containing gas). The carbon-containing gas may be of the type described in the above-mentioned "inorganic compound layer (gas barrier layer)" (ultraviolet ray irradiation treatment).

[Inorganic compound layer (gas barrier layer) in the upper layer]

The gas barrier film obtained by the above-mentioned method of forming the inorganic compound layer (gas barrier precursor layer) and the reformed gas barrier layer in the upper layer comprises a lower gas barrier layer or a precursor layer containing no Si atom and containing no Si atom, And an upper gas barrier precursor layer containing Al atoms formed thereon is modified by vacuum ultraviolet irradiation to form an integrated reformed gas barrier layer having no distinction between upper and lower layers (no interface) (A), (B), (A), (B), and (A) Since the modified gas barrier layer is as described above, the structure (structure) and characteristics of the upper inorganic compound layer (gas barrier layer) including Al atoms will be described below. The constitution (structure) and characteristics of the upper layer of the inorganic compound layer (gas barrier layer) including Al atoms can be obtained by laminating a layered product (sample) having only an inorganic compound layer (gas barrier layer) And is simply obtained by performing various measurements and analysis.

The inorganic compound layer (gas barrier layer) in the upper layer is not particularly limited, but is modified at the interface of the upper and lower layers by irradiation with vacuum ultraviolet light, and a continuous Al atom gradation structure is formed in the film thickness direction. It is preferable that at least Al atoms are contained in an amount of 3 to 40 at% relative to the total amount (100 at%) of all the elements in the inorganic compound layer (gas barrier layer) in the upper layer so as to form an excellent region (modified region) Do. , More preferably 5 to 20 at%, and further preferably 7 to 15 at%. When the upper layer of an inorganic compound layer (gas barrier layer) is formed using the above-mentioned coating liquid A, it is preferable that the Al atoms contain silicon atoms and oxygen atoms and the presence ratio of oxygen atoms to silicon atoms (O / Si) is 1.4 to 2.2, and the ratio of nitrogen atoms to silicon atoms (N / Si) is preferably 0 to 0.4. Even when the upper inorganic compound layer (gas barrier layer) is formed by using the above-mentioned coating liquid B, it is preferable that the ratio of the oxygen atoms to the silicon atoms (O / Si) 1.0 to 2.0, and the presence ratio of nitrogen atoms to silicon atoms (N / Si) is preferably 0 to 1.

In the present specification, "the ratio of the presence of oxygen atoms to silicon atoms (O / Si) is 1.4 to 2.2" means that the depth of any depth of the inorganic compound layer (gas barrier layer) , It means that there is no part showing a value of O / Si of less than 1.4 or more than 2.2. Similarly, the phrase "the ratio of the presence of nitrogen atoms to silicon atoms (N / Si) in the range of 0 to 0.4" means that at any depth in the upper inorganic compound layer (gas barrier layer) , And there is no portion showing a value in which N / Si exceeds 0.4. As for the analysis of the above numerical range of "presence ratio of oxygen atoms to silicon atoms (O / Si)" and "presence ratio of nitrogen atoms to silicon atoms (N / Si)" when the coating liquid B is used It should be understood.

(O / Si) of 1.4 or more (using the coating liquid A) or 1.6 or more (using the coating liquid B) exists in the inorganic compound layer (gas barrier layer) in the upper layer in the presence of oxygen atoms relative to the silicon atoms There is a high effect of preventing the inorganic compound layer (gas barrier layer) in the upper layer from reacting with moisture and greatly lowering the barrier property. On the other hand, in the case of not more than 2.2 (using the coating liquid A) or not more than 2 (using the coating liquid B), the ratio of the silanol groups (Si-OH) present in the molecule becomes smaller and higher barrier properties can be obtained. When the inorganic compound layer (gas barrier layer) in the upper layer is formed using the coating liquid A, the O / Si is more preferably 1.5 to 2.1, and still more preferably 1.7 to 2.0. When the upper inorganic compound layer (gas barrier layer) is formed using the coating liquid B, the O / Si is more preferably 1.4 to 2.0, and still more preferably 1.5 to 1.9.

(N / Si) in the inorganic compound layer (gas barrier layer) in the upper layer is 0.4 or less (using the coating liquid A) or 0.1 or more (using the coating liquid B) Of the inorganic compound layer (gas barrier layer) is prevented from reacting with moisture to lower the barrier property. When the upper inorganic compound layer (gas barrier layer) is formed using the coating liquid A, the N / Si is more preferably 0 to 0.3, and still more preferably 0 to 0.2. When the inorganic compound layer (gas barrier layer) in the upper layer is formed using the coating liquid B, the N / Si is more preferably 0 to 0.4, and more preferably 0 to 0.2.

The O / Si and the N / Si can be measured by the following method. That is, the composition profile of the inorganic compound layer (gas barrier layer) in the upper layer was obtained by preparing a laminate (sample) in which only the inorganic compound layer (gas barrier layer) containing Al atoms in the upper layer was formed on the substrate, Ray photoelectron spectroscopy (XPS). The profile distribution in the depth (film thickness) direction can be calculated by obtaining the actual film thickness by film processing using a FIB (converged ion beam) processing apparatus and a TEM (transmission electron microscope) and correlating with the result of XPS.

In the present invention, the following apparatus and method are used.

(Sputter condition)

Ion species: Ar ion

Acceleration voltage: 1 kV

(X-ray photoelectron spectroscopic measurement condition)

Apparatus: ESCALAB-200R manufactured by VG Scientific Co.

X-ray anode material: Mg

Output: 600 W (acceleration voltage 15 kV, emission current 40 mA)

Furthermore, the resolution of the measurement is 0.5 nm and is obtained by plotting the respective source consumption at each sampling point accordingly.

(FIB processing)

Apparatus: SMI2050 manufactured by SII

Processed ions: (Ga 30 kV)

(TEM observation)

Apparatus: JEM2000FX (acceleration voltage: 200 kV) manufactured by Nihon Denshi Co.,

Electron beam irradiation time: 5 seconds to 60 seconds

(Circle consumption in the depth direction of the film thickness from the surface of the inorganic compound layer (gas barrier layer) in the upper layer)

The results of the XPS measurement (attention to Si, O, and N) at each depth obtained by the sputter from the surface of the inorganic compound layer (gas barrier layer) of the upper layer and the results of the cross-section observation by TEM were compared with each other, / Si &lt; / RTI &gt; Such a measurement method can be similarly applied to the reformed gas barrier layer.

In the inorganic compound layer (gas barrier layer) of the upper layer, the average value of the ratio of the presence of oxygen atoms to silicon atoms in the region from the outermost surface (upper layer surface) to the depth of 10 nm in the film thickness direction, And the average value of the ratio of the presence of oxygen atoms to silicon atoms in the region where the depth in the thickness direction exceeds 10 nm is 0.4 or less. With such a constitution, the compositional change in the surface portion and inside of the inorganic compound layer (gas barrier layer) in the upper layer becomes smaller, and a gas barrier film having better storage stability under high temperature and high humidity becomes. The difference in average value is more preferably 0.3 or less, and more preferably 0.2 or less.

The average value of the abundance ratio of oxygen atoms to silicon atoms in the region from the outermost surface (upper layer surface) to the depth of 10 nm in the film thickness direction and the average value of the ratio of oxygen atoms to silicon atoms in the region exceeding 10 nm from the outermost surface The average value of the abundance ratio of oxygen atoms can be calculated by a combination of the above-described Ar sputter etching apparatus and X-ray photoelectron spectroscopy (XPS).

The film density of the inorganic compound layer (gas barrier layer) in the upper layer can be appropriately set in accordance with the purpose. For example, it is preferable that the film density of the inorganic compound layer (gas barrier layer) in the upper layer is in the range of 1.5 to 2.6 g / cm 3. Within this range, the denseness of the film becomes higher, which is advantageous in that deterioration of the gas barrier property and deterioration of the oxidation of the film due to humidity are difficult to occur.

The inorganic compound layer (gas barrier layer) in the upper layer may be a single layer or a laminated structure of two or more layers.

When the inorganic compound layer (gas barrier layer) in the upper layer has a laminated structure of two or more layers, the inorganic compound layer (gas barrier layer) in each upper layer may be the same composition or different composition.

The ratio of the presence of oxygen atoms to silicon atoms, the presence ratio of nitrogen atoms to silicon atoms in the inorganic compound layer (gas barrier layer) in the upper layer, and the ratio of nitrogen atoms to silicon atoms in the region from the outermost surface And the average value of the abundance ratio of oxygen atoms to silicon atoms in the region exceeding 10 nm in depth from the outermost surface (upper layer surface) in the thickness direction of the film, the average value of the abundance ratio of the oxygen atoms to the silicon atoms in the upper layer (Particularly polysilazane) in the coating liquid A used for forming the inorganic compound layer (gas barrier layer), and the kind and amount of the aluminum compound and the silicon compound (polysilazane) and Al The conditions for modifying the layer containing the metal compound, and the like. Similarly, the kind and amount of the Al-containing metal compound in the coating liquid B used when forming the inorganic compound layer (gas barrier layer) in the upper layer and the conditions for modifying the layer containing the Al- , Can be controlled.

