WO2019065020A1

WO2019065020A1 - Gas barrier film

Info

Publication number: WO2019065020A1
Application number: PCT/JP2018/031245
Authority: WO
Inventors: 望月　佳彦
Original assignee: 富士フイルム株式会社
Priority date: 2017-09-27
Filing date: 2018-08-23
Publication date: 2019-04-04
Also published as: CN111065514A; JP6840255B2; JPWO2019065020A1; CN111065514B

Abstract

The present invention addresses the problem of providing a gas barrier film having excellent bending resistance, transparency, productivity and the like and also having sufficient gas barrier performance and high-temperature/high-humidity resistance. The gas barrier film has at least one set of a combination of an inorganic layer and a mixed layer, wherein the inorganic layer contains silicon nitride and has a thickness of 2 to 15 nm, the mixed layer contains the component for the inorganic layer and also contains a component for a layer corresponding to a surface on which the inorganic layer is formed, and has a thickness of 2 to 25 nm, and the N/Si atom ratio in the inorganic layer is 0.7 to 0.97.

Description

Gas barrier film

The present invention relates to a gas barrier film which is excellent in bending resistance and transparency.

BACKGROUND ART A gas barrier film is used to protect elements such as solar cells, organic electroluminescent elements, and illumination devices using quantum dots, which are deteriorated by moisture and / or oxygen.
Moreover, the gas barrier film which formed inorganic layers, such as a silicon nitride, a silicon oxide, and aluminum oxide, as a gas barrier layer is known as a gas barrier film which has high gas barrier property.

For example, Patent Document 1 has a substrate having a surface made of an organic material, and an inorganic layer (inorganic film) mainly composed of silicon nitride formed on the substrate, and the inorganic layer is N / Si. Composition ratio is 1-1.35, film density is 2.1-2.4 g / cm ² , thickness is 10-60 nm, and the interface between the substrate and the inorganic layer is derived from the substrate (organic material) A gas barrier film having a mixed layer with a thickness of 5 to 40 nm, which contains the component to be added and the component derived from the inorganic layer is described.

Patent Document 2 describes a gas barrier film having a base film and an inorganic layer, wherein the inorganic layer contains Si, N, H, and O, and Si, N, H, and the like at the center in the thickness direction. The uniform region having a uniform ratio to O and having an O ratio represented by the following formula of 10% or less is 5 nm or more, and the region in contact with at least one interface of the inorganic layer has an O ratio A gas barrier film is described, which is an oxygen-containing region in which the change in the O ratio per unit thickness is 2 to 8% / nm, increasing from the uniform region side toward the interface direction.
O ratio [%] = (number of O / total number of Si, N and O) × 100

JP, 2013-203050, A JP, 2015-182274, A

A gas barrier film having an inorganic layer as a gas barrier layer as shown in Patent Documents 1 and 2 exhibits very high gas barrier properties as compared to a gas barrier film having an organic layer made of a resin or the like as a gas barrier layer.

Here, in terms of the bending resistance and transparency of the gas barrier film, it is advantageous that the thickness of the inorganic layer is thin. In addition, a thinner inorganic layer is advantageous in terms of productivity.
However, according to the study of the present inventor, when the inorganic layer is thinned, sufficient gas barrier properties may not be obtained, and further, there arises a problem that the high temperature / high humidity resistance of the gas barrier film is insufficient. .

An object of the present invention is to solve such problems, and to provide a gas barrier film which is excellent in bending resistance, transparency, productivity and the like, and further has sufficient gas barrier properties and high temperature high humidity resistance. It is in.

The present invention solves the problems by the following configurations.
[1] A mixed layer containing silicon nitride and having a thickness of 2 to 15 nm, a component of the inorganic layer and a component of the layer to be the surface on which the inorganic layer is to be formed, and having a thickness of 2 to 25 nm And a combination thereof with at least one pair, and the N / Si atomic ratio of the inorganic layer is 0.7 to 0.97.
[2] The gas barrier film according to [1], wherein the N / Si atomic ratio of the mixed layer is 0.2 to 0.85.
[3] The gas barrier film according to [1] or [2], wherein the N / Si atomic ratio of the mixed layer is lower than the N / Si atomic ratio of the inorganic layer.
[4] The gas barrier film according to [3], wherein the difference between the N / Si atomic ratio of the mixed layer and the N / Si atomic ratio of the inorganic layer is 0.05 to 0.5.
[5] One or more combinations of the inorganic layer and the organic layer to be the base of the inorganic layer are included, and a mixed layer exists between the inorganic layer and the organic layer, [1] to [4] The gas barrier film as described in any of the above.

According to the present invention, a gas barrier film which is excellent in bending resistance, transparency, productivity and the like, and also has sufficient gas barrier properties and high temperature high humidity resistance is provided.

It is a conceptual diagram which shows an example of the gas barrier film of this invention. It is a conceptual diagram which shows another example of the gas barrier film of this invention. It is a conceptual diagram which shows another example of the gas barrier film of this invention. It is a graph which shows the composition ratio of an example of the gas barrier film of this invention. It is a conceptual diagram of an example of the organic film-forming apparatus for manufacturing the gas barrier film of this invention. It is a conceptual diagram of an example of the inorganic film-forming apparatus for manufacturing the gas barrier film of this invention.

Hereinafter, an embodiment of the gas barrier film of the present invention will be described based on the drawings.

(Gas barrier film)
In FIG. 1, an example of the gas barrier film of this invention is shown notionally.
FIG. 1 is a conceptual view of the gas barrier film of the present invention as viewed from the surface direction of the main surface. The main surface is the largest surface of the sheet (film, plate).

The gas barrier film 10 shown in FIG. 1 is configured to have a support 12, a base organic layer 14, a mixed layer 16, and an inorganic layer 18.
In the gas barrier film 10 of the present invention, the inorganic layer 18 is a layer containing silicon nitride. The mixed layer 16 is a layer containing the component of the inorganic layer 18 and the component of the layer to be the surface on which the inorganic layer 18 is formed. The component of the layer to be the surface on which the inorganic layer 18 is to be formed is preferably a component different from the component of the inorganic layer 18, and more preferably a component of the support 12 or a component of the base organic layer 14. In the gas barrier film 10 shown in FIG. 1, the inorganic layer 18 is formed on the surface of the base organic layer 14. Therefore, the mixed layer 16 includes the components of the inorganic layer 18 and the components of the base organic layer 14. In the gas barrier film 10 of the present invention, the inorganic layer 18 has a thickness of 2 to 15 nm, an N / Si atomic ratio of 0.7 to 0.97, and a thickness of the mixed layer 16 of 2 to It is 25 nm.
In the following description, the support 12 side of the gas barrier film 10 is also referred to as “down”, and the side opposite to the support 12 is also referred to as “up”.

In a preferred embodiment, the gas barrier film 10 shown in FIG. 1 has a base organic layer 14 to be a base layer of the inorganic layer 18, and has one set of the base organic layer 14 and the inorganic layer 18 in combination. It has a layer structure of a body 12, an underlying organic layer 14, a mixed layer 16 and an inorganic layer 18. However, the gas barrier film of the present invention is not limited to this layer configuration, and various layer configurations can be used.