The upper inorganic compound layer (gas barrier layer) obtained by conducting the modifying treatment by irradiating vacuum ultraviolet rays preferably has a light transmittance of 172 nm, preferably 50 to 100%, more preferably 70 to 100%, and 80 to 90 % Is more preferable. When the transmittance of the light of 172 nm is 50% or more, it can be said that the residual amount of the silazane as the raw material component is sufficiently reduced when the coating liquid A is used, and even when any one of the coating liquids A and B is used, A gas barrier film in which deterioration of gas barrier property is suppressed can be obtained. The transmittance of light of 172 nm of the coating film is to be a value measured by the following method.

<Measurement of Transmittance of Vacuum Ultraviolet (172 nm Light) of Inorganic Compound Layer (Gas Barrier Layer) of Upper Layer>

Using the coating solutions A to B, the following samples were prepared separately and the vacuum ultraviolet absorption spectrum was measured. More specifically, the coating liquids A to B were coated on a synthetic quartz substrate having a thickness of 0.7 mm to a thickness of 120 nm using a spin coater under the same coating environment to form an inorganic compound layer (gas barrier layer ), That is, before and after the irradiation of the vacuum ultraviolet ray, similarly to the film forming conditions of the reformed gas barrier layer. The prepared sample was directly transferred to a glove box filled with nitrogen (preferably, the water vapor concentration was 100 vol. Ppm or less, more preferably the oxygen concentration was 10 vol. Ppm or less), and mercury lamp manufactured by Hamamatsu Photonics Co., The transmittance (%) at 172 nm can be measured using a manufactured multi-detector (Maya 2000 pro).

[Protective layer]

In the gas barrier film according to the present invention, a protective layer containing an organic compound may be formed on the reformed gas barrier layer. As the organic compound to be used for the protective layer, an organic-inorganic hybrid resin layer using an organic resin such as an organic monomer, an oligomer, or a polymer, a siloxane having an organic group, a monomer of silsesquioxane, an oligomer, a polymer or the like can be preferably used. The forming material of the protective agent, the forming method and the like are described, for example, in International Publication Nos. (Material and method) described in paragraphs &quot; 0157 &quot; to &quot; 0177 &quot; of Japanese Patent Laid-Open Publication No. 2014-100806 can be suitably employed as described in paragraph &quot; 0239 &quot; in WO 2015/053405 A1 .

[Smoothing layer (base layer, primer layer)]

The gas barrier film of the present invention is preferably a substrate having a gas barrier layer of a substrate, preferably a substrate and a gas barrier layer (hereinafter referred to as &quot; substrate side &quot;) among the gas barrier layer (including the reformed gas barrier layer) (Base layer, primer layer) between the gas barrier layer and the gas barrier layer. The smoothing layer is provided to planarize the roughened surface of the substrate on which protrusions or the like are present, or to embed unevenness or pinholes in the substrate-side gas barrier layer by planes existing in the substrate to planarize them. Such a smoothing layer may be formed of any material, but preferably includes a carbon-containing polymer, and more preferably composed of a carbon-containing polymer. That is, it is preferable that the gas barrier film of the present invention further includes a smoothing layer containing a carbon-containing polymer between the substrate and the gas barrier layer on the substrate side.

The smoothing layer also includes a carbon-containing polymer, preferably a curable resin. The curable resin is not particularly limited, and examples thereof include active energy ray-curable resins obtained by curing an active energy ray-curable material by irradiating active energy rays such as ultraviolet rays, and thermosetting resins obtained by curing a thermosetting material. These curable resins may be used singly or in combination of two or more kinds.

As the active energy ray-curable material used for forming the smoothing layer, for example, a composition containing an acrylate compound, a composition containing a mercapto compound containing an acrylate compound and a thiol group, a composition containing an epoxy acrylate, a urethane acrylate, a poly And a composition containing a polyfunctional acrylate monomer such as ester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate. Specifically, an organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series (a compound obtained by bonding an organic compound having a polymerizable unsaturated group to silica fine particles), which is an ultraviolet curable material manufactured by JSR Corporation, can be used. Any composition as described above may be used as long as it is an active energy ray-curable material containing a reactive monomer having at least one photopolymerizable unsaturated bond in its molecule.

Examples of the reactive monomer, the photopolymerization initiator, the thermosetting material, the method of forming the smoothing layer (solvent or additive used in the coating liquid), the smoothness, the surface roughness, the film thickness, and the like used for the active energy ray- For international public numbers; (Material and method) described in paragraphs 0126 to 0137 and 0143 of Japanese Patent Laid-Open Publication No. 2014-141056 are appropriately adopted as described in paragraph 0248 of WO 2015/053405 A1 .

[Anchor coat layer]

An anchor coat layer may be formed on the surface of the substrate according to the present invention as an easy-to-adhere layer for the purpose of improving adhesion (adhesion). Examples of the anchor coat agent used for the anchor coat layer include a polyester resin, an isocyanate resin, a urethane resin, an acrylic resin, an ethylene / vinyl alcohol resin, a vinyl modified resin, an epoxy resin, a modified styrene resin, a modified silicone resin, May be used alone or in combination of two or more. As the anchor coat agent, a commercially available product may be used. Specifically, a siloxane UV curable polymer solution (3% isopropyl alcohol solution of "X-12-2400" manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

To these anchor coat agents, conventionally known additives may be added. The above-mentioned anchor coat agent can be coated by coating on a substrate by a known method such as roll coating, gravure coat, knife coat, dip coat, spray coat, etc. and drying and removing solvents, diluents and the like. The application amount of the anchor coat agent is preferably about 0.1 to 5 g / m 2 (dry state). A commercially available substrate having an easy-to-adhere layer may also be used.

 Alternatively, the anchor coat layer may be formed by a vapor deposition method such as physical vapor deposition or chemical vapor deposition. For example, as described in Japanese Patent Application Laid-Open No. 2008-142941, an inorganic film mainly composed of silicon oxide may be formed for the purpose of improving adhesiveness and the like.

The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 mu m.

[Bleed-Out Prevention Layer]

The gas barrier film of the present invention may further have a bleed out preventing layer. The anti-bleed-out layer is formed on the opposite side of the substrate having a smoothing layer, for the purpose of suppressing the phenomenon that the unreacted oligomer or the like migrates from the substrate to the surface when the film having the smoothing layer is heated, Respectively. The bleed-out preventing layer may basically have the same structure as that of the smoothing layer, provided that it has this function.

Examples of the compound that can be included in the bleed-out preventing layer include a hard coating agent such as a polyvalent unsaturated organic compound having two or more polymerizable unsaturated groups in the molecule or a monovalent unsaturated organic compound having one polymerizable unsaturated group in the molecule.

(The kind or content of the inorganic particles of the matting agent) and other components (such as a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a light-curing resin, a light curing resin, A method for forming a bleed-out preventing layer (a solvent used in a coating liquid), a film thickness, and the like are described, for example, in International Publication Nos. (Material and method) described in paragraphs &quot; 0249 &quot; to &quot; 0262 &quot; of Japanese Patent Application Laid-Open No. 2013-52561 can be suitably employed as described in paragraph &quot; 0252 &quot; of WO 2015/053405 A1.

&Quot; Package form of gas barrier film &quot;

The gas barrier film of the present invention can be continuously produced and wound in a roll form (so-called roll-to-roll production). At this time, it is preferable that a protective sheet is adhered to the surface on which the gas barrier layer is formed and wound. Particularly, when the gas barrier film of the present invention is used as a sealing material for an organic thin film device, it is often the case that a dust (for example, particles) adhering to the surface causes defects, It is very effective to prevent adhesion of dust. In addition, it is effective to prevent scratches on the surface of the gas barrier layer that enters during winding.

The protective sheet is not particularly limited, but general "protective sheet" and "release sheet" having a structure in which a weakly adhesive adhesive layer is given to a resin substrate having a thickness of about 100 μm can be used.

&Quot; Water vapor permeability of gas barrier film &quot;

Water vapor permeability of the gas barrier film produced by the method of the invention, but more preferably lower, for example 1 × 10 ^-3 to ^{1 × 10 -5 g / ㎡ ·} day of and preferably, 1 × 10 ^{- 4} to 1 x 10 ^-5 g / m 2 · day. In the present invention, a value measured by the following method is used for the water vapor transmission rate.

&Quot; Measurement of water vapor barrier property (water vapor permeability WVTR) &quot;

The vapor permeability (vapor barrier property) of the gas barrier film produced by the method of the present invention was measured by depositing metal calcium of 80 nm thickness on the side of the sample gas barrier layer side of the gas barrier film, (WVTR) (g / m &lt; 2 &gt; · day) can be obtained by measuring the time for which the calcium content of the formed calcium is 50% in the acceleration test at 85% RH as the calcium corrosion time.