For example, like the gas barrier film 20 shown in FIG. 2, the gas barrier film of the present invention does not have the underlying organic layer 14, and directly forms the inorganic layer 18 on the support 12. It may have the layer configuration of the inorganic layer 18. In this configuration, the mixed layer 24 includes the components of the inorganic layer 18 and the components of the support 12.
Alternatively, the gas barrier film of the present invention, like the gas barrier film 28 shown in FIG. 3, has two sets of the combination of the base organic layer 14 and the inorganic layer 18, the support 12 · base organic layer 14 · mixed layer 16 · inorganic It may have a layer configuration of the layer 18, the base organic layer 14, the mixed layer 16, and the inorganic layer 18. Furthermore, a configuration having three or more sets of the combination of the underlying organic layer 14 and the inorganic layer 18 is also usable. In addition, one or more combinations of the base organic layer 14 and the inorganic layer 18 may be laminated on the gas barrier film 20 in which the inorganic layer 18 is directly formed on the support 12 shown in FIG. 2.
Furthermore, the gas barrier film of the present invention may have a protective organic layer for protecting the inorganic layer 18 on the top layer, that is, the inorganic layer 18 most separated from the support 12.

In the gas barrier film of the present invention, when the inorganic layer 18 has two or more layers, the inorganic layer 18 does not satisfy at least one of the thickness 2 to 15 nm and the N / Si atomic ratio 0.7 to 0.97. And / or a mixed layer 16 that does not satisfy the thickness of 2 to 25 nm may be present. Furthermore, in the gas barrier film of the present invention, when the inorganic layer 18 has two or more layers, a combination having no mixed layer exists between the inorganic layer 18 and the layer on which the inorganic layer 18 is to be formed. It is also good.
That is, the gas barrier film of the present invention is formed between the inorganic layer 18 having a thickness of 2 to 15 nm and an N / Si atomic ratio of 0.7 to 0.97, and a layer on which the inorganic layer 18 is to be formed. It is sufficient to have one or more sets in combination with the mixed layer 16 with a thickness of 2 to 25 nm.
However, in the gas barrier film of the present invention, even when the inorganic layer 18 has two or more layers, the mixed layer 16 is provided between all the inorganic layers 18 and the layer on which the inorganic layer 18 is to be formed. And preferably, all the inorganic layers 18 and the mixed layers 16 satisfy the conditions of thickness and atomic ratio described above.

<Support>
The support 12 may be a known sheet (film, plate) used as a support in various gas barrier films, various laminated functional films and the like.

The material of the support 12 is not limited, and various materials can be used as long as the underlying organic layer 14 and the inorganic layer 18 can be formed. As a material of the support 12, preferably, various resin materials are exemplified.
Examples of the material of the support 12 include polyethylene (PE), polyethylene naphthalate (PEN), polyamide (PA), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyacritonitrile ( PAN), polyimide (PI), transparent polyimide, polymethyl methacrylate resin (PMMA), polycarbonate (PC), polyacrylate, polymethacrylate, polypropylene (PP), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer ( And ABS), cycloolefin copolymer (COC), cycloolefin polymer (COP), triacetylcellulose (TAC), ethylene-vinyl alcohol copolymer (EVOH) and the like.

The thickness of the support 12 can be set as appropriate depending on the application, material and the like.
The thickness of the support 12 is not limited, but the mechanical strength of the gas barrier film 10 can be sufficiently secured, and the gas barrier film 10 having good flexibility can be obtained. The thickness is preferably 5 to 150 μm, and more preferably 10 to 125 μm in that a flexible gas barrier film 10 which can be thinned can be obtained.

<Base organic layer>
In the gas barrier film 10, the base organic layer 14 is formed on one surface of the support 12.
The underlying organic layer 14 is, for example, a layer formed of an organic compound obtained by polymerizing (crosslinking, curing) monomers, dimers, oligomers and the like. As described above, the underlying organic layer 14 is provided as a preferred embodiment.

The underlying organic layer 14 serving as the lower layer of the inorganic layer 18 is a layer serving as an underlying layer for properly forming the inorganic layer 18.
The underlying organic layer 14 formed on the surface of the support 12 can have the surface on which the inorganic layer 18 is formed appropriate by embedding the irregularities on the surface of the support 12 and foreign matter attached to the surface. Therefore, by having such a base organic layer 14 on the surface of the support 12, it is possible to properly form the inorganic layer 18 that mainly exhibits gas barrier properties.
As described above, the gas barrier film of the present invention may have a plurality of combinations of the inorganic layer 18 and the base organic layer 14. In this case, the second and subsequent base organic layers 14 are formed on the inorganic layer 18, but even in this configuration, the base organic layer to be the lower layer of the inorganic layer 18 (the surface on which the inorganic layer 18 is formed) 14 exerts the same action.

The base organic layer 14 is formed, for example, by curing a composition for forming an organic layer containing an organic compound (monomer, dimer, trimer, oligomer, polymer, etc.). The composition for forming an organic layer may contain only one type of organic compound, or may contain two or more types.
The underlying organic layer 14 contains, for example, a thermoplastic resin, an organic silicon compound, and the like. The thermoplastic resin is, for example, polyester, (meth) acrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluorine resin, polyimide, fluorinated polyimide, polyamide, polyamide imide, polyether imide, cellulose acylate, polyurethane And polyether ether ketone, polycarbonate, alicyclic polyolefin, polyarylate, polyether sulfone, polysulfone, fluorene ring modified polycarbonate, alicyclic modified polycarbonate, fluorene ring modified polyester, and an acrylic compound. Examples of organosilicon compounds include polysiloxanes.

The base organic layer 14 preferably includes a radical curable compound and / or a polymer of a cationic curable compound having an ether group from the viewpoint of excellent strength and the viewpoint of glass transition temperature.
More preferably, the base organic layer 14 contains a (meth) acrylic resin whose main component is a polymer such as a monomer or oligomer of (meth) acrylate from the viewpoint of strength and glass transition temperature.

The underlying organic layer 14 is more preferably a bifunctional compound such as dipropylene glycol di (meth) acrylate (DPGDA), trimethylolpropane tri (meth) acrylate (TMPTA), dipentaerythritol hexa (meth) acrylate (DPHA), etc. The (meth) acrylic resin containing as a main component a polymer of the above (meth) acrylate monomers, dimers and oligomers, etc., and more preferably, a heavy weight such as trifunctional or higher functional (meth) acrylate monomers, dimers and oligomers It contains (meth) acrylic resin whose main component is coalescence. In addition, a plurality of these (meth) acrylic resins may be used. In addition, a main component means the component with the largest contained mass ratio among the components to contain.

The composition for forming an organic layer preferably contains, in addition to the organic compound, an organic solvent, a surfactant, and a silane coupling agent.

When a plurality of underlying organic layers 14 are provided, that is, when there are a plurality of combinations of the underlying organic layers 14 and the inorganic layers 18, the materials of the respective underlying organic layers 14 may be the same or different.

There is no restriction | limiting in the thickness of the base organic layer 14, According to the component contained in the composition for organic layer formation, the support body 12 used, etc., it can set suitably.
The thickness of the underlying organic layer 14 is preferably 0.1 to 5 μm, and more preferably 0.2 to 3 μm. By setting the thickness of the base organic layer 14 to 0.1 μm or more, unevenness on the surface of the support 12 and foreign substances attached to the surface can be embedded, and the surface of the base organic layer 14 can be flattened, etc. Preferred. By setting the thickness of the base organic layer 14 to 5 μm or less, it is possible to prevent the cracks in the base organic layer 14, to increase the flexibility of the gas barrier film 10, and to make the gas barrier film 10 thinner and lighter. Preferred.

When a plurality of underlying organic layers 14 are provided, that is, when there are a plurality of combinations of the inorganic layer 18 and the underlying organic layers 14, the thicknesses of the underlying organic layers 14 may be the same or different.

The underlying organic layer 14 can be formed by a known method depending on the material.
For example, the base organic layer 14 can be formed by a coating method in which the composition for forming an organic layer described above is applied and the composition for forming an organic layer is dried. In the formation of the underlying organic layer 14 by the coating method, the dried organic layer-forming composition is further irradiated with ultraviolet light, if necessary, to polymerize (crosslink) the organic compound in the organic layer-forming composition. Let

The underlying organic layer 14 is preferably formed by roll-to-roll. In the following description, "roll to roll" is also called "RtoR".
As is well known, RtoR refers to a sheet formed from a roll formed by winding a long sheet, and forming a film while conveying the long sheet in the longitudinal direction, and forming a film It is a manufacturing method which winds a sheet in a roll. By using RtoR, high productivity and production efficiency can be obtained.

The gas barrier film of the present invention may have a protective organic layer for protecting the inorganic layer 18 on the surface of the uppermost inorganic layer 18 (the inorganic layer 18 most separated from the support 12).
When such a protective organic layer is provided, the material, thickness, formation method, and the like may be similar to those of the base organic layer 14.

<Inorganic layer and mixed layer>
An inorganic layer 18 is formed on the surface of the base organic layer 14. Further, in the gas barrier film 10 of the present invention, a mixed layer 16 containing the components of the base organic layer 14 and the components of the inorganic layer 18 is formed between the base organic layer 14 and the inorganic layer 18. .
The inorganic layer 18 may be formed on the surface of the support 12 as described above, and in this case, the mixed layer 24 includes the components of the support 12 and the components of the inorganic layer 18. (See Figure 2).

In the gas barrier film 10 of the present invention, the inorganic layer 18 is a layer containing silicon nitride, preferably a layer containing silicon nitride as a main component, and more preferably a layer consisting of silicon nitride.
Therefore, the inorganic layer 18 is derived from not only silicon nitride but also by-products such as silicon oxynitride, hydrogenated silicon nitride, hydrogenated silicon nitride oxynitride, and silicon oxide, and source gases such as silane gas, ammonia gas and hydrogen gas. You may contain the various components contained unavoidable, such as the component to be.

In the gas barrier film 10 of the present invention, the inorganic layer 18 has a thickness of 2 to 15 nm and an N / Si atomic ratio of 0.7 to 0.97.
In addition, as above-mentioned, when the inorganic layer 18 is provided in multiple layers, the thickness of each inorganic layer 18 may be same or different.

The inorganic layer 18 can be formed by a known method depending on the material.
For example, plasma CVD such as capacitively coupled plasma (CCP) -chemical vapor deposition (CVD) and inductively coupled plasma (ICP) -CVD, and atomic layer deposition (ALD) can be used.
Preferably, the inorganic layer 18 is also formed of RtoR.

In the gas barrier film 10, a mixed layer 16 is provided between the inorganic layer 18 and the base organic layer 14 on which the inorganic layer 18 is to be formed.
The mixed layer 16 is a layer formed by, for example, etching the surface of the base organic layer 14 (the layer on which the inorganic layer 18 is to be formed) by plasma when forming the inorganic layer 18 by plasma CVD. . Therefore, the mixed layer 16 contains the components of the inorganic layer 18 and the components of the base organic layer 14. In other words, the mixed layer 16 is a layer in which the component derived from the base organic layer 14 and the component derived from the inorganic layer 18 are mixed.

Here, in the gas barrier film 10 of the present invention, the thickness of the inorganic layer 18 is 2 to 15 nm, and the N / Si atomic ratio (atomic ratio of N / Si) of the inorganic layer 18 is 0.7 to 0.97. The thickness of the mixed layer 16 is 2 to 25 nm.
The gas barrier film of the present invention having such a configuration realizes a gas barrier film having excellent flexibility resistance, transparency, productivity and the like, and further having sufficient gas barrier properties and high temperature / high humidity resistance.

As also shown in Patent Documents 1 and 2, a gas barrier film having an inorganic layer as a gas barrier layer is known as a high performance gas barrier film. Among them, a gas barrier film having a silicon nitride layer as a gas barrier layer exhibits high gas barrier properties.
Here, in the gas barrier film having an inorganic layer, when the inorganic layer is thinner, breakage of the inorganic layer can be prevented when it is bent, that is, it is excellent in bending resistance (flexibility). In addition, it is advantageous in terms of optical characteristics such as transparency that the gas barrier film has a thin inorganic layer. Furthermore, the productivity of the gas barrier film can also be improved by thinning the inorganic layer.

However, according to the study of the present inventor, when the inorganic layer containing silicon nitride is thinned, it becomes difficult to obtain sufficient gas barrier properties, and furthermore, there arises a problem that the high temperature and high humidity resistance is lowered.
The inorganic layer is formed (deposited) by plasma CVD such as CCP-CVD. The surface on which the inorganic layer is formed is a base organic layer (or a support made of a resin) which is an organic compound. As described above, when an inorganic layer is formed on such a base organic layer (a layer containing an organic compound) by plasma CVD, the base organic layer is etched by plasma depending on the film forming conditions of the inorganic layer. A mixed layer containing the component and the component of the base organic layer is formed, and the inorganic layer is formed thereon. That is, the formation surface of the inorganic layer is roughened by etching.
Here, when the inorganic layer has a sufficient thickness, the mixed layer can be entirely covered to form the inorganic layer even if the surface on which the inorganic layer is formed is somewhat rough. Sufficient gas barrier properties can be obtained by the formed inorganic layer.
However, when the inorganic layer is thinned, the inorganic layer can not cover the mixed layer entirely, and moisture intrudes from the non-formed portion of the inorganic layer, so that sufficient gas barrier properties can not be obtained.

Furthermore, according to the study of the present inventor, when the inorganic layer containing silicon nitride is exposed to a high temperature and high humidity environment, oxidation of the inorganic layer is caused, for example, NH ₂ group remaining in the inorganic layer is replaced with OH group etc. As it progresses, the density of the membrane decreases.
When the inorganic layer (silicon nitride layer) has a sufficient thickness, sufficient gas barrier properties can be maintained even if oxidation of the inorganic layer proceeds. However, when the inorganic layer is made thin, when exposed to a high temperature and high humidity environment, the entire inorganic layer becomes like silicon oxide whose density is lower than that of silicon nitride in a short time, and the gas barrier property is significantly reduced. Resulting in.