[Electronic device]

The gas-impermeable film according to the present invention and the gas-impermeable film produced by the method are preferable for a device whose performance deteriorates due to chemical components (oxygen, water, nitrogen oxides, sulfur oxides, ozone, etc.) in the air Can be used. Examples of the device include electronic devices such as an organic EL device, a liquid crystal display device (LCD), a thin film transistor, a touch panel, an electronic paper, and a solar cell (PV). From the viewpoint that the effect of the present invention can be obtained more efficiently, it is preferably used for an organic EL element or a solar cell, and is particularly preferably used for an organic EL element.

The gas barrier film according to the present invention and the gas barrier film produced by the method can also be used for film sealing of a device. That is, the device itself is used as a support, and the gas barrier film of the present invention is provided on the surface of the support. The device may be covered with a protective layer before installing the gas barrier film.

The gas barrier film according to the present invention and the gas barrier film produced therefrom can also be used as a substrate for a device or as a film for sealing by a solid sealing method. The solid sealing method is a method in which a protective layer is formed on a device, and then an adhesive layer and a gas-barrier film are overlaid and cured. The adhesive is not particularly limited, but thermosetting epoxy resin, photo-curable acrylate resin and the like are exemplified.

&Lt; Organic EL device &

Examples of the organic EL device using the gas barrier film are described in the paragraphs &quot; 0259 &quot; to &quot; 0266 &quot; of International Publication No. WO 2015/053405 A1, &Quot; to &quot; 0082 &quot; can be suitably employed.

<Liquid crystal display element>

The reflection type liquid crystal display device has a structure composed of a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a quarter wave plate, and a polarizer film. The gas barrier film in the present invention can be used as the transparent electrode substrate and the upper substrate. For example, the form described in paragraph &quot; 0268 &quot; of International Publication No. WO 2015/053405 A1 can be suitably adopted.

<Solar cell (device)>

The gas barrier film of the present invention can also be used as a sealing film of a solar cell element. Here, it is preferable that the gas barrier film of the present invention be sealed so that the barrier layer is close to the solar cell element. For example, the form described in paragraph &quot; 0269 &quot; of International Publication No. WO 2015/053405 A1 can be suitably adopted

<Others>

Other application examples include a touch panel described in Japanese Patent Application Laid-open No. 10-512104, a touch panel disclosed in Japanese Patent Application Laid-Open Nos. 5-127822 and 2002-48913, Japanese Patent Application Laid-Open No. 2000-98326 And an electronic paper described in the publication.

&Lt; Optical member &

The gas barrier film of the present invention can also be used as an optical member. Examples of the optical member include a circularly polarizing plate and the like.

(Circularly polarizing plate)

By using the gas-barrier film of the present invention as a substrate and laminating a? / 4 plate and a polarizing plate, a circular polarizing plate can be manufactured. In this case, the angle formed by the slow axis of the? / 4 plate and the absorption axis of the polarizing plate is 45 占. It is preferable that such a polarizing plate is stretched in the direction of 45 DEG with respect to the longitudinal direction (MD). For example, those described in JP-A-2002-865554 can be suitably used.

Example

The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments. In the examples, "part" or "%" is used, but "mass part" or "mass%" is used unless otherwise specified. Unless otherwise stated, the operations and physical properties are measured at room temperature (20 to 25 DEG C) / relative humidity of 40 to 50%.

[Comparative Example 1] Production of gas barrier film (111)

The layer structure of the gas barrier film 111 is as shown in Fig. 1 (C).

A first gas barrier layer 18 containing Al by the ALD method and a second gas barrier layer 19 containing Si by the plasma CVD method are formed on the substrate 12 in the following manner To form a gas barrier film 111 (reference numeral 11 'in Fig. 1 (C)).

[Formation of inorganic compound layer (first gas barrier layer) 18 (ALD method of dry method)]

A PET substrate (125 占 퐉 thickness) subjected to clear hard coating made by Kuraray Co., Ltd. was set in the production apparatus shown in Fig. 8, and trimethyl aluminum (TMA) was used as a raw material by Al atomic deposition (ALD) (Inorganic compound layer; ALD layer) was formed on the first gas barrier layer. The thickness of the inorganic compound layer (first gas barrier layer) was set to 10 nm. Film forming conditions were as follows.

The manufacturing apparatus and manufacturing conditions used in Comparative Example 1 will be described below.

[Device for producing first gas barrier layer]

Fig. 8 shows a schematic structure of an apparatus for producing a first gas barrier layer by the ALD method used in Comparative Example 1. Fig. As shown in Fig. 8, the first gas barrier layer production apparatus A according to the ALD method comprises a long PET substrate (125 占 퐉 thickness) 61 on which a clear hard coating made of bristle paper is applied and a first gas And a film forming portion for forming a barrier layer.

The manufacturing apparatus A further includes a plurality of unidirectional winders 71 disposed between the winder 75 and the winder 75 for feeding the PET base 61 And a roller (72). The PET substrate 61 is provided as a roll and is set in the unwinder 71. When the unwinder 71 rolls the roll, the PET base 61 on which the plurality of rollers 72 are wound is successively transported to the film forming portion. The winder 75 is formed by winding a film obtained by forming the first gas barrier layer on the PET substrate 61 and forming a roll.

The film forming section forms a first gas barrier layer which is an inorganic compound layer on the long PET substrate 61 by the ALD method. In the ALD method using the manufacturing apparatus shown in Fig. 8, the raw material is modified by using the PEALD method, which is one kind of ALD method, by using plasma. As shown in Fig. 8, the film forming section is provided with two raw material supplying sections 81 and 82 and a reforming processing section 83. As shown in Fig. The film forming section has a purge section between the raw material supply section 81 and the reforming section 83 and between the raw material supply section 82 and the reforming section 83, respectively. The raw material supply parts 81 and 82 and the reforming part 83 are adjusted by a vacuum pump or the like under vacuum.

A partition plate is disposed between each of the raw material supply units 81 and 82, the reforming unit 83 and the two purge units. The partition plates provide the raw material supply units 81 and 82, the reforming unit 83, Chambers C1 to C4 are formed. The partition plate is provided with an opening on the transport path of the PET substrate 61 so that the partition plate can pass through the long PET substrate 61 in each of the chambers C1 to C4.

The raw material supply parts 81 and 82 supply raw materials of the first gas barrier layer which is an inorganic compound layer into the chambers C1 and C2 in a gaseous state. The raw material is also called a precursor. In the chamber C1, the raw material supplied by the raw material supply portion 81 is adsorbed on the surface of the PET substrate 61. In the chamber C2, the surface of the PET substrate 61 is supplied by the raw material supply portion 82 The raw material is adsorbed.

The reforming processing section 83 supplies the reforming gas of the raw material supplied by the raw material supply sections 81 and 82 into the chamber C3 under the atmospheric pressure. The reforming processing section 83 supplies electric power to a pair of electrodes arranged so as to face each other with the PET substrate 61 sandwiched therebetween by means of an alternating current power source not shown to apply an alternating voltage to the reforming gas, P. The reforming processing section 83 reforms the raw material on the PET substrate 61 by the plasma P to form an atomic layer of the first gas barrier layer. The atomic layer of the first gas barrier layer may actually be a molecular layer of the compound.

In the PEALD method used in Comparative Example 1, a raw material is adsorbed on the PET substrate 61, and then a raw material is modified by using plasma to form a first gas barrier layer of a metal oxide. The first gas barrier layer is formed using a metal compound containing an aluminum (Al) element as a raw material. When the raw material supplied by the raw material supplying sections 81 and 82 is used as the first raw material and the raw material used as the reforming gas by the reforming processing section 83 is used as the second raw material, the first raw material and the second raw material are formed Is selected in accordance with the first gas barrier layer.

In Comparative Example 1, since the first gas barrier layer is an aluminum oxide film, trimethyl aluminum (Al (CH ₃ ) ₃ ) was used as the first raw material. As the second raw material, water vapor (H ₂ O) was used to oxidize the first raw material. The supply time of the first raw material was set to 0.1 second. The treatment time of the reforming treatment was 2 seconds. The temperature of the PET base material 61 when the first gas barrier layer was formed by the raw material supply parts 81 and 82 and the reforming part 83 was set at 75 캜.

The purge section supplies an inert gas into the chamber C4 and exhausts the surplus first raw material or the second raw material on the PET substrate 61 together with the inert gas. In Comparative Example 1, the inert gas refers to a gas having low reactivity with the first raw material or the second raw material, and nitrogen gas was used. The introduction time (purge time) of the inert gas for purging the first raw material and the second raw material was 2.0 seconds.

After the first raw material is supplied onto the PET substrate 61 by the raw material supply unit 81, the film forming unit performs the film forming process for supplying the second raw material by the raw material supply unit 82 to react with the first raw material, Thereby forming the one-atom layer of the first gas barrier layer on the PET substrate 61. [ The plurality of rollers 72 repeatedly transports the long PET substrate 61 to the two raw material supply portions 81 and 82 in order to repeat the film forming process for a plurality of cycles until the desired film thickness is obtained Respectively.

8, a first gas barrier layer, which is an inorganic compound layer, is formed on both sides of the PET substrate 61. In Comparative Example 1, on the other hand, only one side of the PET substrate 61 is covered with a film- The raw material supplying portion 81, the reforming portion 83, the raw material supplying portion 82, and the raw material supplying portion 81 are formed on the conveying path by the belt conveying instead of the roller conveying shown in Fig. 7, And the reforming treatment section 83 in this order to form a first gas barrier layer which is an inorganic compound layer only on one side.