The present inventors diligently studied to solve such a problem that occurs when the inorganic layer 18 containing a silicon nitride layer is thinned.
As a result, even if the inorganic layer 18 is made thin by reducing the amount of nitrogen contained in the inorganic layer 18, that is, by reducing the N / Si atomic ratio, the gas barrier film 10 having excellent gas barrier properties and high temperature high humidity resistance. I found that I could get

According to the study of the present inventor, nitrogen radicals in plasma contribute to the film formation of silicon nitride and also react with the carbon of the underlying organic layer 14 to form the underlying organic layer 14 (the surface on which the inorganic layer 18 is formed). Etch.
By reducing the nitrogen in the inorganic layer 18 (reducing the N / Si atomic ratio), that is, reducing the nitrogen radicals in the plasma, excessive etching of the underlying organic layer 14 can be suppressed. As a result, it is possible to suppress the roughening of the mixed layer 16, that is, the roughening of the film formation surface of the inorganic layer 18. Therefore, even if the inorganic layer 18 is thin, it covers the entire surface of the mixed layer 16. Can be formed. In particular, by further reducing the amount of nitrogen in the mixed layer 24 (reducing the N / Si atomic ratio), this effect can be more suitably obtained.

According to the study of the present inventor, the nitrogen in the inorganic layer 18 is reduced, that is, the N / Si atomic ratio in the inorganic layer 18 is reduced to oxidize the above-mentioned inorganic layer 18 in a high temperature and high humidity environment. It can be difficult to move on.
As a result, even if the inorganic layer 18 is thinned, the gas barrier film 10 having sufficient high temperature and high humidity resistance can be obtained.

As mentioned above, in the gas barrier film 10 of the present invention, the thickness of the inorganic layer 18 is 2 to 15 nm. The thickness of the inorganic layer 18 is preferably 3 to 13 nm, and more preferably 5 to 12 nm.
When the inorganic layer 18 has a thickness of 2 nm or more, the gas barrier film 10 having sufficient gas barrier properties can be obtained.
When the inorganic layer 18 has a thickness of less than 15 nm, the gas barrier film 10 having high transparency and excellent bending resistance can be obtained.

The inorganic layer 18 has an N / Si atomic ratio (atomic ratio) of 0.7 to 0.97. The N / Si atomic ratio of the inorganic layer 18 is preferably 0.75 to 0.95, and more preferably 0.8 to 0.93.
When the inorganic layer 18 has an N / Si atomic ratio of 0.7 or more, the transparency of the gas barrier film 10 is excellent.
When the inorganic layer 18 has an N / Si atomic ratio of 0.97 or less, a gas barrier film 10 having sufficient gas barrier properties and high temperature and high humidity resistance can be obtained.

Although there is no limit to the density of the inorganic layer 18 (film density), preferably 2.1 ~ 2.5g / cm ^2, more preferably ^{2.12 ~ 2.45g / cm 2, 2.14} ~ 2.4g / Cm ² is more preferred.
By setting the density of the inorganic layer 18 to 2.1 g / cm ² or more, the gas barrier film 10 having high gas barrier properties can be obtained, and the gas barrier film 10 having high high temperature and high humidity resistance can be obtained. .
By setting the density of the inorganic layer 18 to 2.5 g / cm ² or less, damage to the inorganic layer 18 caused by film stress and the like can be prevented, which is preferable in that the gas barrier film 10 having high gas barrier properties can be obtained.
The density of the inorganic layer 18 may be measured by XRR (X-Ray Reflectometry). The calculation of the density from the XRR measurement result may be performed by simulation using software. The XRR measurement may be performed using, for example, ATX manufactured by Rigaku Corporation. The simulation may be performed using, for example, analysis software GXRR manufactured by Rigaku Corporation.

In the gas barrier film 10 of the present invention, the thickness of the mixed layer 16 (24) is 2 to 25 nm. The thickness of the mixed layer 16 is preferably 4 to 22 nm, and more preferably 5 to 20 nm.
When the thickness of the mixed layer 16 is less than 2 nm, the inorganic layer 18 and the base organic layer 14 or the inorganic layer 18 and the support 12 easily peel off, which causes problems such as the inability to secure sufficient bending resistance.
If the thickness of the mixed layer 16 exceeds 25 nm, the surface roughness of the surface on which the inorganic layer 18 is formed becomes large, so the inorganic layer 18 can not be properly formed, and the gas barrier film 10 having sufficient gas barrier properties can not be obtained. And, the absorption of light by the mixed layer 16 is increased to cause disadvantages such as a decrease in transparency.

In the gas barrier film 10 of the present invention, the N / Si atomic ratio in the mixed layer 16 is not limited, but is preferably 0.2 to 0.85, more preferably 0.3 to 0.82, and 0.4 to 0. .8 is more preferred. In the present invention, it is preferable to further reduce the N / Si atomic ratio (= nitrogen content) in the mixed layer 16, that is, nitrogen radicals in plasma at the time of formation of the mixed layer 16.
By setting the N / Si atomic ratio in the mixed layer 16 to 0.2 or more, absorption of light by the mixed layer 16 is suppressed, which is preferable in that the gas barrier film 10 having excellent transparency can be obtained.
By setting the N / Si atomic ratio in the mixed layer 16 to 0.85 or less, it is possible to prevent the mixed layer 16 from becoming excessively rough and to form an appropriate inorganic layer 18, and the gas barrier film 10 having high gas barrier properties can be obtained. It is preferable at the point of being obtained etc.

Here, the N / Si atomic ratio of the mixed layer 16 is preferably lower than the N / Si atomic ratio of the inorganic layer 18. That is, the mixed layer 16 preferably has a lower amount of nitrogen to silicon than the inorganic layer 18.

In particular, the N / Si atomic ratio of the mixed layer 16 is preferably lower by 0.05 to 0.5 than the N / Si atomic ratio of the inorganic layer 18, and more preferably by 0.1 to 0.3. . That is, the gas barrier film 10 of the present invention preferably satisfies “0.05 ≦ (N / Si atomic ratio of inorganic layer 18) − (N / Si atomic ratio of mixed layer 16) ≦ 0.5”.
By setting the difference between the N / Si atomic ratio of the mixed layer 16 and the N / Si atomic ratio of the inorganic layer 18 to 0.05 or more, the roughness of the mixed layer 16 can be suppressed and an appropriate inorganic layer 18 can be formed. Therefore, it is preferable in that the gas barrier film 10 having high gas barrier properties can be obtained.
By setting the difference between the N / Si atomic ratio of the mixed layer 16 and the N / Si atomic ratio of the inorganic layer 18 to 0.5 or less, the transparency of the gas barrier film 10 is preferably improved.