[Conditions for producing the first gas barrier layer]

A thickness of 6 nm as a first gas barrier layer was formed as a first gas barrier layer on the PET substrate 61 according to the following film forming conditions using the production apparatus A which had been heated to 80 deg. C and subjected to degassing treatment for 3 hours under a reduced pressure of 0.01 Torr Aluminum oxide film was formed.

(Film forming conditions)

The first raw material of the aluminum oxide film: trimethyl aluminum

Supply time of the first raw material: 0.1 second

Reforming gas: water vapor

Processing time of the reforming process: 2.0 seconds

Inert gas used for purging: nitrogen gas

Purge time: 2.0 seconds

Deposition rate of aluminum oxide film: 0.1 nm / cycle

Transfer speed of base film: 8 m / min

Temperature of base film: 75 캜

[Formation of inorganic compound layer (second gas barrier layer) 19 (plasma CVD method of dry method)]

In order to form a second gas barrier layer (inorganic compound layer; CVD layer) containing Si atoms (silica) on the formed first gas barrier layer, a base material 2 6) was set in the manufacturing apparatus 31 (the vacuum chamber of the manufacturing apparatus 31 is not shown) as shown in Fig. 6, and was transported. Subsequently, a magnetic field is applied between the film-formation roller 39 and the film-formation roller 40, and electric power is supplied to the film-formation roller 39 and the film-formation roller 40, (40) to generate plasma. Subsequently, a mixed gas of a film forming gas (hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (also serving as a discharge gas) as a reaction gas was supplied to the discharge region thus formed, and a substrate (Inorganic compound layer, second gas barrier layer) containing Si atoms (silica) was laminated on the substrate 1 by a plasma CVD method to form a gas barrier film 111. The obtained inorganic compound layer 2 gas barrier layer) had a thickness of 150 nm. The deposition conditions were as follows.

(Film forming conditions)

Feed rate of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute, 0 ° C, 1 atmospheric pressure)

Oxygen gas supply rate: 500 sccm (0 ° C, 1 atmospheric pressure)

Vacuum degree in vacuum chamber: 3 Pa

· Applied electric power from a plasma generating power source: 0.8 kW

Frequency of power supply for generating plasma: 70 kHz

Transfer speed of film (substrate): 1.0 m / min

[Evaluation of Composition of Interfaces between Upper and Lower Layers (First Gas Barrier Layer and Second Gas Barrier Layer) of Inorganic Compound Layer]

Using the X-ray photoelectron spectroscopy (XPS) and the sputtering apparatus, from the second gas barrier layer side of the outermost layer of the prepared gas barrier film 111, the total number of elements The ratio of Al element to Si element was determined. As shown in Fig. 1 (C), in the gas barrier film 111, a second gas barrier layer 19 containing Si in an upper layer formed by the plasma CVD method and a second gas barrier layer 19 A uniform interface 20 exists between the first gas barrier layer 18 containing one lower layer and the composition 20 is discontinuously changed in the thickness direction of the Al atomic layer in the interface 20. The amount of Al atoms in the lower layer 18 is substantially constant and the amount of Al atoms in the upper layer 19 is zero with the interface 20 interposed therebetween. Further, the second gas barrier layer 19 formed by the plasma CVD method and containing Si in the upper layer + the first gas barrier layer 18 containing Al formed in the lower layer formed by the ALD method, The amount of Al atoms on the opposite side (upper layer) is smaller than the amount of Al atoms on the substrate 12 (lower layer) side. The inclination of the film thickness of the gas barrier layer 18 + 19 of the upper and lower layers and the composition (at%) of the Al element (specifically, the depth by XPS to the gas barrier layer 18 + (Increase: +: decrease: -) from the substrate 12 side in the Al distribution curve among the distribution curves of the respective constituent elements based on the measurement of the element distribution in the direction of thickness ) Was -3.0at% / nm (in terms of SiO ₂ ) or less. That is, in the interface region, there was no region in which the composition was continuously changed in the thickness direction of the Al atoms such as the present invention.

[Element composition depth profile measurement method]

The composition ratio of the Al element and the Si element can be measured by the following method. That is, the composition profile of the second gas barrier layer 19 can be obtained by combining an Ar sputter etching apparatus and an X-ray photoelectron spectroscopy (XPS). The profile distribution in the depth direction can be calculated by obtaining the actual film thickness by the film processing by the FIB (converged ion beam) processing apparatus and the TEM (transmission electron microscope) and correlating with the result of XPS.

In each of the Examples and Comparative Examples of the present invention, the following apparatuses and methods were used.

(Sputter condition)

· Ion species: Ar ion

· Acceleration voltage: 1 kV

(X-ray photoelectron spectroscopic measurement condition)

Device: ESCALAB-200R manufactured by VG Scientific Co.

X-ray anode material: Mg

Output: 600 W (Acceleration voltage 15 kV, Emission current 40 mA)

Furthermore, the resolution of the measurement is 0.5 nm and is obtained by plotting the respective source consumption at each sampling point accordingly.

(FIB processing)

Device: SMI2050 manufactured by SII

· Processed ions: (Ga 30 kV)

(TEM observation)

Device: JEM2000FX (acceleration voltage: 200 kV) manufactured by Nihon Denshi Co.,

· Electron beam irradiation time: 5 seconds to 60 seconds

[Comparative Example 2] Production of gas barrier film 112

9 is a diagram schematically showing the layer structure of the gas barrier film of Comparative Example 2. Fig.

A first gas barrier layer 93 containing Si and a second gas barrier layer 94 containing Si are formed on the base material 92 shown in Fig. 9 to form a gas barrier film 112).

[Formation of inorganic compound layer (first gas barrier layer) (plasma CVD method of dry method)]

A PET substrate (125 占 퐉 thickness) which had been subjected to clear hard coating by Kuraray Co., Ltd. was set in a manufacturing apparatus 31 as shown in Fig. 6 and transported. Subsequently, a magnetic field is applied between the film-formation roller 39 and the film-formation roller 40, and electric power is supplied to the film-formation roller 39 and the film-formation roller 40, (40) to generate plasma. Subsequently, a mixed gas of a film forming gas (hexamethyldisiloxane (HMDSO) as a raw material gas and an oxygen gas (also serving as a discharge gas) as a reaction gas is supplied to the formed discharge region and plasma CVD is performed on the substrate 2 (Inorganic compound layer, first gas barrier layer) containing Si was formed on the substrate 1. The thickness of the first gas barrier layer (inorganic compound layer; CVD layer) was 150 nm. The film formation conditions were the same as those of the second gas barrier layer of the film 111. [

[Formation of second gas barrier layer (PHPS layer) (coating method)]

The preparation and film formation of the polysilazane-containing coating liquid were usually carried out in an atmospheric environment (specifically, an environment of 25 ° C and 60% RH).

(N, N, N ', N'-tetramethylpiperidine), which is a dibutyl ether solution containing 20 mass% of non-catalytic perhydropolysilazane (PHPS) (AZMaterials, 20% by mass of a dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAQUA (registered trademark) NAX120 (trade name) manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by mass of N, N'-tetramethyl-1,6-diaminohexane -20) were mixed at a ratio of 4: 1 (by mass ratio), and further mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane became 65:35. The solid content of the coating liquid (Concentration of polysilazane) was adjusted to 5% by mass to prepare coating liquid (1).

The coating liquid 1 obtained above was formed on the above inorganic compound layer (first gas barrier layer as a lower layer) with a spin coater so as to have a thickness (dry film thickness) of 150 nm, left for 2 minutes, Further heat treatment was performed on the hot plate for 1 minute to form a polysilazane coating film (precursor layer).

After forming the polysilazane coating film, a vacuum ultraviolet ray irradiation apparatus as shown in Fig. 7 was used and subjected to vacuum ultraviolet ray irradiation treatment so as to have a vacuum ultraviolet ray of 172 nm at 6 J / cm 2 according to the following method, (PHPS layer) was formed on the first gas barrier layer (inorganic compound layer; CVD layer) as a lower layer. Thus, the gas barrier film 112 was produced. The thickness of the second gas barrier layer (inorganic compound layer; PHPS layer) in the upper layer was 150 nm.

&Lt; Measurement of Vacuum Ultraviolet Irradiation Conditions and Irradiation Energy &

Vacuum ultraviolet irradiation was performed using the apparatus shown in the schematic diagram in Fig.