<Method of controlling N / Si atomic ratio>
As a method of controlling the N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16, that is, the content of nitrogen, the following method is exemplified.
First, a method of adjusting the N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 by adjusting the composition of the source gas when forming the inorganic layer 18 is exemplified. For example, when the inorganic layer 18 is formed by plasma CVD using silane gas, ammonia gas, and hydrogen gas as source gases, the N / Si atomic ratio can be adjusted by adjusting the amount of ammonia gas to silane gas. . For example, as the ammonia gas is reduced, the N / Si atomic ratio can be lowered.
The N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 can also be adjusted by adjusting the plasma excitation power at the time of forming the inorganic layer 18. For example, as the plasma excitation power at the time of forming the inorganic layer 18 is increased, the N / Si atomic ratio is increased.

The N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 can also be adjusted by temperature control when forming the inorganic layer 18. For example, when forming the inorganic layer 18, as the temperature is increased, nitrogen is more easily removed from the inorganic layer 18 and the mixed layer 16, and the N / Si atomic ratio becomes lower.
The temperature control at the time of forming the inorganic layer 18 may be performed by, for example, the temperature control of the support 12 at the time of forming the inorganic layer 18. As an example, as described later, when the support 12 is wound around the drum 102 and the inorganic layer 18 is formed by RtoR, the temperature of the support 12 is adjusted by adjusting the temperature of the drum 102. Good.

Furthermore, the N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 can be adjusted by treating the formation surface of the inorganic layer 18 with hydrogen plasma prior to the formation of the inorganic layer 18. Specifically, the N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 can be reduced by treating the formation surface of the inorganic layer 18 with hydrogen plasma.
Hydrogen plasma generates very strong ultraviolet light. Therefore, by treating the surface on which the inorganic layer 18 is formed with hydrogen plasma prior to the formation of the inorganic layer 18, the curing of the surface on which the inorganic layer 18 is formed can be advanced by the irradiation of ultraviolet light. Thereby, the etching by the plasma at the time of forming the inorganic layer 18 can be suppressed. As a result, when the inorganic layer 18 is formed, mixing of nitrogen into the mixed layer 16 or the like can be suppressed, and the N / Si atomic ratio in the inorganic layer 18 and the mixed layer 16 can be lowered.
This method is particularly effective when the surface on which the inorganic layer 18 is formed is, for example, the underlying organic layer 14 or the like formed by curing (polymerization) of an ultraviolet-curable organic compound such as (meth) acrylate. .

(Method of measuring thickness and N / Si atomic ratio)
In the gas barrier film 10 of the present invention, the thicknesses of the inorganic layer 18 and the mixed layer 16, and the N / Si atomic ratio of the inorganic layer 18 and the mixed layer 16 are XPS (X-ray photoelectron spectroscopy) It is to be noted that XPS is also called ESCA (Electron Spectroscopy for Chemical Analysis).

In the measurement of the thickness and N / Si atomic ratio of each layer using XPS, as an example, first, etching by argon ion plasma etc. and measurement by XPS are alternately performed, and silicon atoms at each position in the thickness direction The amounts of (Si), nitrogen atom (N), oxygen atom (O) and carbon atom (C) are measured. The measurement interval in the thickness direction by XPS may be appropriately set according to the etching rate, the measuring apparatus, and the like.
Next, the position in the thickness direction measured by XPS is detected from the etching rate and the etching time. Furthermore, assuming that the sum of silicon atoms, nitrogen atoms, oxygen atoms and carbon atoms is 1 (that is, 100%), silicon atoms, nitrogen atoms, oxygen atoms and carbon atoms in the thickness direction as schematically shown in FIG. Composition ratio (profile of composition ratio) is detected.
Note that the measurement by XPS is also performed on the base organic layer 14 (the layer to be the surface on which the inorganic layer 18 is formed), but if the measured value by XPS becomes constant in the region of the base organic layer 14 It does not have to be done.

The example shown in FIG. 4 is each in the thickness direction (film thickness) in an example of the gas barrier film 10 having the layer structure of the support 12, the base organic layer 14, the mixed layer 16 and the inorganic layer 18 as shown in FIG. It is the content rate of each atom at the position. Therefore, the position of 0 nm is the surface of the inorganic layer 18.
Here, although oxygen and carbon do not exist in the inorganic layer 18 which is a silicon nitride layer, oxygen atoms and carbon atoms are detected at a thickness of 0 nm and in the vicinity thereof. As described later, in the production of the gas barrier film 10, usually, after forming the inorganic layer 18, a protective film is laminated on the inorganic layer 18 to protect the inorganic layer 18, and the protective film is used at the time of use (at the time of measurement). Peel off. At the time of this peeling, components of the protective film are transferred to the surface of the inorganic layer 18. The oxygen atom and the carbon atom detected at a thickness of 0 nm and in the vicinity thereof are the ones in which the component transferred from the protective film to the inorganic layer 18 is detected.

Next, the maximum value and the minimum value in the composition ratio (amount) of silicon atoms are detected, and as shown in FIG. 4, the maximum value is 100%, and the minimum value is 0%, with 100% therebetween.
When the maximum value in the composition ratio of silicon atoms is set to 100% and the minimum value is set to 0%, the position in the thickness direction where the composition ratio of silicon atoms is reduced by 10% from the maximum value (100%) is mixed with the inorganic layer 18 The interface with the layer 16 and the position in the thickness direction where the composition ratio of silicon atoms is increased by 10% from the minimum value (0%) is the interface between the mixed layer 16 and the base organic layer 14.
In other words, the silicon atom composition ratio profile and the position 1/10 from the top (one step) dividing the range from the maximum value (100%) to the minimum value (0%) of the composition ratio of silicon atoms into 10 equal parts. Position in the thickness direction where it intersects is the interface between the inorganic layer 18 and the mixed layer 16, and the profile of the composition ratio of silicon atoms intersects with the position 1/10 from the bottom (the ninth stage) The position in the thickness direction is an interface between the mixed layer 16 and the base organic layer 14.

Thus, when the interface between the inorganic layer 18 and the mixed layer 16 and the interface between the mixed layer 16 and the base organic layer 14 are determined, the thickness (from the surface (0 nm) to the interface) of the inorganic layer 18 and , Thickness of the mixed layer 16 (from interface to interface) is detected.
Furthermore, the N / Si atomic ratio in the inorganic layer 18 is detected from the detected interface and the composition ratio of silicon atoms and nitrogen atoms at each position in the thickness direction, or further, the N / Si atomic ratio in the mixed layer 16 To detect

In the present invention, the N / Si atomic ratio of the inorganic layer 18 is an average value of the N / Si atomic ratio at each position in the thickness direction of the inorganic layer 18. Further, the N / Si atomic ratio of the mixed layer 16 is an average value of the N / Si atomic ratio at each position in the thickness direction of the mixed layer 16.
Therefore, for example, in the vicinity of the interface between the inorganic layer 18 and the mixed layer 16, the inorganic layer 18 has a region where the N / Si ratio is not in the range of 0.7 to 0.97 partially in the thickness direction. There is also a case. The same applies to the mixed layer 16 in this regard.

As described above, in the gas barrier film of the present invention, the base organic layer 14 may be further formed on the inorganic layer 18 (see FIG. 3), and a protective organic layer is formed on the inorganic layer 18. There is also a case.
At this time, the same XPS measurement is performed including the upper organic layer of the inorganic layer 18 to detect the minimum value and the maximum value of the composition ratio of silicon atoms in the region of the upper organic layer to the inorganic layer 18. Similarly to the above, with the interval being 100%, the position in the thickness direction where the detection result of silicon atoms is 10% lower than the maximum value may be taken as the interface between the upper organic layer and the inorganic layer 18.

The thickness and N / Si atomic ratio of the inorganic layer 18 and the mixed layer 16 hardly change in the region used as a product in the gas barrier film 10.
Therefore, the thickness and the N / Si atomic ratio of the inorganic layer 18 and the mixed layer 16 as described above may be measured in the central region of the gas barrier film 10. For example, if the gas barrier film 10 is manufactured by RtoR, the measurement may be performed in the area of the central 80% in the width direction. In addition, if the gas barrier film 10 is manufactured in a sheet-like manner (cut sheet), the measurement may be performed in an area of 10% or more of the length in the longitudinal direction and the lateral direction.
Preferably, the thickness and the N / Si atomic ratio of the inorganic layer 18 and the mixed layer 16 as described above are measured at five points in the central region, and the average value is calculated as the inorganic layer 18 of the gas barrier film 10 and The thickness and N / Si atomic ratio of the mixed layer 16 are used.

(Method of manufacturing gas barrier film)
The gas barrier film 10 is preferably manufactured using RtoR. An example of the manufacturing method of the gas barrier film 10 is demonstrated using FIG. 5 and FIG.

FIG. 5 shows an organic film forming apparatus 40.
The organic film-forming apparatus 40 is an apparatus which forms the base organic layer 14 or further a protection organic layer by RtoR. The organic film forming apparatus 40 includes a rotating shaft 52, conveyance roller pairs 54a and 54b, a coating unit 56, a drying unit 58, a light irradiation unit 60, a winding shaft 62, a collection roll 64, and a supply roll 66. And

Hereinafter, a method of forming the base organic layer 14 using the organic film forming apparatus 40 will be described.
The base organic layer 14 (protective organic layer) is formed by applying the composition for forming an organic layer while conveying the elongated support 12 in the longitudinal direction.
First, a roll 72 formed by winding the long support 12 is loaded on the rotating shaft 52. Next, the support 12 is pulled out of the roll 72, passed through a predetermined transport path, and transported. The conveyance path is a path from the roll 72 to the winding shaft 62 through the conveyance roller pair 54a, the application unit 56, the drying unit 58, the light irradiation unit 60, and the conveyance roller pair 54b.

The support 12 drawn from the roll 72 is conveyed in the longitudinal direction, and the composition for forming an organic layer is first applied to the surface in the application unit 56. Examples of the coating method in the coating unit 56 include a die coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, and a gravure coating method.

Next, the support 12 to which the composition for forming an organic layer is applied is heated by the drying unit 58. Thereby, the composition for organic layer formation is dried.
The drying unit 58 is a drying unit 58a that performs heating and drying from the front side (the surface on which the base organic layer 14 is formed, the upper side in FIG. 5), and a drying unit 58b that performs heating and drying from the back side (the support 12 side). And can be heated from both the front and back sides.
As a heating method in the drying unit 58, a known method of heating a sheet-like material can be used. For example, hot air drying may be performed by the drying unit 58a, and drying may be performed by the heat roller (pass roller having a heating mechanism) by the drying unit 58b.

Subsequently, the light irradiation part 60 irradiates an ultraviolet-ray etc. to the dried composition for organic layer formation. Thereby, the organic compound is polymerized (crosslinked) to form the underlying organic layer 14. The polymerization of the organic compound may be carried out in an inert atmosphere such as a nitrogen atmosphere, if necessary.

Next, the protective film Ga delivered from the supply roll 66 is laminated on the base organic layer 14 by the transport roller pair 54 b. The protective film Ga is a protective film that protects the underlying organic layer 14. The support 12 on which the protective film Ga is laminated is taken up by a take-up shaft 62 to be a roll 74.

FIG. 6 shows an inorganic film forming apparatus 80.
The inorganic film-forming apparatus 80 is an apparatus which forms the inorganic layer 18 by RtoR.
The inorganic film forming apparatus 80 has a vacuum chamber 82. The vacuum chamber 82 comprises an evacuation means 84. By driving the evacuation means 84, the internal pressure of the inorganic film forming apparatus 80 (vacuum chamber 82) can be adjusted.
In the vacuum chamber 82, a rotary shaft 92, pass rollers 94a to 94c, a recovery roll 98, a first film forming unit 100A, a second film forming unit 100B and a third film forming unit 100C, a drum 102, a supply A roll 104, pass rollers 106a to 106c, and a winding shaft 108 are provided.

In such an inorganic film forming apparatus 80, the inorganic layer 18 is formed on the base organic layer 14 while conveying the long support 12 on which the base organic layer 14 is formed in the longitudinal direction.
First, the roll 74 is loaded on the rotating shaft 92. Next, the support 12 pulled out of the roll 74 is passed through a predetermined transport path leading to the winding shaft 108 via the pass rollers 94a to 94c, the drum 102, and the pass rollers 106a to 106c.

The support 12 pulled out of the roll 74 is guided by the pass rollers 94a to 94c, wound around the drum 102, and conveyed along a predetermined path. The inorganic layer 18 is formed by one or more of the first film forming unit 100A, the second film forming unit 100B, and the third film forming unit 100C. The treatment of the underlying organic layer 14 with hydrogen plasma described above may be performed by the first film formation unit 100A or the second film formation unit 100B.
The drum 102 incorporates a temperature control unit, and the support 12 is cooled or heated by the drum 102 as necessary, while the first film forming unit 100A, the second film forming unit 100B, and the third film forming unit 100 are formed. It is processed by one or more of the membrane units 100C. As described above, by performing such temperature control of the support 12, it is possible to adjust the N / Si atomic ratio in the mixed layer 16 and the inorganic layer 18.
Furthermore, the drum 102 is configured to be able to supply bias power.
When the protective film Ga is laminated on the base organic layer 14, the protective film Ga is peeled off from the base organic layer 14 and collected by the collection roll 98.

The film forming method in the first film forming unit 100A, the second film forming unit 100B and the third film forming unit 100C is, for example, CCP-CVD. Therefore, by adjusting the film forming conditions, the base organic layer 14 is etched by plasma, and the mixed layer 16 is formed between the base organic layer 14 and the inorganic layer 18.
The first film forming unit 100A, the second film forming unit 100B, and the third film forming unit 100C have the same configuration, and the shower electrode 114 constituting the electrode pair with the drum 102, the high frequency power supply 116, and the gas supply And means 118. The shower electrode 114 is a known shower electrode (shower plate) used for plasma CVD, which has an opening for supplying the source gas to the surface facing the drum 102.
The high frequency power source 116 supplies plasma excitation power to the shower electrode 114, and is a known high frequency power source used for plasma CVD. As described above, by adjusting the intensity of plasma excitation power supplied to the shower electrode 114, it is possible to adjust the N / Si atomic ratio and the like in the mixed layer 16 and the inorganic layer 18.
The gas supply means 118 is for supplying the source gas to the shower electrode 114, and is a known gas supply means used for plasma CVD. The gas barrier film 10 of the present invention has the inorganic layer 18 containing silicon nitride, and as a source gas, silane gas, ammonia gas and hydrogen gas are exemplified as an example. As described above, the N / Si atomic ratio and the like in the mixed layer 16 and the inorganic layer 18 can be adjusted by adjusting the supply amounts of the silane gas and the ammonia gas.
The thicknesses of the mixed layer 16 and the inorganic layer 18 can be adjusted by known methods such as adjustment of plasma excitation power, adjustment of film formation time, that is, adjustment of transport speed of the support 12, and adjustment of supply amount of source gas. You can do it.