In Fig. 7, reference numeral 21 denotes an apparatus chamber. An appropriate amount of nitrogen and oxygen is supplied from a gas supply port (not shown) to the inside of the chamber and exhausted from a gas discharge port (not shown) Can be maintained at a predetermined concentration. Reference numeral 22 denotes an Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm, and reference numeral 23 denotes a holder for an excimer lamp also serving as an external electrode. Reference numeral 24 denotes a sample stage. The sample stage 24 can horizontally reciprocate within the apparatus chamber 21 at a predetermined speed by a moving means (not shown). Further, the sample stage 24 can be maintained at a predetermined temperature by a heating means (not shown). Reference numeral 25 denotes a sample having a polysilazane coating film formed thereon. When the sample stage moves horizontally, the height of the sample stage is adjusted so that the shortest distance between the coating layer surface of the sample and the excimer lamp tube surface is 6 mm. Reference numeral 26 denotes a shading plate, which prevents vacuum ultraviolet light from being irradiated onto the coated layer of the sample during aging of the Xe excimer lamp 22. [

The energy irradiated to the surface of the coating film in the vacuum ultraviolet irradiation process was measured using a sensor head of 172 nm using an ultraviolet ray spectrometer: C8026 / H8025 UV POWER METER manufactured by Hamamatsu Photonics. The sensor head was placed at the center of the sample stage 24 so that the shortest distance between the Xe excimer lamp tube surface and the measurement surface of the sensor head was 6 mm and the atmosphere in the apparatus chamber 21 was irradiated with vacuum ultraviolet rays And the sample stage 24 was moved at a speed of 0.5 m / min (V in FIG. 7) to measure the oxygen concentration. Prior to the measurement, in order to stabilize the illuminance of the Xe excimer lamp 22, the aging time was set for 10 minutes after the Xe excimer lamp was turned on, and then the sample stage was moved to start the measurement.

Based on the irradiation energy obtained in this measurement, the moving speed of the sample stage was adjusted to adjust the irradiation energy to 6000 mJ / cm 2. Further, at the time of irradiation with vacuum ultraviolet rays, after the aging for 10 minutes as in the case of measuring the irradiation energy.

[Evaluation of Composition of Interfaces between Upper and Lower Layers (First Gas Barrier Layer and Second Gas Barrier Layer) of Inorganic Compound Layer]

The depth profile of the film composition was measured from the side of the outermost second-layer gas barrier layer 94 of the prepared gas-barrier film 112 according to the above-described element composition depth profile measurement method. 10 is a diagram showing distribution curves of respective constituent elements based on measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy for all gas barrier layers of the gas-barrier film obtained in Comparative Example 2. Fig. 10, in the gas barrier film 112, the gas barrier layers 93 and 94 of the upper and lower layers shown in Fig. 9 each had a composition containing no aluminum component.

[Example 1] Production of gas barrier film 113

11A schematically shows a layer configuration before the second gas barrier precursor layer as a lower layer and the third gas barrier precursor layer as an upper layer which are formed in the production process of the gas barrier film of Examples 1 and 2 are modified Fig. Fig. 11 (B) is a diagram schematically showing the layer structure of the gas barrier film of Examples 1 and 2. Fig. The reason for forming the second gas barrier precursor layer as the lower layer and the third gas barrier precursor layer as the upper layer is to form an integral reformed gas barrier layer in which the upper and lower layers are not distinguished. The layer constructions of the gas barrier films of Examples 1 and 2 are the same (only the vacuum ultraviolet ray irradiation amount when forming the second gas barrier layer is different).

In Example 1, in the production of the gas-impermeable film 112 of Comparative Example 2, a second gas barrier layer containing Si as the lower layer and a second gas barrier layer containing Al as the upper layer were formed on the first gas- The gas barrier film 113 was prepared in the same manner as in the production of the gas barrier film 112 except that the gas barrier film 112 was laminated and modified by ultraviolet irradiation. 11A, a first gas barrier layer 133, a gas barrier layer 134 containing Si as a lower layer, and a gas barrier layer 134 containing a lower layer are formed on a substrate 132 in a manufacturing process, A third gas barrier precursor layer (polysilazane film) 135 containing Al is laminated and modified by vacuum ultraviolet light to form a gas barrier layer on the substrate 132 A gas barrier film 113 having an integral reforming gas barrier layer 136 having no upper and lower layers (without a uniform &quot; interface &quot;) was fabricated on the first gas barrier layer 133 .

Hereinafter, the process (manufacturing method) until the formation of the first gas barrier layer 133 on the base material 132 is the same as the production (method) of the gas barrier film 112 of the comparative example 2, The description is omitted.

[Formation of inorganic compound layer (second gas barrier layer containing Si in the lower layer) (Coating film formation method)]

The second gas barrier layer 134 containing Si in the lower layer was formed by forming the following coating liquid 3. In addition, the liquid preparation operation was performed in a nitrogen glove box having a water concentration of 10 ppm or less.

(N, N, N ', N'-tetramethylpiperidine), which is a dibutyl ether solution containing 20 mass% of non-catalytic perhydropolysilazane (PHPS) (AZMaterials, 20% by mass of a dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAQUA (registered trademark) NAX120 (trade name) manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by mass of N, N'-tetramethyl-1,6-diaminohexane -20) were mixed at a ratio of 4: 1 (by mass ratio), and further mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane became 65:35. The solid content of the coating liquid (Concentration of polysilazane) was adjusted to 2.7% by mass to give a coating liquid (3).

The coating liquid 3 obtained above was formed on the first gas barrier layer 133 by a spin coater and allowed to stand for 2 minutes and then subjected to an additional heat treatment on a hot plate at 100 DEG C for 1 minute to obtain a polysilazane coating film (Second gas barrier precursor layer; not shown) was formed.

After the polysilazane coating film (second gas barrier precursor layer) was formed, the above-described excimer irradiation apparatus shown in Fig. 7 was used, and vacuum ultraviolet ray irradiation treatment was performed so that a vacuum ultraviolet ray of 172 nm was 6 J / The second gas barrier layer 134 as the lower layer is formed (laminated) on the first gas barrier layer (inorganic compound layer) 132, as shown in Fig. 11 (A). The thickness of the second gas barrier layer (inorganic compound layer) was 80 nm.

[Formation of a third gas barrier precursor layer and a reformed gas barrier layer (inorganic compound layer) in an upper layer (Coating film formation method)]

The formation of the upper third Al-containing gas barrier precursor layer 135 and the subsequent modified gas barrier layer (inorganic compound layer) 136 (FIG. 11 (B)) shown in FIG. 11 , And ALCH (aluminum ethylacetoacetate diisopropylate, manufactured by Kawaken Fine Chemicals Co., Ltd.) was diluted with ethanol to 1.3% by mass to prepare a coating liquid (4). In addition, the liquid preparation operation was performed in a nitrogen glove box having a water concentration of (10 ppm) or less.

The coating liquid 4 obtained above was formed on the second gas barrier layer 134 by a spin coater and allowed to stand for 2 minutes and then subjected to an additional heat treatment for 1 minute on a hot plate at 100 DEG C to form an ALCH coating film 3 gas barrier precursor layer) 135 were formed. The thickness of the upper ALCH coating film (third gas barrier precursor layer) 135 was 40 nm.

After forming the ALCH coating film (third gas barrier precursor layer) 135, a vacuum ultraviolet ray irradiation treatment is performed so that the vacuum ultraviolet ray of 172 nm is 3 J / cm 2 in the same manner as the above-mentioned method, Respectively.

2, the slope between the film thickness of the reformed gas barrier layer and the composition (at%) of the Al element (specifically, the element distribution in the depth (film thickness) direction by the XPS to the reformed gas barrier layer) (Inclination of a region continuously changed (indicated by "+", decrease: "-") continuously from the substrate side in the Al distribution curve among the distribution curves of the respective constituent elements based on the measurement) is + 2.3 at% Nm (in terms of SiO ₂ ). The gradient of the film thickness of the reformed gas barrier layer 146 and the composition (at%) of the Si element (specifically, the element distribution in the depth (film thickness) direction by the XPS with respect to the reformed gas barrier layer 146) (Increase: "+", decrease: "-") continuously from the base material 142 side in the Si distribution curve among the distribution curves of the respective constituent elements based on % / Nm (in terms of SiO ₂ ).

2, it can be seen that the Al distribution curve and the Si distribution curve with respect to the total amount (100 at%) of all the elements in the reformed gas barrier layer 136 have a region where Al atoms and Si atoms cross each other . The region where the Al atoms and the Si atoms cross each other is located in the intermediate region of the reformed gas barrier layer 136 (near the interface between the second gas barrier layer 134 and the third gas barrier precursor layer 135, As shown in Fig.

2, it can be seen that all the elements in the modified gas barrier layer 136 are Al atoms, Si atoms, O atoms, N atoms and C atoms.

[Example 2] Production of gas barrier film 114

In the production of the gas barrier film (112) of Comparative Example 2, a second gas barrier layer containing Si below and a gas barrier precursor layer containing Al as the upper layer And a gas barrier film 114 was prepared in the same manner as in the production of the gas barrier film 112 except that the film was laminated and modified by ultraviolet irradiation. 11A, a first gas barrier layer 133, a gas barrier layer 134 containing Si as a lower layer, and a gas barrier layer 134 containing a lower layer are formed on a substrate 132 in a manufacturing process, A third gas barrier precursor layer (polysilazane film) 135 containing Al is laminated and modified by vacuum ultraviolet light to form a gas barrier layer on the substrate 132 Gas barrier film 114 having an integral reforming gas barrier layer 136 having no upper and lower layers (without a uniform &quot; interface &quot;) on the first gas barrier layer 133 .