By using the inorganic film forming apparatus 80 having three film forming units, the thickness and / or the composition of the mixed layer 16 and the inorganic layer 18 can be adjusted with a high degree of freedom.
For example, the inorganic layer 18 is formed using the first film forming unit 100A and the third film forming unit 100C. Thus, by forming the inorganic layer 18 using a plurality of film forming units, the mixed layer 16 is mainly formed in the first film forming unit 100A on the upstream side, and the third film forming on the downstream side is formed. In the unit 100C, mainly by forming the inorganic layer 18, it is possible to independently adjust the thickness and the composition in forming the mixed layer 16 and forming the inorganic layer 18, respectively.
In the first film forming unit 100A, the surface of the base organic layer 14 is treated with hydrogen plasma without film formation, and the third film forming unit 100C or the second film forming unit 100B and the third film forming unit 100B are formed. It is also possible to form the mixed layer 16 and the inorganic layer 18 by the membrane unit 100C.

The inorganic film forming apparatus 80 may form the mixed layer 16 and the inorganic layer 18 by using the first film forming unit 100A and the second film forming unit 100B other than the above, and the second film forming unit The mixed layer 16 and the inorganic layer 18 may be formed by using 100B and the third film forming unit 100C, and the mixed layer 16 and the inorganic layer 18 may be formed by using all of the first film forming unit 100A to the third film forming unit 100C. The mixed layer 16 and the inorganic layer 18 may be formed using only one of the first film forming unit 100A, the second film forming unit 100B, and the third film forming unit 100C.

On the support 12 on which the inorganic layer 18 is formed, that is, the gas barrier film 10, the protective film Gb delivered from the supply roll 104 is laminated on the inorganic layer 18 at the pass roller 106a. The protective film Gb is a film that protects the inorganic layer 18.
The gas barrier film 10 on which the protective film Gb is laminated is guided by the pass rollers 106a to 106c and conveyed to the winding shaft 108, and the gas barrier film 10 on which the protective film Gb is laminated is wound on the winding shaft 108 The roll 110 in which the film 10 is wound is obtained.

After formation of the inorganic layer 18, the vacuum chamber 82 is opened to the atmosphere to introduce clean dry air. The roll 110 is then removed from the vacuum chamber 82.

When two or more sets of the combination of the base organic layer 14 and the inorganic layer 18 are formed, the same base organic layer 14 and the inorganic layer 18 (mixed layer 16) are formed according to the number of combinations to be formed. And repeat. At this time, the formation of the underlying organic layer 14 of the second and subsequent layers is performed after the protective film Gb laminated on the inorganic layer 18 is peeled off by the transport roller pair 54a.
In the case of forming the protective organic layer on the inorganic layer 18, after forming the inorganic layer 18, the protective organic layer may be formed on the inorganic layer 18 in the same manner as the base organic layer 14.
In the case where the mixed layer 16 and the inorganic layer 18 are directly formed on the support 12 as in the gas barrier film 20 shown in FIG. 2, the formation of the underlying organic layer 14 by the organic film forming apparatus 40 is not performed. The inorganic layer 18 may be formed directly on the support 12 by the film forming apparatus 80.

As mentioned above, although the gas barrier film of this invention was demonstrated in detail, this invention is not limited to said aspect, You may perform various improvement and change in the range which does not deviate from the summary of this invention.

The present invention will be specifically described by way of examples. The present invention is not limited to the specific examples shown below.

Example 1
<< Support >>
As a support, a PET film having a width of 1000 mm, a thickness of 100 μm and a length of 100 m (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) was used.

<< Formation of base organic layer >>
A mixture of TMPTA (manufactured by Daicel Ornex Co., Ltd.) and a photopolymerization initiator (manufactured by Lamberti, ESACURE KTO 46) was weighed so as to have a mass ratio of 95: 5, and methyl ethyl ketone ( It melt | dissolved in MEK, and prepared the composition for organic layer formation for forming a base organic layer.
The prepared composition for forming an organic layer was filled in an application part of an organic film forming apparatus having an application part, a drying part, and a light irradiation part as shown in FIG. 5 and forming an organic layer by an application method by RtoR.
In addition, a roll formed by winding a support in a roll was loaded at a predetermined position, and the support unwound from the roll was inserted into a predetermined transport path. Furthermore, the supply roll which wound the protective film made from PE was loaded in the predetermined position, and the protective film was laminated on the foundation organic layer in the conveyance roller pair of the lower stream of a light irradiation part.

In the organic film forming apparatus, the composition for forming an organic layer was applied in the coating part while conveying the support in the longitudinal direction, and the composition for forming an organic layer was dried in the drying part. The application part used the die coater. The heating temperature in the drying part was 50 ° C., and the passing time of the drying part was 3 minutes.
Next, in the light irradiation section, the dried composition for forming an organic layer was irradiated with ultraviolet light (accumulated irradiation amount: about 600 mJ / cm ² ) to cure the composition for forming an organic layer, thereby forming a base organic layer.
After laminating a protective film on the surface of the base organic layer in the conveyance roller pair downstream of the light irradiation part, the support on which the base organic layer was formed was wound around a winding shaft to obtain a roll. The thickness of the formed base organic layer was 1 μm.

<< Formation of inorganic layer >>
The roll obtained by winding the support having the underlying organic layer formed thereon has three film forming units, a first film forming unit, a second film forming unit, and a third film forming unit, as shown in FIG. The substrate was loaded onto a predetermined position of an inorganic film forming apparatus for film formation by CCP-CVD with RtoR while being wound around and transported.
The support (the support on which the base organic layer was formed) unwound from the roll 74 was passed through a pass roller, a drum, and a predetermined transport path passing through the pass roller and reaching the winding shaft. Furthermore, the supply roll which wound the protective film made from PE was loaded in the predetermined position, and the protective film was laminated on the inorganic layer in the pass roller just downstream of a drum.
The protective film is peeled off by the pass roller immediately upstream of the drum while conveying the support unwound from the roll in the longitudinal direction, and then a silicon nitride layer is formed as the inorganic layer on the base organic layer, as shown in FIG. Such a gas barrier film was produced.
In the gas barrier film, a protective film was laminated on the surface of the inorganic layer in a pass roller immediately downstream of the drum, and then wound around the winding shaft. Thus, the roll which wound the laminated body which laminated | stacked the protective film on the inorganic layer of the gas barrier film was obtained.