Hereinafter, the process (manufacturing method) until the formation of the first gas barrier layer 133 on the base material 132 is the same as the production (method) of the gas barrier film 112 of the comparative example 2, The description is omitted.

[Formation of inorganic compound layer (second gas barrier layer containing Si in the lower layer) (Coating film formation method)]

The second gas barrier layer 134 containing Si in the lower layer was formed by forming the following coating liquid 3. In addition, the liquid preparation operation was performed in a nitrogen glove box having a water concentration of 10 ppm or less.

(N, N, N ', N'-tetramethylpiperidine), which is a dibutyl ether solution containing 20 mass% of non-catalytic perhydropolysilazane (PHPS) (AZMaterials, 20% by mass of a dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAQUA (registered trademark) NAX120 (trade name) manufactured by AZ Electronic Materials Co., Ltd.) containing 5% by mass of N, N'-tetramethyl-1,6-diaminohexane -20) were mixed at a ratio of 4: 1 (by mass ratio), and further mixed so that the mass ratio of dibutyl ether to 2,2,4-trimethylpentane was 65:35. The solid content of the coating liquid (Concentration of polysilazane) was adjusted to 2.7% by mass to give a coating liquid (3).

The coating liquid 3 obtained above was formed on the first gas barrier layer 133 by a spin coater and allowed to stand for 2 minutes and then subjected to additional heat treatment on a hot plate at 100 DEG C for 1 minute to obtain a polysilazane coating film A second gas barrier precursor layer (not shown) was formed.

After the polysilazane coating film (second gas barrier precursor layer) was formed, vacuum ultraviolet irradiation treatment was performed so that the vacuum ultraviolet of 172 nm was 3 J / cm 2 in the same manner as the above-mentioned method, As shown in the figure, the lower second gas barrier layer 134 is formed (laminated) on the first gas barrier layer (inorganic compound layer) 132. The thickness of the second gas barrier layer (inorganic compound layer) was 80 nm. As shown in Figs. 3 and 11A, the first gas barrier layer (inorganic compound layer) 133 and the second gas barrier layer (inorganic compound layer) 2, the interface between the first gas barrier layer (inorganic compound layer) 133 and the second gas barrier layer (inorganic compound layer) 134 is the same as that of the vacuum ultraviolet ray It does not disappear even after investigation.

[Formation of a third gas barrier precursor layer and a reformed gas barrier layer (inorganic compound layer) in an upper layer (Coating film formation method)]

The formation of the upper third Al-containing gas barrier precursor layer 135 and the subsequent modified gas barrier layer (inorganic compound layer) 136 (FIG. 11 (B)) shown in FIG. 11 , And ALCH (aluminum ethylacetoacetate diisopropylate, manufactured by Kawaken Fine Chemicals Co., Ltd.) was diluted to 1.3% by mass with dibutyl ether to give a coating liquid (4). In addition, the liquid preparation operation was performed in a nitrogen glove box having a water concentration of 10 ppm or less.

The coating liquid 4 obtained above was formed on the second gas barrier layer 134 by a spin coater and allowed to stand for 2 minutes and then subjected to an additional heat treatment for 1 minute on a hot plate at 100 캜 to obtain an ALCH coating film Gas barrier precursor layer) 135 were formed. The thickness of the upper ALCH coating film (third gas barrier precursor layer) 135 was 40 nm.

After the formation of the ALCH coating film (third gas barrier precursor layer) 135, vacuum ultraviolet ray irradiation treatment was performed so as to have a vacuum ultraviolet ray of 172 nm at 3 J / cm 2 in the same manner as the above- The first gas barrier layer 133 (third gas barrier precursor layer) 135 and the second gas barrier layer 134 as the lower layer are modified as shown in Fig. 11 (B) (Specifically, a reformed gas barrier layer having at least Al atoms and Si atoms; an inorganic compound layer) 136 having no upper and lower layers (without a uniform &quot; interface &quot;), Was prepared. That is, by irradiating vacuum ultraviolet rays, the ALCH coating film (third gas barrier precursor layer) 135 containing Al in the upper layer is modified into a structure having gas barrier properties, and the second gas containing Si in the lower layer By modifying the interface region with the barrier layer (inorganic compound layer) 134, an integral reformed gas barrier layer 136 having no distinction between the upper and lower layers formed with the modified regions in which the intermediate regions of the upper and lower layers reliably cross each other is formed Respectively. In this way, the gas barrier film 114 was produced.

(Evaluation of the composition of the intermediate region (near the interface between the upper and lower inorganic compound layers existing in the manufacturing process) of the reformed gas barrier layer 136 without upper and lower layers (no interface)

The depth profile of the film composition was measured from the modified gas barrier layer 136 side of the prepared gas barrier film 114 according to the above-described element composition depth profile measurement method. 3 is a diagram showing distribution curves of respective constituent elements based on measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy for all gas barrier layers of the gas barrier film obtained in Example 2. Fig.

3, in the gas barrier film 114, the reformed gas barrier layer 136 has Al atoms and Si atoms, and in the middle region of the reformed gas barrier layer 136 (In the vicinity of the interface between the existing second gas barrier layer 134 and the third gas barrier precursor layer 135), the composition of the Al atoms increases continuously in the layer thickness direction have. It can be seen that the amount of Al atoms on the side of the modified gas barrier layer 136 opposite to the base material 132 side is larger than the amount of Al atoms on the substrate 132 side. The slope of the film thickness of the reformed gas barrier layer 136 and the composition (at%) of the Al element (specifically, the element distribution in the depth (film thickness) direction by the XPS to the reformed gas barrier layer 136) (Increase of "+" and decrease of "-") from the base material 132 side in the Al distribution curve among the distribution curves of the respective constituent elements based on the slope of + 1.8at % / Nm (in terms of SiO ₂ ). The gradient of the film thickness of the reformed gas barrier layer 146 and the composition (at%) of the Si element (specifically, the element distribution in the depth (film thickness) direction by the XPS with respect to the reformed gas barrier layer 146) (Increase of "+" and decrease of "-") from the substrate 142 side in the Si distribution curve among the distribution curves of the respective constituent elements based on the slope of -2.5at % / Nm (in terms of SiO ₂ ).

It can also be seen from Fig. 3 that the Al distribution curve and the Si distribution curve with respect to the total amount (100 at%) of all the elements in the modified gas barrier layer 136 have a region where Al atoms and Si atoms cross each other. The region where the Al atoms and the Si atoms intersect is located in the intermediate region of the reformed gas barrier layer 136 (the interface region between the second gas barrier layer 134 and the third gas barrier precursor layer 135, ).

3, it can be seen that all the elements in the modified gas barrier layer 136 are Al atoms, Si atoms, O atoms, N atoms and C atoms.

[Example 3] Production of gas barrier film 115

12A is a diagram schematically showing the layer structure before the second gas barrier precursor layer as the lower layer and the third gas barrier precursor layer as the upper layer which are formed in the process of manufacturing the gas barrier film of Example 3 are modified to be. 12B is a diagram schematically showing the layer structure of the gas barrier film of Example 3. Fig. The reason why the second gas barrier precursor layer is the lower layer and the third gas barrier precursor layer is the upper layer is that the upper and lower layers form an integral reformed gas barrier layer without any distinction.

In the fabrication of the gas barrier film 114 of Example 2, a polysilazane coating film (second gas barrier precursor layer) was formed without forming the second gas barrier layer, and vacuum ultraviolet rays of 172 nm After the polysilazane coating film (second gas barrier precursor layer) was left for 2 minutes without irradiation, the substrate was further subjected to a heat treatment for 1 minute on a hot plate at 100 ° C, and an ALCH coating film (third gas Barrier film 115 was fabricated in the same manner as in the production of the gas barrier film 114 except that the barrier film was formed on the substrate Omitted). 12A, a first gas barrier layer 143, a second gas barrier precursor layer 144 containing a lower Si layer, and a second gas barrier precursor layer 144 are formed on a substrate 142, A third gas barrier precursor layer (polysilazane coating film) 145 containing Al as the upper layer is laminated and irradiated with vacuum ultraviolet light (in detail, vacuum ultraviolet light of 172 nm is irradiated with vacuum ultraviolet light so as to be 3 J / (Specifically, on the first gas barrier layer 143) as shown in Fig. 12 (B) by modifying the upper and lower layers collectively A gas barrier film 115 having an integral reforming gas barrier layer 146 (without a uniform &quot; interface &quot;) was prepared.

(Evaluation of composition of the middle region of the reformed gas barrier layer 146 having no distinction between the upper and lower layers (no interface) (near the interface between the upper and lower inorganic compound layers (the precursor layers) present in the manufacturing process)

The depth profile of the film composition was measured from the modified gas barrier layer 146 side of the prepared gas barrier film 115 according to the above-described element composition depth profile measurement method. 4 is a view showing distribution curves of respective constituent elements based on measurement of element distribution in the depth direction by X-ray photoelectron spectroscopy for all gas barrier layers of the gas barrier film obtained in Example 3. Fig.

4, in the gas barrier film 115, the reformed gas barrier layer 146 has Al atoms and Si atoms, and in the middle region of the reformed gas barrier layer 146 (In the vicinity of the interface between the second gas barrier precursor layer 144 and the third gas barrier precursor layer 145 that existed), the Al atoms are continuously grown in the layer thickness direction . It can be seen that the amount of Al atoms on the side of the modified gas barrier layer 136 opposite to the substrate 132 side is larger than the amount of Al atoms on the substrate 142 side. The slope of the film thickness of the reformed gas barrier layer 146 and the composition (at%) of the Al element (specifically, the element distribution in the depth (film thickness) direction by the XPS to the reformed gas barrier layer 146) (Increase of "+", slope of "-") continuously from the base material 142 side in the Al distribution curve among the distribution curves of the respective constituent elements based on the slope of +0.6 at % / Nm (in terms of SiO ₂ ). The gradient of the film thickness of the reformed gas barrier layer 146 and the composition (at%) of the Si element (specifically, the element distribution in the depth (film thickness) direction by the XPS with respect to the reformed gas barrier layer 146) (Increase: "+", decrease: "-") from the substrate 142 side in the Si distribution curve among the distribution curves of the respective constituent elements based on the slope of -0.8at % / Nm (in terms of SiO ₂ ).

4, it can be seen that the Al distribution curve and the Si distribution curve for the total amount (100 at%) of the total elements in the modified gas barrier layer 146 have a region where Al atoms and Si atoms cross each other . The region where the Al atoms and the Si atoms intersect is located in the intermediate region of the reformed gas barrier layer 146 (the interface between the second gas barrier precursor layer 144 and the third gas barrier precursor layer 145, ).

4, it can be seen that all the elements in the modified gas barrier layer 146 are Al atoms, Si atoms, O atoms, N atoms and C atoms.

"Evaluation of water vapor barrier property (humid heat resistance) under high temperature and high humidity"

The gas barrier films 111 to 115 prepared above were exposed for 500 hours under high temperature and high humidity conditions of 85 캜 and 85% RH, and samples were respectively prepared after the deterioration test. For each gas barrier film before and after the deterioration, the water vapor barrier property was evaluated by the calcium method as shown below. Concretely, when the calcium element having the metal calcium film formed to a thickness of 80 nm as described below is allowed to react with the metal calcium at a temperature of 60 DEG C and 90% RH and the water vapor permeated through the gas-barrier film, % (Calcium deterioration time), respectively (see below).

The following steam barrier properties were evaluated before and after the deterioration test to determine the retention ratio. As an indicator of the maintenance rate, 70% or more is acceptable and less than 70% is not. The retention ratio (%) was calculated from the calcium deterioration time before and after the deterioration test by the following formula.

(Metal calcium film forming apparatus)

Deposition apparatus: vacuum deposition apparatus JEE-400 manufactured by Nihon Denshi Co., Ltd.

· Constant temperature and humidity oven: Yamato Humidic Chamber IG47M

(Raw materials)

· Metal corroded by reacting with moisture: calcium (granular)

· Water vapor impermeable metal: aluminum (particle diameter (φ) 3 to 5 mm, granularity, manufactured by Kajunko Kagaku Kenkyusho Co., Ltd.)

(Preparation of water vapor barrier property evaluation sample)

The surface of the outermost surface gas barrier layer or the surface of the reformed gas barrier layer of the produced gas barrier films 111 to 115 was passed through a mask to form a film having a thickness of 12 mm And metal calcium was deposited in a size of 占 12 mm. At this time, the deposition film thickness was set to 80 nm.

Thereafter, the mask was removed as it was in a vacuum state, and aluminum was vapor deposited on the entire one side of the sheet to temporarily seal it. Subsequently, the vacuum state was released, and the substrate was quickly moved to a dry nitrogen gas atmosphere, and quartz glass having a thickness of 0.2 mm was bonded to the vapor-deposited aluminum surface through a sealing UV curable resin (manufactured by Nagase Chemtech) The resins were cured and bonded to each other and then sealed to obtain samples for evaluating water vapor barrier properties.

Each of the obtained samples was stored under high temperature and high humidity at 60 DEG C and 90% RH, and the state of metal calcium being corroded with respect to the storage time was observed. Observation was made by linearly interpolating the time (calcium deterioration time) at which the metal calcium-corroded area of the metal calcium deposition area of 12 mm x 12 mm became 50% from the observation results.

The samples before and after the deterioration test were similarly evaluated, and the retention ratio (%) was determined according to the following formula.

&Quot; (2) &quot;

In Examples 1 and 2 in Table 1, the second gas barrier layer in the lower layer and the third gas barrier layer (precursor layer) in the upper layer were irradiated with vacuum ultraviolet rays under the conditions shown in the third gas barrier layer, It is an integral reforming gas barrier layer. Therefore, the compositional gradient of the interfacial Al element actually shows the compositional gradient of the Al element in the middle region (region A) of the reformed gas barrier layer.

In Example 3 of Table 1, the second gas barrier layer (the precursor layer) as the lower layer and the third gas barrier layer (the precursor layer) as the upper layer were subjected to vacuum ultraviolet irradiation under the conditions shown in the third gas barrier layer, The reformed gas barrier layer is an integral reformed gas barrier layer without any distinction of layers. Therefore, the compositional gradient of the interfacial Al element actually shows the compositional gradient of the Al element in the middle region (region A) of the reformed gas barrier layer.

As apparent from the above Table 1, the gas barrier films 113 to 112 produced according to Examples 1 to 3 of the present invention, compared with the existing gas barrier films 111 to 112 produced by Comparative Examples 1 and 2, To 115) exhibit excellent storage stability under a severe condition (high temperature and high humidity conditions), with almost no deterioration of gas barrier property accompanying composition change (with a high retention rate) even after prolonged exposure under high temperature and high humidity .

In comparison with the gas barrier films 113 to 115 produced in Examples 1 to 3 of the present invention, as shown in Example 2, the second gas barrier precursor layer as the lower layer is referred to as the second gas barrier film (High retention ratio) higher than 6 J / cm 2 (Example 1) and 0 J / cm 2 (Example 3: batch reforming) can be obtained when the ultraviolet ray irradiation amount when the ultraviolet ray is modified by 3 J / have.

&Quot; Fabrication of organic thin film electronic devices &quot;

Organic EL devices as organic thin film electronic devices were produced using the gas barrier films (111 to 115) obtained in Comparative Examples 1 to 3 and Examples 1 to 3 as sealing films.

[Production of organic EL device]

(Formation of first electrode layer)

ITO (indium tin oxide) having a thickness of 150 nm was formed on the outermost layer (the second gas barrier layer or the reformed gas barrier layer) of each gas-barrier film by the sputtering method and patterning was carried out by photolithography, One electrode layer was formed. The pattern was a pattern in which the light emitting area was 50 mm square.

(Formation of hole transport layer)

The following coating liquid for forming the hole transport layer was applied on the first electrode layer of each gas barrier film having the first electrode layer formed thereon by an extrusion coater under the environment of 25 ° C and a relative humidity of 50% Drying and heating treatment were performed to form a hole transporting layer. The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

Prior to application of the coating liquid for forming the hole transport layer, the cleaning surface modification treatment of each gas-barrier film was carried out using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm 2 and a distance of 10 mm. The electrification elimination treatment was carried out using electric power by weak X-rays.

&Lt; Preparation of coating liquid for forming hole transport layer >

PEDOT / PSS 30% by volume, pure water 65% by volume, methanol 5% by volume) diluted with pure water and methanol (polyethylene content: Was prepared as a coating liquid for forming a hole transport layer.

&Lt; Conditions for drying and heat treatment >

After the application liquid for forming the hole transport layer was applied, the solvent was removed toward the film formation surface at a height of 100 mm, a discharge air velocity of 1 m / s, a wind velocity distribution of width of 5% and a temperature of 100 ° C, When the temperature was 150 deg. C, heat treatment in an electric heating system was performed to form a hole transporting layer.

(Formation of light emitting layer)

The following coating liquid for forming a white light emitting layer was applied on the above-described hole transporting layer by an extrusion coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. The coating liquid for forming a white light emitting layer was applied so that the thickness after drying was 40 nm.

&Lt; Coating liquid for forming white light emitting layer &

1.0 g of a compound represented by the formula HA as a host material, 100 mg of a compound represented by the following formula (D) as a dopant, 0.2 mg of a compound represented by the following formula (DB) as a dopant, Was dissolved in 100 mg of toluene to prepare a coating liquid for forming a white light emitting layer.

<Coating Conditions>

The coating process was carried out at an application temperature of 25 캜 and a coating rate of 1 m / min in an atmosphere having a nitrogen gas concentration of 99% or more.

&Lt; Conditions for drying and heat treatment >

After applying the coating liquid for forming a white light emitting layer, the solvent was removed toward the film formation surface at a height of 100 mm, a discharge air velocity of 1 m / s, a wind speed distribution of 5% at a width of 5%, a temperature of 60 캜, Was performed to form a light emitting layer.