For the formation of the inorganic layer (silicon nitride layer), the most upstream first film formation unit and the most downstream third film formation unit were used.
The transport speed of the support was 15 m / min.
As source gases, silane gas, ammonia gas and hydrogen gas were used. The feed rates of the source gas were 150 sccm for the first film forming unit, 300 sccm for the ammonia gas, and 500 sccm for the hydrogen gas, and the third film forming unit was 150 sccm for the silane gas, 350 sccm for the ammonia gas, and 500 sccm for the hydrogen gas.
In both of the first film forming unit and the third film forming unit, the plasma excitation power (power) was 2.5 kW, and the frequency of the plasma excitation power was 13.56 MHz.
The drum was supplied with bias power at a frequency of 0.4 MHz and 0.5 kW. Also, the drum was temperature controlled to 30 ° C. by the cooling means.
The deposition pressure was 50 Pa.

[Examples 2 to 13, Comparative Examples 1 to 5]
The formation of the inorganic layer is the same as in Example 1 except that the film forming unit used, the supply amount of each raw material gas, the plasma excitation power, and the transport speed of the support are changed as shown in Table 1 below. Then, an inorganic layer (silicon nitride layer) was formed on the base organic layer to prepare a gas barrier film, and a protective film Gb was laminated and wound up.
In Example 2 only, the inorganic layer was formed directly on the support without forming the underlying organic layer. In Example 2, a PEN film (Teijin Ltd., Theonex Q65HA) having a width of 1000 mm, a thickness of 100 μm and a length of 100 m was used as the support. This support had an easy adhesion layer on one side, and the formation of the inorganic layer was performed on the side without the easy adhesion layer.

[Thickness of mixed layer and inorganic layer, and N / Si atomic ratio]
Each of the produced gas barrier films is subjected to etching by argon plasma and measurement by XPS as described above to detect the relationship with the composition ratio of silicon atoms, nitrogen atoms, oxygen atoms and hydrogen atoms, and to obtain a mixed layer and an inorganic material. The thickness and N / Si atomic ratio of the layers were measured. XPS was performed using ESCA-3400 manufactured by Shimadzu Corporation.
The measurement was performed at five points in the central region, and the average was taken as the thickness and N / Si atomic ratio of the mixed layer and the inorganic layer in each gas barrier film. In addition, in any gas barrier film, there was almost no difference in the measured value at each point.
The results are shown in Table 2 below.

Furthermore, the gas barrier properties and the total light transmittance of each of the produced gas barrier films were measured and evaluated.

[Gas barrier property]
Water vapor transmission rate (WVTR) [g / (m ² · day) of a gas barrier film under the conditions of temperature 25 ° C. and relative humidity 50% RH by the calcium corrosion method (method described in JP 2005-283561 A) ] Was measured.
The water vapor transmission rate is measured immediately after preparation of the gas barrier film (immediately after preparation), after standing for 1000 hours in an environment with a temperature of 85 ° C. and a relative humidity of 85% RH (after high temperature and high humidity), and a cylinder with a diameter of 6 mm Then, it was carried out under three conditions of bending and bending for 100,000 times so that the inorganic layer was on the outer side (bending for 100,000 times).

[Total light transmittance]
The total light transmittance [%] of each gas barrier film was measured according to JIS (Japanese Industrial Standards) K 7361-1 (1996) using NDH-7000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

[Evaluation]
All water vapor transmission rates less than 1 × 10 ^-4 g / (m ² · day) and total light transmission rates exceeding 85% A;
B which does not enter into the evaluation A and which satisfies both the water vapor transmission rate of 5 × 10 ^-4 g / (m ² · day) or less and the total light transmission rate of 82.5% or more;
A water vapor transmission rate of 1 or more, which is more than 5 × 10 ^-4 g / (m ² · day), and a total light transmission rate of less than 82.5%, which is one or more applicable, was evaluated as C;
The results are shown in Table 2 below.

As shown in the above table, the gas barrier film of the present invention maintains high gas barrier properties not only immediately after film formation, but also after being left in a high temperature and high humidity environment and after conducting a bending test. In addition, the gas barrier film of the present invention has a total light transmittance of 82.5% or more, and also has high transparency.
In particular, as shown in Example 2 and the other examples, by having a base organic layer to be a base of the inorganic layer, more excellent gas barrier properties can be obtained. Further, as shown in Example 5 and other examples, by setting the N / Si atomic ratio of the mixed layer to a range of 0.2 to 0.85, more excellent gas barrier properties can be obtained. As shown in Example 10 and other examples, by setting the N / Si atomic ratio of the mixed layer to be lower than the N / Si atomic ratio of the inorganic layer, more superior gas barrier properties can be obtained. Furthermore, as shown in Example 9 and other examples, the N / Si atomic ratio of the mixed layer is made lower than the N / Si atomic ratio of the inorganic layer, and the difference is 0.05 to 0. By setting the range of .5, higher transparency can be obtained.
On the other hand, in Comparative Example 1, the gas barrier property is low because the mixed layer is too thick. In Comparative Examples 2 and 3, since the inorganic layer is too thick, the gas barrier property is lowered when the bending test is conducted, and the transparency is also low. In Comparative Example 4, since the N / Si atomic ratio of the inorganic layer is too high, the gas barrier property is lowered when left in a high temperature and high humidity environment. Furthermore, Comparative Example 5 has low transparency because the N / Si atomic ratio of the inorganic layer is too low.
From the above results, the effects of the present invention are clear.

It can use suitably as sealing materials, such as a solar cell and an organic electroluminescent element.

DESCRIPTION OF

SYMBOLS

10, 20, 28 Gas barrier film 12 Support body 14 Base

organic layer

16, 24 Mixed layer 18 Inorganic layer 40 Organic film-forming

apparatus

52, 92

Rotating shaft

54a, 54b Conveying roller pair 56

Application part

58, 58a, 58b Drying part 60

Light Irradiator

62, 108 Winding shaft 64, 98

Recovery roll

66, 104

Supply roll

72, 74, 110 Roll 80 Inorganic film forming apparatus 82 Vacuum chamber 84 Vacuum evacuation means 94a to 94c, 106a to 106c Pass roller 100A First film forming unit 100B second film forming unit 100C third film forming unit 102 drum 114 shower electrode 116 high frequency power supply 118 gas supply means Ga, Gb protective film

Claims

An inorganic layer containing silicon nitride and having a thickness of 2 to 15 nm, and a mixed layer containing a component of the inorganic layer and a component of the layer to be a surface on which the inorganic layer is to be formed, and having a thickness of 2 to 25 nm At least one combination of
A gas barrier film, wherein the N / Si atomic ratio of the inorganic layer is 0.7 to 0.97.
The gas barrier film according to claim 1, wherein the N / Si atomic ratio of the mixed layer is 0.2 to 0.85.
The gas barrier film according to claim 1, wherein an N / Si atomic ratio of the mixed layer is lower than an N / Si atomic ratio of the inorganic layer.
The gas barrier film according to claim 3, wherein the difference between the N / Si atomic ratio of the mixed layer and the N / Si atomic ratio of the inorganic layer is 0.05 to 0.5.
5. The combination of the inorganic layer and the organic layer to be the base of the inorganic layer is one or more, and the mixed layer is present between the inorganic layer and the organic layer. The gas barrier film according to any one of the above.