(Formation of electron transport layer)

The following coating liquid for forming an electron transport layer was applied on the above-formed light emitting layer by an extrusion coater under the following conditions, and then subjected to drying and heat treatment under the following conditions to form an electron transport layer. The coating liquid for forming the electron transport layer was applied so that the thickness after drying was 30 nm.

<Coating Conditions>

In the application step, the application temperature of the coating solution for forming an electron transport layer was set to 25 캜 and the application speed was 1 m / min in an atmosphere having a nitrogen gas concentration of 99% or more.

&Lt; Coating liquid for forming electron transport layer >

The electron transporting layer was prepared by dissolving the compound represented by the following formula (E-A) in 2,2,3,3-tetrafluoro-1-propanol to prepare a 0.5 mass% solution to prepare a coating liquid for forming an electron transport layer.

&Lt; Conditions for drying and heat treatment >

After the application liquid for forming the electron transport layer was applied, the solvent was removed toward the film formation surface at a height of 100 mm, a discharge air velocity of 1 m / s, a wind speed distribution of 5% at a width of 60%, and a temperature of 200 Lt; 0 &gt; C to form an electron transporting layer.

(Formation of electron injection layer)

An electron injection layer was formed on the electron transport layer formed above. First, the substrate was placed in a decompression chamber, and the pressure was reduced to 5 10 ^-4 Pa. In advance, cesium fluoride prepared in a tantalum deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of Second Electrode)

Aluminum was used as the second electrode forming material under a vacuum of 5 10 ^-4 Pa above the electron injecting layer formed above and except for the portion serving as the extraction electrode of the first electrode 22, A mask pattern was formed so as to have an electrode with a light emitting area of 50 mm square by vapor deposition, and a second electrode having a thickness of 100 nm was laminated.

(Foundation)

As described above, the respective stacked bodies up to the second electrode were again moved in a nitrogen atmosphere and cut with a ultraviolet laser at a specified size to produce an organic EL device.

(Electrode lead connection)

A flexible printed circuit board (base film: polyimide 12.5 占 퐉, rolled copper foil 18 占 퐉, coverlay: polyimide 12.5 占 퐉, and a surface of polyimide) was formed on the resulting organic EL device by using an anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Treated NiAu plating) was connected.

Compaction conditions: Compression was performed at a temperature of 170 占 폚 (ACF temperature 140 占 폚 as measured using a separate thermocouple) and a pressure of 2 MPa for 10 seconds.

(Sealed)

As a sealing member, a polyethylene terephthalate (PET) film (12 탆 thick) was laminated to a 30 탆 thick aluminum foil (manufactured by Toyo Aluminum Co., Ltd.) using an adhesive for dry lamination (a two-component reaction type urethane adhesive) Thickness of the adhesive layer: 1.5 mu m).

A thermosetting adhesive agent was uniformly applied on the aluminum surface of the prepared sealing member along the adhesive surface (glossy surface) of the aluminum foil to a thickness of 20 mu m using a dispenser to form an adhesive layer.

At this time, as the thermosetting adhesive, an epoxy adhesive containing each component of bisphenol A diglycidyl ether (DGEBA), dicyandiamide (DICY), and epoxy adduct type curing accelerator was used.

The sealing member was tightly sealed with a compression roll at a compression roll temperature of 120 占 폚, a pressure of 0.5 MPa, and an apparatus speed of 0.3 m / min by using a pressing roll so as to cover the junction of the extraction electrode and the electrode lead.

&Quot; Evaluation of organic EL device &quot;

The thus-prepared organic EL device was evaluated for durability according to the following method.

[Evaluation of durability]

(Acceleration deterioration processing)

Each of the prepared organic EL devices was subjected to accelerated deterioration treatment for 500 hours under an environment of 85 캜 and 85% RH, and then evaluated for the following dark spots.

(Evaluation of dark spots (DS, black spots)

A current of 1 mA / cm &lt; 2 &gt; was applied to the organic EL device subjected to the accelerated deterioration treatment, and the light was continuously emitted for 24 hours. A portion was enlarged and a photograph was taken. The photographed image was cut out to a size corresponding to 2 mm square and the area ratio of dark spots was determined. The durability was evaluated according to the following criteria. When the evaluation grade is?, It is judged to be a practical property, a more practical property if?, And a preferable property having no problem if it is?.

◎: Dark spot occurrence rate is less than 0.3%

○: Dark spot occurrence rate is 0.3% or more and less than 1.0%

?: Dark spot occurrence rate is 1.0% or more and less than 2.0%

X: Dark spot occurrence rate is 2.0% or more

The evaluation results of the dark spots are shown in Table 2 below.

As is clear from Table 2, the gas barrier film produced by the embodiment of the present invention is used as a sealing film of an organic EL element, and even when exposed to an environment of 85 ° C and 85% RH, The effect of decreasing the generation of gas is remarkable, and it can be seen that the gas barrier property is very high.

In Examples 1 to 3, the gas barrier layers (upper and lower layers) of the gas barrier layers (upper and lower layers) were subjected to vacuum ultraviolet ray irradiation treatment separately, (Example 3) obtained by batch reforming by a single vacuum ultraviolet ray irradiation treatment can obtain a good evaluation result (DS generation rate is small). Further, the modified gas barrier layer (Example 3) which was formed by reforming in a batch by vacuum ultraviolet ray irradiation treatment more than the modified gas barrier layer (Examples 1 and 2) separately formed by modifying by vacuum ultraviolet ray irradiation treatment Can be fabricated in a shorter process because the number of times of the vacuum ultraviolet ray irradiation treatment is at least sufficient. Thus, it can be seen that it is excellent also from the viewpoint of productivity (mass productivity).

The present application is based on Japanese Patent Application No. 2014-108556 filed on May 26, 2014, the disclosure of which is incorporated herein by reference.

1: Gas barrier film
2, 12, 92, 110, 132, 142:
3, 133, 143: the first gas barrier layer
11, 113, 114 and 115: The gas barrier film
11 ', 111, 112: Conventional gas barrier film
13: layer composed of lower polysilazane
14: A layer containing an aluminum compound in the upper layer
15: Vacuum ultraviolet light
16: modified region (continuously changing region of Al atoms)
17, 136, and 146: An integrated reforming gas barrier layer (not having a uniform interface) with no distinction between upper and lower layers
18: Aluminum-containing layer in the lower layer
19: Gas barrier layer containing Si in the upper layer
20: a uniform interface in which the intermediate regions of the upper and lower layers do not substantially cross each other
21: Device chamber
22: Xe excimer lamp
23: holder of an excimer lamp which also serves as an external electrode
24: sample stage
25: Layered sample
26: Shading plate
31: Manufacturing apparatus
32: delivery roller
33, 34, 35, 36: conveying rollers
39, 40: Deposition rollers
41: gas supply pipe
42: Power source for generating plasma
43, 44: magnetic field generator
45: take-up roller
61: PET substrate with clear hard coating
71: Un Winder
72: Roller
75: Winder
81 and 82:
83:
93: a first gas barrier layer containing Si
94: a second gas barrier layer containing Si
101: Plasma CVD apparatus
102: Vacuum tank
103: cathode electrode
105: susceptor
106: Heat medium circulation system
107: Vacuum exhaust system
108: Gas introduction system
109: High frequency power source
134: gas barrier layer containing Si in the lower layer
135, and 145: a third gas barrier precursor layer (polysilazane coating film) containing Al in the upper layer,
144: a second gas barrier precursor layer containing Si in the lower layer
160: Heating and cooling device
C1 to C4: chamber
P: Plasma

Claims (7)

A gas barrier film having a gas barrier layer having at least Al atoms and Si atoms on a substrate,
A distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and a distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, In the Al distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer,
The Al atoms of the gas barrier layer have regions in which the composition continuously changes in the layer thickness direction,
Wherein the amount of Al atoms on the side opposite to the substrate side of the gas barrier layer is larger than the amount of Al atoms on the substrate side. The method according to claim 1,
Wherein the gas barrier layer has a region in which the Al atoms continuously increase from the substrate side. 3. The method of claim 2,
Characterized in that, in the Al distribution curve, the region continuously increasing from the substrate side has a slope of not less than 0.5 at% / nm (in terms of SiO ₂ ) and not more than _{2 at} % / nm (in terms of SiO ₂ ) Barrier film. 4. The method according to any one of claims 1 to 3,
Wherein all the elements in the gas barrier layer are Al atoms, Si atoms, O atoms, N atoms, and C atoms. 5. The method according to any one of claims 1 to 4,
A distance from the surface of the gas barrier layer in the layer thickness direction of the gas barrier layer and a distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, The region continuously decreasing from the substrate side in the Si distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer has a slope of -2 at% / nm (in terms of SiO ₂ ) Gas barrier film. 6. The method according to any one of claims 1 to 5,
Wherein the gas barrier film has a region where Al atoms and Si atoms intersect in an Al distribution curve and an Si distribution curve with respect to the total amount (100 at%) of all the elements in the gas barrier layer. An electronic device, characterized by using the gas barrier film according to any one of claims 1 to 6.

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